Mrs

Abstracts: Symposium L: Zinc Oxide and Related Materials http://www.mrs.
org/f07-abstract-l/
Home
Symposium L: Zinc Oxide and Related Materials

Zinc Oxide and Related Materials
November 26 - 30, 2007
Chairs
David P. Norton Chennupati Jagadish

Dept. of Materials Science and Engineering Research School of Physical
University of Florida Sciences and Engineering
Gainesville, FL 32611 Australian National University
352-846-0525 Canberra, ACT 0200 Australia
61-2-6125-0363
Irina Buyanova Gyu-Chul Yi

Dept. of Physics and Measurement Technology Dept. of Materials Science and Engineering
Linkping University Pohang University of Science and
Linkoping, S-581 83 Sweden Technology (POSTECH)
46-13-281745 Pohang, Kyungbuk, 790-784 R. O. Korea
82-54-279-2155
Proceedings to be published online

(see Proceedings Library at www.mrs.org/publications_library)
as volume 1035E
of the Materials Research Society
Symposium Proceedings Series.
* Invited paper
SESSION L1: ZnO Nanowires for Applications

Chair: David Norton
Monday Morning, November 26, 2007
Constitution A (Sheraton)
8:30 AM *L1.1
ZnO Nanopiezotronics. Zhong L. Wang, School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia.
Developing novel technologies for wireless nanodevices and nanosystems are of critical importance for in-situ, real-time and implantable
biosensing, biomedical monitoring and biodetection. It is highly desired for wireless devices and even required for implanted biomedical devices
to be self-powered without using battery. Therefore, it is essential to explore innovative nanotechnologies for converting mechanical energy
(such as body movement, muscle stretching), vibration energy (such as acoustic/ultrasonic wave), and hydraulic energy (such as body fluid and
blood flow) into electric energy that will be used to power nanodevices without using battery. We have demonstrated an innovative approach for
1 of 72 Tuesday 29 December 2015 04:27 PM

Abstracts: Symposium L: Zinc Oxide and Related Materials http://www.mrs.org/f07-abstract-l/
converting nano-scale mechanical energy into electric energy by piezoelectric zinc oxide nanowire (NW) arrays [1-3]. We have recently
developed DC nanogenerator driven by ultrasonic wave [4], which is a gigantic step towards application in practice. The operation mechanism of
the electric generator relies on the unique coupling of piezoelectric and semiconducting dual properties of ZnO as well as the elegant rectifying
function of the Schottky barrier formed between the metal tip and the NW. Based on this principle, piezoelectric-field effect transistor [5],
piezoelectric gated diode [6], sensors and resonators have been fabricated, which are the fundamental components of nano-piezotronics.
Piezotronics is a field of using piezoelectric-semiconducting coupled property for fabricating novel and unique electronic devices and
components [7]. [1] Z.L. Wang and J.H. Song Piezoelectric Nanogenerators Based on Zinc Oxide Nanowire Arrays, Science, 312 (2006)
242-246. [2] P.X. Gao, J.H. Song, J. Liu and Z.L. Wang Nanowire Nanogenerators on Plastic Substrates as Flexible Power Source, Adv.
Mater., 19 (2007) 67-72. [3] J.H. Song, J. Zhou, Z.L. Wang Piezoelectric and semiconducting dual-property coupled power generating process
of a single ZnO belt/wire - a technology for harvesting electricity from the environment, Nano Letters, 6 (2006) 1656-1662. [4] X.D. Wang,
J.H. Song J. Liu, and Z.L. Wang Direct current nanogenerator driven by ultrasonic wave, Science, 316 (2007) 102-105. [5] X.D. Wang, J.
Zhou, J.H. Song J. Liu, N.S. Xu and Z.L. Wang Piezoelectric-Field Effect Transistor and Nano-Force-Sensor Based on a Single ZnO
Nanowire, Nano Letters, 6 (2006) 2768-2772. [6] J. H. He, C.H. Hsin, L.J. Chen, Z.L. Wang Piezoelectric Gated Diode of a Single ZnO
Nanowire, Adv. Mater., 19 (2007) 781. [7] Z.L. Wang Nano-piezotronics, Adv. Mater., 19 (2007) 889.
9:00 AM L1.2
Gas Sensor Array made of ZnO Nanorods. Junghwan Huh1, Hyeyoung Kim1,2, Kangho Lee1, Jonghyurk Park2 and Gyutae Kim1; 1School of
Electrical Engineering, Korea University, Seoul, South Korea; 2Electronics and Telecommunications Research Institute, Daejeon, South Korea.
The array of ZnO nanorod networks were fabricated by the sol-gel process, which was selectively grown on the patterned Si 3N4 substrates. The
exposure of the active region of electrodes to the sols following the lithographic process could form the ZnO nanorods at the pre-defined
positions. After the annealing process under the nitrogen environment at the temperature of T=300C, a considerable enhancement of the
conductance was observed. Under the hydrogen environments, the electrical conductance of the ZnO nanorod device increased with the response
time of about 360sec, fitting to the reductive process by the hydrogen ions. The validity of the passivation was approved by coating with the 5%
PVA solution on the array of ZnO nanorods. The easy process for the array of nanowire devices enables a large scale and a low cost fabrication
with the longer life time.
9:15 AM L1.3
Abstract Withdrawn
9:30 AM L1.4
Electrical Properties of ZnO Nanowire Field Effect Transistors on Bended Flexible Substrate. Soon-Shin Kwon, Woong-Ki Hong, Jongsun
Maeng, Tae-Wook Kim, Gunho Jo and Takhee Lee; GIST, Gwangju, South Korea.
One-dimensional nanostructures such as nanowires and nanobelts have been extensively studied as build blocks for nanoscale electronic devices.
Recently, ZnO nanowires have attracted considerable interest in wide applications for optoelectronics, piezoelectric devices, chemical sensors,
and solar cells due to high transparency, piezoelectricity, and direct wide bandgap (3.37 eV) semiconductor with large exciton binding energy.
(60meV) [1]. In addition, the electronic devices on plastic substrate have attracted extensive attention owing to many attractive properties
including biocompatibility, flexibility, light weight, shock resistance, softness and transparency [2]. The combination of these advantages can
give a wide range of applications in displays, sensors, medical devices, and other systems [3]. In this presentation, we report on the electrical
properties of ZnO nanowire field effect transistors (FETs) on a flexible substrate as a function of bending configuration of the substrate. We
fabricated ZnO nanowires FETs on a flexible PET substrate with poly(4-vinylphenol) (PVP) and cross-linked PVP as a gate dielectric layer. The
transistor characteristics such as drain current-drain voltage characteristics and drain current-gate voltage characteristics of the ZnO nanowire
FETs on the flexible substrate will be explained under different bending configuration of the flexible substrate. [1] Z. L. Wang et al., Adv. Funct.
Mater. 14, 943 (2004). [2] R. H James et al., Nature Mater. 6, 379 (2007). [3] B.J. David et at., Nature Nanotechnology 2, 378 (2007).
9:45 AM L1.5
ZnO Nanorod Arrays as Efficient Antireflection Coatings in Solar Cells. Yun-Ju Lee, Douglas S. Ruby, David W. Peters, Bonnie B.
McKenzie and Julia W. P. Hsu; Sandia National Laboratories, Albuquerque, New Mexico.
Antireflection coatings (ARCs) play an important role in improving the performance of solar cells utilizing high refractive index materials such
as Si and GaAs. Current ARCs typically consist of layer(s) of dielectric films or etched textured surfaces to generate a refractive index gradient
and decrease reflectance. Here, we investigate solution-grown ZnO nanorod arrays on Si as ARCs. By varying the synthetic chemistry, we grew

nanorods with different nanoscale morphology, which leads to significant changes the macroscopic reflectance response. The effect of
parameters such as nanorod dimensions and amount of tapering at the nanorod tips on the reflectance spectra are examined. Compared to
traditional single layer ARCs, ZnO nanorod arrays exhibited a much more wavelength independent suppression of reflectance from 400 to 1200
nm. By reducing the average tip diameter of a tapered ZnO nanorod array to 10 nm, a weighted global front surface reflectance of 6.6% was
achieved, superior to commercially used single-layer SiN ARC. The experimental data are compared to results from rigorous coupled wave
analysis to determine the parameters most critical to ARC performance and to suggest possible future direction for optimizing ARC
characteristics through nanorod array synthesis. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin
Company for the United States Department of Energys National Nuclear Security Administration under contract DE-AC04-94AL85000.
10:30 AM L1.6
Nanostructured Degeneratively Doped ZnO as a Solution-processable Transparent Conductor for Solar Cells. Alberto Salleo, Sam J
Rosenthal and Ludwig Goris; Materials Science and Engineering, Stanford University, Stanford, California.
Currently, the material most widely used as transparent electrode in thin-film solar cells is Sn-doped In2O3 (ITO). The natural abundance of In
however is insufficient for high-volume production of low-cost solar cells. Moreover, ITO made by vacuum deposition at temperatures
compatible with transparent flexible substrates, as needed for high-throughput roll-to-roll manufacturing, has poor crystalline quality and high
sheet resistance (Rs>50 O/sq.). Zn-based oxides are extremely attractive replacement materials for ITO due to the great natural abundance and
low toxicity of Zn. ZnO can be made conductive by doping with heteroatoms, like Al and Ga. The performance of these films approaches that of
state-of-the-art ITO. Currently however, the only methods available to deposit high-quality degeneratively-doped ZnO films involve costly
vacuum processing techniques. Therefore, the same throughput and temperature limitations as those described for vacuum processing of ITO
apply to ZnO. Moreover, uniform Al doping of ZnO by sputtering or CVD is challenging because of the high reactivity of Al with residual O2.
We opted to explore colloidal chemistry as a cheap and simple alternative to manufacture ZnO nanostructures and thin film, transparent
electrodes. ZnO is known to form nanostructures of varied shapes. For instance, ZnO nanowires have been grown by many methods in aqueous
solvents. Doping of these wires however is problematic because the dopant atoms typically form stable inert aquo-complexes. In order to solve
this problem, we synthesized ZnO nanowires in a non-aqueous solvent. A dispersion of these highly doped nanowires is effectively a solution-
processable precursor to a transparent conducting film. We successfully synthesized ZnO nanowires in liquid phase by refluxing a solution of Zn
acetate in tri-octylamine at 365C under nitrogen for 15 minutes to 2 hours. SEM characterization confirmed the formation of nanowires with a
width typically smaller than 50 nm. TEM characterization confirmed by X-ray diffraction indicated that the nanowires are crystalline. By
introducing Al acetate in the reaction vessel, Al-doped nanowires were successfully synthesized as confirmed by TEM and EDS. We cast films
from nanowire solutions. Electrical testing showed that films made with pure ZnO are insulating while those made with Al-doped ZnO are
conductive thus providing a convincing proof-of-principle that introducing Al salts in the reaction bath produces indeed doped nanowires.
Thermal annealing at moderate temperatures (T~200C) increased the conductivity by almost 5 orders of magnitude. The process described here
decouples the materials synthesis from successive device fabrication, which constitutes a great advantage from the standpoint of materials and
process integration. Indeed, ZnO nanowires with the most suitable properties can be obtained regardless of the thermal budget limitations
imposed by successive device fabrication steps or substrates.
10:45 AM L1.7
Optical Properties of Surface-Related States in ZnO Nanowires and ZnO-Al2O3 Nanowire Core-Shell Structures. Lars Wischmeier1,
Tobias Voss1, Dong Sik Kim2 and Margit Zacharias2; 1Institute of Solid State Physics, University of Bremen, Bremen, Germany; 2Max Planck
Institute of Microstructure Physics, Halle, Germany.
ZnO nanowires have recently attracted much attention due to their high potential as nanoscale optoelectronic devices. Although the properties of
these nanostructures are mainly governed by the well-known ZnO bulk properties, the influence of the surface increases with decreasing wire
diameter [1]. For nanowire-based applications a detailed knowledge of the microscopic processes in this surface layer is mandatory. We
performed micro-photoluminescence investigations on individual ZnO nanowires with diameters ranging from 34 nm to 520 nm. Here the
nanowires are grown by vapour transport method using Au nanoparticles as catalyst [2]. The photoluminescence of the as-grown nanowires
shows pronounced deep-level and near-band-edge emission. After keeping the samples in air for a few days, the deep-level emission is
drastically reduced. All wires exposed to air show near-band-edge emission that is comparable to our previous results [1,3]. In all cases, surface-
related excitonic emission strongly contributes to the near-band-edge emission in addition to the emission caused by the recombination of
excitons bound to neutral donors and free excitons. The observation of the surface-related excitonic emission from wires grown with different
conditions underlines that this emission is a general phenomenon for ZnO nanowires. To analyze possible interconnections between the reduction
of deep-level emission and the occurrence of surface-related excitonic emission for nanowires exposed to air, we measured the
photoluminescence in regular time intervals starting directly after the growth to trace the changes of the optical properties. We compare the
results to those obtained with a second sample that was grown under the same conditions but additionally covered with a thin Al 2O3 layer
directly after the growth process. The results show the effect of the passivation of the ZnO surface layer and the influence of the shell on the

optical properties of the ZnO core.

[1] L. Wischmeier et al., Appl. Phys. A 84 , 111 (2006) [2] D. S. Kim et al., Small 3 , 76 (2007) [3] L. Wischmeier et al., Phys. Rev. B 74 ,
195333 (2006)
11:00 AM L1.8
Fabrication of Vertically Aligned Single-Nanometer-Diameter ZnO Nanorods Using MOVPE with a Two-Step Temperature Growth
Method. Kokoro Kitamura1, Takashi Yatsui2, Motoichi Ohtsu1,2 and Gyu-Chul Yi3; 1Department of Electronic Engineering, The University of
Tokyo, Tokyo, Japan; 2Solution-Oriented Research for Science and Technology, Japan Science and Technology, Tokyo, Japan; 3Department of
Materials Science and Engineering, Pohang University of Science and Technology, Pohang, South Korea.
Zinc oxide (ZnO) nanostructures have attracted much attention for use in optical and electrical devices because of the large exciton binding
energy and large oscillator strength of ZnO. ZnO also has great potential as a material for room temperature nanoscale photonic devices. A
nanophotonic switch using one-dimensional ZnO nanorod double-quantum-well structures has been reported. Additional functional devices can
be realized using the additional radial quantum confinement effect of ZnO nanorods. Although ultrafine (less than 10 nm in diameter) ZnO
nanorods exhibiting the quantum confinement effect have been reported, they grow in random directions. In this study, we used a two-step
temperature growth method to fabricate vertically well-aligned ultrafine ZnO nanorods. The ZnO nanorods were grown on sapphire (0001)
substrate using a catalyst-free metalorganic vapor phase epitaxy (MOVPE) system. Diethylzinc (DEZn) and oxygen were used as the reactants
and argon as the carrier gas. The pressure inside the reaction chamber was maintained at 5 Torr. Our method consists of low-temperature growth
for the vertical alignment of ZnO nanoneedles and high-temperature growth for the ultrafine nanorod structure. In the first step, vertically
well-aligned ZnO nanoneedles measuring 1 m in length and 100 nm in diameter were grown at 450 C for 35 min. Before the second step, the
substrate temperature was raised to 750 C without DEZn gas flow. In the second step, we supplied DEZn gas with oxygen for 10 min at 750 C.
Consequently, ultrafine ZnO nanorods structures were grown from the tips of the preformed nanoneedles. Furthermore, the ultrafine ZnO
nanorods were aligned in the direction of the preformed vertically well-aligned nanoneedles; that is, the ultrafine ZnO nanorods were vertical to
the substrate. Scanning electron micrographic images revealed that the minimum diameter of the ZnO was less than 10 nm and the length was
500 nm with a uniform diameter along the axis. Since the diameter of the nanorods is decreased with increasing temperature, the successful
fabrication of well-aligned ultrafine ZnO nanorods described here is a promising step toward designing three-dimensionally controlled
nanophotonic devices.
11:15 AM L1.9
Correlating the Optical and Electrical Properties of Electrodeposited ZnO Nanowires. Chegnui Bekeny1, Tobias Voss1, Juergen Gutowski1,
Ramon Tena-Zaera2, Jamil Elias2, Claude Levy-Clement2, Ivan Mora-Sero3 and Juan Bisquert3; 1Institute of Solid State Physics, University of
Bremen, P.O. Box 330440, 28344 Bremen, Germany; 2Institut de Chimie et Matriaux de Paris-Est (ICMPE), CNRS, UMR 7182 Bat. F, 2-8 rue
Henri Dunant, 94320 Thiais, France; 3Departament de Fsica, Universitat Jaume I, Av. de Vicent Sos Baynat s/n, 12071 Castell de la Plan,
Spain.
Nanowire arrays of ZnO (bandgap at room temperature 3.37 eV, exciton binding energy 60 meV) have a large surface to volume ratio and are
nowadays under intense investigation for use as building blocks in a new generation of devices such as light emitting diodes, gas sensors and
solar cells. We report on the optical characterization of both as-grown and annealed nanowire arrays grown by electrodeposition. We correlate
their optical and electrical properties to understand the microscopic origin of the near-band-edge emission and the dependence of both optical
and electrical properties on post-growth annealing treatments. We perform electrochemical deposition in a three-electrode electrochemical cell to
obtain large arrays of ZnO nanowires at a growth temperature of 80 C. A transparent conducting SnO2:F-glass coated with a thin ZnO buffer
layer is used as substrate. The electrolyte is an aqueous solution of ZnCl2 and KCl saturated with bubbling O2 [1]. The photoluminescence (PL)
spectra of the as-grown nanowire samples show near-band-edge emission with a linewidth of 18 meV. This rather broad emission with maximum
at 3.366 eV and the absence of sharp excitonic transitions are indications of high donor densities leading to the formation of a band of donor
states which overlaps with the conduction band [2]. Therefore, the recombination of electrons and holes is a kind of band to band transition.
After annealing the nanowire samples at 500 C, sharp excitonic emission lines become visible, independent of the annealing time and
atmosphere. The appearance of a donor-bound exciton emission line located at 3.361 eV with linewidth of 3 meV and the free-exciton emission
are indications of a remarkable reduction in the donor concentration and an improvement in quality. The difference of 5 meV in the energy
position of the main emission peaks in the as-grown and annealed samples supports this fact. Excitation density dependent measurements reveal
a donor-acceptor-pair transition located at 3.318 eV in the annealed samples. To confirm the existence of a high donor density in the as-grown
nanowires and its reduction in the annealed samples, we performed electrochemical impedance spectroscopy measurements [3] on the nanorod
ensembles. For the as-grown nanowires, we find a donor density of 1020 cm-3 while the annealed samples show a reduction of the donor density
by nearly two orders of magnitude. As in the case of the PL spectra, the donor density in the annealed samples is found to be independent of the
annealing atmosphere and time. This result points out that oxygen vacancies are not the main origin of the high donor density in these ZnO
nanowires. Our results strongly suggest that zinc interstitials are a likely candidate to play this role in electrodeposited ZnO nanowires. [1] R.

Tena-Zaena et al, Thin Solid Films 483, 372 (2005) [2] Bekeny et al., J. Appl. Phys. 100, 104317 (2006) [3] Ivn Mora-Ser et al, Appl. Phys.
Lett. 89, 203117 (2006)
11:30 AM L1.10
Inkjet Printing of ZnO Nanorods for Low Cost Field Effect Transistors. Cyril Martini1, Guillaume Poize1, Sebastien Sanaur2, Michael
Barret2, Philippe Collot2, Frederic Fages1 and Joerg Ackermann1; 1Laboratoire des Matriaux Molculaires et des Biomatriaux, GCOM2 UMR
CNRS 6114, , Universit de la Mditerrane, Facult des Sciences de Luminy, Case 901, 163, avenue de Luminy,, Marseille, France; 2Center for
Microelectronics of Provence Georges Charpak (CMP-GC, Department of Packaging and Flexible Substrates (PS2), Laboratoires Morandat -
impasse de la Plaine, Gardanne, France.
ZnO nanorods represent promising nanomaterials for future low cost flexible electronics such as RFID tags or solar cells. Recently high mobility
field effect transistors, hybrid bulk heterojunction solar cells, hydrogen storage and light emitters based on ZnO nanorods have been reported.
Therefore combining these materials with low cost deposition techniques such as inkjet printing could overcome the limite of organic
semiconducting materials usually used in flexible electronics. In this communication we present our results on ink jet printing of ZnO nanords
and show prelimimary resutls on printed ZnO field effect transistors. The effect of surface functionalization of the ZnO nanorods as well as
thermal annealing treatment on the charge carrier transport properties of the resulting ZnO transistors will be discussed
11:45 AM L1.11
Electrospun InGaZnO4 Nanofiber Based Field-effect Transistors. Seung-Hoon Choi, Jae-Min Hong and Il-Doo Kim; Korea Institute of
Science and Technology, Seoul, South Korea.
Transparent ZnO, GaZnO (GZO), and InGaZnO4 (IGZO) films have been used as an active channel in exhibiting n-type semiconductor
characteristics with high optical transmittance in the visible spectrum. In particular, the ZnO based thin-film field-effect transistors (FETs) are of
great interest due to their high field-effect mobility and good compatibility with plastic substrates. In addition, the pursuit of new materials
and/or structures with novel functionalities has led, over the past several years, to the use of wide band gap semi-conducting oxides comprising
one-dimensional (1D) nanostructures. Efforts have been focused on achieving increased surface-to-volume ratios and reduced cross sections,
offering more effective charge transport. In this regard, we report on the fabrication of low-voltage operating FETs using IGZO nanofiber as an
active channel. ZnO/PVA, GZO/PVA, and IGZO/PVA composite nanofibers utilizing sol-gel precursors(i.e., InCl 3, GaCl3, Zn acetate /
Poly(vinyl alcohol) were directly electrospun onto the patterned gate insulators, i.e., Mg doped Ba 0.6Sr0.4TiO3, and calcined at 450-550C for 1
hr. The morphology, crystal structure and element analysis of ZnO, GZO, and IGZO nanofbiers were investigated by FE-SEM, XRD, EPMA and
TEM. These resulted in polycryatalline ZnO, GZO nanofibers and amorphous-like IGZO nanofibers composed of 200-600 nm diameter cores.
Electrical transport of each nanofibers were measured by semiconductor device analyzer (Agilent B1500A). We observed that the IGZO
nanofibers exhibited much enhanced conductivity as compared to those ZnO and GZO of nanofibers. The semiconducting behavior of ZnO,
GaZnO, and InGaZnO4 nanofibers and FETs characteristics are discussed in detail in an accompanying presentation.
SESSION L2: ZnO Nanowire Synthesis and Properties

Chair: Zhong Lin Wang
Monday Afternoon, November 26, 2007
1:30 PM L2.1
Second-harmonic Generation and Thermal Effects in ZnO Nanorod Arrays. Iryna Kudyk1, Lars Wischmeier1, Bianca Postels2, Andrey
Bakin2, Andreas Waag2 and Tobias Voss1; 1Institute of Solid State Physics, University of Bremen, Bremen, Germany; 2Institute of
Semiconductor Technology, Braunschweig University of Technology, Braunschweig, Germany.
Densely packed arrays of hexagonal ZnO nanorods are currently considered as basic platforms for the realization of complex optoelectronic
devices. In addition to their excellent crystalline structure and preferentially c-axis orientation, these nanorods possess a large surface-to-volume
ratio which allows to efficiently functionalize their surface. We present investigations of the non-linear optical properties of ZnO nanorod
ensembles fabricated by an aqueous-chemical growth technique. For the excitation, we used a tunable femtosecond oscillator providing 50-fs
pulses with 12 nJ in a spectral range between 700 nm and 900 nm. The signal was detected spectrally resolved in both reflection and

transmission geometry at room temperature. The emission from the nanorods consists of second-harmonic generation (SHG), near-band-edge
photoluminescence (PL), and deep-level emission (DLE). The PL and DLE are generated by multi-photon excitation and absorption of SHG
photons. We find that the ratio of SHG, PL, and DLE contributions strongly depends on the photon energy of the femtosecond pulses. We
analyze the wavelength and excitation-power dependence of the non-linear emission for different angles between the incident laser pulses and
the c-axis of the nanowires. From the results we determine the non-linear optical (NLO) coefficients of the ZnO nanorod ensemble. We present
corresponding results for samples with different nanorod lengths and compare the NLO coefficients of the nanorod arrays to those of ZnO bulk
crystals. Due to the wurtzite structure of the single-crystal nanorods the obtained values for the second-order NLO coefficients ? (2)311 and ?(2)333
are of opposite sign. For both the nanorod arrays and the bulk crystals we find |?(2)311/ ?(2)333| = 0.10 pointing to comparable crystalline qualities
of the samples. The peak spectral position of near-band-edge PL is shifted to a range of 400 - 415 nm due to local heating of the sample by the
femtosecond excitation pulses. This thermal effect is a result of the reduced thermal conductivity of the nanorod ensemble compared to
conventional bulk crystals. The shift of the PL allows us to determine the local temperature in the nanorods under sub-bandgap
femtosecond-pulse excitation. We present simulations of the heat transport in ZnO nanorods and investigate the correlation between nanorod size
and heat transport.
1:45 PM L2.2
Heteroepitaxial Orientations of ZnO Nanorods on Ag. Jerrold A. Floro1, Joseph R. Michael2, Luke N. Brewer2 and Julia W. P. Hsu2;
1Materials Science and Engineering, University of Virginia, Charlottesville, Virginia; 2Sandia National Labs, Albuquerque, New Mexico.
Fine-grained polycrystalline silver is an effective nucleation layer for growth of spatially well-aligned ZnO nanorod arrays from aqueous
solution. In order to explore heteroepitaxy in the ZnO/Ag system, wurtzite ZnO nanorods were grown onto coarse-grain bulk polycrystalline Ag
substrates, providing a means to efficiently investigate the range of preferred heteroepitaxial orientations. Scanning electron microscopy shows
that ZnO nanorods grow only on select grains, which are found to have <111> fiber-texture using electron backscatter detection analysis. The
nanorods, which are faceted and grow perpendicularly to the {111} surface, exhibit a tightly-defined epitaxial orientation of (0001) ZnO ? {111}
Ag and <11-20> ZnO || <1-10> Ag. This hex-on-hex orientation has a nominal 11% lattice misfit, but is characterized by a near-coincidence
site lattice with reasonable coincidence site density and very small CSL misfit strain. We will discuss the use of CSL concepts in understanding
heteroepitaxy in highly dissimilar materials systems. This work was supported by the Sandia LDRD program and the DOE Office of Basic
Energy Sciences. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States
Department of Energys National Nuclear Security Administration under contract DE-AC04-94-AL-85000.
2:00 PM L2.3
Characterization of Vertical Arrays of ZnO Nanorods by AFM. Christian Teichert1, Yue Hou1, Andrey Andreev1, Gerhard Brauer2, Kai
Hang Tam3 and Aleksandra Djurisic3; 1Institute of Physics, University of Leoben, Austria, Leoben, Austria; 2Institut f. Ionenstrahlphysik und
Materialforschung, Forschungszentrum Rossendorf, Dresden, Germany; 3Department of Physics, University of Hong Kong, Hong Kong, China.
One-dimensional nanostructures, such as nanorods or nanotubes, exhibit technological potential for many device applications, like efficient
low-cost ZnO nanorod-polymer solar cells [1]. However, achieving control over the growth of such nanostructures leading to proper dimensional
confinement (like nanorod diameter, length, density and orientation) is still a challenging task. On the other hand, atomic-force microscopy
(AFM) is well known as a valuable tool for nanometer scale characterization of different types of nanostructures [2]. The capabilities of AFM
techniques are demonstrated for the characterization of vertical arrays of various ZnO nanorods. In detail, the topography of the ZnO nanorods,
grown on Si and ITO substrates, was examined. It was found that tapping mode AFM is an appropriate tool to reveal the morphological features
of vertical ZnO nanorods on the nanoscale, i.e. 3D rod shape, lateral size, average height, and rod height uniformity [3]. Moreover, by cross-
sectional measurements it was established that intermediate {10-13} facets appear between the top (0001) and side {10-10} facets. Further,
polymer coated ZnO nanowires have been investigated with respect to the possibility of measuring their elcetric properties by Conductive
Atomic Force Microscopy. [1] E. Greene, et al., Nano Lett. 5 (2005) 1231. [2] C. Teichert, Phys. Rep. 365 (2002) 335. [3] G. Brauer, W.
Anwand, D. Grambole, W. Skorupa, Y. Hou, A. Andreev, C. Teichert, K. H. Tam, A. B. Djurisic, Nanotechnology 18 (2007) 195301.
2:15 PM L2.4
Direct Formation of ZnO Nanowire Arrays by Exposure of a Zn Compound to Extreme Ultraviolet Interference Patterns. Vaida
Auzelyte1, Harun H. Solak1 and Gerald Egeland2; 1Laboratory for Micro and Nanotechnology, Paul Scherrer Institut, Villigen, Switzerland;
2Spallation Neutron Source Division, Paul Scherrer Institut, Villigen, Switzerland.
Regular arrays of ZnO nanowires are of high interest for their potential use in new devices such as transparent transistors or light emitting
diodes. ZnO nanostructures can be fabricated via synthesis or lithographic lift-off techniques. In general the synthesis route does not lead to the
creation of regular, addressable structures and the lift-off method faces limitations in resolution. Here, we demonstrate a technique for the

fabrication of large arrays of dense and regular ZnO nanowires by exposure of a Zinc Naphthenate film with extreme ultraviolet interference
lithography (EUV-IL). Zinc Naphthenate works as a negative resist when it is exposed to energetic radiation such as electron beam or EUV light,
i.e. it becomes insoluble in certain solvents [1]. We deposited this compound onto Si wafers with spin-coating and exposed the resulting films
using EUV-IL at a wavelength of 13.5 nm. We measured the EUV lithographic sensitivity and contrast of Zinc Naphthenate to be 500 mJ/cm2
and 3.45, respectively. High-quality arrays of regular and parallel lines with periods from 100 nm down to 32 nm were achieved. The highest
resolution lines were only 12 nm wide. They exhibited very low line edge roughness and had a height-to-width aspect ratio of 2:1. The cross
sections showed vertical side walls and complete clearing of the spaces between the lines. Patterned Zinc Naphthenate lines were annealed to
form poly-crystalline ZnO nanowires. The lines shrank by about 30%, and the structures became transparent. The nanowire arrays were
characterized using SEM, TEM, and XRD. Creation of large area ZnO nanowire arrays through EUV-IL exposure may enable use of these
structures in research and industrial applications. Use of EUV light in the exposure brings certain benefits including high-resolution and high
exposure dose sensitivity due to the exceptionally efficient absorption of EUV radiation by Zn. 1. S. M. Saifullah, K. R. V. Subramanian, D.-J.
Kang, D. Anderson, W. T. S. Huck , G. A. C. Jones, M. E. Welland, Adv.Mater. 17 (2003) 1757
3:00 PM L2.5
New Insights in how to Control Size Dispersion and Surface Roughness of Solution-phase Grown ZnO Nanorods. Cyril Martini1, Aurore
Said2, Wladimir Marine2, Suzanne Giorgio2, Frederic Fages1 and Joerg Ackermann1; 1Laboratoire des Matriaux Molculaires et des
Biomatriaux, GCOM2 UMR CNRS 6114, , Universit de la Mditerrane, Facult des Sciences de Luminy, Case 901, 163, avenue de Luminy,
Marseille, France; 2Centre de Recherche en Matire condense et Nanosciences UPR CNRS 7251, Campus de Luminy, 163 Avenue de Luminy,,
Marseille, France.
The synthesis of semiconductor nanorods and -wires has attracted much interest due to their unique electronic and optical properties during the
last decade. Among these semiconductors Zinc oxide are of particular interest because of its low cost solution synthesis, environmental and
biomedical compatibility. Furthermore high mobility field effect transistors, hybrid bulk heterojunction solar cells, hydrogen storage and light
emitters based on ZnO nanorods have been reported which stimulate the research for further improved ZnO nanomaterials. Amongst the
different solution-phase route for the synthesis of ZnO nanorods, the alkaline hydrolysis of zinc salts in alcoholic or aqueous media has been the
most widely applied. These synthesis methods lead to highly crystalline nanorods of high yields, but are usually accompagnied by a high degree
of polydispersity in length and diameter. Although the control of size distribution is very crucial for improved material performance, so far only
small attention has been paid to study the underlying processes leading to the statistical distribution and the question in how far it can be
controlled. We present in this communication a detailed investigation of the influence of the base on the growth of ZnO nanorods synthesized by
alkaline hydrolysis of zinc salts in methanol. The synthesis of the ZnO nanorods are performed in a two step process (Ref 1) in which first
spherical nanoparticles are formed by the reaction of Zinc acetate with different bases (KOH, NaOH, LiOH and CsOH) followed by a
condensation step which induces the nanorod growth. Histograms representing length and diameter distribution at different stage of the ZnO
nanorod growth obtained from TEM analysis are used to study the nanorod formation in detail. In general, our results reveal that high quality
nanorods can be synthesized with all four alkalis, and surface roughness as well as length and diameter of the nanorods are strongly effected by
the nature of the alkali. From studies of the early stage of nanorod formation, we find that the growth mode is alternated by the base. In the
presence of KOH, mainly oriented attachement along the C-axis is observed, while a isotropic oriented attachement leads first to the formation of
large nanoparticles followed by an anisotropic Oswald in the case of NaOH. This change in the growth process leads to ZnO nanorods of better
crystallinity and narrower size distribution with atomically flat surfaces in the case of NaOH.
3:15 PM L2.6
Rapid, Microwave Synthesis of Aligned Zinc Oxide Nanowires. Husnu Emrah Unalan, Pritesh Hiralal and Gehan Amaratunga; Engineering
Department, University of Cambridge, Cambridge, United Kingdom.
Solution growth approach for zinc oxide (ZnO) nanowires is highly appealing because of the low growth temperature and possibility for large
area synthesis. Reported reaction times for ZnO nanowire synthesis, however, are too long which span from several hours to days. In this work,
we have rapidly synthesized ZnO nanowires on various substrates (such as PET, silicon and ITO) using a commercially available microwave
oven. The average growth rate of our samples is determined to be larger than 1 m/h depending on the microwave power. We have analyzed the
as-grown ZnO nanowires with high resolution transmission electron microscope (TEM), field-emission scanning electron microscope (SEM),
and photoluminescence and absorption spectroscopy. Electrical properties of individual nanowires were obtained by lithographical patterning in
a field effect transistor configuration. SEM showed the nanowire diameters of 20-50 nm and lengths up to several microns and TEM analysis
revealed single crystalline lattice of the nanowires. We will present a detailed analysis of the growth properties of ZnO nanowires as functions of
growth time and microwave power. In brief, our work demonstrates the possibility of a fast synthesis route using microwave heating for
nanomaterials synthesis.

3:30 PM L2.7
Selective Area Growth of ZnO Nanowires on Diamond-like Carbon Film and Applications for UV Emission and Detection. R. D Vispute,
Sheng-Yu Young, Brian Tran, Arun Luykx and T. Venketesan; CSR, University of Maryland, College Park, Maryland.
New generation of electronics needs multifunctional materials, devices, and sensors integrated in a single platform via nanotechnology. To
realize faster, compact and efficient electronics, various nanostructures could be integrated using selective area growth approach. Here we report
selective area growth of ZnO nanowires using diamond-like-carbon (DLC) nucleation layers. DLC is of interest due to its hardness, insulating
properties, high thermal conductivity, and high chemical inertness. Zinc oxide (ZnO) was chosen for nanowire growth because of its direct
optical band-gap (3.37 eV) and its large exciton binding energy (60 meV) which boasts near UV emission, tunable electrical conductivity,
piezoelectricity, and chemical sensing characteristics; these can all be used for photonics, optoelectronics, and chemical and bio-sensors. The
nanowires were grown using vapor phase deposition, with 99.999% pure zinc and argon and oxygen as the carrier gasses. The deposition took
place at around 650-700C. The DLC layer was deposited using a pulsed laser deposition system at room temperature with a graphite target. The
grown nanowires were characterized using a scanning electron microscopy, photoluminescence, electroluminescence, and x-ray photoelectron
spectroscopy. Our results indicate that the nanowires grow selectively on the DLC surface. Interestingly, nanowires do not grow on regions of the
substrate where no DLC was deposited. The average diameter size ranged from about 15-40 nm, depending on the growth temperature. An
emission of UV light at 386 nm (with a considerably lower green band emission) was clearly observed. Our results clearly indicate selective and
high density nucleation ZnO on DLC. Dependence of thickness of DLC on nucleation, selectivity, orientation of nanostructures will be
discussed. Results on material compatibility with DLC and silicon that can yield nanostructures with minimum inter-diffusion of chemical
constituents of nanostructure across interfaces and dependence of the surface morphology and thickness of the DLC on the nucleation of ZnO
nanowires will be presented. Applications such as UV emitter and UV detector based on the ZnO nanostructures fabricated using our approach
will be highlighted. Generic comments will be made on the possibility of fabrication of nanostructure with tunable band gaps for tunable UV
applications.
3:45 PM L2.8
Strong UV Emission from Electrodeposited ZnO Nanorods on Non-epitaxial Au coated Si(100). Soo-Jin Chua1,2, Miao Wang2 and Carl V
Thompson3; 1Institute of Materials Research and Engineering, 3 Research Link, Singapore, Singapore; 2Siingapore-MIT Alliance, E4-04-10, 4
Engineering Drive 3, Singapore, Singapore; 3Department of Materials Science and Engineering, MIT, Cambridge, Massachusetts.
Various approaches have been developed to synthesize ZnO nanostructures. Among them, electrodeposition possesses the advantages of low
temperature, low cost, high throughput and high deposition rate. Considerable work has been done on electrodepostion of ZnO on epitaxial Au
and a heteroepitaxial electrodepostion of (0001)-oriented ZnO has been reported on single-crystalline Au (111) [1,2]. However, there are very
few reports regarding the growth of ZnO on non-epitaxial Au. In our work, we demonstrated that good quality of polycrystalline ZnO nanorods
with mainly preferred (0001) orientation and with comparable photoluminescence property could be grown on non-epitaxial Au. A template-free
potentiostatic cathodic electrochemical deposition method was employed to grow one-dimensional ZnO facet nanorods in zinc nitrate aqueous
solution. The experiment was conducted under low temperature from 60 DegC to 80 DegC. The concentration of zinc nitrite was 0.005 M and
the potential were ranging from -1 to -1.4 V (with current density varied from 100 to 1000 uA/cm2). Facet ZnO nanorods were grown on both
epitaxial Au (111) and non-epitaxial Au coated Si (100) substrates. Under more positive deposited potential with current density within 100 to
300 uA/cm2, the as-grown ZnO nanorods deposited on these two substrates both show a strong narrow UV peak (FWHM 270 meV) at around
370 nm wavelength and a weak wide peak at visible light wavelength in room temperature photoluminescence spectrum. It is impressive that the
ZnO nanorods grown on non-epitaxial Au possess a comparable intensity ratio between UV light and visible light peak, which are considered as
evidence of the high quality of (0001) oriented ZnO. In our result, the highest intensity ratio of as-electrodeposited sample is 15, which is higher
than the former reported value of 1.3 from ZnO grown by electrodepositon, 1.0 by MOCVD and 0.18 by MBE from other groups [2]. Under
more negative deposition potential with increased current density, more defects will be introduced, resulting in a decrease of the UV peak
intensity and an increase of the visible light peak intensity. Two peaks within visible light range: 580 nm (yellow) and 680 nm (red) were
detected. The result is different from the normal green light emission reported from other deep level emission of electrodeposited ZnO. The
origin of these emissions are being investigated and results of post-annealing of electrodeposited ZnO nanorods will be reported as well. [1] R.
Liu, A. A. Vertegel, E. W. Bohannan, T. A. Sorenson, J. A. Switzer, Chem. Mater. 2001, 13, 508 [2] M. Izaki, S. Watase, H. Takahashi, Adv.
Mater. 2003, 15, 2000
4:00 PM L2.9
Synthesis and Mechanical Properties of Zinc oxide Nanowires. Baomei Wen and John J. Boland; Trinity College Dublin, Dublin, Ireland.
Nanowires have attracted great attention because of potential application in the area of nanoscale interconnects and the active components of
nanodevices. Nanowires also provide a good system to investigate the dependence of electrical and mechanical properties on dimensionality and
size reduction. ZnO is a wide band gap (3.37 eV) semiconductor with a large exciton binding energy (60 meV). ZnO nanowires are of interest in

nanodevice applications such as light-emitting diodes, field-effect transistors, gas sensors, and solar cells. Here, we report a mild sovolthermal
route to fabricate ZnO nanowires using a thin nucleation layer of nanostructural ZnO deposited by room temperature magnetron reactive
sputtering. Small nanowires with typical diameters of 20 nm have been successfully synthesized. By adjusting reaction parameters, diameters in
the range of 100-300 nm nanowires have been also obtained. These nanowires exhibit excellent single crystalline structure with [0001] growth
direction. Mechanical properties of these nanowires were measured using a AFM tip-induced lateral bending technique developed recently by
our group, which in contrast to earlier methods, allows the full spectrum of mechanical properties to be measured. During nanowire manipulation
both the normal and lateral force (F) signals are recorded as a function of displacement (d). The results demonstrate that in contrast to previous
reports [1], Youngs modulus E of ZnO nanowires is essentially diameter-independent and comparable to that of bulk ZnO. The average value of
Yangs modulus E is 114 25 GPa in this work. The yield strength sy will also be discussed. References [1] C. Q. Chen, Y. Shi, Y. S. Zhang, J.
Zhu, and Y. J. Yan, Phys. Rev. Lett. 2006, 96, 075505.
4:15 PM L2.10
Growth and Luminescence of Doped ZnO Nanoplate and Nanowire Arrays. Javier Piqueras, Ana Urbieta, Yanicet Ortega and Paloma
Fernandez; Dpt. Fisica de Materiales, Universidad Complutense de Madrid, Madrid, Spain.
Elongated ZnO nanostructures, as wires, rods or belts have been grown by different methods in the last years and their properties have been
reported. Contrary to the case of one-dimensional nanostructures, plate shaped ZnO nanostructures have been less investigated. In the present
work, Sn and Mg doped ZnO nano- and microstructures, including stacks of nanoplates, have been grown by thermal treating of compacted
mixtures of ZnO-SnO2, ZnS-SnO2 and ZnO-MgO powders under argon flow. The starting materials were commercial powders of ZnO, ZnS,
SnO2, and MgO. ZnO-SnO2 powders containing 1, 5 and 10 wt % of SnO2, ZnS-SnO2 powders with 1 and 5 % wt of SnO2 and ZnO-MgO
powders with 1, 5 and 20 wt % of MgO, were prepared by milling the corresponding mixtures in a centrifugal ball mill. The final powder was
compacted under a compressive load to form disk shaped samples. The samples were annealed under argon flow and were then characterized by
XRD and the SE, cathodoluminescence (CL) and EDS modes of SEM. The annealing lead to the growth of elongated structures in the sample
surface as previously found in undoped ZnO powder (1) (2). In the case of the ZnO-SnO2 sample containing 1 wt % of SnO2 rods with, cross-
sectional dimensions from hundreds of nanometers to few microns, formed by stacked nanoplates, are observed. In some rods the stacks present
two well defined orientations. The plates have specific orientations which correrspond to the slip systems in ZnO. The presence of Sn in ZnO
influences the internal stress resulting in slip structures. Cathodoluminescence measurements show that the near band edge emission in the
undoped powder appears at 3.26 eV, while in the doped samples the band is peaked at about 3.33 eV which is explained by the increase of band
gap due to Sn doping. When ZnS-SnO2 mixture is used as precursor, nanowire arrays with 6-fold symmetry are formed in a first stage of growth.
In a more advanced stage of growth arrays of stacks of nanoplates with 6-fold symmetry are formed. The formation of the 6-fold structures
depends on the presence of Sn and on the defect structure. In the samples prepared from ZnO-MgO mixtures containing 5 or 20 wt. % of MgO,
rods formed by oriented stacks of nanoplates have been observed. Contrary to the case of the samples containing Sn, the nanoplates have not
different orientations, but appear normally perpendicular to the growth axis . In addition needles grow along the growth axis. Local EDS
measurements show that the at. % of Mg in the needles and in the plates is in the range 5- 10 %. The CL spectra in the nanoplate stacks,
correspond to that of ZnO, while in the surface background of the disk, luminescence features associated to Mg are observed. 1) J.Grym,
P.Fernandez and J.Piqueras, Nanotechnology 16, 931 (2005) 2) L.Khomenkova, P.Fernandez and J.Piqueras, Crystal Growth and Design, 7, 836
(2007)
4:30 PM L2.11
ZnO/TiO2 Nanohybrid Structures Synthesized by Site-Specific Deposition. Cheng Chun1,2 and Wang Ning1,2; 1the Institute of Nano Science
and Technology, the Hong Kong University of Science and Technology, HongKong, China; 2Department of Physics, the Hong Kong University
of Science and Technology, HongKong, China.
Semiconductor nanostructured composites are of interest in many technological applications, such as biolabels, photochemical solar cells, photo
catalysis, and sensors. Considerable effort has been devoted to combining semiconductor nanoparticles with suitable materials to synergize the
properties of both components, which has led to many promising applications such as the enhancement of photocatalytic performance through
the deposition of metal or metal islands on ZnO and TiO2 nanoparticles [1]. Compared to pure ZnO and TiO2, coupled ZnO/TiO2 polycrystals
display a greater photocatalytic activity [2]. In our previous works, we have systematically investigated the formation mechanisms of ZnO [3]
and TiO2 [4] nanostructures synthesized by our unique methods. Currently, we developed a simple hydrothermal method for the preparation of
ZnO/TiO2 nanohybrid structures through the site-specific deposition of TiO2 on ZnO nanorods. Each ZnO nanorod is assembled with one TiO2
cap at one end of the rod. We have found that the polarity of the ZnO (0001) surface plays an important role in the formation of ZnO/TiO2
nanohybrid structures. Using high-resolution transmission electron microscopy, we observed that the amorphous TiO2 particles that are
connected to ZnO nanorods are transformed to nanocrystals of the anatase and rutile phases, which have a particular relationship with the
orientation of ZnO nanorods and good interface structures. This work provides a rational approach to the assembly of complex nanohybrids
using the intrinsic properties of ZnO nanocrystals that allows the size, aspect ratio, and TiO2 cap structures to be fully controlled in the

fabrication process and by subsequent annealing treatments [5]. [1] C. Pacholski, A. Kornowski, H. Weller, Angew. Chem. Int. Ed. 2004, 43,
4774. [2] V. Sukharev, R. Kershaw, Photochem. Photobiol. A: Chem. 1996, 98, 165. [3] B.D Yao, Y. F. Chan, N. Wang, Appl. Phys. Lett. 2002,
81, 757. [4] B.D. Yao, Y.F. Chan, X.Y. Zhang, W.F. Zhang, Z.Y. Yang and N. Wang, Appl. Phys. Lett. 2003, 82, 281. [5]C. Cheng, K. F. Yu, Y.
Cai, and K. K Fung N. Wang, Submitted to Angew. Chem. Int. Ed.
4:45 PM L2.12
Investigation of Copper Incorporation into ZnO Nanowires. Susie Eustis, Douglas Meier and Babak Nikoobakht; Surface and Microanalysis
Science Division, National Institute of Standards and Technology, Gaithersburg, Maryland.
The applications of zinc oxide (ZnO) nanowires (NWs) in devices are promising due to the optical, mechanical and electrical properties of these
one-dimensional structures, but current uses are limited by the ability to produce high quality nanowires at desired locations. Copper is an
attractive catalyst for generating zinc oxide nanowires due to the long length and high density of ZnO NWs produced. However, defects due to
impurities, oxygen deficiencies, and structural defects lead to decreased optical and electrical transport. Photoluminescence (PL) microscopy
found that ZnO NWs grown by high temperature evaporation on a bulk copper substrate display the expected band gap emission at 380nm. A
larger visible emission is also observed in the PL spectrum around 520nm due to defect states. High-resolution transmission electron microscopy
(HR-TEM) shows the ZnO nanowires are single crystalline with hexagonal structure. Auger electron spectroscopy (AES) reveals that copper
atoms are present all along the length of the NW. AES also confirmed that the surface of NWs is oxygen deficient. The metallic tip shows a
polycrystalline structure in HR-TEM images and a mixture of zinc, copper and oxygen atoms are detected in AES. The results and implications
to uses of ZnO NWs will be discussed.
SESSION L3: ZnO Doping and Defects

Chairs: Irina Buyanova and Bengt Svensson
Tuesday Morning, November 27, 2007
8:30 AM *L3.1
Impurity and Point-Defect Issues in ZnO. David C. Look, Semiconductor Research Center, Wright State University, Dayton, Ohio; Materials
and Manufactuing Directorate, Air Force Research Laboratory, Wright-Patterson AFB, Ohio.
Here we report on recent progress in our understanding of impurities and point defects in ZnO, including those associated with surfaces. One of
the most common impurities is H, but the role of H in affecting electrical properties seems to be under continuous revision. There is little doubt
that H produces a 45-meV donor, as evidenced by the I4 donor-bound-exciton PL line, and indeed Hall-effect measurements find a donor of
similar energy. However, the Hall and PL donors have differences, such as in their annealing properties. Also, the possible structures of H-related
donors are in question, because recent theory suggests that interstitial H is unstable at temperatures much above 300 K. Furthermore,
forming-gas (5% H2 in N2) annealing of hydrothermal ZnO at 600 C produces large increases in both concentration and mobility, and evidence
suggests that passivation of acceptors (e.g., H+ + LiZn- ? H-LiZn) and/or depassivation of donors (e.g., H+ + OI-AlZn ? H-OI + AlI +) may be as
important as the direct creation of donors. Note that passivation of acceptors by H may also be useful for the successful production of p-type
ZnO, as is the case in p-type GaN. For example, the formation of neutral H-LiZn- complexes during growth may suppress the formation of
compensating lattice donors (e.g., VO) and allow a subsequent anneal to break up the H-LiZn- complexes, drive out the H, and leave isolated and
uncompensated LiZn. Besides H, other donor-type co-dopants, such as Al, Ga, and In, in conjunction with acceptor dopants such as N, have
enabled p-type material to be realized. With regard to point defects, there is now evidence that Zn-interstitial donor complexes may be important
in some cases. Also, the O vacancy VO continues as perhaps the most studied point defect in ZnO. Recent work has correlated a V O-related
ODMR signal with the 2.45-eV PL band and the 0.55-eV DLTS trap. Conductive n-type surfaces are present in almost all as-grown ZnO
samples. Fortunately, the donor concentrations near the surface can now be determined with a fair degree of accuracy by low-temperature
Hall-effect measurements; however, the thicknesses of these conductive layers still elude easy measurement. Its likely that H is either directly or
indirectly involved in producing the surface donors, since forming-gas anneals usually increase the net donor concentration, Finally, the presence
of H in highly conductive ZnO nanorods has been confirmed by nuclear magnetic resonance. A certain portion of this H is quite stable, surviving
at 500 C in air. Other recent results regarding impurities and point defects in ZnO will be included in the discussion.
9:00 AM L3.2

Improvements in the Conductivity of n-type ZnO Through Codoping with Al and In. Steven D. Kirby and R. B. van Dover; Material
Science and Engineering, Cornell University, Ithaca, New York.
ZnO has been identified as a viable candidate to replace expensive Sn-doped In2O3 due to its high transparency and good conductivity. ZnO has
been successfully doped with many elements including Al and In to achieve resistivities near or below 10 -4 O-cm. One of the limiting factors in
improving conductivity beyond this is the limited solubililty of the dopants in ZnO. We proposed that codoping with Al and In will increase the
overall dopant solubility, since Al3+ and In3+ are smaller and larger than Zn2+ respectively. This will increase the carrier concentration with less
degradation of mobility due to formation of secondary phases. We have studied the effect of codoping ZnO with Al and In using a combinatorial
technique. Cosputtering from three elemental targets in the presence of oxygen allows for a range of ZnO:(Al, In) compositions to be deposited
on a single substrate. Deposition temperatures range from room temperature to 350C. High temperature annealing is performed in air to
eliminate the effect of oxygen vacancies as an uncontrolled variable. The material properties are determined using XRD, electron microprobe,
four-point resistivity probe, Hall effect, and reflection and transmission spectroscopy at optical wavelength. These films are found to be highly
c-axis oriented. Measurements demonstrate an improvement in the maximum conductivity attributed to codoping: conductivities in the range of
104 S/cm are achieved along with greater than 85% transmission in visible light.
9:15 AM L3.3
Optical Properties of ZnO Including Fresh Dislocations Induced by Plastic Deformation. Yutaka Ohno1, Haruhiko Koizumi1, Toshinori
Taishi1, Ichiro Yonenaga1, Katsushi Fujii1,2, Hiroki Goto1,2 and Takafumi Yao1,2; 1Institute for Materials Research, Tohoku University, Sendai,
Japan; 2Center for Interdisciplinary Research, Tohoku University, Sendai, Japan.
Defects inducing long-range strain fields, as dislocations, are of considerable importance in semiconductor electronics, since they are frequently
introduced during crystal growth, device fabrication, device operation, etc. and affect the electronic and optical properties of semiconductor
devices. Recently, ZnO is expected for UV light-emitting devices and is supposed that dislocations are more easily introduced than GaN and SiC.
However, the nature of optical properties of dislocations in ZnO has not been fully elucidated. This paper reports photoluminescence study of the
optical properties of ZnO in which dislocations are freshly induced by the plastic deformation. Wurtzite ZnO bulk single-crystals, purchased
from Goodwill (Russia), were compressively deformed at elevated temperatures 650 ~ 850 degrees C. In photoluminescence studies at 11 K, a
deformed ZnO shows an intense light emission with photon energy around 3 eV, while no emission of the light was observed in non-deformed
ZnO. The higher the light intensity was, the lower the deformation temperature was. These results suggest that the light emission should be
originated from induced fresh dislocations.
9:30 AM L3.4
Degradation Mechanism and Reversible Recovery of Electrical Properties in Al-doped ZnO Thin Films. Jun Hong Noh1, Hyun Suk Jung2,
Jung Kun Lee3, Jin Young Kim1, Chin Moo Cho1, Jae Sul An1 and Kug Sun Hong1; 1Materials Science and Engineering, Seoul National
University, Seoul, South Korea; 2Advanced Materials Engineering, Kookmin University, Seoul, South Korea; 3Mechanical Engineering and
Materials Science, University of Pittsburgh, Pittsburgh, Pennsylvania.
Aluminum-doped zinc oxide (AZO) films have been extensively explored as a transparent conducting oxide (TCO) to alternate ITO film.
However, the AZO films shows the most abrupt increase in resistivity after air annealing among the known TCOs such as ITO, FTO, and
SnO2:Sb, etc. This is known as a thermal degradation issue of AZO films. Therefore, studies about a mechanism of the thermal degradation and
methods to prevent the degradation or to recover the degraded film are need. We prepared undoped ZnO and aluminum (1.6 at%)-doped ZnO
(AZO) films epitaxially grown on sapphire (0001) substrates using pulsed laser deposition (PLD). To exclude grain boundary effect on
conductivity for AZO film, we chose the epitaxial films. As-deposited AZO films shows a low resistivity of 8.0110 -4 Ocm with carrier
concentration (n) of 1.72 1020 cm-3 and Hall mobility () of 45.4 cm2/V-S. However, after annealed at 450 oC in ambient air atmosphere, the
electrical resistivity of AZO film increased to 1.9710-1 Ocm, which was traced to the decrease in the carrier concentration to 2.13 1018 cm-3.
Subsequent annealing of air-annealed AZO films in H2 was found to recover the electrical conductivity of the AZO films. We calculated
concentrations of neutral and ionized scattering center (NN, NI) using Dingles model for a degenerate electron gas. The result shows that the
total concentration of scattering centers (NI+NN) in air-annealed AZO film is much larger than that in as-deposited AZO film, while as-deposited
and reducing-environment treated AZO films have almost a same amount of scattering centers. Neutral or negatively charged scattering centers
are newly produced during the air-annealing. In photoluminescence study, it is notable that strong orange emission (1.9 eV) is only showed in
air-annealed AZO films. The overall consensus of previous studies is that single negatively charged interstitial oxygen plays an important role in
emitting the orange light in ZnO. Al doping drastically suppressed the formation of intrinsic defects such as oxygen vacancies or zinc interstitials
which can promote the formation of oxygne interstitial. The single negatively charged interstitial oxygen act as acceptors in ZnO and provide
one hole per one interstitial. Therefore, the formation of the oxygen interstitial during air-annealing reduces the electron concentration and
increases density of scattering center. Our study suggests that the degraded electrical properties of transparent conducting ZnO films can be
recovered by removal of the oxygen interstitial through subsequent annealing at reducing atmosphere or the degradation is prevented by using

the less sensitive donors to form the oxygen interstitial because oxygen interstitial is a critical material-parameter for the degradation of electrical
conducting properties of Al-doped ZnO films.
9:45 AM L3.5
Visible Luminescence Related to Defects in ZnO. Michael A. Reshchikov1, Hadis Morkoc2,1, Bill Nemeth3, Jeff Nause3, Junqing Xie4, Brian
Hertog4 and Andrei Osinsky4; 1Physics Department, Virginia Commonwealth University, Richmond, Virginia; 2Electrical Eng. Dept., Virginia
Commonwealth University, Richmond, Virginia; 3Cermet, Inc., Atlanta, Georgia; 4SVT Associates, Inc., Eden Prairie, Minnesota.
ZnO is promising material for optoelectronics owing to its direct wide band gap and large exciton binding energy. A typical low-temperature
photoluminescence (PL) spectrum of undoped ZnO contains sharp excitonic lines in the UV range and one or more broad bands in the visible
part of the spectrum. While the excitonic spectrum of ZnO is well studied, available data on defect-related broad bands in the visible part of the
PL spectrum are highly controversial. In particular, the bands having maxima in the range from 2.1 to 2.5 eV (yellow and green luminescence
bands) in n-type ZnO are commonly attributed to oxygen vacancy. However, the oxygen vacancy is a deep donor which should not play a
significant role in PL of n-type ZnO. Numerous reports can be found on red, orange, yellow, green, and blue broad bands, mostly studied at room
temperature. However, comprehensive studies of defect-related PL bands in ZnO are rare. In this presentation, we will briefly review the
luminescence bands associated with defects in ZnO, categorize them, and focus on those for which most knowledge has been garnered. We
studied in detail several of the PL bands in undoped, Li-, Ga-, and N-doped high-quality ZnO bulk crystals and thin films grown by different
techniques. By studying PL in a wide range of excitation power densities, sample temperature, and decay time after a laser pulse, we were able to
classify and analyze in detail more than 10 broad bands with unique luminescence properties. Among these bands, only the Cu-related green
band with a characteristic fine structure was well-studied and reliably identified in the past. Two other PL bands in undoped ZnO, namely the
orange luminescence (OL) band peaking at 1.96 eV at 10 K and the yellow luminescence (YL) band at 2.19 eV, will be discussed in more detail
owing to their unusual properties. The OL band, distinguished by its enormous blue shift with temperature and fluorescence lasting for hours
after termination of excitation at 10 K, is attributed to transitions from shallow donors to a deep acceptor having an activation energy of
0.560.11 eV. The YL band quenches with an activation energy of 85 meV, yet the related acceptor level is located at about 0.5 eV above the
valence band. We suggest that the defect responsible for the YL band is either isolated zinc vacancy or a Zn-vacancy-based complex.
10:30 AM *L3.6
Kinetics of Capture, Relaxation and Recombination in ZnO-based Nano-structures: nm-spatially- and ps-time-resolved
Cathodoluminescence Spectroscopy. Juergen Christen and Frank Bertram; Natural Science, Magdeburg University, Magdeburg, Germany.
The relaxation and recombination kinetics of free and bound excitons in ZnO from thermal equilibrium into true steady state excitation condition
and back into thermal equilibrium is investigated by spectrally-(ps-) time-resolved cathodoluminescence (CL). A high quality 8 m thick ZnO
epi-layer grown by MOVPE on a ZnO/GaN/sapphire template is investigated. At T = 4 K the CL spectrum is dominated by the impurity bound
exciton (BE) I8. The free exciton XA, the BEs I1, I2, and I6, as well as I9 are clearly resolved. Three additional peaks can be assigned as excited
states of these BEs, i.e. I6*, I8*, and I9*, respectively. Spectral-time-resolved CL was performed using rectangular excitation pulses with ps rise
and fall times (t(10% - 90%) << 100 ps ), however, very large pulse lengths (?t > 20 ns - 50 ns) assure the excitonic system reaching true quasi
equilibrium during the excitation pulse. In this way, both the onset, i.e. the excitation from equilibrium into steady state as well as the transient
decay from steady state can be investigated. While no spectral shift with time is observed for all lines a distinct change in intensity ratio of I8 / I9
as compared to I1 / I2 is found in time-delayed (td-) spectra: I8 and I9 exhibit a perfectly time-constant intensity ratio. While I1 and I2 are less
intense in the in-pulse-spectrum they catch up with I8 / I9 with ongoing delay time eventually dominating the td-spectra after 1.9 ns. XA and the
excited state I6/8* disappear extremely fast after the in-pulse spectrum having already completely vanished in the td-spectrum after 0.9 ns. The
neutral impurity bound excitons I8, and I9 exhibit a delayed, however, strictly mono-exponential decay over three orders of magnitude yielding
t(I8) = 310 ps, t(I9) = 270 ps, respectively. The same is found for XA , however, exhibiting a very short life time of t (XA)= 90 ps. In complete
contrast, the ionized impurity bound excitons I1 and I2 show a non-exponential decay, starting with a very fast initial decay (tinitial = 140 ps /
160 ps) followed by a persistent slow stretched-exponential decay. The fast initial drop results from the carrier capture by the ionized impurities
thus feeding the neutral impurity bound exciton channels. Consequently, the decays of I8 and I9 are delayed with respect to the initial fast I1 / I2
decay. This capture kinetics is also observed in the CL onset. Alloying ZnO with MgO (Eg = 7.8 eV) further expands the optical properties into
the UV and far UV - however further complicating the kinetics. A nano-scale characterization of MgZnO/ZnO/MgZnO quantum wells is
presented and the impact of potential fluctuations in the MgZnO-barriers on the kinetics of carrier transfer and capture into the quantum well is
investigated in spatially(nm)-time(ps)-resolved CL experiments.
11:00 AM L3.7
Effect of Growth Polarity on the Formation of Zn Vacancies in Heteroepitaxial MOCVD-ZnO. Filip Tuomisto1, Asier Zubiaga1, Jesus
Zuniga-Perez2 and Vicente Munoz-San Jose2; 1Laboratory of Physics, Helsinki University of Technology, TKK Espoo, Finland; 2Departamento

de Fisica Aplicada i Electromagnetisme, Universitat de Valncia, Valencia, Spain.
The growth polarity has been shown to have a dramatic effect on the in-grown point defects in GaN [1, 2], a material similar to ZnO in the sense
of structure and properties defined by the spontaneous polarization [3, 4]. In c-plane GaN, the incorporation of impurities and formation of native
defects are significantly enhanced in growth in the N polar (as opposed to Ga polar) direction and their distributions of impurities and native
defects is highly nonuniform as a function of the distance from the GaN/sapphire interface. On the other hand, in non-polar a-plane GaN the
defect distributions are flat and the concentrations are similar to N polar GaN. We have applied positron annihilation spectroscopy to study the
effect of growth polarity on the vacancy defects in ZnO grown by metal-organic vapor phase deposition (MOCVD) on sapphire. Both c-plane
and a-plane ZnO layers were measured, and Zn vacancies were identified as the dominant defects detected by positrons. The results are
qualitatively similar to those of earlier experiments in GaN. The Zn vacancy concentration decreases in c-plane ZnO by almost one order of
magnitude (from high 1017 cm-3 to low 1017 cm-3) when the layer thickness is increased from 0.5 to 2 m [5]. Interestingly. in a-plane ZnO the
Zn vacancy concentration is constant at a level of about 2 1017 cm-3 in all the samples with thicknesses varying from 0.6 to 2.4 m. [1] F.
Tuomisto, K. Saarinen, B. Lucznik, I. Grzegory, H. Teisseyre, T. Suski, S. Porowski, P. R. Hageman, and J. Likonen, Applied Physics Letters 86,
031915 (2005). [2] F. Tuomisto, T. Paskova, R. Krger, Figge, D. Hommel, B. Monemar, and R. Kersting, Defect distribution in a-plane GaN on
Al2O3, Applied Physics Letters 90, 121915 (2007). [3] F. Bernardini, V. Fiorentini, and D. Vanderbilt, Phys. Rev. B 56, R10024 (1997). [4] C.
Morhain, T. Bretagnon, P. Lefebvre, X. Tang, P. Valvin, T. Guillet, B. Gil, T. Taliercio, M. Teisseire-Doninelli, B. Vinter, and C. Deparis, Phys.
Rev. B 72, 241305(R) (2005). [5] A. Zubiaga, F. Tuomisto, F. Plazaola, K. Saarinen, J.A. Garcia, J. F. Rommeluere, J. Zuiga-Prez, and V.
Muoz-San Jos, Applied Physics Letters 86, 042103 (2005).
11:15 AM L3.8
Exposure of ZnO(0001)-Zn to H2 at Different Temperatures. Johannes vandenHeuvel and Erdny Batyrev; Chemistry, Universiteit van
Amsterdam, Amsterdam, Netherlands.
Cu-ZnO based catalysts are very active and selective in methanol synthesis, however, the reaction mechanism and nature of active sites are still
under debate. It is known that ZnO plays an important role which ranges from hydrogen supplier by spillover to anti-sintering agent, and even as
active site. Reduction at 750 K strongly enhances the activity of the ZnO promoted Cu catalyst. Little information is available on the surface
structure of the activated catalyst after reduction at high temperature. This study is devoted to the characterization of the ZnO phase after
exposure to H2 at different temperatures. Since in polycrystalline powder catalysts it was shown that only the polar Zn-terminated ZnO face is
active in methanol synthesis, a sputter/annealed ZnO (0001)-Zn single crystal was studied in a UHV system with a base pressure of 2x10-10
mbar. The preparation chamber was equipped with a high pressure reaction cell and a mass spectrometer for TDS, the analysis chamber enabled
XPS, STM and STS. STM reveals that the clean ZnO (0001)-Zn single crystal contains substantial structural defects, i.e. triangular islands and
pits with mono-atomic step height; the edges of these defects are terminated by oxygen. This structure completely disappears after exposure to
10-5 mbar H2 at T > 500 K to yield a rough surface. Some reduction of the surface is obvious from STS, which shows that the initial
semiconducting character has become more metallic. Furthermore, XPS revealed that stable OH groups were formed at the surface up to 700 K.
After exposure to 1 bar H2 at 700 K significant amounts of H2 dissolved in the ZnO matrix, as apparent from TDS spectra. Desorption of
metallic Zn confirmed that the ZnO subsurface layer was significantly modified by the exposure to H2 at 700-800 K. These findings support the
idea of ZnO being not only a hydrogen reservoir, but also a catalyst for methanol synthesis. Additional SANS on polycrystalline hydrogen
(deuterium) saturated Cu-ZnO was performed at LLB, Saclay, France. Upon cooling to 4 K, H2 (D2) fills the nanopores of the ZnO matrix. In
the temperature range of 90-300 K, approximately one-third of the hydrogen participates in the fast diffusion (~810-9 m2/s), while the other
two-thirds are immobilized. At 20 K, the mobile fraction decreases to ~10%. Analysis of the results demonstrates that the energy barriers
retaining hydrogen in defect regions are relatively low. This offers interesting perspectives for the development of hydrogen storage
technologies.
11:30 AM L3.9
Influence of Hydrogen on the Electrical Transport in Zinc Oxide. N. H. Nickel, L. P. Scheller, M. A. Gluba and M. Weizman; Hahn-Meitner-
Institut Berlin, Berlin, Germany.
Research on zinc oxide (ZnO) is driven by a strong desire for blue and ultraviolet light emitting devices. So far, however, the major shortcoming
is the lack of reliable p-type doping. Interestingly, the unique properties of hydrogen have been identified as a significant problem that interferes
with effective p-type doping. Recently, it was proposed that substitutional hydrogen accommodated at an oxygen site is the cause for the
commonly observed n-type conductivity. Theory suggests that this complex is thermally stable up to about 500 C [1]. In this paper we present
an extensive study on the role of hydrogen for electrical transport. For this purpose single crystal ZnO samples with a c-axis orientation were
homogeneously hydrogenated using an ampoule hydrogenation. For electrical measurements titanium contacts where evaporated. These contacts
showed ohmic behavior in a temperature range from 20 to 300 K. The electrical transport properties of hydrogenated and as-grown ZnO samples
were investigated with temperature dependent Hall-effect measurements. Hydrogenation causes an increase of the electron concentration, n, by

about 310^17 cm^-3 at room temperature. This is accompanied by a decrease of the mobility, , from 1100 to about 250 cm^2/Vs; the
temperature at which the maximum value of occurred increased from 70 to 100 K. This observation confirms that H acts as a shallow donor.
The hydrogenated samples are not stable; n and decrease and increase with time, respectively. To study the kinetics of this process the time and
temperature dependence of the recovery of n and were measured. For this purpose the samples were isothermally annealed and subsequently
T-dependent Hall-effect measurements were performed. With increasing annealing time the electron concentration decreases and the mobility
increases due to a decrease of the concentration of shallow H donors. The temperature dependence of the recovery of n and exhibits an
activated behavior with an activation energy of 0.9 eV. Interestingly, neither n nor approach the original values observed for as-grown ZnO. It
is likely that the difference is related to a more stable H-related shallow donor complex such as substitutional H at an oxygen site. [1] Anderson
Janotti and Chris G. Van de Walle, Nature Materials 6, 44 (2007)
11:45 AM L3.10
Hydrogen Migration in Single Crystalline ZnO. Klaus Magnus Johansen, Jens S. Christensen, Edouard V. Monakhov, Andrej Yu. Kuznetsov
and Bengt G. Svensson; Department of Physics/Centre of Material Science and Nanotechnology, University of Oslo, Oslo, Norway.
Hydrogen has been proposed as one of the contributors to the native n-type doping in as-grown ZnO and can also be used as an active
(intentional) n-type dopant. In this work we have employed Secondary Ion Mass Spectrometry (SIMS) to study deuterium diffusion profiles in
single crystalline Zinc Oxide (ZnO). Because of an improved detection limit by more than 2 orders of magnitude in the SIMS measurement
relative to that of hydrogen, the chemically equal isotope of deuterium is used to study the diffusion. The samples used are hydrothermally
grown, high-resistive (10 kO cm) monocrystalline ZnO. They have been implanted with deuterium at an energy of 1.4 MeV to a dose of 110 15
cm-2 through a 15 m Al-film. The implantation result in a peak concentration of approximate 510 182H/cm3 at a depth of 2.2 m. Diffusion
profiles have been studied after 30 minutes isochronal heat treatments from 100C up to 400C in steps of 50C. The observed redistribution can
be explained by employing a diffusion model which includes trapping of 2H by Li-impurities. We have used this model to extract the diffusion
activation energy for 2H in ZnO.
SESSION L4: ZnO Crystal Growth and Properties

Chair: David Look
Tuesday Afternoon, November 27, 2007
1:30 PM *L4.1
Hydrothermally Grown Single-crystalline Zinc Oxide; Characterization and Modification. Bengt Gunnar Svensson1, Thomas
Moe-Borseth1, Klaus Magnus Johansen1, Ramon Schifano1, Ulrike Grossner1, Jens Sherman Christensen1, Peter Klason2, Qing Xiang Zhao2,
Magnus Willander2, Filip Tuomisto3, Wolfgnag Skorupa4, Eduoard Monakhov1 and Andrej Kuznetsov1; 1Physics, University of Oslo, Oslo,
Norway; 2Physics, University of Gothenburg, Gothenburg, Sweden; 3Physics, Helsinki University of Technology, Helsinki, Finland;
4Forschungszentrum Rossendorf, Dresden, Germany.
In this overview four different topics will be discussed and they are briefly illustrated below, (i) - (iv). The zinc oxide (ZnO) samples investigated
are bulk ones grown by hydrothermal (HT) techniques. (i) Photoluminescence spectroscopy has been employed to characterize samples
heat-treated in inert Zn-rich and O-rich atmospheres, and a striking correlation is observed between the ambient and the position of the so-called
deep band emission (DBE), commonly detected in ZnO. Treatment in O-rich ambient yields a DBE peak at 2.350.05 eV while the
corresponding peak position after treatment in Zn-rich ambient is shifted to 2.530.05 eV. Consequently, it is tempting to assign the former band
to zinc-vacancy (VZn) related defects and the latter to oxygen-vacancy related defects. (ii) Lithium (Li) occurs typically with concentrations in
the range of 1017 cm-3 in the HT-samples and is anticipated to compensate both n- and p-type doping because of its amphoteric nature.
However, by a combination of ion implantation and flash lamp annealing (duration 20 ms) in the 900-1400 C range VZn-clusters are formed
which trap and deactivate Li. As a result, low-resistivity layers occur where the electrical properties are determined by other impurities and
defects. Outdiffusion of Li is observed after heat treatment above ~1200 C with a duration of the order of 1 h. (iii) The evolution of implanted
hydrogen (H) in high-resistivity samples during post-implant annealing has been investigated by secondary ion mass spectrometry (SIMS) and
scanning nanoprobe microscopy (SPM) measurements. Varying the H-dose the n-type conductivity can be tuned over at least five orders of
magnitude and the n-type doping persists after annealing up to temperatures in excess of 600 C. Further, a detailed comparison between the
SIMS and SPM depth profiles reveals that a substantial fraction of the hydrogen is not electrically active and provides experimental evidence of
more than one atomic configuration of H in ZnO. (iv) Finally, the issue of realizing Schottky diodes with a high barrier height and long term
stability is addressed.

2:00 PM L4.2
Electronic Structure of the Oxygen Vacancy in ZnO Including a Self-consistent Band-gap Corrected Approach. Tula R. Paudel and Walter
R. L. Lambrecht; Department of Physics, Case Western Reserve University, Cleveland, Ohio.
The electronic structure of the oxygen vacancy in ZnO has been controversial. Two models have been proposed in recent literature: one in which
the 0/++ transition level lies in the lower and one in which it lies in the upper half of the band gap. Both can be reconciled with experimental data
on the 0/+ level extracted from electron paramagnetic resonance. The reason for this controversy lies in the underestimate of the band gap by the
local density approximation (LDA) and the different a-posteriori approaches used to correct for it. Here we propose an extension of the LSDA+U
approach by adding a U shift for the Zn-s as well as the Zn-d levels, implemented in a full-potential linearized muffin-tin orbital method. While
the main reason for the underestimate of the gap by LDA is due to long-range Coulomb effects, the resulting upward shift can be mimicked by
adding a shift to the Zn-s level. LSDA+U achieves this by adding a potential V_s=U_s( -n_s). For the density matrix n_s0, this leads to an
upward shift by U_s/2. The total energy functional is consistently updated. We also study the size dependence on the supercell. We found no
clear evidence for a 1/L dependence as suggested by Makov and Payne and instead extrapolate the results of three different cell sizes using a
1/Volume linear fit from supercells ranging from 72 to 192 atoms. We find that the system is a negative U system but with slightly smaller
|U|=0.7 than found in previous work. The 0/++ transition level is found at 2.16 eV above the valence band maximum, clearly supporting the
defect level position is in the upper half of the gap. In contrast to previous approaches, ours is not based on an a-posteriori correction. The full
band gap correction is included consistently within the total energy formalism.
2:15 PM L4.3
Origin of the Near-Band-Edge Emission in ZnCdO Alloys. Irina A Buyanova1, J. P. Bergman1, G. Pozina1, W. M. Chen1, S. Rawal2, D. P.
Norton2, S. J. Pearton2, A. Osinsky3 and J. W. Dong3; 1Physics, Chemistry and Biology, Linkoping University, Linkoping, Sweden; 2Department
of Materials Science and Engineering, University of Florida, Gainesville, Florida; 3SVT Associates, Eden Prairie, Minnesota.
The desire for blue and ultraviolet optoelectronic devices has prompted extensive research efforts into wide-bandgap group III-nitride
semiconductors as well as ZnO and related alloys. ZnO-based alloys, such as ZnCdO, add tunability in the alloy bandgap that can be utilized for
bandgap engineering. For example, by choosing an appropriate Cd content the bandgap energy of the alloy can be tuned as desired within the
blue-yellow spectral range. Therefore, ZnCdO can be used as an active material in modern Zn(Mg)O/ZnCdO heterostructures and superlattices,
which are among key elements of ZnO-based light emitters and detectors. In spite of that, many fundamental optical properties and associated
recombination processes in ZnCdO are still not fully understood. For example, the origin of the near band edge emission in ZnCdO alloys
remains largely unknown. The purpose of the present study is to gain a better understanding of the dominant mechanisms for the radiative
recombination near the band edge in ZnCdO alloys with high Cd compositions by employing temperature dependent cw- and time resolved
photoluminescence (PL) spectroscopies combined with absorption measurements. The near-band-edge emission is attributed to recombination of
excitons localized within band tail states likely caused by non-uniformity in Cd distribution. Energy transfer between the tail states is argued to
occur via tunneling of localized excitons. The transfer is shown to be facilitated by increasing Cd content, due to a reduction of the exciton
binding energy and, therefore, an increase of the exciton Bohr radius in the alloys with a high Cd content.
3:00 PM L4.4
Microwave Growth of ZnO Bulk Crystals. Jiping Cheng, Yunjin Zhang and Ruyan Guo; Pennsylvania State University, University Park,
Pennsylvania.
A microwave self-encapsulated melting growth technique is developed for fabrication of ZnO single crystals, which features a
contamination-free, high rate and good quality crystal growth process. The microwave grown ZnO crystals sized in millimeters came out in light
brown color due to high oxygen vacancies, and turned to colorless and highly transparent crystals after annealing in air. The X-ray diffraction,
Laue back reflection, Hall Effect and photoluminescence spectrum measurements were carried out for characterization of microwave grown ZnO
single crystals.
3:15 PM L4.5
Optically Induced Changes to the Surface Conduction in Hydrothermal ZnO Studied by Photo-Hall-effect. Bruce Claflin1,2 and David C
Look1,2; 1Materials and Manufacturing Directorate, AFRL/MLPS, WPAFB, Ohio; 2Semiconductor Research Center, Wright State University,
Dayton, Ohio.
High quality, bulk, ZnO crystals grown by Tokyo Denpa using the hydrothermal process typically exhibit a room temperature carrier

concentration in the low 1014 cm-3 range and low temperature conduction dominated by a degenerate surface layer with a sheet concentration of
2x1012 cm-2 and low mobility. In the sample discussed here, bulk conduction is controlled by two donor levels at 52 and 400 meV with
concentrations of 1.2x1016 cm-3 and 1.5x1016 cm-3 respectively. Temperature-dependent photo-Hall-effect measurements up to 400 K, in
vacuum, using blue/UV light, show an increase in the surface sheet carrier density to more than 1x10 13 cm-2 at low to intermediate temperatures
while the two bulk donors continue to dominate the high temperature behavior. Long-lived persistent photoconductivity (PPC) is observed when
the sample is returned to the dark. When the PPC is allowed to fully relax, there is surprisingly no longer any surface conduction at low
temperature, while the two bulk donors remain unaffected. In this state, the 52 meV bulk donor level is observed to control the conduction over
five orders of magnitude, down to a concentration of 1.0x109 cm-3. This corresponds to an upper limit for the surface sheet carrier density of
5.5x107 cm-2. This is the lowest surface concentration we have ever observed in any ZnO sample and demonstrates that exposure to blue/UV
light, in vacuum, at moderate temperatures is very effective at cleaning the surface.
3:30 PM L4.6
MEMSA Analysis of Transport Properties in Bulk ZnO (and Evidence of Conduction Channels). Celine Tavares, Johan Rothman and
Ivan-Christophe Robin; Leti-MINATEC, CEA-Grenoble, DOPT, Grenoble, France.
The characterization of transport properties in Zn0 is known to be challenging , particularly due to surface [1] or interface [2] conduction
channels, which puts severe limitations on the interpretation of Hall Effect measurements. In this communication, we report the first study of
transport properties of n-type ZnO bulk material grown by the hydrothermal method using Hall mobility spectrum analysis estimated through the
algorithm known as full Maximum Entropy Mobility Spectrum Analysis, f-MEMSA [3]. f-MEMSA is a complete version of the simplified
MEMSA, which was first proposed by Kiatgamolchai [4]. Using the concept of mobility spectrum analysis, proposed by Beck and Anderson in
1987 [5], the distribution of carrier type and mobility can be estimated from magnetic field dependant Hall measurements. The transport
properties of bulk Zn0 will be discussed in terms of Mobility spectra estimated from Hall data measured for applied magnetic fields 0H in the
range 0T-9T and for temperature between 50K and 400K. In the measured ZnO bulk material, Hall data analysis at fixed fields yields low
mobility, H < 100 cm2/Vs, n-type conduction and a temperature dependence which gives a low ionisation energy, Ea= 20 meV. The f-MEMSA
analysis shows that this observation correlates with the presence of two different types of carriers, which is consistent with the existence of a low
mobility conduction channel at the surface: S(50K) ~ 100cm2/Vs and a high mobility bulk conduction B(50K) ~ 1000cm2/Vs, in agreement
with the bulk values reported by Look[6]. Hence, f-MEMSA analysis gives a strong indication that surface conduction is an issue in bulk ZnO
and allows for a correct estimation of the transport properties in the bulk of the material. In addition, X-ray diffraction measurements showing
the existence of a surface layer with a lattice parameter different from that of bulk ZnO give an indication as to the origin of the surface
conduction channel. [1] D. C. Look, H. L. Mosbacker, Y. M. Strzhemechny, L. J. Brillson, Superlat. and Microstruct. 38, 406 (2005) [2] H.
Tampo, A. Yamada, P. Fons, H. Shibata, M. Matsubara, K. Iwata, S. Niki, APL 84, 4412(2004) [3] J. Rothman, J. Meilhan,G. Perrais, J-P. Belle,
O. Gravand, J. Electron Mater. 35, 1174 (2006) [4] S. Kiatgamolchai, M. Myronov, O.A. Mironov, V. G. Kanter, E. H. C. Parker, T. E. Whall,
Phy. Rev. E 66, 36705 (2002) [5] W. A. Beck, J. R. Anderson, J. Appl. Phys. 62, 541 (1987) [6] D. C. Look, D. C. Reynolds, J. R. Sizelove, R. L.
Jones, C. W. Litton, G. Cantwell, W. C. Harsch, Solid State Communications 105, 399 (1998)
3:45 PM L4.7
Role of Neutral Impurity Scattering in the Analysis of Hall Data from ZnO and Other II-VI Materials. Xiaocheng Yang, Chunchuan Xu
and Nancy C. Giles; Department of Physics, West Virginia University, Morgantown, West Virginia.
Zinc oxide is a wide band-gap semiconductor with bright UV emission. To determine donor and acceptor concentrations affecting electrical
properties in n-type ZnO crystals, the relaxation time approximation (RTA) has been used to analyze mobility and carrier concentration data
measured from 80 to 400 K. Five scattering mechanisms are included: polar-optical-phonon, piezoelectric potential, deformation potential,
ionized impurity, and neutral impurity (NI) scattering. The NI scattering is often ignored but plays an important role in limiting the total mobility.
By including NI scattering, the experimental deformation potential E1 = 3.8 eV for ZnO can be used, rather than treating E1 as a fitting
parameter. At 300 K, pure ZnO has an electron mobility of about 210 cm2/Vs and an intrinsic Hall mobility of about 230 cm2/Vs. Analysis of
Hall data from n-type ZnO crystals grown by high pressure melt, hydrothermal and chemical-vapor-transport techniques is presented. The RTA
approach with the five scattering mechanisms was also used to analyze Hall data from other wide-bandgap II-VI semiconductors. Experimental
E1 values were used and intrinsic Hall mobilities at room temperature are predicted to be 210, 380 and 600 cm 2/Vs for ZnS, CdS, and CdSe,
respectively. Temperature dependences of the Hall r factors were calculated for each case and used to obtain corrected electron mobility and
carrier concentrations. Acceptor concentrations, donor concentrations, and donor activation energies were determined in each case. The
temperature dependence of the intrinsic hole mobility in ZnO has also been predicted, and the 300-K value is about 50 cm 2/Vs. The effect of
acceptor concentration on Hall mobility in p-type ZnO has been determined and compared to reported work on ZnO:As [1,2]. This work was
supported by NSF Grant No. DMR-0508140 and Oak Ridge National Laboratory. [1] D. C. Look, Semicond. Sci. Technol. 20 S55-61 (2005). [2]
Y. R. Ryu, T. S. Lee and H. W. White, Appl. Phys. Lett. 83 87-89 (2003).

4:00 PM L4.8
Separation of Surface and Bulk Conduction in Hydrothermally grown ZnO Using Variable Magnetic Field Hall Effect Measurements.
Craig H Swartz1,2, Steven M Durbin1,2, Martin W Allen1,2 and Thomas H Myers3; 1Electrical and Computer Engineering, University of
Canterbury, Christchurch, Canterbury, New Zealand; 2The MacDiarmid Institute, Christchurch, New Zealand; 3Physics and Astronomy, West
Virginia University, Morgantown, West Virginia.
A major advantage of ZnO over other wide bandgap semiconductors is the availability of bulk, single crystal growth of high quality material. In
particular, the hydrothermal growth of ZnO can be used to achieve carrier concentrations 2 - 3 orders of magnitude lower than other bulk ZnO,
likely due to compensation from unintentionally introduced Li and Na acceptor impurities. The high resistivity of the bulk material makes the
measurement of its electrical properties particularly susceptible to complications such as persistent photoconductivity, increased temperature
sensitivity, and surface conduction effects. The surface conductivity of ZnO is known to depend strongly on the ambient atmosphere and can
increase significantly under vacuum conditions. After being placed in a vacuum, atmosphere-induced surface effects can persist for several hours
at room temperature, and even after an equilibrium condition is reached, the surface conductivity can in some situations dominate electrical
measurements. The separation of surface conducting layers from the bulk conductivity of a given sample can be performed by the use of variable
magnetic field Hall effect measurements. Here we examine temperature dependent (80 - 300 K), variable magnetic field (up to 12 T) Hall effect
measurements on ZnO single crystal wafers from Tokyo Denpa Co. Ltd. (Japan) grown using a hydrothermal technique. Multiple carrier fitting
was used at each temperature to remove surface conduction effects and extract the mobility and carrier concentration data for the bulk carriers
only. A significantly higher bulk carrier mobility was found than is apparent from standard single field Hall effect measurements. The
temperature dependence of the mobility was then fitted to a theoretical model accounting for the various scattering mechanisms believed to be
prevalent in ZnO, polar optical phonon, acoustic phonon, and ionized impurity scattering. This resulted in an order of magnitude lower ionized
impurity concentration. These results also indicate that the use of single field, temperature dependent Hall effect measurements to determine
donor concentration and activation energies may be problematic in resistive hydrothermallly grown material unless the bulk conduction is
isolated from surface conduction effects.
4:15 PM L4.9
Stabilization Mechanisms of Polar ZnO Surfaces Revisited. Mao-Hua Du1,2,3, Shengbai Zhang3, Steven C. Erwin2 and John E. Northrup4;
1Materials Science & Technology Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee; 2Center for Computational Materials
Science, Naval Research Laboratory, Washington, District of Columbia; 3National Renewable Energy Laboratory, Golden, Colorado; 4Palo Alto
Research Center, Palo Alto, California.
Identifying the mechanisms responsible for the morphology of surfaces is crucial to gaining better control of materials grown both by epitaxial
and colloidal methods, for which surface structure can strongly affect crystal quality and even impurity incorporation. The polar (0001) surfaces
of ZnO exhibit a variety of different morphologies. The mechanisms underlying this diversity have not been definitively identified. Many efforts
to understand the polar surfaces of ZnO have focused on electrostatic considerations. For example, the formation of triangular islands and pits
observed on ZnO(0001)-Zn has been argued to originate from the requirements that the macroscopic electrostatic field arising from the polar
wurtzite structure be electrostatically compensated through surface reconstruction. Here we evaluate the role of several possible surface
stabilization mechanisms. We show that electrostatics does not play a significant role. Instead, we propose that surface morphology is determined
by a competition between two other mechanisms. The first is the electron counting rule, which leads to semiconducting surfaces. The second
arises from the large cohesive energy of ionic crystals such as ZnO, which tends to preserve the surface stoichiometry at its bulk value, leading to
metallic surfaces. Our calculations show a crossover between semiconducting and metallic surfaces as the O chemical potential is varied. On the
(000-1)-O surface, semiconducting surfaces with 1/4 monolayer (ML) oxygen vacancies are stable at low O chemical potential (O-poor
conditions), and the unreconstructed metallic surface is stable at high O chemical potential (O-rich conditions). Analogously, on the (0001)-Zn
surface, semiconducting surfaces with 1/4 ML O adatoms are stable at high O chemical potential, while metallic surfaces are stable at low O
chemical potential. Near the crossover, triangular islands and pits of varying sizes may form on both surfaces. Experimentally, ZnO surfaces are
usually prepared in ultrahigh vacuum with only residual O2 pressure, corresponding to O-poor conditions. Under O-poor conditions, our
calculations predict the formation of triangular islands/pits with varying sizes on the (0001)-Zn surface, consistent with experimental
observations. On the (000-1)-O surface our prediction of 1/4 ML O vacancy must await STM images with atomic resolution. To experimantally
test our model at O-rich conditions, oxygen-plasma treatment may offer a route. Indeed, a recent STM study of the (000-1)-O surface after
O-plasma treatment at 800 C shows the first atomically resolved image of the unreconstructed surface, consistent with our calculations.
4:30 PM L4.10
Defects and Diffusion of Fe3+ in ZnO. Herbert Schmid1, Oliver Koester-Scherger1, Markus Waelle2, Detlef Guenther2 and Werner Mader1;
1Chemistry, University of Bonn, Bonn, Germany; 2Chemistry, ETH Zrich, Zrich, Switzerland.

ZnO doped with trivalent transition metal ions (< 2 % cations) may have potential properties for spintronic applications as well as for realizing
p-type semiconductivity in ZnO. In the present study ZnO with additions of Fe3+ was produced as (i) sintered polycrystalline material, and (ii)
as diffusion couples of iron oxide layers on single crystals of ZnO. TEM investigations on the sintered material revealed a characteristic
microstructure of oriented inversion domains. The domains nucleate primarily at grain boundaries of the sintered material and at the surface of
the ZnO crystal where the iron content exceeds 0.5 at.% of the metal ions. The domain formation starts with a complex fault at the basal plane
which subsequently emits a second fault perpendicular to the primary fault (along the c axis of ZnO), finally forming the domain structure. It is
shown by energy-filtered imaging and quantitative electron energy-loss spectroscopy that the two types of domain boundaries contain iron. The
basal plane domain boundaries contain a full close-packed monolayer of iron whereas the pyramidal domain boundaries are occupied by iron at
2/3 of the content of the basal boundary. It is also shown that the Fe3+ in solid solution is built in the pyramidal domain boundary when
sweeping across the ZnO crystal. ZnO regions swept by this boundary are inverted, and a low iron content 0.1 at.% was measured in these
inverted domains. Based on experimental observations and arguments of structural chemistry a mechanism is proposed explaining the nucleation
and anisotropic growth of the inversion domains which are finally induced and driven by the trivalent iron ions at octahedral sites in the primary
complex defects. Diffusion profiles were measured by laser ICP-MS with high spatial resolution in ZnO single crystals in which Fe3+ was
allowed to diffuse into from prism plane surfaces for 0.5h, 1h and 2h, respectively. The resulting profiles consist of a plateau with nearly constant
Fe concentration close to the surface and of a regular exponential decline to zero content at the diffusion front in the ZnO bulk. The plateau is
interpreted as the crystal region containing inversion domains, whereas the decline region is a typical diffusion zone of constant source of Fe3+
in solid solution in ZnO.
4:45 PM L4.11
Structural, Electrical and Optical Properties of Epitaxial Zn1-xGaxO Films Grown on Sapphire (0001) Substrate. Ashutosh Tiwari and
Michael Snure; Materials Science & Engineering, university of utah, Saltlake city, Utah.
Here we report the structural, electrical and optical properties of epitaxial Zn 1-xGaxO films (x=0-0.05) grown on single crystal Sapphire (0001)
substrate. Thin film processing was performed using pulsed laser deposition technique. Structural and elemental analysis was performed using
high resolution X-ray diffraction (?-2? and F scan) and energy dispersive X-ray spectroscopy (EDX). Temperature dependent electrical resistivity
and thermoelectric power measurements were performed over the temperature range of 77-300 K and 296-373 K, respectively. Hall effect and
optical transmission measurements were preformed at room temperature. All these studies showed that the structural, electrical as well as the
optical characteristics of Zn1-xGaxO films depend very sensitively on the Ga contents. As the Ga doping concentration is increased, initially an
increase in carrier concentration and optical bandgap is observed (till x=0.04), which is followed by a decrease at higher concentrations. These
features were attributed to the combined effect of band filling (Burstein Moss effect), electronic correlation and epitaxial strain present in the
system. Above parameters also affected the electrical properties of the films quite significantly. Zn 1-xGaxO films with 1% of Ga doping (x=0.01)
showed metal-like electrical resistivity. However, for higher doping levels, enhanced scattering potential, arising from randomly distributed
impurity atoms, resulted in the Anderson localization of electronic states.
SESSION L5: Poster Session

Chairs: Irina Buyanova, Chennupati Jagadish, David Norton and Gyu-Chul Yi
Tuesday Evening, November 27, 2007
8:00 PM
Exhibition Hall D (Hynes)
L5.1
Excitonic Transport in ZnO - Investigated by Temperature, Time, and Spatially Resolved Cathodoluminescence. Barbara Bastek1, Juergen
Christen1, Frank Bertram1, Martin Noltemeyer1, Heiko Frenzel2, Holger Hochmuth2, Michael Lorenz2, Matthias Brandt2 and Marius
Grundmann2; 1Institute of Experimental Physics, University of Magdeburg, Magdeburg, Germany; 2Institut fr Experimentelle Physik II,
Universitt Leipzig, Leipzig, Germany.
In this work we investigate the microscopic excitonic transport in ZnO bulk material (substrate) and its temperature dependence on an nm-scale
by highly spatially and ps time resolved cathodoluminescence (CL) spectroscopy. The characteristic T-dependence gives information about the
underling scattering mechanism. Covering the ZnO surface with 156 nm thick rectangular Ti-masks allows the excitation by electrons with a
primary energy of 7 keV (zBethe =356 nm) through this masks while completely absorbing the emerging excitonic luminescence of the subjacent
ZnO. The Ti-masks where deposited by electron beam evaporation and structured by optical lithography. They have an edge length of 520 m x

460 m and exhibit a lateral distance of 210 m and 160 m, respectively. The structure allows the realization of CL-linescans perpendicular to
the masks edge on the one hand and the undisturbed time resolved transient measurements on the other hand for the identical sample structure
on the unmasked ZnO layer. Only the fraction of generated free excitons which are able to reach the uncovered ZnO surface area by lateral
transport within their lifetime contribute to the CL intensity. All luminescence of the excitons generated below the Ti-masks is blocked. A fit of
the cw CL-linescans of the free exciton luminescence to the one-dimensional diffusion equation yields the excitonic diffusion length ? FX. The
perfectly exponential time-decay of the free exciton is recorded at an undisturbed position > 100 m away from any Ti-mask on the identical
ZnO sample and yields tFX. By variation of the temperature during the experiment in the range from 5 K to 300 K the temperature dependence of
the diffusion length ?FX(T) as well as tFX(T)are determined. The decline of the diffusion length ?FX for T < 30 K visualizes directly the
exceeding effective capture of the free exciton and their binding to neutral donors. At T = 30 K the diffusion length ? FX reaches its maximum of
22 m. With further rising T (30 K < T < 300 K) ?FX decreases monotonously. In contrast, the integral diffusion length, which means the
spatial decay of the cumulative CL intensity integrated over all recombination channels including donor-bound excitons (D 0,X) increases
monotonously with decreasing temperatures, reaching 29 m at 5 K. From the measured ?FX(T) and tFX(T)we calculate the mobility of the free
exciton FX(T) in ZnO. Astonishingly, the mobility of the free exciton FX monotonously increases by more than three orders of magnitude with
decreasing T from a value of 0.55 cm2/Vs at 300 K to 1.48*103 cm2/Vs at 5 K. This is a clear hint for the reduction or screening of ionised
impurity scattering for the excitons. We will also present our microscopic results achieved on ZnO layers PLD (pulsed laser deposition) grown
on sapphire as well as on ZnO substrates and will correlate these microscopic results with macroscopic Hall-effect measurements and (unipolar)
mobility data from FET structures.
L5.2
Effect of ZnO Buffer Layer on ZnO Nanorods Growth by MOCVD. Changa Ha Kwak1, Sang Wook Han2, Sun Hong Park1, Soo Young
Seo1, Yong Byung Lee1 and Seon Hyo Kim1; 1Department of Materials Science and Engineering, Postech, Pohang, South Korea; 2Chonbuk
University, Jeonju, South Korea.
We present the growth and structural properties of ZnO nanorod arrays on ZnO buffer layers. Previous studies reported the observation of a
natural buffer layer between the nanorods and substrates in the beginning of ZnO nanorod growth by a catalyst-free metal organic chemical
vapor deposition (MOCVD) procedure. To understand the role of the homo-buffer layer in the ZnO nanorod growth, we intentionally deposited a
ZnO film with thickness of 200nm on the Al2O3 substrates by MOCVD, and subsequently, synthesized ZnO nanorods on the pre-grown film
in-situ. The ZnO nanorods had the lengths of 0.2, 0.3 and 0.7m. The structure properties were characterized using various techniques, x-ray
diffraction (XRD), polarization-dependent x-ray absorption fine structure (XAFS) and tunneling electron microscopy (TEM). XRD
measurements on the ZnO (0002) Bragg peaks of the ZnO nanorods grown on ZnO-buffer layer/Al2O3 and on bare sapphire revealed that the
crystal quality of the ZnO nanorods was little difference. However, ?-rocking curves at the ZnO (0002) peak showed that the FWHM of the ZnO
nanorods with the homo-buffer layer had a smaller value than that of the nanorods without the buffer layer. It implied that the homo-buffer layer
didnt affect on the crystal qualities of ZnO nanorods much but contributed to the mosaicity of the nanorods. FE-SEM image confirmed the XRD
?-rocking measurements, showing that the ZnO nanorods with the homo-buffer layer vertically better aligned than without the buffer layer.
Orientation-dependent x-ray absorption fine structure (XAFS) measurements revealed that ZnO nanorods with about 0.1 m had substantial
amounts of disorders and distortion in the bonding lengths of Zn-O pairs in the ab-plane as well as along the c-axis. When the nanorod length
became longer than 0.1m, the disorder of the Zn-O pairs in the ab-plane reduced, however, the disorder of the Zn-O pairs located along the
c-axis was still observed. TEM measurements corresponded with the XAFS results. Our observation of the ZnO nanorod growth on the ZnO
homo-buffer layer with unchanging the crystal quality strongly suggested that this technique can be widely applicable to synthesize ZnO
nanorods on various substrates with the ZnO homo-buffer layer.
L5.3
Properties of Zinc Oxide Doped Indium, Magnesium and Aluminum Oxide Films used on Flexible Substrates. Shih Hsiu Hsiao1,
Yoshikazu Tanaka1 and Ide-Ektessabi Ari2; 1Mechanical Engineering and Science, Kyoto University, Kyoto, Japan; 2International Innovation
Center, Kyoto University, Kyoto, Japan.
Zinc oxide was considered to be substitute for Indium Tin oxide (ITO) as the transparent conductive oxide (TCO) films used in display industry
according to Indium is a rare and expensive metal. For the flexible display, the polymeric materials used as the flexible substrates are more
bendable and lighter weight compared to the glass substrates used in flat panel display. However, the thermal sensitivity of polymer affects the
properties of TCO layers when it was deposited at room temperature. In this study, we doped the different ratio of Indium oxide, Magnesium
oxide and Aluminum oxide into Zinc oxide to improve the properties of Zinc oxide used as the TCO films deposited by the sputtering method.
The Polyethylene Terephthalate (PET) was used as the flexible substrate without thermal process and the glass was used as the comparison
substrate with annealing. The light transmittance and the surface resistivity were measured. The chemical composition and the crystal structure
were analyzed by using Rutherford Backscattering Spectrometry and X-ray Diffraction measurement.

L5.4
Effect of Fabrication Variables on the Performance of Zinc Oxide Metal-Semiconductor-Metal Photodetectors. Tingfang Yen, Michael
DiNezza, Sung Jin Kim and Wayne A. Anderson; EE, SUNY-Buffalo, Amherst, New York.
The performance of ZnO metal-semiconductor-metal (MSM) photodetectors can be significantly influenced by modifications in the fabrication
process. This paper identifies the effects of some of these modifications. Zinc oxide (ZnO) thin films were deposited onto silicon substrates by
radio frequency magnetron sputtering using argon and oxygen ratios of 15 mT/ 5 mT or 5 mT/ 15 mT. Substrates were heated to 400 C during
ZnO deposition and later annealed by conventional furnace, rapid thermal anneal or laser anneal. Atomic force microscopy revealed surface
features for the different annealing methods. Stoichiometry of the films was verified by electron photoelectron spectroscopy analysis and
photoluminescence spectroscopy (PL) was used to reveal the optical bandgap. The PL analysis revealed that laser annealing at 200 mW/cm^2
increased the 370 nm peak from 500 to 1300 a.u. and reduced the defect peak from 250 to 50 a.u.. ZnO films behaved as n-type upon deposition
but as p-type after annealing in nitrogen. Values of Hall effect mobility ranged from 100-200 cm^2/V-s. MSM photodetectors were fabricated
using an interdigitated metal pattern with metal and spacing dimensions ranging from 25 microns to 2 microns. Performance levels were
compared for different Schottky metals such as Cr, Al, Pd, and Yb. Values of current responsivity ranged from about 200 A/W to above 800 A/W
depending upon fabrication conditions. Performance was also modified using ozone treatment of the ZnO or the introduction of about 2 nm of
silicon oxide between the ZnO and silicon substrate.
L5.5
Abstract Withdrawn
L5.6
Effects of Substrate and Post-Gas-Annealing Temperature on Electric Properties of Al and Ti doped-ZnO Films. Shinji Takayama,
Systems and Control Engineering, Hosei University, Tokyo, Japan.
Zinc oxide films are now receiving high attention as alternative materials to widely used Indium-tin-oxide (ITO) films, which have high
conductivity and optical transparency in visible range. In this report, we systematically investigated the effect of substrate temperature and
post-annealing in various gas atmospheres on properties of TM (TM=Al, Ti, Zr, Nb, Y) doped ZnO films. Samples were prepared in pure Ar gas
atmosphere using RF magnetron sputtering method. Among these adding elements, Al and Ti doped films showed a lower resistivity than other
adding elements after annealing in hydrogen gas (reducing) atmosphere. So, more extensive investigations were further performed on Al and
Ti-doped ZnO films as functions of substrate temperatures and post-annealing temperatures in various gas atmospheres (O2, N2 and O2). On
post-annealing in H2 gas, Al and Ti doped ZnO samples prepared at room temperature showed the lowest values of 5x10-4Ocm and 9x10-4Ocm,
respectively,after annealing at 573K. They also show about 90% high transparency in visible range. On the other hand, Internal stresses of
as-deposited Al or Ti doped ZnO films showed the compressive stress of about 300MPa and did not change significantly even after 673K anneal.
In the case of the effect of a substrate temperature (Ts) during sputtering, Al and Ti doped ZnO films prepared at Ts=573K showed 2.0 and 17 x
10-4Ocm, respectively. Particularly, Al-doped ZnO films showed nearly the same values as that of ITO films. They also showed a high
transparency, about 90% in visible range. However, the internal stress of all Ti or Al doped ZnO samples showed nearly constant values of about
300MPa at substrate temperatures in the range from room temperature to 673K. From these results, we obtained Al-ZnO films with low
resistivity and high transparency comparable to those of ITO films. However, compared with ITO films, the processing temperature and internal
stress of Al-doped ZnO films are still high and hence need to be improved further in future work.
L5.7
Abstract Withdrawn
L5.8
Annealing Effect on the Structure of RF Sputtered ZnO Thin Films. Xu Lu1, Rui Yang1, Zhuo Xu1, Wei Ren1, Zhong yang Cheng2 and
Shao kang Li1; 1Electronic science, Electronic Martial Research Lab, Xi'an, Shannxi, China; 2Mechanical Engineering, Materials Research and
Education Center, Auburn, Alabama.
ZnO as a functional material may have different structures and exhibit different electric properties, from semiconductor to insulator. The electric
properties and structure of ZnO thin film prepared using RF sputtering technique were investigated in this work to determine the optimized
condition for preparing piezoelectric ZnO films. A thermal annealing process was used to modify the structure and properties of the sputtered
films. The microstructure including morphology of the films was determined using XRD and SEM. It is experimentally determined that the

optimized thermal annealing temperature is 550C. Under this annealing condition, a single crystalline film with hexagonal structure was
obtained. The electric properties and piezoelectric performance of the films under different annealing conditions are also reported in this paper.
The fabrication conditions: Substrate: Si(111) Power:200W Substrate temperature:200C O2:8vccm/Ar:12vccm Base pressure :of 4.910-5 Pa
Pressure:0.5Pa Time: 100min ZnO thin films were annealed at various temperature from 350 C to 750 C by the rate 3C /min. The XRD results
is showed in Fig.1. We can find that the most XRD spectra of ZnO films show only (0 0 2) ZnO peak . we can ascertain the obtained ZnO thin
film is c-axis and the strongest(002) ZnO peak appears at the 600C. So we took 600C as the possible fabrication temperature. The SEM results
are showed as Fig.2. The SEM result is showed in Fig.2.We can find that the film annealed under 550C appear the best surface property. So we
considered 550C as the possible temperature. The best annealing temperatures that given by XRD and SEM are different. We took 550 C as the
best annealing temperature to split the difference. This paper is supported by the China National Natural Science Fund.
L5.9
Structural and Physical Ccharacterisation of Zinc Oxide Thin Films Prepared from Zinc Acetate via the Sol-gel Method. Lee H.K.
Koh1,2, Shane O'Brien1, Mehmet Copuroglu1,2 and Gabriel M. Crean1,2; 1Tyndall National Institute, University College Cork, Cork, Ireland;
2Department of Microelectronic Engineering, University College Cork, Cork, Ireland.
The Zinc oxide material system has significant potential application in electronic, optoelectronic and information technology device platforms
due to its direct wide band-gap electrical and optical properties. The deposition process and annealing temperature are the two primary factors
which influence the microstructure and resultant properties of ZnO sol-gel prepared thin films. In general, studies on sol-gel derived ZnO films
have involved investigation of the influence of annealing temperature on sol-gel films prepared from a single zinc acetate concentration, or
investigation of the influence of zinc acetate concentration for a fixed annealing temperature. However, to-date, sufficient experimental data has
not been available to obtain a clear understanding of their relative influences on the crystallization process. In this study, a detailed investigation
of the influence of the deposited sol-gel zinc acetate concentration over the range 0.3 to 1.3M and process annealing temperature from 450 to
650 degrees C, on the microstructural, physical, electronic and optical properties of a novel single-step ZnO thin film process [1,2,3] is
presented. Zinc oxide thin films were prepared using zinc acetate via the sol-gel method. The influence of zinc acetate concentration and
annealing temperature on the microstructure, in particular c-axis or (002) preferred orientation, of zinc oxide films prepared by the sol-gel
method was investigated. The zinc acetate concentration of the sol-gel deposited was found to be the major influence on the microstructure of the
resulting film. Desired preferentially orientated (002) films were obtained from 0.3M zinc acetate sol-gels at all temperatures and 100% (002)
films were obtained at both 450 and 550oC, with greater crystallite size at 550oC, as expected. An increase in concentration to 0.6M resulted in
preferentially oriented (002) films being produced only when annealed at 500oC. Further increases in concentration of zinc acetate resulted in
films which were polycrystalline in nature and it was not possible to prepare preferentially oriented (002) films under these conditions. A
suitable process window was identified. 1. S. OBrien, L.H.K. Koh and G. M. Crean, Applied Surface Science, accepted, in press [TSF-D-
06-00968] 2. L. H.K. Koh, S. OBrien, P. Lovera, G. Redmond and G. M. Crean, Proceedings MRS Fall Meeting, Boston, November 2006 -
Accepted, in press 3. S. OBrien, L. H. K. Koh and G. M. Crean, Thin Solid Films, doi: 10.1016/j.tsf.2007.03.160.
L5.10
Transport Measurements on Artificially Structured ZnO Epitaxial Layers. M. Piechotka, M. Elm, S. Lautenschlaeger, T. Henning, Bruno K.
Meyer and P. J. Klar; Institute of Experimental Physics, Justus Liebig University, Giessen, Germany.
ZnO layers of about 1000 nm thickness were grown homoepitaxially on ZnO substrates by chemical vapor deposition. The layers are n-type with
electron concentrations of about 1017 cm-3. Stripes of the as grown samples were artificially structured by photolithography. Each pattern
consists of two contact pads with a regular array of wires of the same width. The wire thickness varies throughout the series of patterns from 4
m to 100 m whereas the total cross section area of the wires is kept constant. The patterns were transferred either by wet-chemical etching or
by ion-beam etching. The resistance of the wire patterns was measured in the temperature range of 2 K to 300 K. The analysis of the resistivity
as a function of wire width yields information about the depth of the surface layer damaged during the etching process.
L5.11
Synthesis, Magnetism, and Exchange Bias of Cu- and Mn-Doped ZnO Nanocrystals. Xuefeng Wang and Jianbin Xu; Department of
Electronic Engineering, The Chinese University of Hong Kong, Hong Kong, China.
In this presentation, we present a reaction-limited aggregation-based growth of 2 at.% Cu- and 5 at.% Mn-doped ZnO nanocrystals and their
above-room-temperature ferromagnetism. Interestingly, they both display exchange biasing phenomena at low temperatures after field cooling,
revealing the complexity of magnetic phases therein. (i) For Cu-doped ZnO, a spin-split acceptor impurity band model is proposed to explain the
high-temperature ferromagnetism in the Cu-poor cores, while in the Cu-rich surface layers, the shallow donorlike defects generated during
aggregation-based growth can not only compensate a few holes but also readily occupy the empty Cu 3d states to destroy CuO4 tetrahedra where

magnetic interactions are highly restricted, thus resulting in the short-range antiferromagnetic clusters [1]. This exchange-coupling structure
[Zn1-xCuxO (core)/Zn1-yCuyO (shell); x < y] is thought to be the origin of exchange bias. (ii) For Mn-doped ZnO, a Curie temperature is found
at ~43 K and a blocking effect occurs at ~40 K, which is characteristic of ZnzMn3-zO4 secondary phase [2]. The room-temperature hysteresis
loop is ascribed to the locally p-type (Zn, Mn)O in terms of the spin-split acceptor impurity band model, while the exchange biasing effect is
attributed to the exchange interaction between ferrimagnetic ZnzMn3-zO4 [or ferromagnetic (Zn, Mn)O] and antiferromagnetic (or
spin-glass-like) phase in (Zn, Mn)O. [1] X. F. Wang, J. B. Xu, W. Y. Cheung, J. An, and N. Ke, Appl. Phys. Lett. 90, 212502 (2007). [2] R. K.
Zheng, H. Liu, X. X. Zhang, V. A. L. Roy, and A. B. Djurisic, Appl. Phys. Lett. 85, 2589 (2004).
L5.12
Visible Green Luminescence from ZnO Nanobrushes and Nanocombs Prepared by a Direct Atmosphere Evaporation Method using Zn
Metal. Shubra Singh1,2 and Mamidanna S.Ramachandra Rao1,2; 1Physics, Indian Institute of Technology, Chennai, TamilNadu, India; 2Materials
Science Recearch Centre, Indian Insitute of Technology Madras, Chennai, India.
ZnO nanostructures find applications as nano-power generators. Several self assembly and synthesis processes have emerged recently for
production of nanomaterials. These techniques are based on atomic or clustering interactions which can organize atoms or clusters to form
nanosized materials. ZnO exhibits a large family of nanostructures. In addition to the conventional nanowire and nanobelt structures, many
interesting morphologies have been discovered recently, such as nanocages, nanocombs, nanorings, nanosprings, nanobows, and nanodisks. In
this paper we have discussed about ZnO nanobrushes and nanocombs prepared by a direct atmosphere evaporation method using Zn metal.
Activated charcoal and metallic Ni powder were used as catalyst for nanobrushes and nanocombs respectively that aids in the formation of
interesting nanostructures. The nanocombs are 2-3 m in length and a single teeth is 100-150 nm in width. The growth of ZnO nanocombs is
most likely due to the vapor-solid (VS) growth mechanism. The special structures appear to be related to the morphological instability in a
supersaturated environment and its growth is generally attributed to the diffusion-limited process. On the other hand, we found that using carbon
during the evaporation method resulted in the formation of nanobrushes with the brush stems ranging from 15-20 m in length and the bristles
(100-200 nm thick) are made up of nanofibrous ZnO observed by microstructural and compositional analysis. ZnO prepared without the aid of
carbon did not have any characteristic structure. Presently ZnO nanocombs are being studied for biosensors for glucose detection. The bristles of
ZnO nanobrushes can maintain mechanical stability during operation and they are therefore promising candidates for high aspect ratio probes. In
this work, we found that the bristles are tilted at the tip with respect to center axis of the tip. This can find potential applications in the tilt angle
based cantilevers for AFM and can allow symmetrical imaging of vertical sidewalls of samples. Based on our recent results, we are pursuing the
preparation of doped ZnO nanobrushes that can open up a new area of ZnO nanostructures with the ability to control the electrical conductivity
and optical properties. Microstructural, optical and application aspect of these nanostructures will be presented in detail and the possible growth
mechanisms of the formation of nanocombs and nanobrushes will be discussed.
L5.13
Order and Disorder in Covalent Semiconductors and Ionic Oxides. Rodrigo Ferrao de Paiva Martins1,2, Luis MN Pereira1,2, Pedro
Barquinha2,1 and Elvira Maria Correia Fortunato2,1; 1CEMOP, Uninova, Caparica, Portugal; 2CENIMAT I3N, FCTUNL, Caparica, Portugal.
This paper aims to discuss the effect of order and disorder on the electrical performances of covalent silicon semiconductors and ionic oxide
semiconductors namely the Zinc oxide alloys used as active channel layer in thin film transistors or p-n junctions like solar cells. The effect of
disorder on covalent semiconductors affects directly their electrical transport properties due to the asymmetric behavior of sp states while in
ionic oxide semiconductors it is found that this effect is small, because angular disorder has no effect on spherical symmetry of s states. To this,
we have to add that the carriers mobility in both systems is quite different, being also affected by electron-phonon interactions (weak in silicon
and strong in ionic oxides leading to formation of polarons). Besides, the impurity doping effect and the presence of vacancies in disordered
silicon and in ionic oxides has different behaviours, which will influence the thin film properties and so, the performances of the devices
produced.
L5.14
Preparation and Characterization of Ga-Doped ZnO Nano powder by Sol-Gel Process. Kuo-Chuang Chiu and Ren-Der Jean; Industrial
Technology Research Institute, Chutung, Hsinchu, Taiwan.
Ga-doped ZnO powder was prepared by the low temperature Soft Chemical route Process. X-ray diffraction patterns indicate a pure phase is
formed by 600C without impure phase. TEM observations show an average 80nm particle size of the powder after annealing at 700C by using
H2 as a carrier gas. Electrical properties of Ga-doped ZnO film resistivity was 6.2 10-4 Ocm which deposited on glass substrates by
Atmospheric Plasma annealing method at room temperature. This paper reports the preparation of the fine grains size powder and low resistivity
high mobility film.

L5.15
Electrophoretic Deposition of ZnO Quantum Dots, from Substrate Coverage to Local Deposition. Petra Leona Lommens1, Dries Van
Thourhout2 and Zeger Hens1; 1Department of Inorganic and Physical Chemistry, Ghent University, Ghent, Belgium; 2Department of Information
Technology, Ghent University, Ghent, Belgium.
To use colloidal quantum dots in devices like sensor, LEDs or transistors, controllable deposition processes are needed. A possible technique to
fabricate films or micropatterns of quantum dots is electrophoretic deposition (EPD). It is based on the idea that charged particles in suspension
will be driven to and deposit on a surface when an electric field perpendicular to the substrate is applied. We have prepared layers of ZnO
quantum dots with tunable thickness by EPD. The ZnO quantum dots, 2 to 3 nm in diameter, are prepared using a well-established colloidal
synthesis route. After washing and resuspending the quantum dots in an appropriate solvent, thin layers of ZnO can be deposited on bare silicon
or gold substrates. This is done by applying voltages from 20 to 60V over a distance of 1-3 cm between a Cu-electrode and a substrate,
submerged in the quantum dot suspension. By varying this concentration from 5 to 30 M and deposition time and voltage, deposits covering the
entire substrate and ranging from monolayer coverage to 250 nm can be made. Besides homogeneous substrate coverage, we showthat EPD can
also be used to deposit quantum dots on silicon substrates covered with a patterned, developed photoresist. Using the appropriate combination of
resist and solvent, it is possible to remove the resist after the EPD process, without damaging the ZnO deposit. In this way, small micropatterns,
with dimensions in the range of 5x5 m and a thickness, varying between 10 and 300 nm, can be fabricated. In summary, this work shows that
EPD is a versitale technique for depositing charged particles, with the advantage of short deposition times, low voltages and the possibility to
deposit on bare or lithographically patterned substrates at low cost.
L5.16
Deposition of Piezoelectric ZnO Films by RF Magnetron Sputtering and its Application to SAW Devices. Seol Hee Choi and Chan Hyoung
Kang; Department of Advanced Materials Engineering, Korea Polytechnic University, Kyonggi-Do, South Korea.
Highly c-axis oriented, dense, and fine-grained polycrystalline ZnO films with smooth surface and high resistivity were deposited on 4 inch
silicon wafers by employing ZnO targets in a radio-frequency magnetron sputtering system. By changing applied rf power, substrate temperature
and O2/Ar gas ratio, the optimum process parameters were found to be 150 W, 200oC and 30/70, respectively. Applying the ZnO films deposited
under these optimum conditions, surface acoustic wave (SAW) devices of ZnO/IDT/SiO2/Si structure were fabricated by conventional
photolithography and etching processes. The interdigital transducers (IDT), made of aluminium deposited by DC magnetron sputter, were
patterned with 2.5/2.5 m finger width/spacing. Another type of SAW filter of IDT/ZnO/diamond/Si structure was fabricated. High-quality
nanocrystalline diamond (NCD) films were deposited on 4 inch silicon wafer by direct current (DC) plasma assisted chemical vapor deposition
method using H2-CH4 mixture as precursor gas. On the top of the diamond films, ZnO films were deposited under the optimum conditions. Then
aluminium IDTs were fabricated on the ZnO/diamond/Si layered films. The characteristics of the fabricated SAW devices were evaluated in
terms of center frequency, insertion loss and wave propagation velocity.
L5.17
Tailoring of Optical and Field Emission Properties of Aligned ZnO Naorods. O. N. Srivastava1, Jai Singh1 and R. S. Tiwari1; 1physics, bhu,
Varanasi, u.p., India; 2Physics, Banaras Hindu University, Varanasi, U.P., India; 3Physics, Banaras Hindu University, Varanasi, U.P., India.
Zinc oxide is a unique material that exhibits semiconducting and piezoelectric properties. Recently, nanostructured ZnO have received broad
attention due to their distinguished performance in optoelectronics devices, bio-chemical sensors, diagnosis marker, medicine and hydrogen
storage etc.ZnO nanostructures with diverse morphologies such as nanowires, nanotetrapods, nanocombs, nanosprings, nanotubes, nanorods,
nanobelts and so on, have been widely studied. ZnO is receiving renewed attention for wide band-gap device applications as compared to wide
band-gap materials GaN and CNT (carbon nanotube), because it has larger excition binding energy (~ 60 meV), better and stable field emission
and low cost synthesis. Many techniques, such as pulsed-laser deposition (PLD), molecular beam epitaxy (MBE), metalorganic chemical vapor
deposition (MOCVD),reactive electron-beam evaporation, sputtering (magnetron and radio-frequency), spray pyrolysis etc, have been used to
fabricate epitaxial and textured ZnO nanostructures and thin films.High-quality aligned ZnO nanorods were usually grown at relatively high
substrate temperature by MBE and MOCVD on single crystal Al2O3, Si, SiO2, AlN, GaN etc. Although above approach can produce aligned
ZnO nanostructures but it needs high quality substrates, high vacuum and metal catalyst particles to direct the aligned growth, which makes them
costly. We,report the synthesis of the high quality aligned ZnO nanorods using simple thermal vapor deposition method without any vacuum
system, substrates and metal catalysts. This is the first work of its type. In order to optimize the growth conditions for the synthesis of
well-aligned ZnO nanorods we have studied the effects of the various parameters affecting the growth mechanism. We have investigated effects
of , (i) rapid quenching in different mediums like liquid N2, water around 00C, ice and air(ii) oxygen and argon flow rate, on the growth of
various ZnO nanostructures. The optimum condition for aligned growth and its relation to the reaction kinetics are discussed. This approach is

simple, efficient and inexpensive, which significantly facilitates device fabrication. These aligned ZnO nanorods were characterized using
scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-Ray Diffraction (XRD). Detailed structural
characterizations reveal that the as-synthesized aligned ZnO nanorods are single crystalline with a hexagonal phase and having growth along the
[0001] direction. The room-temperature photoluminescence spectra showed a weak ultraviolet emission at ~ 380nm, a broad blue band at ~
435nm, and a strong orange-red emission at ~ 630nm. In order to explore the application aspect of these aligned nanorods, we have investigated
the field emission characteristics of these aligned ZnO nanorods. For field emission a threshold field of ~ 1.76 V/m was needed which is lowest
field reported so far for ZnO nanostructures.
L5.18
Proposal of High Temperature MBE Growth of ZnO Films with Using Ionized Zn Flux. Koji Omichi1, Yoshikazu Kaifuchi1, Munehisa
Fujimaki1, Talai Jin2 and Akihiko Yoshikawa2,3,4; 1Optics and Electronics Laboratory, Fujikura.Ltd, Sakura, Chiba, Japan; 2Graduate School of
Electrical and Electronics Engineering, Chiba University, Chiba, Chiba, Japan; 3Venture Business Laboratory, Chiba University, Chiba, Chiba,
Japan; 4InN-project as a CREST program of JST, Chiba University, Chiba, Chiba, Japan.
ZnO is one of the most promising materials for ultraviolet light emitting devices. Although a lot of papers have been reported for achieving
p-type ZnO epilayers, these methods are not reproducibly/widely followed by other groups. One of the key points for successful p-type doping is
to improve the quality of ZnO epilayers, e.g., higher crystalline structural quality with remarkably low threading dislocation density and much
more reduced concentration of residual impurities, etc. Higher growth temperatures are favorable for improving the quality of ZnO epilayers due
to the effects of enhanced surface migration of adsorbed Zn species and reduced residual impurities as well. However, the growth rate of ZnO
epilayers drastically decreases with increasing growth temperature, in particular in MBE. In this paper, we propose a novel method to achieve
higher growth temperatures in MBE up to 900 C with using ionized Zn (Zn+) flux leading to higher Zn-sticking coefficient. Effects of using Zn+
flux on the crystalline quality are also investigated. ZnO epilayers were grown on a sapphire (0001) substrate using a conventional low
temperature ZnO buffer layer grown at 400 C. A high power laser diode module was used for heating the substrate to perform high temperature
crystal growth. A novel structure Zn ionizer with extraction grid and energy-acceleration functions was designed to realize effective
Zn-ionization and higher Zn-sticking coefficient at high growth temperatures, and it was set between the Zn cell and substrate. ZnO epilayers
were grown at 650-900 C under two different conditions with and without Zn-ionization, and the results in both cases were comparatively
studied. First we have confirmed that the growth rate was increased with using Zn+ flux. In particular, this was remarkable at the growth
temperature of 900 C; the growth rate was 2 times higher when using Zn+ flux. As for their properties in 190 nm-thick ZnO epilayers grown at
850 C using Zn+ flux, the rms surface roughness was about 20 nm in 10 m x 10 m area, and the electron concentration and Hall mobility
were ~3x1016 cm3 and ~190 cm2/Vs, respectively. Thus it was confirmed that the growth of ZnO epilayers with using Zn+ flux is an effective
method to achieve higher growth rate and higher crystalline quality at high growth temperature in MBE.
L5.19
Morphology Dependence of Lasing Characteristic in ZnO Nanostructures. SangHyun Lee1, Takenari Goto1, Hiroshi Miyazaki2,
Meoung-Whan Cho3 and Takafumi Yao1,3; 1Center for Interdisciplinary Research, Tohoku University, Sendai, Japan; 2Department of Applied
Physics, Tohoku University, Sendai, Japan; 3Institute for Materials Research, Tohoku University, Sendai, Japan.
An interesting topic of recent ZnO research is the relationships between its own properties and morphologies including dimensionality, size, and
shape. It is revealing through the analysis of fundamental properties and realization of device using various shaped nanostructures. The optical
properties of ZnO nanostructures provide hope applying it to a UV optoelectronic nano-device material instead of GaN due to more easy growth
technology of high quality ZnO nano-crystal and a large excition binding energy of 60 meV. Here, we present the optical properties of various
ZnO nanostructures with different size and morphologies; rod, needle, and multi-tapered structures. The temperature and excitation intensity
dependence of photoluminescence (PL) in ZnO nanostructures was accomplished. These nanostructures showed strong and sharp excitonic
emissions comparable to bulk ZnO at 10 K. Emission spectra and images using micro PL measurement system proved different emission
distributions within single nanoneedle and multi-tapered. The strong emission was observed in the 100 ~ 400 nm diameter region, while the
emission was significantly decreased at the part by decreasing the diameter. The results suggest that the generated emission within crystal cant
progress into narrow structure. No stimulated emission from ZnO nanorods and needle could be also understood in terms of high optical loss and
transmission of light wave in nanorods due to smaller diameter than wavelength. We observed interestingly the stimulated and laser emission
from only tapered structures from 5 m to 30 nm. The laser emission was observed near the tip of tapered structure. We also suggest the possible
mechanism and optical cavity for laser emission in a multi-tapered ZnO structure at room temperature. A prediction of optical behavior within
single nanoneeldle and tapered structure using 3D-FDTD simulation is discussed.
L5.20
Tunable N-type Conductivity and Transport Properties of Ga-doped ZnO Nanowire Arrays. Guodong Yuan, Wenjun Zhang, Jiansheng Jie,

Xia Fan, Chunsing Lee and Shuittong Lee; Department of Physics and Materials Science, Center of Super-Diamond and Advanced Films,
Hongkong, China.
In this work, we demonstrate a controlled growth and doping process of well-aligned ZnO nanowire (NW) arrays by introducing Ga2O3 as a
dopant source. First, we show the crystallographic orientation of NWs is dictated by dopant content, while all nanowires possess high crystal
quality. We then systematically study the electrical and transport properties of Ga-doped ZnO nanowires via field-effect transistors (FETs)
fabricated from single nanowires. FET measurements show, with high reproducibility, that increasing Ga2O3 in the source material from 0 to 1%
can realize tunable and controllable n-type conductivity, with resistivity decreasing from 0.25 Ohm cm to 2.210-3 Ohm cm. All NWs show
sharp near-band edge PL with negligible defect-related emissions suggesting good crystal quality. The emission peak for the undoped ZnO
nanowires is centered at 374 nm, which is red-shifted by 1.8 and 15 nm respectively in the lightly and heavily Ga-doped ZnO nanowires. The
capability of tuning n-type conduction and the understanding of the transport properties of ZnO NWs are important for the development of ZnO
NW-based electronic and photoelectronic devices.
L5.21
Abstract Withdrawn
L5.22
Optical Characterization of Acceptors Implanted into ZnO. Joachim Drr1, Daniel Stichtenoth1, Sven Mueller1, Lars Wischmeier2, C.
Bekeney2, Tobias Voss2 and Carsten Ronning1; 1II. Institute of Physics, University of Goettingen, Goettingen, Germany; 2Institute for Solid
State Physics, University of Bremen, Bremen, Germany.
Nitrogen and phosphorus are the most promising candidates for p-type doping of ZnO. We doped ZnO bulk crystals using ion implantation
because this technique offers several advantages compared to other growth methods, e.g. precise control of the lateral and vertical dopant
concentration even beyond solubility limits. After implantation and annealing of the introduced defects we performed photoluminescence
measurements in order to monitor the optical activation of the dopants. Temperature- and power-dependent measurements reveal that a new line
appearing at 3.23 eV for the N-implanted samples is due to Donor-Acceptor-Pair (DAP) transitions. We investigated the dependence of this
feature on co-implantation as well as on the implantation and annealing temperature. First experiments on phosphorus-implanted ZnO will also
be presented.
L5.23
Abstract Withdrawn
L5.24
Shape-controlled Solution-synthesis of Single Crystalline ZnTe 1D Nanocrystals. Jun Zhang1, Amar Kumbhar2 and Jiye Fang1; 1Department
of Chemistry, State University of New York at Binghamton, Binghamton, New York; 2Electron Microscope Facility, Clemson University,
Anderson, South Carolina.
One dimensional nano-structured ZnTe have attracted more interests because of their potential applications of optoelectronic devices in the
blue-green region of the spectrum. Our study demonstrates shape-controlled synthesis of high-quality ZnTe nanobelts and nanorods in
high-temperature organic solution. Zinc acetate was dissolved in benzyl ether under argon protection in the presence of oleic acid. Solution of
metallic tellurium in trioctylphosphine (TOP) was introduced into this zinc solution along with superhydride (lithium triethyl borohydride),
forming a stock solution as reaction precursor. The reactions were carried out by multiple injections of such stock solution into pre-heated benzyl
ether. The products were isolated by centrifugation and were re-dispersed in hexane, resulting one-dimensional (1D) ZnTe nanocrystals (NCs).
The size and morphology were observed using transmission electron microscopic technique (TEM), whereas the phase structure was analyzed
using powder x-ray diffraction method (XRD). Photoluminescence (PL) spectra of these 1D ZnTe NCs were also explored. Investigation reveals
that these 1D ZnTe NCs are monodispersed and single crystalline.
L5.25
Electrochemical Fabrication of Zn1-xMgxO Films from an Aqueous Solution Containing Magnesium Nitrate and Zinc Sulfate. Hiroki
Ishizaki1,2 and Hideaki Maeda1,2; 1Nanotechnology Research Institute, National Institute of Advanced Industrial Science and Technology, Tosu,
Saga, Japan; 2Crest, Japan Science and Technology Agency, Tosu, Saga, Japan.

Recently, oxide films with wide band gap energy were paid much attention for many applications such as optic devices, electric luminescence
devices and transparent conductive oxide of solar cells. Many authors reported the preparation of oxide film with the band gap energy, such as
ZnO:Ga, Zn1-xMgxO, and Zn1-xCdxO. In particular, Zn1-xMgxO films presented interesting electrical and optical properties, which found wide
applications in the fields of optoelectronic and transparent conductive oxide. Because the band gap energy of Zn 1-xMgxO films was easily
controlled by Mg/(Mg+Zn) atomic ratio. Zn1-xMgxO films were prepared commonly by the physical vapor deposition such as RF-magnetron
sputtering, molecular beam epitaxy, metal organic chemical vapor deposition and pulsed laser deposition. On the other hand, the electrochemical
preparation of oxide films presented the several advantages over these techniques; (1) the thickness and morphology of film could be controlled
by electrochemical parameters, (2) the relatively uniform films could be obtained on the substrates with complex shape, (3) the films could be
grown on substrates with a melting point below 373K such as polymer, (4) the technique was considered to be less hazardous and thus more
environmentally friendly and (5) the equipment was less expensive. In this work, we investigated the evaluation and the electrochemical
preparation of Zn1-xMgxO films on the conductive glass substrates from a 0.1mol/L magnesium nitrate and 0.001mol/L zinc sulfate at the
cathodic potential ranging of -0.8V and -0.95V. The Mg/(Zn+Mg) atomic ratio, the structural and optical properties of these Zn 1-xMgxO films
were investigated using inductively coupled plasma spectroscopy (ICP), X-ray diffraction, scanning electron microscope (SEM) and the
UV-VIS-NIR scanning spectrophotometer. Zn1-xMgxO films with the wurtzite structure were electrochemically grown on the NESA glass
substrates from a 0.1 mol/L magnesium nitrate aqueous solution containing 0.001mol/L zinc sulfate, regardless of the cathodic potential. And the
lattice length of the c-axes increased with the decreasing the cathodic potential. The bandgap energy and Mg/(Zn+Mg) atomic ratio of
Zn1-xMgxO film decreased with a decrease in the cathodic potential. Thus, the present results indicate that the band gap energy and the lattice
parameters depend on the cathodic potential. In the conclusion, the optical, structural properties and Mg/(Zn+Mg) atomic ratio of Zn 1-xMgxO
films can be controlled by the cathodic potential.
L5.26
Tunneling Spectroscopy of Magnetic Impurities (=Co,Mn,Fe) in ZnO. Takashi Tamura, Changman Kim, Yasushi Oikawa and Hajime Ozaki;
Waseda university, Tokyo, Japan.
Recently, ZnO has attracted interest in the spintronics as a candidate for a diluted magnetic semiconductor (DMS) which shows the room
temperature ferromagnetism and has been investigated by many workers. However there is a lot of controversy on the origin of the magnetic
properties and it is important to know fundamental characteristics of magnetic impurities in ZnO to elucidate the origin of the magnetism. In this
study we firstly observed the density of states (DOS) of M-doped ZnO (M=Co,Mn,Fe) by tunneling spectroscopy which is one of the useful
methods for analyzing the DOS directly with high resolution. M-doped ZnO single crystals were prepared by chemical vapor transport (CVT)
method using ZnCl2 or ZnCl2 plus C as transport agents. The composition x of magnetic impurity M in MxZn1-xO was about 0.07 for Co and
about 0.10 for Mn and Fe. A swelling was observed in the dI/dV vs. V tunneling characteristics around 2.8 eV- 3.2eV below the Fermi level and
just above the valence band edge of ZnO which is about 3.2eV below the Fermi level. This swelling in DOS is considered to indicate the 3d
states of Co ions which is in agreement with the result of a theoretical calculation. [1] In the conference the tunneling spectroscopies will be
reported also for Mn and Fe doped ZnO. [1] M.Toyoda, H.Akai, K.Sato, H.Katayama- Yoshida :Physica B, Vol:376-377 (2006), 647
L5.27
Structural and Optical Properties of High Quality Homoepitaxial ZnO Layer. Frank Bertram, Alexander Franke, Juergen Christen, Thomas
Hempel, Soeren Heinze, Armin Dadgar and Alois Krost; Otto-von-Guericke-University Magdeburg, Magdeburg, Germany.
In recent years, ZnO and related alloys are attracting attention as promising candidates for the use of light emitters and detectors. Although ZnO
single crystals were available for a long time epitaxially ZnO are usually grown on foreign substrates. Despite of the advantages of homoepitaxy,
i.e., perfect matching of lattice constants and thermal expansion coefficients and the expected lower dislocation densities, only a few reports on
optical properties of homoepitaxially grown ZnO layers exist. In this work, we report on a comprehensive characterization of homoepitaxially
grown ZnO films by means of scanning electron microscopy (FE-SEM), photoluminescence (PL) and spatially and spectrally resolved
cathodoluminescence spectroscopy (CL). The nominal 500 nm thick epitaxial ZnO layer is grown by MOVPE on commercially available
(0001)-oriented ZnO substrate. The ZnO layer is directly deposited on the thermally pretreated ZnO substrate without any buffer layer. The ZnO
layer has a flat, mirror-like surface and exhibits no features in plan view SEM. In cross- sectional FE-SEM images, the substrate merges
smoothly into the ZnO layer: no contrast is visible at the ZnO-substrate-to-ZnO-epilayer homo-interface! This visualizes the structural perfect
quality of the ZnO/ZnO homointerface which is further evidenced by TEM investigations. The low temperature (4 K) PL spectrum of the
substrate and of the homoepitaxial layer is dominated by the neutral impurity bound exciton line I8 (E = 3.360 eV). The free exciton line XA (E
= 3.377 eV) and the ionized impurity bound excitons I1 (E = 3.371 eV) as well as a deeply bound exciton at E = 3.342 eV are also observable.
An additional new luminescence line in the spectral region between I9 and I10 (E = 3.355 eV) is exclusively visible in the ZnO layer. Intense and
very homogeneous CL intensity with a narrow spatial distribution of emission wavelength is obtained in plan view CL microscopy. The
dominating I8 exhibits a standard deviation of s = 0.4 meV. We further focus on the spectral evolution as a function of depth to the interface of
the ZnO/ZnO homostructure. Cross-sectional CL spectrum linescan, i.e., sets of CL spectra recorded while scanning the e-beam in the growth

direction along the freshly cleaved cross section were recorded. The ZnO substrate and the subsequent following ZnO layer can be clearly
resolved: The CL of the ZnO substrate is completely governed by a strong I8 emission while slight variations of intensity and spectral position
indicate the limited structural quality of the commercial substrate. In contrast, the CL of the ZnO epilayer is characterized by an additional line in
the spectral region between I9 and I10 as has been recorded in plan view PL / CL. No shift or fluctuation of spectral position or intensity of these
excitonic lines is observed across the ZnO/ZnO homointerface and along the layer thickness indicating the high optical quality of the ZnO
epilayer.
L5.28
Solution-deposited ZnO-organic diodes with high current density and high frequency rectification under ambient conditions Bhola Nath
Pal, Department of Material Science and Engineering, Johns Hopkins University, Baltimore, Maryland.
n-ZnO/p-Pentacene and n-ZnO/poly(bis(dodecyl)quaterthiophene) (p-PQT-12) vertical p-n junction diodes were prepared on ITO-coated glass. A
continuous film of ZnO nanoparticles was grown on the ITO glass by dip-coating and subsequent heat treatment of a zinc acetate film. Pentacene
was then thermally evaporated to form the ZnO/Pentacene diode, whereas PQT-12 was spin coated for the ZnO/PQT-12 diode. Based on the
band energies of ZnO, pentacene and PQT-12, for efficient carrier injection, gold was chosen as the top electrode to complement the ITO for
both diodes. The microstructures of ZnO and pentacene films are studied by AFM and show a layer of pentacene grains with about twice the
extent of the underlying layer of ZnO grains, implying substantial interfacial contact between them The current density-voltage (J-V)
measurement shows that the maximum current density for ZnO/Pentacene and ZnO/PQT12 are 160 A/cm2 and 350 A/cm2 respectively.
Capacitance-voltage (C-V) data also provides evidence of formation of the p-n junction. The rectification was characterized by observation of
full input-half output waves. Data indicate that these devices can operate up to frequencies of 20 MHz and 9 MHz for ZnO/Pentacene and
ZnO/PQT12, respectively, under ambient environment conditions. This rectification frequency is higher than other reported organic and polymer
Schottky diodes under these conditions. Turn on voltages of these diodes are also much lower than for the reported organic and polymer diodes.
L5.29
Aqueous Chemical Synthesis of Small Diameter ZnO Nanorods with Superb Photocatalytic Activity. Yao-An Chung, Yu-Cheng Chang,
Ming-Yen Lu and Lih-Juann Chen; Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu, Taiwan.
ZnO nanorods have been prepared from aqueous solution containing Zn(OH)42- ions, manganese acetate and sodium dodecyl sulfate (SDS) at
room temperature. Zn(OH)42- ions were produced with zinc acetate and sodium hydroxide. The as prepared products were characterized by
SEM, EDS, TEM, SAED, HRTEM, XRD, BET and CL. The SEM and TEM images showed that the nanorods are 300 - 400 nm in length and 10
- 20 nm in diameters. The EDS, XRD, SAED, and HRTEM confirmed the product is single crystal ZnO nanorods with the growth direction
along [001]. The CL spectrum shows a strong and broad emission at 580 nm. The surface area of sample is 80 m2/g determined by BET. Superb
photocatalytic activity of ZnO nanorods toward NO gas was detected.
SESSION L6: Magnetically Doped ZnO

Chair: Gyu-Chul Yi
Wednesday Morning, November 28, 2007
8:30 AM *L6.1
ZnO for Spintronics: Some Critical Issues. Weimin M Chen1, Irina A Buyanova1, A. Murayama2, Y. Oka2, D. P Norton3, S. J Pearton3, A.
Osinsky4 and J. W Dong4; 1Linkoping University, Linkoping, Sweden; 2Institute of Multidisciplinary Research for Advanced Materials, Tohoku
University, Sendai, Japan; 3Department of Materials Science and Engineering, University of Florida, Gainesville, Florida; 4SVT Associates,
Eden Prairie, Minnesota.
Due to their attractive physical and chemical properties, ZnO and related materials have emerged to be one of the most promising material
systems for potential applications in optoelectronics operating within the UV-blue spectral range and also in chemical and bio sensing. The
demonstration of room temperature ferromagnetism in its magnetic counterpart, i.e. diluted magnetic semiconductors based on ZnO, has also
shown the potential of this material system for future applications in spintronics. Progress in this research topic has unfortunately been hindered
by rather poor understanding of the spin-dependent phenomena in the materials, apart from the difficulties in material preparation and control. In
this talk, we shall review our recent work on spin injection and spin detection in ZnO-based materials by spin-polarized cw and time-resolved

magneto-optical spectroscopy. We shall address some critical issues that are important for future applications in spintronics, such as spin loss in
spin detectors and the fundamental limits in the efficiency of spin detection by using the ZnO-based hetero- and quantum structures. Detailed
physical mechanisms leading to spin depolarization and strategy for improvement will be discussed.
9:00 AM L6.2
Growth and Properties of ZnxMn1-xO Thin Films Grown by Plasma-assisted MBE on (0001) Sapphire Substrates. Christiane Deparis1,
Christian Morhain1, Jesus Zuniga-Perez1, Pascal Sati2, Jean-Michel Chauveau1,3, Marguerite M. Laugt1, Philippe Vennegues1, Borge Vinter1,3
and Anatoli Stepanov2; 1Centre de Recherche sur l'Htro-Epitaxie et ses applications CRHEA-CNRS, Valbonne Sophia Antipolis, France;
2L2MP - Universit Paul Czanne, Facult de St-Jrme, Marseille, France; 3Physics Dept, University of Nice-Sophia-Antipolis, Nice, France.
In the search for a high Tc ferromagnetic semiconductor, p-type doped ZnxMn1-xO appears as an attractive diluted magnetic semiconductor
(DMS) since it has been predicted that this material would be a ferromagnet at room temperature. Contradictory results regarding the magnetic
properties of ZnMnO have been published so far, showing the importance of sample quality and the need to avoid any Mn-related secondary
phases which could mask the intrinsic magnetic properties. MBE appears therefore an excellent technique to deposit ZnO-based DMS and to
investigate their growth and properties, especially since it offers the possibility of monitoring the growth. In this communication, we shall report
on the growth of ZnMnO DMS by plasma assisted MBE on (0001) sapphire substrates. The Mn content was varied from x=0.001 to x=0.16. The
role of the growth conditions on the structural and optical properties of ZnMnO samples as well as the effect of Mn incorporation on the growth
kinetics were investigated in detail. It was found that Mn concentrations as low as ~1% could induce dramatic changes in the RHEED diagrams
and growth rate of ZnMnO as observed by in situ monitoring of the growth by reflection high energy electron diffraction as well as optical
reflectivity. Indeed, a key feature is that Mn incorporation results in a clear (3x3) RHEED pattern. While 3x reconstructions are often observed
after the growth of ZnO epilayers when cooling down the samples, here the reconstruction is present during the growth. This change in the
surface stoichiometry is clearly related to Mn and manifests itself also on the growth rate which was measured to increase by >50% in the
investigated Mn composition range. Mn incorporation has also been found to strongly modify the surface morphology of the samples (AFM)
which present very smooth terraces with randomly distributed dips with hexagonal symmetry. The sample microstructure and the origin of the
dips are under investigation by means of TEM. Finally, the influence of Mn incorporation on the change in electronic properties has been
investigated (PL) as well as the local surrounding of the Mn ions (EPR), and high resolution X ray diffraction measurements show that both
lattice parameters linearly increase with Mn content, although the a([Mn]) and c([Mn]) dependence is different.
9:15 AM L6.3
Ferromagnertic Properties Controlled by Carrier Concentrations in Co:ZnO Thin Films on ZnO Single Crystals. Hitoshi Tabata1,
Hiromasa Saeki2 and Hiroaki Matsui2; 1School of Engineering, The University of Tokyo, Bunkyo-ku, Tokyo, Japan; 2ISIR-Sanken, Osaka
University, Ibaraki, Osaka, Japan.
We reported ferromagnetic properties of ZnO:Co thin films formed on sapphire substrates.[1] Ferromagneticities of them are confirmed by
SQUID, XMCD and anomalous hall effect measurements.[2, 3] Here, we have described a new growth technique realizing the simultaneous
control of growth mode and ferromagnetic ordering in Co-doped ZnO layers on ZnO single crystals.[4] Remarkable changes in growth occurred
as a result of doping with Co ions. Exposure to O2 plasma to generate an oxygen-rich atmosphere was indispensable for the fabrication of
undoped ZnO layers given stabilization of the negatively charged growing surface in a twodimensional(2D) mode. In contrast, the 2D mode of
Zn0.94Co0.06O layers was adequately retained in the absence of a plasma source, and was attributable to the covalence provided by the 3d
character of Co ions compared with the 4s character of Zn ions. Spontaneous magnetization of Zn0.94Co0.06O layers was closely correlated
with the number of free electrons, which was controlled by the activation energy of donor levels. This was also confirmed for O-polar
Zn0.94Co0.06O layers. Ferromagnetic _FM_ ordering was observed at ne values close to the Mott transition and led to hopping conduction
between shallow donor bands. However, levels of p_O2_ below 10-6 mbar that yielded FM ordering generated a pitted surface and led to
crystalline deterioration. Given our understanding of the formation mechanism of pits, we applied a periodic oxygen pressure-modulated epitaxy
that resulted in the coherent growth of Co-doped ZnO layers with a 2D mode. This specific growth was effective in producing pit-free surface
uniformities over large areas that maintained FM ordering. 1) Appl.Phys.Lett., 79 (2001) 988. 2) J.Phys.:Condens. Matter, 16 (2004) S5533. 3)
Phys. Rev. B, 72 (2005) 201201(R) 4) Phys. Rev. B. 75 (2007) 014438
10:00 AM *L6.4
Magnetic Dopants and Charge Carriers in Colloidal ZnO Nanocrystals and Epitaxial ZnO Thin Films. Daniel R. Gamelin, Department of
Chemistry, University of Washington, Seattle, Washington.
Carrier-dopant magnetic exchange interactions in diluted magnetic semiconductors (DMSs) provide the basis for many important magneto-
electronic and magneto-optical phenomena, including carrier-mediated ferromagnetism, magnetic polaron nucleation, giant excitonic Zeeman

splittings, and proposed spin-based quantum information processing schemes. This talk will describe our group's recent investigations into the
use of magnetic and magneto-optical techniques to probe dopant-carrier exchange interactions in ZnO DMS thin films and colloidal quantum
dots. Apart from the technological interest in these materials, this research is motivated by the new fundamental insights it provides into the
microscopic origins of cooperative magnetization in this class of materials. Related references: Liu, W. K.; Whitaker, K. M.; Kittilstved, K. R.;
Gamelin, D. R., Stable Photogenerated Carriers in Magnetic Semiconductor Nanocrystals. J. Am. Chem. Soc. 2006, 128, 3910-3911. Kittilstved,
K. R.; Schwartz, D. A.; Tuan, A. C.; Heald, S. M.; Chambers, S. A.; Gamelin, D. R. "Direct Kinetic Correlation of Carriers and Ferromagnetism
in Co2+:ZnO." Phys. Rev. Lett., 2006, 97, 037203. Kittilstved, K. R.; Liu, W. K.; Gamelin, D. R. "Electronic Structure Origins of Polarity
Dependent High-TC Ferromagnetism in Oxide Diluted Magnetic Semiconductors." Nature Materials, 2006, 5, 291-297. Kittilstved, K. R.;
Norberg, N. S.; Gamelin, D. R. "Chemical Manipulation of 300K Ferromagnetism in ZnO Diluted Magnetic Semiconductors." Phys. Rev. Lett.,
2005, 94, 149049.
10:30 AM L6.5
Dopant Incorporation in Co:ZnO Colloidal Quantum Dots. Petra Leona Lommens1, Philippe F. Smet2, Frank Loncke2, Henk Vrielinck2,
Dirk Poelman2 and Zeger Hens1; 1Physics and Chemistry of Nanostructures, Ghent University, Ghent, Belgium; 2Department of Solid State
Sciences, Ghent University, Ghent, Belgium.
Being a well-established technique to alter the electric and optical properties of a bulk semiconductor, doping of semiconductor nanocrystals or
quantum dots has been intensively investigated over the last ten years. Nevertheless, controlled dopant incorporation in semiconductor
nanocrystals remains an important issue. With colloidal quantum dots for example, dopants often end up adsorbed at the nanocrystals surface
rather than incorporated in the nanocrystals core. We have performed a case study on the incorporation of Co2+ ions in ZnO quantum dots. This
is an interesting system, not only because of its possible ferromagnetic properties, but also because Co2+ ions can be observed with a variety of
spectroscopic techniques. The Co:ZnO colloidal nanocrystals were prepared using a colloidal synthesis route. A general characterization of the
quantum dots was performed using XRD, XPS, ICP-MS and TEM, while optical spectroscopy and electron paramagnetic resonance (EPR)
spectroscopy were used to investigate the Co2+ ions. We found that three different types of Co2+ ions are present in Co:ZnO nanocrystals.
Firstly, optical spectroscopy confirmed that a part of the Co2+ ions substitutionally replace Zn2+ ions in the ZnO lattice. Secondly, using an
amine surface treatment that detaches Co2+ ions from the Co:ZnO nanocrystals surface, we could demonstrate that about 50 % of the Co2+ ions
entering synthesis end up adsorbed at the nanocrystals surface. This observation is confirmed by growing an undoped ZnO shell around the
Co:ZnO core. Shell growth leads to a threefold increase of the substitutional Co2+ absorption, while no extra Co-precursor was added. This
shows that shell growth leads to the incorporation of surface adsorbed Co2+ ions in the core/shell nanocrystals. Finally, EPR spectra of as
synthesized Co:ZnO powders contain contributions of two different types of Co2+ ions. One can be related to substitutional Co2+. The other
contribution could however not be attributed to surface adsorbed ions since neither amine treatment nor shell growth significantly changes the
intensity ratio of the two contributions. This means a third type of Co2+ ions must be present in the Co:ZnO nanocrystals. Simulations of our
EPR spectra show that this additional type of Co2+ ions have an octahedral coordination. We therefore suggest that these Co2+ ions actually are
Co2+ interstitials.
10:45 AM L6.6
Study of the Role of the Free Carrier Concentration on the Ferromagnetism in Co- and Mn-implanted ZnO. Zheng Yang1, Leelaprasanna
J Mandalapu1, Jianlin Liu1, Biasini Maurizio2 and Ward P Beyermann2; 1Department of Electrical Engineering, University of California at
Riverside, Riverside, California; 2Department of Physics, University of California at Riverside, Riverside, California.
Diluted magnetic semiconductor (DMS) materials have attracted a great deal of attention for their potential application in spintronics. ZnO is
attracting much attention toward this application because of its above room-temperature ferromagnetism based on theoretical calculations. The
carrier-mediated ferromagnetism is one of the most widely accepted theories for DMS, in which the ferromagnetic coupling between the
moments from the localized magnetic dopants is mediated by itinerant carriers. However, very few experiments have been done so far to verify
this theory. In this presentation, we will show our experimental results on the role of the free carrier concentration on the ferromagnetism in ZnO
DMS materials. The ZnO thin films were grown on sapphire substrates by molecular-beam epitaxy. The free electron carrier concentrations of
the ZnO films were tuned by precisely-controlled doping Ga into the ZnO. The free electron carrier concentrations from 1.410^18 cm^-3 to
1.210^20 cm^-3 were achieved. The Co- and Mn-implantations were performed on the as-grown ZnO samples with different free carrier
concentrations. All the samples were annealed at 900 degree C for 5 minutes after implantation to activate the implanted ions and recover the
crystalline quality. The X-ray diffraction measurements show that the ZnO samples after implantation are still of very high crystalline-quality,
and no Co or Mn related phase separation was detected. The secondary ion mass spectroscopy measurements show that very tiny amount of the
Co/Mn atoms penetrate the ZnO thin films and reach the sapphire substrate. Even though the amount of the residual implanted ions in the
substrate is very small, they have been eliminated by subtraction in the measurements. The ferromagnetic hystereses were observed in both Co-
and Mn-implanted ZnO samples at room-temperature. The temperature-dependent magnetization measurements were performed on the Co- and
Mn-implanted ZnO samples up to 800 K, showing far-above room-temperature ferromagnetism. The Co-ZnO samples show free carrier

dependent saturation magnetizations: the larger carrier concentrations, the larger saturation magnetizations. However, when the carrier
concentration reaches near 10^20 cm^-3, the saturation magnetization reaches a maximum value and saturates even if more carriers are added.
This result gives an experimental support to the carrier-mediation theory of the ferromagnetism from DMS materials. Unlike Co-ZnO, the
Mn-ZnO samples do not show any electron concentration dependent behavior. This is interesting since the existing theory predicts that the
Mn-ZnO would be ferromagnetic only in hole-mediated heavily doped p-type ZnO. Possible reasons are discussed.
11:00 AM *L6.7
Microscopic Properties of ZnCoO and ZnMnO: The Role of the Defects and Hydrogen Impurity in Spin-spin Interactions. C. H. Park1,
D. J. Chadi2 and I. J. Kang1; 1Department of Physics, Pusan National University, Pusan, South Korea; 2NEC Laboratories America, Princeton,
New Jersey.
It is well-known that Zn-interstitial and O-vacancy can be easily formed in ZnO. In addition, ZnO can be easily contaminated by hydrogen
impurity. Theoretical calculations have indicated that their formation enthalpies are very small. Therefore it is suggested that these defects and
hydrogen can lead to the natural n-type conductivity and also prevent the achievement of p-type doping. Since the concentrations can be easily
high in the DMS, it is important to understand the role of defects and hydrogen in the magnetic properties of the diluted magnetic
semiconductors. Many experimental data have indicated that the O-vacancy may play an important role in the ferromagnetism of ZnCoO. In this
work, we investigated the role of these low-energy defects and hydrogen in the ZnO-based magnetic semiconductors (DMS) such as ZnCoO and
ZnMnO, We performed the first-principles calculations using local spin density approximation (LSDA) and LSDA+U to investigate the
electronic structures and the formation enthalpies of the defects and impurities. It is shown that the hydrogen can induce the strong ferromagnetic
coupling between the Co ions and also between the Mn ions with the formation of a bridge bond composed of Co-3d orbitals. The Monte-Carlo
calculation using Heisenberg-type artificial Hamiltonian indicates that the contamination of H in the magnetic semiconductors can induce the
high-T ferromagnetism. The roles of O-vacancy and the interstitial defects in the spin-spin interaction will be discussed based on the
calculational results.
11:30 AM L6.8
Effect of Defects and Free Carriers on the Magnetic and Electrical Properties of Cu Doped ZnO Based Diluted Magnetic Semiconductor
Thin Films. Deepayan Chakraborti1, John T Prater2,1 and Jagdish Narayan1; 1Materials Science and Engineering, North Carolina State
University, Raleigh, North Carolina; 2Materials Science Division, Army Research Office, Research Triangle Park, North Carolina.
The exciting possibility of combining the charge and spin functionality of an electron and to incorporate them into novel spintronic devices like
spin FETs, spin LEDs, quantum qbits, etc has led to an extensive search for materials in which semiconducting properties can be integrated with
magnetic properties. Recent studies have found transition metal doped ZnO to display room temperature ferromagnetism. pbyBut there still
exists a debate over the mechanism responsible for the ferromagnetic ordering in these systems. Earlier reports claimed a free carrier mediated
mechanism (RKKY) to be responsible for the ordering of spins in ZnO based DMS. But more recent studies found room temperature
ferromagnetism in systems with low carrier concentrations indicating that defects like oxygen vacancies play an important role in stabilizing
ferromagnetic ordering. For successful fabrication of devices involving injection of spin polarized electrons it is very important to have a good
understanding of the origin of ferromagnetism and also how free carriers interact with the electron spins. In this study we have grown Cu doped
and Cu,Al co-doped ZnO thin films epitaxially on (0001) a-Al2O3 by pulsed laser deposition technique and annealed them in oxygen at high
temperature (600 0C) to study the role of defects like oxygen vacancies on the ferromagnetic properties of these films. Cu-doped ZnO thin films
not only rule out the possibility of ferromagnetism arising from extrinsic sources like magnetic secondary phases or nanoclusters, but have also
been found to display very high spin polarization.1 The doping of Cu:ZnO specimens with Al changed the carrier concentration by three orders
of magnitude (from 1017 to 1020 cm-3) without altering the ferromagnetic ordering. On the other hand, a reduction in the number of oxygen
vacancies brought about by high temperature oxygen annealing had a large detrimental effect on the ferromagnetism reducing the total saturation
magnetization by almost an order of magnitude. These results tend to rule out a free carrier mediated mechanism as being responsible for the
ferromagnetism in ZnO based DMS systems.These studies point towards a defect mediated mechanism, such as a bound magnetic polaron
mediated exchange as being responsible for stabilizing the ferromagnetic ordering in these systems. 1 D. Chakraborti, J. Narayan and, J.T. Prater,
App. Phys. Lett. 90(6),062504 (2007)
11:45 AM L6.9
Structural and Luminescence Properties of Zn1-xCuxO Thin Films. Kousik Samanta1, Pijush Bhattacharya2 and Ram S Katiyar1; 1Physics,
University of Puerto Rico, San Juan, Puerto Rico; 2Physics, Fisk University, Nashville, Tennessee.
High electronic conductivity, optical transparency, and direct band gap (3.37 eV) energy with stable free excitonic binding energy (60 meV) of
ZnO make it the most promising multifunctional semiconducting material for the application in optoelectronics devices operating in blue and

ultraviolet (UV) region. Moreover, the 3d transition metal (Co, Ni, Mn, Cu, etc.) doped ZnO can be the most promising ferromagnetic
semiconductor at room temperature for spintronic applications. In this work we have carried out the structural and optical properties of PLD
grown nanocrystalline thin films of Zn1-xCuxO (x = 0, 1, 3, and 5%) on Al2O3 substrate. The structural analysis of these samples was done by
micro-Raman scattering studies using 514.5 nm Ar+ laser source. The Raman spectrum of Zn1-xCuxO thin films shows the characteristic normal
modes of wurtzite ZnO at 98.5, 378.7, and 439 cm-1 corresponding to the E2low, A1TO, and E2high respectively, no other secondary phase was
detected in our samples. The crystalline grain sizes of 1, 3, and 5% Cu doped ZnO samples were calculated by phonon confinement model as
85.2, 67.6, and 63.6 nm, respectively. The PL spectrum of Zn1-xCuxO thin films at 77 K shows the basic excitonic feature of ZnO with the
splitting of free exciton peak and additional transitions at 3.159 eV and 3.09 eV due to the Cu doping. This radiative recombination belongs to
the electronic transition between the valance band and the CuZn acceptor at different charge state 3d9 and 3d10 respectively. The splitting of the
free exciton corresponding to G5 and G6 excitons in Zn1-xCuxO samples was due to the induced strain by Cu doping. The decrease of optical
band gap from 3.276 eV to 3.263 eV with increase in Cu concentration was due to the p-d inter-valance charge transfer (IVCT) transition from p
(O2-) to eg (Cu3+).
SESSION L7: P-type Doping

Chairs: W. Chen and C.H. Park
Wednesday Afternoon, November 28, 2007
1:30 PM L7.1
Study of p-type Codoped ZnO Films Grown by Pulsed Laser Deposition. Heungsoo Kim, Mike Osofsky, Ray C.Y. Auyeung, Dave Knies,
Catalina Cetina and Alberto Pique; Code 6364, Naval Research Laboratory, Washington, District of Columbia.
The ability to deposit both p- and n-type ZnO thin films of high quality is essential for the development of ZnO based optoelectronic devices
such as p-n homojunctions. However, it is very difficult to obtain p-type ZnO due to self-compensation from its native intrinsic defects and the
low solubility of most p-type dopants. One approach to improve the solubility of the p-type dopants is to use co-doping deposition methods
during film growth. Recently, at NRL, we have shown the ability to deposit thin films of Zr-N codoped p-type ZnO by pulsed laser deposition on
sapphire substrates. The carrier type and conduction depend on the N2O deposition pressure and film growth temperature. The best Zr-N
codoped ZnO films were grown at 500C in 5x10-5 Torr of N2O. These films showed p-type conduction behavior with a low resistivity of 0.026
O-cm, a carrier concentration of 5.5x1019 cm-3, and a mobility of 4.4 cm2V-1s-1. We have investigated the use of these p-type ZnO films for
making p-n heterojunctions on n-type Si substrates (p-ZnO/n-Si) as well as p-n homojunctions on sapphire substrates (p-ZnO/n-ZnO/Al 2O3). In
this talk, we will discuss our work to date on the growth of Zr-N codoped ZnO thin films by PLD and present electrical and optical
characterization results from the various types of films deposited. This work was supported by the Office of Naval Research.
1:45 PM L7.2
Role of Microstructure and Defects in Epitaxial p-Type ZnO Thin Films. Xiaoqing Pan1, Arnold Allenic1, Wei Guo1, Yanbin Chen1, Yong
Che2, Zhendong Hu2 and Bing Liu2; 1The University of Michigan, Ann Arbor, Michigan; 2IMRA America, Inc., Ann Arbor, Michigan.
The potential of ZnO for short-wavelength optoelectronic devices is enormous and to fully exploit this potential, it is imperative to understand
the roles of native and doping-induced defects. In this talk, we will focus on our understanding of the role of crystal defects and processing
conditions on the optoelectronic properties of p-type ZnO epitaxial thin films. In this talk, we will show that the interplay between dopants and
extended defects such as threading dislocations and stacking faults is of fundamental importance for the achievement of p-type conductivity in
ZnO. ZnO thin films doped with antimony (Sb) or phosphorus (P) were grown by pulsed laser ablation. We found that dislocations can, under
certain conditions, aid the formation of shallow acceptors. The role of dislocations on the dopant solubility, electrical transport properties and
photoluminescence will be addressed. We will also show that depending on the oxygen chemical potential, different defect levels can be
introduced in the gap. These defects result in various optical transitions which can provide useful information on the donors and acceptors
formed. Finally, issues of homoepitaxy and p-n junction fabrication will be presented.
2:00 PM L7.3
Chemical Nature of N Incorporated in ZnO During Epitaxial Film Growth. Christian Pettenkofer, Patrik Hoffmann and Stefan Andres; SE6,
Hahn-Meitner-Institut, Berlin, Germany.

Epitaxial ZnO films are grown by MOMBE. During film growth the samples are exposed to N2+ions with energies ranging from 5kV to 300V. In
XPS the observed binding energies are those of O-N-O, N2, and N bonded to Zn. Exposing a grown film after growth to ions yields an O-N-O as
the predominant species followed by N2 N-Zn is observed comparingly strong for N admission during film growth. XPS data taken with
synchrotron radiation at varying kinetic energies reveal that only the N-Zn componenet is predominantly present in the bulk of the film. These
results are corroborated by NEXAFS data taken at the same samples which show an increased signal for N admission during film growth. The
overall doping activity of N is still supressed by a high level of hydrogen incorporated in the film. The presence of N 2 species is nicely
demonstrated by the vibrational features of the molcule in the NEXAFS spectrum.
2:15 PM L7.4
P-type ZnO Prepared by Microwave Enhanced Nitrogen Plasma Diffusion. Paris Y. Liu1,2, Jiping Cheng2 and Ryuan Guo1,2; 1Department
of Electrical Engineering, The Pennsylvania State University, University Park, Pennsylvania; 2Materials Research Institute, The Pennsylvania
State University, University Park, Pennsylvania.
Nitrogen doped regions and predominant p-type ZnO crystals and microtubes are obtained using a microwave enhanced nitrogen plasma
diffusion process. The enhanced plasma process appears to activate the nitrogen dopant and to enhance its solubility limit in ZnO crystals. An
overall p-type doping is verified by Hall effect measurement conducted on the ZnO samples with plasma treated diffusion surfaces. Such
nitrogen doping is found to be stable over time, in contrast to the diminishing p-type effects reported by several other groups. A detailed study on
diffusion profiles, chemical binding energy determination, and other related defect mechanisms will be presented.
2:30 PM L7.5
Electrical and Optical Properties of ZnMgO:P Films grown by Pulsed Laser Deposition. Hyunsik Kim1, Stephen J Pearton1, David P
Norton1 and Fan Ren2; 1Department of Materials Science and Engineering, University of Florida, Gainesville, Florida; 2Department of Chemical
Engineering, University of Florida, Gainesville, Florida.
The ZnMgO:P films were grown on sapphire c-plane by pulsed laser deposition with different substrate temperatures in the range of 550 ~ 650
oC. The 5 and 10 at % Mg mixed ZnMgO:P targets were used for the comparison. After the growth, rapid thermal annealing was performed at
600 ~ 900 oC under oxygen ambient. The 10 at % Mg mixed ZnMgO:P films showed p-type conductivity, while the 5 at % Mg mixed ZnMgO:P
films showed only n-type conductivity at as-deposited state. However, the 5 at % Mg mixed ZnMgO:P film which showed n-type conductivity at
as-deposited state converted to p-type after the post thermal annealing. ZnMgO:P films containing 10 at. % Mg showed only visible defect levels
without the band edge emission, while those containing 5 at % Mg showed the band edge emission even though the defect level is dominant. The
properties of these films will be described. This research was sponsored by the Department of Energy (grant DE-FC26-04NT42271)
2:45 PM L7.6
Surface Doping of p-type ZnO Nanowires using Molecular Adsorption. Sung-Hoon Lee, Jongseob Kim, Ki-Ha Hong and Jaikwang Shin;
Samsung Advanced Institute of Technology, Yongin, South Korea.
With a direct wide band gap and a large exciton binding energy, ZnO is considered as one of the best materials for photonic applications.
Moreover, ZnO can be easily grown into nanowires or nanoribbons, allowing a rich spectrum of nanoscale engineering. Despite this high
potential of ZnO nanowires, their applications have been hindered by the extreme difficulty to obtain p-type doping, mainly due to the deep
valence band edge of ZnO. Here we propose a novel method of p-type doping of ZnO nanowires, exploiting the high surface to volume ratio. In
our approach, p-type dopants that trap electrons from and leave holes onto semiconductor hosts are added on the surfaces of nanowires, not into
the bulk as used in the conventional method. As electron-trapping surface dopants, we consider atoms or molecules having a half-filled highest
occupied molecular orbitals (HOMO), since they show high electronegativity. Among the several molecules examined by first-principles
atomistic calculations, we find fluorine molecules (F2) would be one of good candidates. Fluorine molecules adsorb strongly on the surfaces of
ZnO nanowires and dissociate into two fluorine atoms spontaneously. Each of the adsorbed F atoms attracts an electron from valence band of the
ZnO nanowire and thus leaves a hole state in the nanowire. Our calculations show that the resulting F-passivated ZnO nanowire surfaces are
stable under ambient gas conditions and normal temperature ranges.
3:30 PM L7.7
Infrared Lattice Viblations of Nitrogen-doped ZnO Thin Films. Makoto Hirai1 and Ashok Kumar2,1; 1Nanomaterials and
Nanomanufacturing Research Center, University of South Florida, Tampa, Florida; 2Department of Mechanical Engineering, University of South
Florida, Tampa, Florida.

Zinc oxide (ZnO) is a transparent II-VI semiconductor with direct band gap of 3.4 eV. Nitrogen (N) is widely considered to be the most
promising p-type dopant, producing a shallow acceptor level in ZnO compared to the other V-group elements as phosphorus (P) and arsenic (As).
Additionally, since Paulings electronegativity values of Zn, N and O atoms are 1.65, 3.04 and 3.44 respectively, the substitution of N atoms for
partial O atoms in wurtzite structure is predicted to cause the slight change in bonding state. In this investigation, examining c-axis length, band
gap and phonon frequency of ZnO thin films with x-ray, ultraviolet-visible and infrared techniques respectively, the authors have investigated the
effect of N doping on the bonding state of the ZnO thin films. N-doped ZnO thin films were synthesized by a pulsed laser depostion (PLD)
method. In the measurements with Fourier transform infrared (FTIR) spectroscopy, the absorption peak of the N-doped ZnO thin film emerged at
406 cm-1, and was attributable to E1 (TO) mode. The three samples on the N-doped ZnO thin films were synthesized at the same experimental
conditions, and the average frequency (vav) of E1 (TO) mode was 408 2 cm-1. W. Gordy has reported an empirical relation of the form on
force constant (k), k = aN(xAxB/dAB2)3/4 + b, which applies to the bonds of a large number of diatomic and simple polyatomic molecules. In
this equation, xA and xB are electronegativities of the atoms A and B; N and dAB are bond order and bond distance respectively; and a and b are
constants for certain broad classes of molecules. We will introduce in this talk that the change in frequency induced by N doping is related to
reduced mass, electronegativity, and interionic distance.
3:45 PM L7.8
A Density Functional Theory Study of the Band Gap Tuning by Atomic Doping in ZnO. Muhammad N. Huda, Yanfa Yan and Mowafak M.
Al-Jassim; National Renewable Energy Laboratory, Golden, Colorado.
ZnO is a potential candidate as a photoelectrode for hydrogen generation by breaking water through photo-electro-chemical process. For
spontaneous generation of H2 several criteria have to be met for the ZnO to be used as a photoelectrode. These include, among others, the band
edges have to be matched with the water-splitting potential, as well as the band gap needs to be around 2 eV to operate in the visible spectrum of
solar energy. With this goal in mind, we will present density functional theory (DFT) and DFT+U studies of different atomic doping in ZnO and
discuss their electronic properties. In particular we would consider nitrogen atom doping, both interstitial and substitutional, and discuss the
relative shifting of the band edges. Several codoping situations and transition metal atom doping will also be presented. In general, band gap
reduction was found as a common result due to the formation of impurity bands. In addition to this, shift of the band edges, for example valence
band maxima, depend critically on the doping concentration and the type of doping.
4:00 PM L7.9
New Theoretical Approach for Controlling the p-type Doping in ZnO. George Mihai Gavaza, Zhigen Yu and Ping Wu; Computational
Materials Science And Engineering, Institute for High Performance Computing, Singapore, Singapore.
Systematic realization of the p-type doped ZnO by any usual experimental technique (sputtering, ion implantation, MOCVD, etc) is problematic
as the optimal "window" of experimental parameters is very narrow and difficult to determine empirically. Our first-principles studies reveal that
p-type dopants such as P would be substituted at Zn or O site under the different oxygen partial pressure. The desired configuration of P
substituted at O site (PO) is the potential acceptor in ZnO. We found that P would substitute at Zn site and O site under oxygen rich and poor
conditions, respectively. However, with a poor oxygen growth condition, the dense oxygen vacancy would act as hole killer and dilute p-type
conduction. Hence, we demonstrated that p-type conduction would be achieved in a narrow oxygen partial pressure window. Within the many
particle scattering with rearrangements theory framework, we further calculate the probability of obtaining the required atomistic configuration
by a certain physical process and in given experimental conditions. This allows us to theoretically estimate the rate of success of the doping
process function of experimental parameters. Thus, we can predict the outcome of an experiment function of its parameters (type of experiment,
temperature, concentrations, etc) and determine the optimal window for the doping process.
4:15 PM L7.10
Photoluminescence Characterization of Defects in Nitrogen-Implanted and Thermally Annealed ZnO. Xuemin Dai1, Shijie Xu1, Qilin
Gu1, Francis C. C. Ling1, Habil Gerhard Brauer2, Dipl.-Phys. Wolfgang Anwand2 and Wolfgang Skorupa2; 1Physics, The University of Hong
Kong, Hong Kong, Hong Kong, China; 2Institut fr Ionenstrahlphysik und Materialforschung, Dresden, Germany.
Ion implantation is an important technology for modifying electrical and even optical properties of semiconductor materials. Recently, ZnO has
attracted a great deal of renewed research interest due to its unique optoelectronic properties and new application potential in short-wavelength
efficient light-emitting devices including laser diodes. Usually undoped ZnO exhibits N-type conductivity, which indicates the presence of native
defects. It still remains a challenging issue to realize efficient P-type doping in ZnO nowadays. We thus attempt to prepare P-type ZnO by means
of nitrogen implantation. In this work, we concentrate on photoluminescence characterization of defects in ZnO implanted and post-implantation
annealed. ZnO samples employed in nitrogen implantation show N-type electrical conductivity and weak green emission. However, a new broad

red luminescence peak was observed in all as-implanted ZnO samples, which implies that somewhat new deeper defects are induced by nitrogen
implantation. Thermal treatment at different temperatures was adopted to activate the implanted ions and eliminate the implantation-induced
lattice distortion. Interestingly, the defect emissions in the implanted ZnO show a strong dependence on the treatment temperature. As the
treatment temperature increases, the red emission is significantly suppressed whereas the green emission greatly enhances. In particular, two sets
of fine structures with a fixed energy separation of about 30 meV superimposing on the broad background were observed in the samples
annealed at moderate high temperatures. The multimode Brownian oscillator (MBO) model accounting for electron-phonon coupling was
employed to determine the energetic positions of defects producing the green and red emissions. Excellent agreement between theory and
experiment is achieved over the entire experimental temperature range. Our experimental data favor the electronic level structure of native
oxygen vacancy theoretically obtained by Janotti and Van de Walle(1) using the first principles calculation. A physical model is proposed to
interpret the observed luminescence behavior of defects in ZnO. (1)Anderson Janotti and C. G. Van de Walle, Appl. Phys. Lett. 87, 122102
(2005).
4:30 PM L7.11
Structural and Optical Properties of Silver Ion Implanted ZnO Crystals. Lakshmanan Hariharan Vanamurthy, Mengbing Huang and
Hassaram Bakhru; College of Nanoscale science and Engineering, University AT Albany , State University of New York, Albany, New York.
A recent first-principle calculation predicted that silver could readily replace Zn in ZnO and therefore would be a good candidate for p-type
acceptors in ZnO crystals (Appl. Phys. Lett. 89, 181912 (2006)). In this work, we have made an experimental investigation of the structural and
optical properties of Ag doped ZnO crystals. We relied on ion implantation to incorporate Ag into ZnO crystals. The Ag ion implantation was
done at 400 C using four different energies with a total Ag dose of 4X1E15 atoms/cm2 in order to form a uniformly doped thin layer of 100 nm
near the surface. Post-implantation annealing was conducted in the range of 700-1100 C. Rutherford backscattering/channeling techniques were
utilized to evaluate the crystal quality and the lattice location of Ag in ZnO. Ion channeling measurements along both [0001] and [1011]
directions show that the Ag-implanted ZnO crystal starts to recover around 800 C and following post-implantation annealing at 1000 C, its
crystal quality is comparable to that of the as-grown ZnO single crystal. Our results suggest that the majority of implanted Ag does not appear to
occupy the Zn substitutional site. Even in the case for the 1000 C anneal, the percent of implanted Ag cannot exceed 30%. Furthermore, the
optical properties of Ag-implanted ZnO were studied with photoluminescence measurements at liquid helium and room temperatures. The
presence of Ag results in dramatic quenching of photoluminescence lines typically found for as-grown ZnO crystals including the green
luminescence band and various exciton-associated transitions. Photoluminescence signals suggested for shallow Ag acceptors in ZnO are not
detected. These experimental evidence implies that additional mechanisms, possibly related to interactions between Ag and defects in ZnO, may
need to be included in theoretical modeling of Ag doping in ZnO crystals.
4:45 PM L7.12
Comprehensive Review on Doping Mechanism of Group I, III and V Elements into ZnO Thin Films. Sang Yeol Lee, Center for Energy
Materials, Korea Institute of Science and Technology, Seoul, South Korea.
ZnO thin films have been fabricated by pulsed laser deposition. Doping mechanism of ZnO thin films has been investigated using group I, III
and V elements, such as Ag, Ga, P, and As. Two different doping mechanism has been observed with simple model and complex model. Ag and
Ga have been easily doped into ZnO resulting in the change of carrier concentration by simple doping model. As has been observed to be doped
into ZnO by complex doping model. Structural, electrical and optical properties have been investigated and well agreed with simple and complex
doping model.

Wednesday Evening, November 28, 2007
8:00 PM
L8.1
Abstract Withdrawn

L8.2
UV-Enhanced Photo Response and Quantum Efficiency of PLD Grown n-ZnO/p-Si Photodiode. E. Senthil Kumar1,2 and Mamidanna
S.Ramachandra Rao1,2; 1Department of Physics, Indian Institute of Technology, Chennai, Tamil Nadu, India; 2Materials Science Research
Centre, Indian institute of Technology Madras, Chennai, Tamil Nadu, India.
Recently considerable efforts have been directed towards the development of ZnO based UV-photo detectors, since Si-based photo detectors are
limited to UV region. Indeed, ZnO is very promising material due to its wide band gap (3.37 eV), high transparency (>80%) in the visible region,
excess electrons and holes from tightly bound excitons, which leads to very efficient near band gap recombination at room temperature even at
higher. As grown ZnO is n-type, where as high quality, reproducible p-ZnO with sufficiently high mobility and hole concentration is difficult
because of self compensation effects due to native defects. In an alternate approach ZnO based heterojunctions have been focused for short
wavelength optoelectronics. We report on the quantum efficiency and photo response of the n-ZnO/p-Si heterojunction photodiode, which detect
UV-photons. n-ZnO films were deposited on p-Si (100) substrates (0.2-100O cm) at different oxygen partial pressures (3.5x10-6 mbar - 0.25
mbar) and at different substrate temperatures (300oC - 700oC) by a versatile pulsed laser deposition technique. The thickness of the deposited
films was typically 200 nm. X-ray diffraction pattern reveals that films are oriented along (002) direction. Resistivity of the films were measured
by four probe method and a very low resistivity of 0.002 Ocm was observed for the film grown at 400oC and 3.6x10-6 mbar. Carrier
concentration of the same film was found to be 3.7x1018 cm-3. I-V characteristics of the diodes were measured in the dark (UV-off) and under
UV-illumination (? = 365 nm, optical power = 12 W) at room temperature. The rectifying I-V characteristic was obtained at a forward turn on
voltage of 3 V and at a reverse leakage current of 1.4 A at -2 V for the diode grown at 400oC and 3.6x10-6 mbar. We observed that the diode
shows photo response in both forward and reverse biased condition. Photoresponsivity and quantum efficiency of the diode at the forward
voltage of 6 V are 0.17 A/W, 56% respectively, and is found to be comparable that of the reported values. At the reverse voltage of -4 V the
photoresponsivity and quantum efficiency are 0.08 A/W, 25% respectively. We conclude that our n-ZnO/p-Si diode can be a UV enhanced
photodiode. Dependence of photoresponsivity and quantum efficiency on the growth conditions will be discussed in detail in the paper.
L8.3
Indium Zinc Oxide Transparent Thin Film Transistors with MgO Gate Oxide. W. Lim1, H. S Kim1, Y. L Wang1, D. P Norton1, Stephen J.
Pearton1, F. Ren2, I. I Kravchenko3 and J. M Zavada4; 1Materials Science, University of Florida, Gainesville, Florida; 2Chemical Engineering,
University of Florida, Gainesville, Florida; 3Physics, University of Florida, Gainesville, Florida; 4Electronics Division, US Army Research
Office, Research Triangle Park, North Carolina.
Transparent depletion-mode amorphous indium zinc oxide (IZO) channel thin film transistors with 1 m gate length and 100 m gate width were
fabricated on glass substrates from layers deposited at room temperature using rf magnetron sputtering. The n-type carrier concentration in the
channel was 2x1016 cm-3. The gate oxide was 90 nm of MgO, deposited by pulsed laser deposition at room temperature. The threshold voltage
of the transistors was -1.6V with a gate-voltage swing of 1.55 V/decade and the drain current on-to-off ratio was >103.The maximum field effect
mobility in the channel was ~0.3 cm2.V-1.s-1, lower than the Hall mobility of ~6.5 cm2.V-1.s-1 in the same layers, suggesting the presence of
scattering due to trapped charges at the MgO-IZO interface. The addition of the gate and source/drain contacts caused a relatively small decrease
in transmittance of the structure at visible wavelengths.
L8.4
Indium Zinc Oxide Thin Films Deposited by Sputtering at Room Temperature. W. Lim1, Y. L Wang1, F. Ren2, D. P Norton1, I. I
Kravchenko3, J. M Zavada4 and Stephen J. Pearton1; 1Materials Science, University of Florida, Gainesville, Florida; 2Chemical Engineering,
University of Florida, Gainesville, Florida; 3Physics, University of Florida, Gainesville, Florida; 4Electronics Division, US Army Research
Office, Research Triangle Park, North Carolina.
The deposition of amorphous indium zinc oxide (IZO) thin films on glass substrates with n-type carrier concentrations between 1014 and 3x1020
cm-3 by sputtering from single targets near room temperature was investigated as a function of power and process pressure. The resistivity of the
films with In/Zn of~ 0.7 could be controlled between 5x10-3-104 O.cm by varying the power during deposition. The corresponding electron
mobilities were 4-18 cm2.V-1.s-1.The surface root-mean-square roughness was < 1nm under all conditions for film thicknesses of 200 nm. Thin
film transistors with 1 m gate length were fabricated on these IZO layers, showing enhancement mode operation with good pitch-off
characteristics, threshold voltage 2.5V and a maximum transconductance of 6 mS/mm. These films look promising for transparent thin film
transistor applications.
L8.5
Abstract Withdrawn

L8.6
Room Temperature Deposited Indium Zinc Oxide Thin-Film Transistors. Y. L Wang1, F. Ren2, W. Lim1, D. P Norton1, Stephen J. Pearton1,
I. I Kravchenko3 and J. M Zavada4; 1Materials Science, University of Florida, Gainesville, Florida; 2Chemical Engineering, University of
Florida, Gainesville, Florida; 3Physics, University of Florida, Gainesville, Florida; 4Electronics Division, US Army Research Office, Research
Triangle Park, North Carolina.
Depletion-mode indium zinc oxide (IZO) channel thin film transistors were fabricated on glass substrates from layers deposited at room
temperature using rf magnetron sputtering. The threshold voltage was in the range -5.5 to -6.5V depending on gate dielectric (SiO2) thickness
and the drain current on-to-off ratio was ~105.The maximum field effect mobility in the channel was ~4.5 cm2.V-1.s-1, lower than the Hall
mobility of ~17 cm2.V-1.s-1 in the same layers, suggesting a strong influence of scattering due to trapped charges at the SiO2-IZO interface. The
low deposition and processing temperatures may these devices suitable for applications requiring flexible substrates.
L8.7
Structural and Electrical Properties of Amorphous InGaZnO4 and GaZnO2 Sputtered Thin Films. Martin E. Kordesch and Mohammad
Ahmad Ebdah; Department of Physics and Astronomy, Ohio University, Athens, Ohio.
Amorphous InGaZnO4 (a-IGZO) thin films have been recently of great interest due to its flexibility, optical, and transport properties. The
incorporation of a-IGZO in device applications such as thin-film transistors (TFTs) has been reported in the literature. In this work, a-IGZO films
were successfully fabricated using rf sputtering technique with a sputtering target of polycrystalline In, Ga, and Zn species under the flow of
Oxygen and deposited on Si substrate. The structure has been investigated by the x-ray diffraction (XRD), scanning electron microscopy (SEM)
and energy dispersive x-rays (EDX) spectroscopy techniques. Multiple crystallographic phases are detected. The ZnO phase has been identified
for both non-annealed and 500 C annealed thin films. The existence of Gallium Oxide (Ga 2O3) and Indium Oxide (In2O3) phases is under
investigation. Characterization of the electrical conductivity, concentration of free carriers, energy gap and optical properties are included within
this study. The same study has been made again for amorphous thin films after excluding the Indium due to the formation of Indium islands on
the surface of a-IGZO films during the growth, namely for amorphous GaZnO2 (a-GZO) thin films. The corresponding properties and phases
have been compared to the findings of other growth conditions of both sputtered films.
L8.8
Application of ZnO to Passivate the GaN-based Device Structures. Eliana Kaminska1, Anna Piotrowska1, Marie-Antoinette di Forte
Poisson2, Christian Brylinski2, Hacene Lahreche3, Norbert Kwietniewski1, Iwona Pasternak1, Piotr Boguslawski4, Elzbieta Dynowska4, Renata
Kruszka1, Zuzanna Sidor1 and Witold Rzodkiewicz1; 1Institute of Electron Technology, Warsaw, Poland; 2Thales-Alcatel III-V Lab.,
Marcoussis, France; 3Picogiga, Courtaboeuf, France; 4Institute of Physics, Polish Academy of Sciences, Warsaw, Poland.
The same crystalline structure with a close lattice match, similar band gaps, and thermal stability of ZnO and GaN or other III-nitrides have
previously been used in fabrication of ZnO/GaN hybrid substrates and heterojunctions. Here, we propose to farther exploit these features, and
use highly resistive ZnO as passivating coating for GaN-based heterostructures. In fact, GaN-based heterostructures are intensively studied
owing to their excellent properties for applications in high power/high frequency electronics. While high output power devices have been
demonstrated, one of the key unsettled issues is that of large leakage currents in Schottky gates fabricated on GaN and AlGaN surfaces, seriously
limiting their performance. It is believed that the dominant leakage mechanism is the tunnelling via donor states (nitrogen vacancy or oxygen
impurity) introduced near the semiconductor surface during surface processing of devices [1]. Various surface treatments, such as N2 plasma
exposure and/or passivation with dielectric films have been investigated [2]. A novel approach to solve this problem, presented in our work,
relies on application of semi-insulating ZnO as passivating lattice-matched coating. AlGaN/GaN structures were grown by MOCVD and MBE.
The processing towards fabrication of Schottky barriers and high electron mobility transistors (HEMTs) involved mesa etching, ohmic contacts
fabrication and deposition of Ir/Au Schottky gates. Passivating ZnO was deposited by magnetron sputtering. Since nominally undoped ZnO
exhibits n-type conductivity we apply additional acceptor doping to achieve semi-insulating material. Finally thin silicon nitride film was
deposited to protect ZnO from humidity. Characterisation techniques such as VASE ellipsometry, AFM, current-voltage-temperature, and
capacitance-voltage measurements were used to optimise the passivation procedure. Analysis of ZnO/GaN interfaces performed with SIMS and
XRD shows their pseudomorphic microstructure. We demonstrate that ZnO-passivation suppresses leakage currents in Schottky diodes by more
than one order of magnitude and substantially improves output characteristics of HEMT. Possible mechanisms of surface passivation are
discussed. Part of the research was supported by the grant from the European Commission HYPHEN (IST contract n027455), and by national
grants from the Ministry of Science and Higher Education N50703131/0743 and 72/E-67/SN-033/2006. [1]. J. Kotani et al., J. Vac. Sci. Technol.
B 24, 2148 (2006). [2]. P. Kordos et al., Semicond. Sci. Technol. 21, 1592 (2006).
L8.9Transferred to L11.38

L8.10
Fabrication of ZnO Nanoarrays. PilHo Huh1, Fadong Yan1, Lian Li1, Jayant Kumar1, Ravi Mosurkal2, Lynne A Samuelson2 and Myunghwan
Kim3; 1Center for Advanced Materials, Departments of Chemistry and Physics, University of Massachusetts Lowell, Lowell, Massachusetts;
2U.S. Army Natick Soldier Center RDEC, Natick, Massachusetts; 3Samsung Electronics Semiconductor Divison, Suwon, South Korea.
ZnO nanostructures were fabricated by a simple method using surface relief patterns on azobenzene functionalized polymer. The resultant ZnO
nanostructures were periodic, composed of 1-dimensional and 2-dimensional arrays over fairly large area. The uniformity and continuity of ZnO
nanostructures were characterized by atomic force microscopy and scanning electron microscopy. Optical properties were investigated by using
UV-Vis-NIR and photoluminescence spectroscopy. These ZnO nanopatterned structures can be utilized in applications such as bio/chemical
sensors, diffractive optical element, and for solar cell applications.
L8.11
Raman Spectroscopy of Different Morphologies of ZnO Nanostructures. Aurangzeb Khan1,2, Wojciech M Jadwisienczak3 and Martin E
Kordesch1; 1Physics & Astronomy and CMSS Program, Ohio University, athens, Ohio; 2Physics, University of Peshawar, Peshawar, NWFP,
Pakistan; 3School of Electrical Engineering and Computer Science, Ohio University, athens, Ohio.
Raman spectra of different morphologies of ZnO nanostructures were investigated. The nanostructures were synthesized via vapor transport
method from different precursors, Zn powder, ZnO powder, ZnO powder mixed with graphite powder in ambient Ar/air. XRD and HRTEM
analysis revealed that the grown structures are ZnO with wurtzite hexagonal phase. A 1:1 ratio was found from the EDX analysis for all the ZnO
nanostructures. The Raman E2 (High) which comes from the oxygen atoms is normally found at 437 cm-1 for the bulk ZnO crystal, is blue
shifted by a small for different nanostructures, such as 441 cm-1 for nanosheets, 444 cm-1 for nanotubes, 447 cm-1 for flower like-structures, 450
cm-1 for spheres, 446 cm-1 for nanorods and so on. The low frequency mode E2(Low) related to Zn normally observed at 101 cm-1 for the bulk,
is found to be at ~ 99 cm-1 for all the nanostructures. Room temperature PL spectra of the nanostructures revels a sharp band edge emission at
~380 nm and a broad peak related to deep level defects centered at ~500 nm (green/blue region) are observed. From the PL spectra it also
observed that ratio of green/blue band to the band edge is significantly variable for different nanostructures.
L8.12
Luminescence of Er-doped ZnO Films: Effects of Thermal Annealing and Doping Concentration. Zhengda Pan, S. H. Morgan, A. Ueda, R.
Aga Jr., A. Steigerwald and R. Mu; Fisk University, Nashville, Tennessee.
Photoluminescence (PL) of Erbium-doped Zinc Oxide films with nano-sized grains was studied. The films were grown on fused silica substrates
using e-beam evaporation. The evaporating targets used were sintered pellets of ZnO and Er2O3 mixtures with different Er concentration. The
films were subsequently annealed at 700 C in air for an hour. PL was measured at two excitation wavelengths, 325 and 488 nm. The 325 nm is
used for exciting the host semiconductor ZnO and 488 nm is used for directly exciting Er3+ ions in the ZnO host. Strong Er3+ luminescence of
4S3/2 ? 4I15/2 and 4F9/2 ? 4I15/2 transitions was observed from annealed film with 4.5 % Er2O3 concentration using either 325 or 488 nm
excitation. With 325 nm excitation, the Er3+ luminescence observed is attributed to energy transfer from the excitons in ZnO host to the Er3+
ions doped. The effective energy transfer from ZnO host to the doped Er3+ ions is an essential property for the realization of actual current-
injection opto-electronic devices operating at wavelengths of Er3+ emission, for example, at 1.54 m for the erbium-doped fiber amplifier
(EDFA). Our PL results indicate that thermal annealing played an important role for optically activating the doped Er3+ ions in ZnO
nano-crystalline grains of the film. This research is supported by US National Science Foundation NSF-CREST- CA: HRD-0420516, NSF-STC
CLiPS - grant no. 0423914, and US Department of Defense (DOD)/ARO contracts: W911NF-05-1-0453, and W911NF-04-1-0400.
L8.13
Characterizing Solid-State Reactions of ZnO Nano-rods. Joysurya Basu1, Divakar Ramachandran3, Jessica Lori Riesterer1,2 and C. Barry
Carter1; 1Chemical, Materials Science & Biomolecular Engineering, University of Connecticut, Storrs, Connecticut; 2Chemical Engineering and
Materials Science, University of Minnesota, Minneapolis, Minnesota; 3Metallurgy & Materials Group, Indira Gandhi Centre for Atomic
Research, Kalpakkam, India.
ZnO is becoming an increasingly important material and is in the forefront of solid-oxide fuel cell and photovoltaic cell development. ZnO
nano-rods can be grown on reconstructed c-plane (0001) sapphire via hydrothermal synthesis. Alignment of the nano-rods with the sapphire
substrate is ensured by prior deposition of a c-plane oriented ZnO thin-film by pulsed-laser deposition (PLD). Electron backscatter diffraction
(EBSD) confirms orientation relationships observed with the TEM between the nano-rods and the sapphire substrate and has the advantage of

requiring less sample preparation. Working with TEM-ready sapphire substrates, specimens suited for a direct comparison of interfacial reaction
between the sapphire substrate and the ZnO in nano-rod and thin-film forms have been designed. In situ and ex situ TEM may both be carried
out in order to understand the reaction kinetics. In situ studies have shown differences in the effect of heat-treatment on the microstructure in the
vicinity of the nanorods as compared to the thin-film regions without the nano-rods.
L8.14
Zinc Vacancies and Oxygen Vacancies in an Electron-Irradiated ZnO Crystal. Sean M. Evans1, Nancy C. Giles1, Larry E. Halliburton1 and
Lawrence A. Kappers2; 1Dept. of Physics, West Virginia University, Morgantown, West Virginia; 2Dept. of Physics, University of Connecticut,
Storrs, Connecticut.
A bulk n-type zinc oxide crystal grown by the seeded chemical vapor transport method was irradiated near room temperature with 1.5 MeV
electrons from a Van de Graaff accelerator. Before the irradiation, the primary defects in the crystal were shallow Group III donors and deep Fe 2+
donors. The crystal remained n type after the irradiation, but the concentration of carriers at room temperature decreased from 7 x 10 16 to 3 x
1013 cm-3. Electron paramagnetic resonance (EPR) at 30 K was used to monitor zinc vacancies, oxygen vacancies, and Fe 3+ ions after the
irradiation. Because of long spin-lattice relaxation times, these EPR spectra were greatly enhanced by operating the EPR spectrometer in an
out-of-phase mode [1]. After the electron irradiation, but before illumination, Fe3+ ions and nonaxial singly ionized zinc vacancies were
observed. The Fe3+ ions were observed at this stage because the electron irradiation significantly lowered the Fermi level (the presence of these
Fe3+ ions was critical to our study as they provided deep traps to hold photoexcited electrons when the crystal was subsequently exposed to light
at low temperature). Illumination with 325 nm light at low temperature (30 K) destroyed the EPR signal from the Fe 3+ ions and simultaneously
produced EPR spectra from singly ionized oxygen vacancies, neutral zinc vacancies, and axial zinc vacancies, as electrons were pumped from
the lower lying vacancy states to the higher lying Fe3+ state. The 325 nm light also produced two previously unreported EPR spectra from zinc
vacancies that had an adjacent hydrogen (in the form of an OH- ion) in axial and basal positions. The observation of forbidden EPR transitions
(?mS = 1, ?mI = 1) provided direct evidence that a proton was associated with these zinc vacancies. Using a lamp and monochromator, the
response at 30 K of the irradiated crystal to illumination wavelengths out to 750 nm was determined. Wavelengths shorter than 580 to 600 nm
convert the Fe3+ ions to Fe2+ ions and convert the neutral oxygen vacancies to singly ionized oxygen vacancies. Warming above 130 K in the
dark reverses the effect of the illuminations. This observation of a threshold near 2.1 eV for light to produce singly ionized oxygen vacancies
places the ground state of the neutral oxygen vacancy less than 1.3 eV above the valence band. For illumination wavelengths shorter than 480 to
500 nm, an additional excitation path emerges. These higher energy photons pumped electrons to the conduction band from isolated singly
ionized zinc vacancies, and thus formed neutral zinc vacancies. This threshold near 2.5 eV places the ground state of the singly ionized zinc
vacancy approximately 0.85 eV above the valence band. This work was supported by NSF Grant DMR-0508140. One of the authors (SME)
acknowledges support from the West Virginia STEM Fellowship Program. [1] J. R. Harbridge et al., Journal of Magnetic Resonance 156, 41
(2002).
L8.15
The ZnO/Zn3N2 Material System Investigated by Soft x-ray Emission and Absorption Spectroscopy: Impact of Air-Exposure on the
Chemical and Electronic Surface Properties. Marcus Bar1, Lothar Weinhardt1, Clemens Heske1, Kwang-Soon Ahn2, Yanfa Yan2, Mowafak
Al-Jassim2, Oliver Fuchs3, Monika Blum3 and Jonathan Denlinger4; 1Chemistry, University of Nevada, Las Vegas, Las Vegas, Nevada;
2National Renewable Energy Laboratory, Golden, Colorado; 3Exp. Physik II, Universitt Wrzburg, Wrzburg, Germany; 4Advanced Light
Source, Lawrence Berkeley National Laboratory, Berkeley, California.
In recent years, ZnO has become a potential candidate for photoelectrochemical (PEC) applications such as H2 production [1], due to its optical
and electronic properties. For example, it has a direct band gap and higher electron mobility than TiO2 (which has received much attention in the
PEC community). As with all PEC material candidates, sufficient chemical stability needs to be demonstrated. The band gap (Eg) of ZnO (3.3
eV) is too large to effectively use the main portion of the solar spectrum. One option to reduce Eg is to alloy ZnO with Zn3N2 (Eg = 2.1 eV).
Since the chemical activity of O is much higher than that of N [2], it is a challenge to incorporate N into ZnO. Recently, an RF sputter-based
deposition method was developed at the National Renewable Energy Laboratory (Golden, CO) that uses the RF sputter power as a parameter to
control the amount of nitrogen incorporated in the ZnO. The expected reduction of the optical band gap with increasing RF sputter power was
indeed observed [3]; however, little is known about the actual composition and the electronic band gap of the surface-near regions of the films,
which is of central importance for PEC applications. We present soft x-ray emission (XES) and absorption (XAS) spectroscopy measurements of
such nitrogen-enriched ZnO thin films deposited on glass substrates. The RF sputter power was varied to change the N:O ratio in the films. For
comparison, pure ZnO and Zn3N2 films as well as respective powder references were also investigated. In this presentation we will show how
XES can be used to determine the atomic composition of the characterized samples, as well as give quantitative information about the chemical
environment of the respective atom. Furthermore, the combination of XES with XAS gives a surface-near approach to monitor the band gap
change of the ZnO:N films with increasing N content. As a result, we find that, with increasing RF power, the N amount near the sample surfaces
increases. Likewise, the electronic band gap of the respective samples decreases with increasing N content. In fact, we find an overall good

agreement with the previously determined optical bulk Eg values [3]. Upon air exposure, we find that the surface-near composition and
electronic band gap of the ZnO:N samples are significantly changed: the N content of respective samples decreases and the corresponding Eg
values increase. In contrast, the chemical and electronic surface properties of ZnO:N films stored in ultra-high vacuum do not show such
changes. [1] M. Grtzel, Nature 414, 338 (2001). [2] B.S. Li et al., J. Mater. Res. 18, 8 (2003). [3] K.-S. Ahn, Y. Yan, and M.M. Al-Jassim, J.
Vac. Sci. Technol. B, (in press).
L8.16
Microwave-assisted Aqueous Synthesis of c-axis Oriented ZnO Nanorods on ZnO Film Coated Glass Substrates. Ken-ichi Ogata, Kazuto
Koike, Shigehiko Sasa, Masataka Inoue and Mitsuaki Yano; Osaka Institute of Technology, Osaka, Japan.
ZnO nanorod structures are of great interest because of their unique properties as well as large surface area that enhance the performance of
sensing devices. Toward the realization of high sensitive bioFETs based on ZnO/ZnMgO heterostructure grown by molecular beam epitaxy [1],
fabrication of ZnO nanorods on FET structures in order to increase the number of immobilized enzymes is one of the key issues. In this
contribution, microwave-assisted aqueous synthesis, which has lots of advantages such as less energy consumptions and rapid heating, was
employed for the fabrication of c-axis oriented ZnO nanorods. For the ZnO nanorod growth, teflon bottles with autoclavable caps were filled
with an equimolar (1-100mM) aqueous solution of zinc nitrate hexahydrate (Zn(NO3)2 6H2O) and hexamethylenetetramine (C6H12N4).
Subsequently, boronsilicate glass substrates with ZnO films coated by means of RF magnetron sputtering at room-temperature were immersed in
the bottles and heated at about 95oC for 3h via irradiation of 2.45GHz microwave. ZnO-coated glass substrates were placed with the bottom-side
up configuration to prevent from undesirable precipitation. X-ray diffraction measurement of the as-sputtered ZnO films indicated that they were
c-axis oriented, but that the average grain size of ZnO was smaller than 50nm. Therefore, in prior to the aqueous synthesis, thermal annealing
was conducted at 500oC in air atmosphere for 1h. Top view SEM observation revealed that hexagonal nanorods were formed on the ZnO-coated
glass substrates; however, their average diameter and orientation were dependent on the properties of base ZnO films. Namely, on the thermally
annealed ZnO films, highly c-axis oriented ZnO nanorods with a diameter of about 100nm were grown, while tilted nanorods with much larger
diameter were obtained on the as-sputtered films. Although detailed mechanism of those differences is not clarified yet, properties of underlying
ZnO films strongly affect the synthesis of ZnO nanorods on them. Effects of concentration of source materials in the solution will be also
discussed. [1] K. Koike, D. Takagi, M. Kawasaki, Y. Nakamura, Y. Hirano, S. Sasa, M. Inoue, M. Yano, The 13th International Conference on
II-VI Compounds, 10p-17, Jeju, Korea, Sep. 10-14, 2007.
L8.17
Abstract Withdrawn
L8.18
Comparison of Gas Sensing Performance of Thin Film ZnO Chemiresistors and ZnO-based TFTs. Yoonsil Jin, George C Whitfield and
Harry L Tuller; Materials Science and Engineering, MIT, Cambridge, Massachusetts.
Metal oxide semiconductors such as SnO2, ZnO, and WO3 have been extensively studied as thin or thick film chemoresistive gas sensors owing
to their high sensitivity, stability and low cost. The large band gaps (>3eV) of these metal oxides allows them to operate at elevated temperature
(200-500degree), a key advantage for solid state gas sensors, given the need to accelerate gas chemisorption kinetics. Recently, there has been
growing interest in ZnO-based thin film transistors due to their transparency, relatively high mobility and low processing temperatures, e.g.[ ]. In
this study, we report on the relative response of thin film ZnO chemiresistors and ZnO-based thin film transistors to a variety of gases including
NOx, CO, O2 under controlled temperature to examine the possible advantage of the FET structure for gas sensing. Bottom gate ZnO TFTs, with
variable ZnO channel thickness, are prepared to aid in the analysis of the combined effects of chemisorption and electrical bias on the device I-V
characteristics.
L8.19
Abstract Withdrawn
L8.20
An NO2 Gas Sensor of Sol-gel Synthesized Zinc Oxide Nano-rods. Hong Yeol Lee, Seong Eon Moon, Eun Kyong Kim, So Jeong Park, Jun
Hyuk Kwak, Kang Ho Park and Jong Dae Kim; Electronics and Telecommunications Research Institute (ETRI), Daejeon, South Korea.
We present a NO2 gas sensor have been fabricated using a novel zinc oxide nano-rods synthesized by the sol-gel process on an inter-digitated
electrodes and their electrical transport properties and gas sensor properties have been measured. EDAX, XRD, and TEM were used in order to

do constituent analysis and the structure of being grown up of the ZnO NRs. Moreover, the I-V characteristic was measured with varying the
measuring temperature to acquire the temperature dependant device resistance. The reactivity experiment about the NO2 gas was performed so
that it could confirm whether an application was possible as the gas sensor or not. The result of the I-V measurement revealed that good ohmic
contact was formed between electrodes and NRs, and that resistance decreased with increases in measurement temperature In the case of the
reactivity experiment about NO2 gas, the sensitivity of a sensor linearly increased according to the concentration of NO2 gas.
L8.21
ZnO Nanowire-based Logic Circuits: NOT, NAND, and NOR Logic Gates. Kihyun Keem1, Jeongmin Kang1, Dong-Young Jeong1,
Changjoon Yoon1, Donghyuk Yeom1 and Sangsig Kim1,2; 1Electrical Engineering, Korea University, Seoul, South Korea; 2Institute for Nano
scicence, Seoul, South Korea.
ZnO nanowires have been particularly interested in the application of the nanodevices due to their high crystalline quality and simple synthetic
process. These oxide nanowires have been utilized as the channels of nanodevices including field-effect transistors (FETs) and logic gates. In this
study, inverter logic circuits (or NOT logic gates) were built with two top-gate ZnO nanowire-based FETs with Al2O3 gate layers in series on a
chip; each of the top-gate FETs was fabricated by a conventional Si processing, and its electrical characteristics were evaluated by the general
electrical measurements. Their output to input voltage characteristics exhibited the inverting operation. The logic swing of their voltage transfer
characteristics was 98%, and their transition width was 4.35 V. Furthermore, NAND and NOR logic circuits were built by fabricating three
top-gate FETs on a chip, and their operation characteristics corresponded to the truth tables.
L8.22Transferred to L5.29
L8.23
Abstract Withdrawn
L8.24
Coating Characteristics of Aligned ZnO Nanorods with ZnS:Mn Layers by Chemical Vapor Deposition Cooperated with Laser Ablation
of Mn. Takashi Hirate, Kenta Kakio and Tomomasa Satoh; Department of Electronics and Informatics Frontiers, Faculty of Engineering,
Yokohama, Japan.
ZnO is an attractive II-VI compound semiconductor material for various optoelectronic devices. Recently, growth of various nanostructures of
ZnO such as nanorod, nanobelt, nanowall, etc. has been reported, and ZnO has been considered as a promising material for nanodevices. We
have studied on fabrication of aligned ZnO nanorods by a low-pressure thermal chemical vapor deposition (CVD) method cooperated with laser
ablation of Mn pellet. In this paper, we report on coating characteristics of the surface of aligned ZnO nanorods with ZnS:Mn layers by CVD
method, intending to develop a new electroluminescent device including ZnO nanorods. The fabrication method of ZnO nanorods is almost same
method used in our previous study. Metal Zn vapor and O2 gas are used as precursors to synthesize ZnO, and N2 is used as carrier gas. A Mn
pellet is placed near a Si(111) substrate in a deposition chamber and ablated by a pulsed Nd:YAG laser beam (wavelength =1.064 mm, pulse
width = 8 ns, repetition frequency = 10 shots/sec). The pressure is 26.6 Pa, the temperature is 550 C and O2 mass flow rate is 0.88 SCCM.
Aligned ZnO nanorods with 100 nm diameter and 1700 nm height are grown for 10 min growth-time. After the growth of ZnO nanorods, only
the laser ablation of Mn is performed for 5 min without O2. We call this process as intermediate laser ablation process. Finally, ZnS:Mn are
grown for 10 min by changing the precursor to H2S. The pressure is from 67 Pa to 133 Pa, and the mass flow rate of H2S is from 2.0 to 4.0
SCCM. It is found that the intermediate laser ablation of Mn has a drastic effect on growth of ZnS:Mn on the surface of ZnO nanorods. When the
intermediate laser ablation is not performed, the ZnS:Mn grows mainly along the axis-direction of ZnO nanorod with little growth along the
lateral direction, i.e. the length of nanorods becomes longer by the length of ZnS:Mn with little growth of the diameter. However, when the
intermediate laser ablation is performed, the growth along the lateral direction becomes dominant, while the growth rate along the axis-direction
is not so changed. For example, when the mass flow rate of H2S is 2 SCCM and pressure is 67 Pa, the total length of nanorod is 3600 nm and
diameter is 100 nm when the intermediate laser ablation is not performed. On the other hand, when the intermediate laser ablation is performed
the total length of nanorod is 3000 nm and diameter is 540 nm. It is concluded that the intermediate laser ablation has a drastic effect to enhance
the growth rate of ZnS:Mn for the lateral direction of ZnO nanorods. We estimate that the Mn species that are ablated from a Mn pellet and
reaches the surface of ZnO nanorods change any quality of the surface of ZnO nanorods. We are now studying of finding the optimum growth
condition of ZnS:Mn for electroluminescent devices.
L8.25
ZnO-based Electroluminescent Devices Using Molecular Precursor Solutions. Kaori Yoshioka1, Shinichi Egawa1, Toshiaki Kobayashi1,
Yoshihiro Mashiyama1, Hirohisa Nomura2, Mitsunobu Sato2 and Tohru Honda1; 1Electronic Engineering, Kogakuin University, Tokyo, Japan;

2Coordination Engineering Labortory, Kogakuin University, Tokyo, Japan.
Zinc oxide (ZnO) is one of the candidates for light-emitting devices operating in the UV spectral region [1]. Its spin-coating enables the
fabrication of low-cost and large-scale devices. In our previous work, ZnO films fabricated by Sol-Gel processing were investigated [2]. Here,
the possibility of ZnO films fabricated by spin-coating technique was confirmed. Although the near-band-edge (NBE) emission was dominated,
the deep-level emission band (peak wavelength: 650nm) was observed. For the reduction of the deep level emission band, precise control of
process condition will be required. In this paper, the fabrication of ZnO films using molecular precursor solu-tions is reported. The molecular
precursor method has an advantage for doping other metal ions and control of the crystal orientation [3]. Furthermore, ZnO-based
electroluminescent devices (ELDs) are also reported. UV light emission was observed from the devices. A solution was prepared by the reaction
of Zn nitrilotriacetic acid (Zn-nta) complex. It was ob-tained from the reacted aqueous solution of nitrilotriacetic acid with zinc acetate, with
butylamine in ethanol. Also, prepared by the reaction of Ga ethylenediaminetetraacetic acid (Ga-edta) complex, then, which doped Zn-nta with
zinc acetate, with butylamine in ethanol. The solutions include Ga impuriti-es in this study. ZnO:Ga clear solution was spin-coated on substrate.
It is annealed in O2 atmosphere. ZnO-based ELDs were fabricated using the molecular precursor solutions. A double-insulator struc-ture was
adapted for the ELDs. The ELDs were operated using a pulsed voltage. The applied voltage was created using a rectangular shape pulse and a
transformer. A purplish white emission including UV-light emission was observed form the device during the operation at RT. Using the
optimized conditions, the ZnO-based ELDs were fabricated. A purplish white emission including UV-light emission was observed from the
device under the pulsed operation. This means that the ZnO film fabricated by the molecular precursor method have a possibility for the
fabrication of cost-effective ELDs. [1] D. C. Look, Mater. Sci. Eng. B. 80, 383 (2001). [2] K. Yoshioka, S. Egawa, T. Kobayashi, T. Baba, K.
Sugimoto, M. Arai, H. Nomura, M. Sato and T. Honda, physica status solidi (c) 4, No.1, 162-165 (2007). [3] H. Nomura, C. S. Mochizuki, I.
Takano, T. Honda and M. Sato, 13TH International SPACC-CSJ symposium, P05.
L8.26
Synthesis and Characterization of Sisal-like ZnO Nanostructures via Low-temperature Simple Solution Process. Rizwan Wahab, Sg
Ansari, Young soon Kim, Song Min Woo, Hyung Kee Seo and Hyung-Shik Shin; School of Chemical Engineering, Chonbuk National
University, Jeonju, Chollabukto, South Korea.
Optimization of the shape and size of the nanocrystalline materials according to ones desire is a key challenge in current nanoscience research.
Recently much more efforts are being put on the control of size, shape and dimensionality of nanocryastallines materials because of their novel
unexplored properties and their technical importance in the filed of nanoelectronics. Among various semiconductor material ZnO has a wide
band-gap (3.37 eV) and large exciton binding energy (60 meV), as compared to other semiconductor materials such as ZnSe (22 meV) and GaN
(25 meV) at room temperature. Due to wide band gap and large-exciton binding energy, ZnO is exploring itself as a promising material for
ultraviolet optoelectronic devices and lasers operating at room temperature. In this papers we are presenting the synthesis of Sisal-like ZnO
structures composed of sharp-hexagonal ZnO nanorods. Hydroxylamine hydrochloride (NH2OH.HCl) was used as a capping molecule with
refluxing time of 20 min at 60Cusing zinc nitrate hexahydrate (Zn(NO3)2.6H2O) and sodium hydroxide. The detailed structural
characterization using high-resolution transmission electron microscopy (HRTEM), X-ray and selected area electron diffraction patterns
confirmed that the obtained products are single-crystalline with the wurtzite hexagonal phase. The IR spectrum shows the standard peak of zinc
oxide at 423 cm-1 while the X-ray photoelectron spectroscopic (XPS) measurement showed the presence of Zn, O and C peaks only.
L8.27
Low Resistivity Gallium-doped Zinc Oxide Films Deposited by Low Temperature Radio-frequency Magnetron Sputtering. Jiun-Yi
Tseng1, Cheng-Yi Wang2, Wang-Chieh Yu1, Chih-Wei Hsu1, Chao-Jen Ho1, Yung-Fu Hsu2, Sea-Fue Wang2 and Tzer-Shen Lin1; 1Material and
Chemical Research Laboratories, Industrial Technology Research Institute, Chutung, Hsinchu, Taiwan; 2Institute of Materials Science and
Engineering, National Taipei University of Technology, Taipei, Taiwan.
Transparent and conductive gallium-doped zinc oxide (GZO) films were deposited on 1737F Corning glass by RF magnetron system using a
GZO ceramic target with the Ga2O3 contents in the range of 5 wt.%. In this work, the effects of the sputtering parameters on the structural,
optical and electrical properties of GZO films on glass were studied and discussed in detail. The GZO films were grown with a constant RF
power of 400 W and lower substrate temperature of 150 ~ 200 ?C. The crystal structure and orientation of GZO thin films were inspected by
x-ray diffraction analyses and the all GZO films at different sputtering pressure revealed highly c-axis (002) preferred orientation. High optical
transparency (>80%) was in a wide spectral range from 200 nm to 700 nm. According to the electrical experiment data, the resistivity of the
single-layer GZO films was significantly affected by sputtering pressure, and optimized for ~ 8x10 -4 O-cm. In further research, the sandwich
structure of GZO film / Au metal / GZO film was demonstrated to improve the electrical properties of the single-layer GZO.
L8.28

Nonlinear I-V Characteristics of ZnO Films. Jung-Wook Lim, Jun Kwan Kim, Sun Jin Yun and Hyun Tak Kim; Tera-electronic device team,
ETRI, Deajeon, South Korea.
ZnO is an important material in various fields of applications, such as ceramics and varistors. In our study, ZnO films without additives were
prepared at 200 C by a sputtering method and exhibited nonlinear current-voltage (I-V) characteristics. In the film deposition, various ratios of
O2 to Ar gases were used and then heat treatments were performed under O2 ambient at 400, 500 and 600 C. For the samples deposited with O2
gas, nonlinear I-V characteristics were not observed. While, for the samples without O2 gas, strong nonlinear behavior, obtained from I-V
curves, clearly appears after heat treatments. These results indicate that carriers generated from defects such as oxygen vacancy or zinc
interstitial may cause nonlinear I-V characteristics. The nonlinear coefficients were ranged from 12 to 15. The current increases abruptly by an
order and then ohmic behavior of I-V curves was observed at higher fields. When the in-situ heat treatment was performed on ZnO films, the
current increases by three orders and nonlinear coefficient was 13.
L8.29
ZnO Thin Films Fabricated by Plasma Enhanced Atomic Layer Deposition. Doo Hyong Lee, Sae Rom Kwon, Young Hwan Park, Bo Hyun
Chung, Hee Soo Kim, Jun Won Hyun, Yongmin Kim and Seung Jeong Noh; Applied Physics, Dankook University, Seoul, South Korea.
Various deposition techniques such as pulsed laser deposition, metal-organic chemical vapor deposition, and atomic layer deposition have been
employed for ZnO fabrication; however, reliable and reproducible p-type ZnO thin films for optoelectronic devices are still very limited. In order
to study p-type ZnO films, we have constructed a plasma enhanced atomic layer deposition (PEALD) system adopting an inductively coupled
plasma source; carried out a series of plasma generation; and fabricated ZnO thin films by using both PEALD and ALD. Diethylzinc was used as
a zinc precursor, H2O as an oxidant, nitrogen as a dopant, and argon as a carrier and purge gas. Self-limiting growth and doping effects were
investigated at various flow rates, reaction times and radio-frequency powers. Electrical and optical properties of these films were investigated
using Hall measurement, photoluminescence measurement, Auger electron spectroscopy, x-ray diffraction, etc. *This work was supported by
HANBIT Users Cultivation Program of National Fusion Research Center, and also by Seoul R&BD program(10555 cooperate Org92862). *
E-mail: sjnoh@dankook.ac.kr
L8.30
Direct Fabrication of ZnO Whiskers Bridging Between Micron-gap Electrodes in Aqueous Solution for Highly Gas Sensing. Hattori
Reiko1, Imamoto Hiroshi1, Kametani Keisuke2 and Fujita Shizuo2; 1Advanced Device Lab., OMRON Co.Ltd, Kizugawa, Japan; 2International
Innovation Center, Kyoto University, Kyoto, Japan.
Zinc oxide (ZnO) has been conventionally used in the field of gas sensors such as H2 and CO. High sensitive gas sensors have been increasingly
expected for safety as monitoring devices of living environment and chemical processes. In recent years, there are also many reports about the
fabrication and characteristics of ZnO gas sensors composed of nanostructures as a sensing area owing to their high surface-to-volume ratio. But,
it is actually difficult to control the nanostructures placing at the desired positions. We propose an approach for artificially fabricating the ZnO
whisker gas sensor between micron-gap electrodes using electrolytic deposition in order to realize the high sensitivity for gases. This method can
be safe and easy to handle because of adopting an aqueous solution. The factors effecting the formation of bridging the ZnO whiskers were
studied by the observation with a scanning electron microscope equipped with energy dispersive X-ray spectroscopy and then characteristics of
H2 gas response as well. Hydrogen has been focused on much attention for fuel cell application, but the high sensitive sensing is essential
necessary against the slight leakage of the flammable gas. Micron-gap electrodes (Au/Cr), used both for the sensor device and the plating
electrodes, were fabricated by conventional photolithography. In order to optimize the reagent for the electrodepotion, several reagents were
examined such as zinc nitrite, zinc acetate, and so on. The concentration of reagent solution was varied from 0.005 to 0. 5 mol/L. The AC bias
voltage was applied. The values of voltage and frequency were varied from 1 to 15V and from 100 Hz to 100 kHz, respectively. An additional
oxidation process of the deposits was continuously conducted using dry or wet process, if desired. From the analyses of morphology and
composition, metal zinc is preferentially electrodeposited under the condition of higher ion concentration of Zn2+, lower frequency, no solvent
additive and higher voltage. After oxidation, a typical sample with resistance level in megaohm range was found to have no significant
improvement in gas sensitivity. However, under the condition of lower ion concentration, higher frequency, oxidant addition, lower voltage, ZnO
is directly deposited without the successive oxidation. This sample with resistance level in gigaohm range is found to respond well for H2 gas of
100 ppm even at room temperature. We propose the simple but convenient method of ZnO fabrication selectively and artificially between two
micron-gap electrodes using the electrolytic deposition in aqueous solution. The growth condition with oxidant addition makes it possible that
one ZnO whisker bridging between two electrodes is directly electrodeposited. The electrodes for deposition can be diverted to the contact
electrodes for sensors in this process. These advantages such as the technological simplicity can facilitate the realization of high sensitive gas
sensor for H2 gas.

L8.31
Optical Quenching of NiO/Ni coated ZnO Nanowires. Young Hwan Park1, Yong Ho Shin1, Doo Hyong Lee1, Hee Soo Kim1, Seung Jeong
Noh1, Jun Won Hyun1, Yongmin Kim1 and Ki Seok An2; 1Applied Physics, Dankook University, Seoul, South Korea; 2Chemical Technology,
Korea Research, Seoul, South Korea.
Low temperature photoluminescence (PL) measurements were carried out to investigate optical transition characteristics of ZnO nanowires
(NW), Ni nanodot and NiO coated ZnO nanowires. For ZnO NW, PL emission spectra show emission peaks of two distinctive bound exciton to
neutral donor (D0X) transitions and bound exciton to neutral acceptor (A0X) transition. The major PL emission peak for ZnO NW was switched
from D0X to A0X for Ni-ZnO nanodot (ND)-NWs. This is due to the reason that diffusion of hydrogen atoms into ZnO NWs during thermal
annealing played as acceptors. We found that the optical quenching was drastic with increasing temperature and the activation energies are
unusually small. Such a drastic optical quenching and small activation energies are associated with surface states due to the large surface to
volume ratio of NWs. *This work was supported by Seoul R&BD program(10555 cooperate Org92862), and also by HANBIT Users Cultivation
Program of National Fusion Research Center.
L8.32
The Charge Sheet Density in Non-polar ZnO Films at the ZnO-Sapphire Interface Determined by Generalized Ellipsometry. Ch. Sturm1,
T. Chavdarov1, R. Schmidt-Grund1, B. Rheinlaender1, C. Bundesmann3, H. Hochmuth1, M. Lorenz1, M. Schubert2 and M. Grundmann1;
1Institut fr Experimentelle Physik II, Semiconductor Physics, Universtt Leipzig, Leipzig, Germany; 2Department of Electrical Engineering,
University of Nebraska, Lincoln, Nebraska; 3Leibniz-Institut fr Oberflchenmodifizierung e.V., Leipzig, Germany.
ZnO is a wide band gap semiconductor and promising material for ultraviolet optoelectronic devices, due to its properties such as the exciton
binding energy (Eexb ~ 60 meV) and band gap energy (Eg ~ 3.4 eV). Of special interests are non-polar films since they avoid electric fields at the
interfaces, which will influence the performance of the devices. The infrared dielectric function of non-polar a-plane ZnO was determined by C.
Bundesmann et al. [1], however, a detailed study of the interface with the substrate was not given. In this work we will report about the
investigation of the charge sheet density at the ZnO-sapphire-interface in non-polar a-plane ZnO films.
Two series of a-plane ZnO films were deposited by Pulsed Laser Deposition on r-plane sapphire substrates at constant growth temperature
TG=730C. The first series contains samples with different film thicknesses in the range (30 - 610) nm, whereas, the samples of the second series
have nearly the same film thickness of d ~ 240 nm. The samples of the second series were annealed after deposition at T G up to 105 min. All
samples were investigated by generalized infrared spectroscopic ellipsometry (gIRSE) in the spectral range (370 - 1300) cm -1.
The dielectric function of the ZnO films was obtained by a line shape analysis using a model dielectric function, which consists of contributions
of lattice vibrations and free charge carriers. H. v. Wenckstern [2] reported on diffusion of aluminium (Al) atoms from the sapphire substrates
into the ZnO film, which act as donors in the ZnO film. They change the electrical and the infrared-optical properties of the ZnO film near the
ZnO-sapphire interface. Hence, an inhomogenous distribution of the free charge carriers was assumed with concentration (n) at the ZnO-sapphire
interface larger than in the rest of the ZnO film, which is below the gIRSE detection limit of n ~ 5 10 16 cm-3. Due to the small thickness (d) of
the highly conductive part of the ZnO film, only the product s=nd could be determined, representing a charge sheet density. For the first series,
s increases with increasing film thickness, which is related to a longer growth time. Hence this behaviour can be interpreted as an effect of time,
e.g., the diffusion of aluminium from sapphire into ZnO. However, s of the second series shows an opposite behaviour compared to the first
series: s decreases with increasing annealing time. Responsible for the decrease of s can be the diffusion of Al atoms from the highly conductive
part into the main part of the ZnO film, which could not be detected, or the formation of a zinc aluminate layer. The latter one was observed by
several groups [3, 4].
1. C. Bundesmann et al., Thin Solid Films 455 , 041301 (2004).
2. H. v. Wenckstern et al., Advances in Solid State Physics 45 , 263 (2005).
3. Gorla et al., J. Appl. Phys. 87 , 3736 (2000).
4. Fan et al., Nature Materials 5 , 627 (2006).
L8.33
Gas-Phase Synthesis and Characterization of ZnO Nanoparticles from a Microwave Flow Reactor. Klemens Hitzbleck1, Matthias Offer2,
Hartmut Wiggers1 and Christof Schulz1; 1Institute for Combustion and Gasdynamics, University Duisburg-Essen, Duisburg, Germany; 2Institute
of Physics, University Duisburg-Essen, Duisburg, Germany.
Nano-sized ZnO is a very promising candidate for future nano-technological applications such as varistors, UV-emitting devices, TCOs,
transistors or gas sensors. A lot of the unique optical and electrical properties of ZnO nanoparticles originate from the high surface-to-volume
ratio which varies with the size. Therefore the synthesis of ZnO particles with tuneable size plays an important role for scientific research. In this
study the formation and size dependent properties of ZnO nanoparticles in dependency of different reaction parameters were investigated. The
particles were synthesized in a microwave flow reactor by decomposition of Diethylzinc in an argon-oxygen plasma. The precursor material was

diluted in argon using a bubbler system and supplied to the reactor via a central nozzle. Additional argon and oxygen were injected trough a
surrounding ring nozzle. For argon / oxygen ratios smaller 5:1 a small, discrete plasma torch was formed at the tip of the central nozzle. For
higher ratios a diffuse, voluminous plasma downstream the reactor tube was observed. The best results with respect to reaction rate and particle
formation were achieved at a ratio of about 3:1. For lower ratios an increasing percentage of the precursor material was lost due to CVD at the
reactor walls. Hardly any particles could be sampled under the conditions of the diffuse plasma. A particle laden molecular beam extracted from
the reactor was deflected in a particle mass spectrometer to receive the size distribution of the synthesized particles. Depending on the synthesis
parameters, the mean particle size was found to be in the range of 2 to 7 nm. Furthermore, the molecular beam device was used for the
deposition of size-selected particles for further analysis. X-Ray diffraction of the product reveals the hexagonal crystalline structure of ZnO. The
crystallite size, calculated from Scherrers equation, was found to match the particle size determined before. The crystalline structure turned out
not to depend on the argon / oxygen ratio in the discrete plasma. PL-spectroscopy of the as-prepared nanoparticles exhibits strong
photoluminescence in the visible spectrum. The spectra show two broad emission bands, a near bandgap excitonic luminescence in the range of
375 to 440 nm, and a broad defect-luminescence in the range of 500 to 750 nm. They indicate a dependency of the emission band intensity on the
argon / oxygen ratio during synthesis, which is under investigation.
L8.34
Characteristics of Zinc Oxide and Gallium Doped Zinc Oxide Thin Film Transistors Fabricated at Room Temperature by Radio
Frequency Magnetron Sputtering. Hoonha Jeon1, Ved Prakash Verma2, Sookhyun Hwang1, Kyoungseok Noh1, Sooyeon Lee1, Chiyoung
Park1, Joonhee Moon1, Jaekyu Kim1, Dohyun Kim1, Wonbong Choi2 and Minhyon Jeon1; 1Department of Nano Systems Engineering, Inje
University, Gimhae, South Korea; 2Department of Mechanical and Materials Engineering, Florida International university, Maimi, Florida.
We present zinc oxide (ZnO) and gallium (1wt%) doped ZnO (GZO) thin film transistors (TFTs) with low operating voltage and low leakage
current, fabricated by radio-frequency (RF) magnetron sputtering at room temperature. ZnO and GZO films deposited on SiO2 substrate show
uniformity and transmittance (>80%). ZnO TFTs operate in the enhancement mode with a threshold voltage of 2.5 V while GZO TFTs operate in
the depletion mode with a threshold voltage of -3.44 V. GZO TFTs show mobility of 0.023 cm2/(V s) and on/off ratio of 10^3 compared to ZnO
TFTs which have typical value of 0.018 cm2/(V s) and 10^(-4), respectively. This low mobility of thin films can be attributed to small grain size
and high impurity scattering of electrons. ZnO and GZO (1wt%) are new class of transparent channel materials for future high performance
TFTs.
SESSION L9: Epitaxial Growth of ZnO

Chair: Chennupati Jagadish
Thursday Morning, November 29, 2007
8:30 AM *L9.1
Growth and Characterisation of ZnO. Bruno K. Meyer, 1. Physikalisches Institut, Giessen, Germany.
In order to realize controlled p-type doping in ZnO it is absolutely necessary to control and understand the role of point and extended defects in
the epitaxial films. This starts with the choice of the substrate since for sapphire and GaN on sapphire substrates there is a severe contamination
by diffusion of the group III elements in the ZnO films. However, also the choice of a ZnO substrate matters. In the first part of the talk we
address to the properties of the ZnO substrates in terms of crystallinity, surface morphology and preparation, polarity etc. Secondly, we report on
the homoepitaxial growth and on the structural, electrical and optical properties of the films. In the last part the recombinations caused by
excitons bound to donors and/or acceptors will be discussed.
9:00 AM L9.2
Effect of Growth Conditions on Defect-related Photoluminescence in ZnO Thin Films Grown by Plasma Assisted MBE. Vitaliy Avrutin1,
Mikhail A. Reshchikov2, Natalia Izyumskaya1, Ryoko Shimada1 and Hadis Morkoc1,2; 1Electrical Engineering, Virginia Commonwealth
University, Richmond, Virginia; 2Physics Department, Virginia Commonwealth University, Richmond, Virginia.
ZnO has attracted a considerable interest owing to its outstanding optical properties. Therefore, it comes as no surprise that a great number of
articles have been dedicated to investigation of photoluminescence (PL) in this material. Most studies focus on the excitonic spectral range,
whereas much less attention has been paid to defect-related luminescence from ZnO. However, investigation of emission bands (usually

classified as yellow-green and red) and their relation with growth conditions can shed some light on the nature of defects responsible for these
bands and pave the way to control the defect composition of ZnO that is believed to be a key to successful p-type doping. In this contribution, we
report on systematic study of the effect of growth conditions on defect-related PL in ZnO thin films fabricated by plasma-assisted molecular
beam epitaxy on a-plane sapphire and GaN/c-sapphire substrates. As confirmed by reflection high-energy electron diffraction, all the samples
discussed in this work were grown in two-dimensional mode. The layers were grown at different substrate temperatures and different oxygen-
plasma powers. In case of GaN templates on c-plane sapphire, one set of samples was grown with employing low-temperature (LT) buffer layer
and another set was fabricated without LT buffer. It was found that the layers grown with the LT buffer show pronounced red PL band in addition
to the yellow-green one, in contrast to ZnO films grown without LT buffers, whose defect-related spectra are dominated by the yellow-green
emission. PL spectra from layers grown on a-sapphire substrates show only yellow-green line. To study possible contribution of plasma damage
caused by high-energy ions into defect formation, plasma power was varied in a wide range. The intensity of excitonic lines was found to
increase with reducing plasma power for both types of substrates, whereas the yellow-green emission band red shifts towards the energy position
(about 2.2 eV) typical for PL spectra measured from ZnO samples grown using H2O2 oxygen source. This finding indicates that point defects
and their complexes induced by plasma irradiation may have a drastic impact on the optical and electronic properties MBE-grown ZnO .
9:15 AM L9.3
Growth and Doping of ZnO. Stefan Lautenschlaeger, Joachim Sann, Niklas Volbers, Jan E. Stehr, Felizitas Eylert, Andreas Laufer and Bruno
K. Meyer; 1st Physics Institute, University of Giessen, Giessen, Hessen, Germany.
The so far not reliably resolved acceptor doping of ZnO is clearly the main obstacle for the successful development of working devices based on
ZnO. On the other hand an n- type doping with high carrier densities is required as well. We report on the possibilities of both, acceptor and
donor doping of ZnO. To achieve the incorporation of an acceptor we used the group V element arsenic. Donors have been introduced using
Aluminium and different group VII elements. We investigated mainly epitaxially grown thin films, some comparison with Ion- implanted
samples have been undertaken. All the samples have been analyzed using photoluminescence spectroscopy, secondary ion mass spectrometry,
atomic force microscopy and scanning electron microscopy.
9:30 AM L9.4
ZnO Epitaxy on (111) Si Substrates Using Intervening Epitaxial Lu2O3 Buffer Layers. Wei Guo1, Wei Tian2, Arnold Allenic1, Yanbin
Chen1, Carolina Adamo2, Darrell G Schlom2 and Xiaoqing Pan1; 1Materials Science and Engineering, University of Michigan, Ann Arbor,
Michigan; 2Materials Science and Engineering, Pennsylvania State University, University Park, Pennsylvania.
ZnO epitaxial films are widely explored for optoelectronic applications. Besides the commonly used sapphire substrate, it is significant to grow
epitaxial ZnO films on Si substrates for integration of ZnO-based multi-functional devices into Si electronics. However, direct growth of ZnO on
Si usually results in polycrystalline or textured films due to the large lattice and thermal expansion mismatches. Here we report on the growth
and characterization of high quality epitaxial ZnO films on (111) Si using intervening epitaxial Lu 2O3 buffer layers. The epitaxial Lu2O3 thin
films were grown by reactive molecular-beam epitaxy and the ZnO films were subsequently grown using pulsed laser deposition. X-ray
diffraction shows that the epitaxial orientation relationships are (0001)ZnO||(111)Lu2O3||(111)Si and [11-20]ZnO||[1-10]Lu2O3||[1-10]Si. Our
ZnO epilayers have the narrowest (0002) and (10-12) ?-rocking curves ever reported, for a growth on Si, with full width at half-maximum values
of 374 arcsec and 565 arcsec. The films are conductive with a mobility of 80 cm2/Vs. Temperature-dependent photoluminescence spectra show
sharp transitions, with three free exciton and five bound exciton recombination lines. Cross-sectional and high-resolution transmission electron
microscopy studies will be presented. In summary, the epitaxial growth of ZnO on Si represents a significant step toward the integration of
ZnO-based optoelectronic devices and complementary metal-oxide-semiconductor devices on Si.
9:45 AM L9.5
Growth and Characterization of Non-Polar ZnO Epitaxial Films on ?-LiAlO2 Substrates. Jih-Jen Wu1, Wan Hsien Lin1, Sian-Jhang Lin1,
Mitch M.C. Chou2, Liuwen Chang2, Hsiao-Yi Chung2, Teng-Hsing Huang2, Chien-Chih Tao3 and Chun-Wei Chen3; 1Department of Chemical
Engineering, National Cheng Kung University, Tainan, Taiwan; 2Department of Materials Science & Opto-electronic Engineering, National Sun
Yat-Sen University, Kaohsiung, Taiwan; 3Department of Materials Science and Engineering, National Taiwan University, Taipei, Taiwan.
M-plan ZnO epitaxial films have been successfully grown on ?-LiAlO2 substrates using metalorganic chemical vapor deposition. The
dependence of growth characteristics on the growth temperature was investigated. The (10-10) nonpolar ZnO films of uniform surface were
obtained when the growth temperature was higher than 650oC whereas both m- and c- plane ZnO crystals were formed on the LiAlO2 substrates
at lower temperatures. TEM analyses reveal that the m-plane ZnO films were grown on the LiAlO2 substrates by the lattice-match growth
mechanism. The micro-PL spectrum of the m-plane ZnO film shows a strong UV emission peaking at around 375 nm. We believed that LiAlO2
single crystal substrate is a potential material to nonpolar ZnO epitaxial growth.

10:30 AM L9.6
Properties of ZnO Thin Films Grown Homoepitaxially by Pulsed-laser Deposition. Holger vonWenckstern, H. Schmidt, M. Brandt, C.
Czekalla, G. Benndorf, G. Biehne, A. Rahm, H. Hochmuth, M. Lorenz and M. Grundmann; Institut fr Experimentelle Physik II, Semiconductor
Physics, Universtt Leipzig, Fakultt fr Physik und Geowissenschaften, Leipzig, Germany.
We report the structural, morphological, optical, and electrical properties of ZnO thin films grown homoepitaxially by pulsed-laser deposition
(PLD). Two-dimensional growth and excellent material properties open the path to homoepitaxial devices. Prior to epitaxy the (000-1) oriented
hydrothermal substrates were annealed for two hours in oxygen (850 mbar) at 1000C. This is indispensable in order to obtain atomically flat or
vicinal surfaces (depending on the substrate miscut) perfectly suited for homoepitaxy [1]. A sample series with undoped layers of nominal
thickness between 8 nm and 1 m was used to study the evolution of growth. Already for 8 nm tick films the step edges bend most probably due
to pinning by dislocations emerging from the substrates. For thickness exceeding 100 nm, closed loop spirals with step heights of c or c/2
between the loops determine the morphology of the thin films. Nominally undoped 1 m thick ZnO films were deposited at an oxygen partial
pressure of 0.016 mbar at growth temperatures TG ranging from 470C to 700C. For temperatures above 600C smooth surfaces with steps of
c/2 are visible. Photoluminescence (PL) measurements (2 K) reveal recombination of free (XA, XB) and bound excitons (I0, I3a, I6, I6a) [1].
The intensity ratio of I6 (3.3608 eV) and I3a (3.365 eV) decreases with decreasing TG. Thermal admittance spectroscopy on an undoped sample
grown at 650C shows three prominent defect levels labelled T1, T2 and T3. The thermal activation energy of T1 is 56(5) meV; it is attributed to
AlZn in accordance with the observation of the I6 line in the PL measurements. The concentration of Al Zn is only in the 1013 cm-3 range [1]. Due
to superposition the levels T2 and T3 cannot be evaluated by Arrhenius analysis, however, their activation energies are estimated in the range
from 200 meV to 400 meV. Phosphorous (P-content: 0.01 wt.% - 4 wt.%) doped ZnO thin films were grown by PLD at 650C. Two-dimensional
growth is achieved for the lowest P-content and an oxygen partial pressure of 0.1 mbar. As-grown ZnO:P thin films have I3a and I6 as main
recombination features. Their transport properties are comparable to that of commercially available ZnO wafers grown by seeded chemical
deposition or pressurized melt growth (H,max = 800cm2/Vs @ 70 K). The activation of the phosphorus dopants by thermal annealing will be
discussed in this contribution.
[1] H. von Wenckstern, H. Schmidt, C. Hanisch, M. Brandt, C. Czekalla, G. Benndorf, G. Biehne, A. Rahm, H. Hochmuth, M. Lorenz, and M.
Grundmann, phys.stat.sol. (RRL) 1 , No. 4, 129-131 (2007).
10:45 AM L9.7
New Method of Reducing Threading Dislocation in Epitaxial ZnO Films Grown on C-sapphire Substrates. Yuekui Sun1, David Cherns1
and Rachel Doherty2; 1H.H.Wills Laboratory, Physics Department, University of Bristol, Bristol, United Kingdom; 2Chemistry Department,
University of Bristol, Bristol, United Kingdom.
We present a transmission electron microscopy study of threading dislocations (TDs) in epitaxial ZnO films grown on (0001) sapphire substrates.
The films were produced by a two-step method. Firstly, ZnO was deposited by pulsed laser deposition (PLD) on (0001) sapphire substrates at
temperature of 600 C. This gave an epitaxial deposit comprising a continuous buffer ZnO, with thickness about 80 nm and a predominant
alignment of (0001)ZnO//(0001)sapphire and [11-20]ZnO//[10-10]sapphire. On the top of buffer layer there was a high density of c-aligned nanorods,
which revealed few, if any, TDs, in contrast with the buffer layer where TD density is about 1011/cm2. A further layer of ZnO was then grown
under conditions favouring nanorods growth. This was carried out using either chemical vapor deposition in a furnace tube, where ZnO and
graphite powders acted as source materials heated to 1000 C, or hydrothermal deposition, where the PLD pre-deposited samples were put into
an aqueous solution of Zn(NO3)2 and HMT for 6 hours at 90 C. In both cases the nanorods grew laterally and eventually coalesced to form a
continuous overgrowth. It was found that the nanorods remained mostly free of dislocations, but that some subgrain boundary dislocations were
generated as the nanorods coalesced. Some of these dislocations were subsequently migrated laterally, leading to reactions where many were
annihilated. The result was a substantial reduction in the total TD density, which was estimated to be around 10 9/cm2, two orders of magnitudes
down from that in the initial buffer layer. The mechanism by which TDs are reduced during the two-step growth will be illustrated and explained.
The wider significance of this method for reducing the density of TDs in epitaxial growth will also be discussed.
11:00 AM L9.8
A Theoretical Study of Ultra-Thin Films with the Wurtzite and Zinc Blende Structures. Frederik Claeyssens1, Colin L Freeman2, Neil L
Allan1 and John H Harding2; 1School of Chemistry, University of Bristol, Bristol, United Kingdom; 2Department of Engineering Materials,
University of Sheffield, Sheffield, United Kingdom.
The structure and composition of the substrate often controls the structure of materials grown on them, particularly for ultra-thin films. The
interfacial energy between the growing film and the substrate (often determined by matching the structures) dominates the effect of the bulk
cohesive energy of the film. Thus the film may initially grow in a phase that is not the thermodynamically stable bulk phase. However, once the

film is thick enough, it transforms to the stable phase. An example of this is Stranski-Krastanov growth; where the initial layers of the film are
strained to produce epitaxial matching, but the film ultimately grows as islands when the bulk cohesive term dominates. This type of behaviour
assumes that there is an easy transition from the initial metastable state to the final stable state at a given film thickness. This need not be the
case. If there is no low-energy pathway to the more stable state, the system may become kinetically trapped. This enables crystals to grow in
unusual, metastable structures or in unexpected directions. One good example of this behaviour is the growth of polar directions for wurtzite
structures on ceramic substrates, e.g. ZnO.[1,2] These produce high-energy surfaces because the macroscopic dipole generated in such a
direction must be quenched by massive electronic or ionic reconstruction. Such surfaces are rarely observed for that reason. We show how such
directions can initially be favoured for thin enough films and become kinetically trapped beyond a certain film thickness. In this study we
demonstrate, using density functional theory calculations, that the stable crystal structure in ultra-thin films of ZnO is a low-energy graphitic-like
structure, which initially stabilizes the growth in the (001) direction. This is equivalent to the polar direction in the wurtzite structure and
explains why this high-energy face is seen in grown films. Additionally, we confirm this behaviour in other common wurtzite and zinc blende
materials, indicating a general mechanism for these crystal structures. [1] C.L Freeman et al., Physical Review Letters 96 (2006), 066102 [2] F.
Claeyssens et al., Journal of Materials Chemistry, 15 (2005): 139-148
11:15 AM L9.9
Growth Mechanism and Raman Spectroscopy Analysis of Solution Derived ZnO Films. Sang Hoon Yoon1, Dan Liu1, Chiwon Kang1,
Minseo Park2 and Dong-Joo Kim1; 1Materials Engineering, Auburn University, Auburn, Alabama; 2Physics, Auburn University, Auburn,
Alabama.
Chemical solution deposition (CSD) has been employed for the fabrication of piezoelectric ZnO films. For the application to acoustic wave
device, the degree of c-axis preferred orientation of ZnO films is a crucial material issue to produce piezoelectric property of the film. In this
study, the effect of polymeric sol precursors modified by two different additives, Monoethanolamine (MEA) and Diethanolamine (DEA) has
been focused. The phase transformation, texture evolution, and internal stress and defects of solution derived ZnO films were systematically
investigated. The XRD results showed that no textured structure was found in ZnO films on amorphous silicon nitride substrates from the
solution modified with DEA, while ZnO films from the solution with MEA exhibited strong (002) oriented structure regardless of the substrate
types. The results are in good agreement with the results of Raman spectroscopy. The growth of ZnO films from the solution modified with DEA
is more dependent on the surface configuration of substrates than that of those with MEA, which indicates different energy barriers for the
nucleation and growth of films depending on the solution precursors. The result of Raman spectroscopy also showed the higher internal stress
and carrier concentration of ZnO films from DEA-modified solution, comparing with ZnO films with MEA. The internal stress and defect of
solution derived ZnO films will be discussed along with the effects of the substrate and the solution additives.
11:30 AM L9.10
Growth of High Quality (Zn,Mg)O Thick Films on ZnO Sybstrates by Liquie Phase Eptaxy. Jun Kobayashi1,2, Hideyuki Sekiwa1,2, Miyuki
Miyamoto1, Isao Sakaguchi2, Naoki Ohashi2 and Hajime Haneda3; 1Tokyo Laboratory, Mitsubishi Gas Chemical Co., Inc., Tokyo, Japan;
2Optoelectronics Group, National Institute for Materials Science, Tsukuba, Ibaraki, Japan; 3Sensor Materials Center, National Institute for
Materials Science, Tsukuba, Ibaraki, Jamaica.
Recently, wide band gap semiconductors are considered to be very important materials for optoelectronic devices, such as transparent transistors
and short wavelength light emitting diodes (LEDs). To utilize ZnO based optoelectronic devices, band engineering, designing and controlling
band gap energy and lattice parameters, is one of the most important key technologies. Band engineering is absolutely necessary for fabrication
of double hetero structures and multi-quantum-well structure in LED devices. It is well-known that making (Zn,Mg)O alloy (ZMO) enables us to
expand band-gap of ZnO, and the double hetero structure such as n-ZMO/i-ZnO/p-ZMO is regarded as the most desirable one to achieve LEDs
made from ZnO. From this viewpoint, synthesis of ZMO wafers having very high crystallinity, sufficiently large wafer diameter for industrial
applications, and well-controlled optical and electric properties is an indispensable technology for development of ZnO based optoelectronic
devices. In the present study, we examined growth of ZMO films on ZnO single crystalline substrate by a liquid phase epitaxy (LPE) technique.
Since ZnO single crystal wafers more than two inches diameter have been commercially available, LPE growth of ZMO on ZnO wafers is one of
the most appropriate way to produce (Zn,Mg)O layer for device applications. Thus, we studied LPE growth of ZMO layer on ZnO wafers and
electric and optical properties of ZMO layers grown by the LPE method. We used single crystalline c(+)-ZnO wafers, 10 10 0.5 mm 3, as the
substrates for LPE growth of ZMO layers. The substrate surface was put into the molten precursor including ZnO and MgO, and the ZMO layers
were grown on ZnO substrate. The obtained ZMO layers were single crystalline layer. Subsequent compositional analysis and
photoluminescence measurements revealed that the highest Mg/(Zn+Mg) ratio in the LPE grown ZMO reached to more than 10% and the near
band edge luminescence was found at 354 nm, corresponding to photon energy of 3.5 eV. This Mg concentration is close to the solubility limit of
Mg in ZnO lattice under equilibrium condition. We also examined carrier injection into the LPE grown ZMO film by Al-doping. Here,
Al-doping was done by adding Al2O3 into the precursor for LPE growth. Since obvious increase of electron concentration corresponding to
Al-concentration was observed and temperature dependence of hall coefficient measurement indicated that activation energy of mobile electron

in Al-doped ZMO film was several tens meV, Al-doping is found to be an appropriate way to introduce very shallow donor into ZMO films.
Thus, we can conclude that growth of ZMO layer on ZnO and controlling of band gap up to 3.5 eV and electron concentration in the ZMO layer
are possible by applying LPE technique.
11:45 AM L9.11
Abstract Withdrawn
SESSION L10: Issues with Optical and Electronic Devices

Chair: Bruno Meyer
Thursday Afternoon, November 29, 2007
1:30 PM *L10.1
Electrical Pumped ZnO UV Random Lasers. S. F. Yu, School of Electrical and Electronic Engineering, Nanyang Technological University,
Nanyang Avenue, Singapore.
Ultraviolet semiconductor laser diodes find enormous applications in commercial products (e.g., ultrahigh-density storage in CDs and DVDs),
scientific research (e.g. low-cost activated biological or chemical sensors) as well as military applications (e.g., portable on-site detector for
natural or human caused epidemics). ZnO has a band-gap of 3.37 eV and a large exciton binding energy of 60 meV at room temperature.
Furthermore, ultraviolet lasing has demonstrated from mirrorless ZnO thin films with random media at room and evaluated temperature. Hence,
it is believed that ZnO semiconductor is one of the most promising candidates to realize ultraviolet laser diodes. However, the practical
application of ZnO random media as the active layer in semiconductor laser diodes is still a major challenge due to the problems of 1) achieving
high optical gain under electrical excitation and 2) high scattering loss from the random media. In this presentation, we will discuss on our recent
development of the fabrication of high-crystal-quality ZnO films which are suitable for the realization of device-quality ultraviolet light emitting
devices. We will also demonstrate the fabrication of hetero-junction light emitting diodes with ultraviolet emission by our filtered cathodic
vacuum arc technique. Hence, the approach to realize ultraviolet ZnO random hetero-junction laser diodes will be explained. Furthermore, we
will study the possible methods to enhance the internal and external conversion efficiency of the ZnO random media as the active layer. It is
believed that our proposed modification of ZnO random media is suitable to realize practical room-temperature operated ultraviolet laser diodes.
2:00 PM L10.2
Exciton-Polaritons in All-oxide ZnO-based Resonator Structures. R. Schmidt-Grund, J. Sellmann, C. Sturm, C. Czekalla, B. Rheinlaender, J.
Lenzner, H. Hochmuth, G. Zimmermann, M. Lorenz and M. Grundmann; Institut fr Experimentelle Physik II, Semiconductor Physics,
Universtt Leipzig, Leipzig, Germany.
Bose-Einstein condensation of exciton-polaritons in semiconductor micro-cavities at room temperature is an attractive subject of current
research. By using the optical emission from such a Bose-Einstein condensate, future lasers with a very low threshold can be realised. ZnO-based
micro-cavity resonators are promising systems for Bose-Einstein condensation of micro-cavity exciton-polaritons at room temperature and
above, owing to the large binding energy (60 meV) and the high oscillator strength of the free excitons in ZnO. For ZnO-based resonators,
exciton-polaritons are expected to be stable up to temperatures of about 560 K and huge values of the vacuum Rabi splitting of about 190 meV at
room temperature are predicted.
We report on recent results towards Bose-Einstein condensation of exciton-polaritons in ZnO-based all-oxide resonator structures. The resonators
consist of a half-wavelength thick ZnO cavity, which acts simultaneously as active medium, and which is embedded between lower and upper
Bragg reflectors. High band-gap oxide materials are appropriate candidates for Bragg reflectors operating in the ultraviolet spectral range
because of their wide band-gap, i.e. transparency at the ZnO band-gap, and variety in the refractive index. We have studied Bragg reflectors
consisting of ZrO2 as high-index material and MgO respective Al2O3 as low-index material.
For optimising the properties (crystal structure, surface respective interface properties, homogeneity of the layer thickness, reproducibility of the
materials dielectric functions) of the cavity and Bragg reflector layers with regard to their application in resonators, we have varied the PLD
(pulsed laser deposition) growth conditions and the crystallographic orientation of the used substrates [(0001)- and (1-102)-oriented sapphire,
and (100) oriented silicon]. The single layers, Bragg reflectors and resonator structures have been structurally and optically characterised by
means of X-ray diffraction measurements, atomic force microscopy, secondary electron microscopy, spectroscopic ellipsometry, reflection
measurements, and measurements of the photoluminescence.

All-oxide Bragg mirrors with very low surface roughness, Ra=0.46 nm after 10.5 pairs, and very high reflectivity of 99.8% near the the ZnO
band egde have been fabricated. We have observed strong coupling of exciton and photon modes in ZnO-based resonators. Here, the photon
modes are the first order cavity mode and two Bragg band-edge modes. The exciton-polariton modes have been observed in both,
photoluminescence and reflectivity spectra at temperatures between 4 K and 306 K and for various incidence and exit angles of the light at room
temperature. We have observed very large energy splitting of the exciton-polariton branches of about 75 meV in maximum, stable at room
temperature.
2:15 PM L10.3
Suppression of the Internal Piezoelectric Field in ZnO/Zn0.7Mg0.3O Quantum Wells by Oxygen Ion Implantation. Jeffrey Allan Davis1,
Lap Van Dao1, Xiaoming Wen1, Peter Hannaford1, Victoria Coleman2, Hoe H Tan2 and Chennupati Jagadish2; 1Centre for Atom Optics and
Ultrafast Spectroscopy, Swinburne University of Technology, Hawthorn, Victoria, Australia; 2Department of Electronic Materials Engineering,
Research School of Physical Sciences and Engineering, The Australian National University, Canberra, Australian Capital Territory, Australia;
3Nanomaterials Microdevices Research Center, Osaka Institute of Technology, Osaka, Japan.
The strong piezoelectric field in ZnO/ZnMgO quantum wells means that the quantum-confined Stark effect can counteract quantum confinement
effects in larger quantum wells and can lead to transition energies up to 500 meV below the ZnO exciton bandgap. Implantation with low energy
oxygen ions and subsequent rapid thermal annealing at 800C induces intermixing of Zn and Mg atoms. Large blue-shifts are observed as a
result, and can be explained by a combination of three mechanisms: the increased Mg content in the QW region changing the inherent band gap;
the change in the confinement potential due to the change in the shape and depth of the well; and as is reported here, the change in the internal
electric field reducing the quantum-confined Stark shift. By studying the photoluminescence and time-resolved photoluminescence from
ZnO/ZnMgO quantum wells of different width and with varying ion implantation doses we observe that even with the weakest implantation dose
(51014 cm-2) the internal electric field is substantially reduced. In the 4 nm quantum well, where quantum-confined Stark effects dominate over
confinement effects, the depth of the QW and the Mg content in the middle of the well is largely unchanged by the weak implantation dose. It
might therefore be expected that the blue-shift observed is smaller than for the narrower wells. However, the interface between the barrier and
the QW is smoothed which leads to a major reduction in the strain and hence the piezoelectric field. The ensuing suppression of the quantum-
confined Stark shift leads to a blue-shift in the optical transition, which is greater than that observed in narrower wells where quantum
confinement effects dominate. Higher implantation doses lead to further blue shifts of similar magnitude largely independent of well width and
are largely due to changes in the band gap as a result of the changed Mg concentration. Similar behaviour is also observed for exciton lifetimes;
for the weakest implantation dose the lifetime decreases from 35 ns to 10.8 ns, whilst for higher doses further reductions in the lifetime are small,
down to 9.2 ns at 11016 cm-2, and are due to the decreased confinement. This suggests that decreases in the exciton lifetimes are mostly due to
the reduction of the piezoelectric field, caused by the intermixing, and the associated increased overlap of electron and hole wave functions.
Hence, by carefully controlling the implantation dose it becomes possible to suppress the internal piezoelectric field in ZnO/ZnMgO quantum
wells without significantly altering the QW structure. This will be of great advantage to applications where the internal field provides a barrier to
greater optical gain such as ZnO-based QW lasing, and is also of significance for GaN based structures where the strong piezoelectric field may
also be suppressed by intermixing.
2:30 PM L10.4
Quantum Hall Effect in ZnO. Akira Ohtomo1, Atsushi Tsukazaki1, Tomohiro Kita2,3, Yuzo Ohno3, Hideo Ohno2,3 and Masashi Kawasaki1,4;
1Institute for Materials Research, Tohoku University, Sendai, Japan; 2ERATO Semiconductor Spintronics Project, JST, Tokyo, Japan;
3Laboratory for Nanoelectronics and Spintronics, Research Institute of Electrical Communication, Tohoku University, Sendai, Japan; 4CREST,
JST, Toky, Japan.
ZnO exhibits high electron mobility at room temperature, especially the highest among oxide semiconductors. This leads to some interests for
extracting its potential to such applications as high electron mobility transistor. Intrinsic electronic properties superior to bulk single crystals have
been obtained in ZnO/MgxZn1-xO heterostructures grown by pulsed-laser deposition [1]. Recently, we were able to observe the quantum Hall
effect in a high-mobility (~5000 cm2/(Vs) at 1 K) two-dimensional electron gas (2DEG) in the polar (0001) interface [2]. The density of 2DEG
was controlled in a range of 0.7 ~ 3.7x1012 cm-2 by tuning polarization mismatch between the ZnO and MgxZn1-xO layers, i.e., the Mg content in
the barriers, epitaxial strain and the growth polarity. From the temperature dependence of the amplitude of Shubnikov-de Haas oscillations
(SdHOs), the effective mass of the 2DEG was derived as 0.32 0.03m0. We found anomalous behavior in the 1/B period of the SdHOs
suggesting possibility of a spin-splitting effect arising from the asymmetric triangular well and a strong internal electric field. Furthermore we
applied gate electric field or optical excitation by using an ultraviolet laser to the heterostructures. This resulted in a significant influence on the
conductivity demonstrating insulator-to-metal transition in its temperature dependence and switching of a quantum state. [1] A. Tsukazaki, A.
Ohtomo, M. Kawasaki, Appl. Phys. Lett. 88 , 152106 (2006). [2] A. Tsukazaki, A. Ohtomo, T. Kita, Y. Ohno, H. Ohno, M. Kawasaki, Science
315 , 1388 (2007).

3:15 PM *L10.5
Control of Crystal Polarity of ZnO Layers and Applications to Nonlinear Optical Devices. T. Minegishi1, J. S. Park1 and Takafumi Yao1,2;
1Center for Interdisciplinary Research, Tohoku University, Sendai, Japan; 2Institute for Materials Research, Tohoku University, Sendai, Japan.
Since the exciton binding energy of ZnO is as large as 60 meV, exciton survives even at room temperature. Hence, exciton plays an important
role in optical processes in ZnO both at weak and high excitation. Photoluminescence spectra of both ZnO layers and bulk crystal with
reasonable crystalline quality are dominated by free exciton emission, which cannot be realized in other semiconducors. Hence, optically-
pumped exciton lasing becomes possible even at higher temperatures than room temperature. Exciton is characterized by enhanced oscillator
strength and nonlinear optical effects of materials become enhanced as the oscillator strength of the associated optical processes is increased.
Therefore, nonlinear optical effects of ZnO will be greatly strengthened, if exciton resonance is included in the optical processes. This paper will
introduce our recent work towards this end. We have established the selective growth technique of Zn-polar and O-polar ZnO layers on sapphire
substrate using MgO buffer. The crystal polarity of ZnO layers are successfully controlled by varying the thickness of MgO buffer. Very recently,
we have found that ZnO layers grown on CrN/sapphire show Zn polar, while those grown on Cr oxides/sapphire result in O-polar. By combining
this technique with photolithography technique, we have fabricated periodically-polarity inverted (PPT) structures with periodicity ranging from
60 m to 0.5 m. Such PPI structures enable quasi-phase matching in nonlinear optical effects to achieve effective frequency conversion of the
incident laser light. We have succeeded for the first time in the generation of the second harmonics at 402.5 nm of the incident laser light at 805
nm. Detailed analysis shows that quasi-phase matching is achieved. It is possible to fabricate periodically corrugated structures from such PPI
structures. Such periodically corrugated structures offer either distributed feed-back cavity or distributed Bragg reflector mirror. We have
achieved optically-pumped distributed-feed-back lasing of periodic corrugated ZnO structures for the first time.
3:45 PM L10.6
Mechanisms in the Formation of High Quality Schottky Contacts to n-type ZnO. Martin Allen1, Craig Swartz1, Martin Henseler2, Roger
Reeves2, James Metson4, Holger von Wenckstern3, Marius Grundmann3, S.A. Hatfield5, P.H. Jefferson5, P.D.C. King5, Timothy Veal5, Chris
McConville5, Masakazu Kobayashi6 and Steve Durbin1; 1Department of Electrical and Computer Engineering, University of Canterbury,
Christchurch, New Zealand; 2Department of Physics and Astronomy, University of Canterbury, Christchurch, New Zealand; 3Institut fr
Experimentelle Physik II, Universitt Leipzig, Leipzig, Germany; 4Department of Chemistry, University of Auckland, Auckland, New Zealand;
5Department of Physics, University of Warwick, Coventry, United Kingdom; 6Faculty of Science and Engineering, Waseda University, Tokyo,
Japan.
Compared to GaN, its main rival as a wide bandgap semiconductor in the UV spectrum, ZnO has a significantly higher ionicity and spontaneous
polarization along the c-axis. The former causes the Zn-polar (0001) and O-polar (000bar1) surfaces to be electrostatically unstable requiring
some form of a) surface reconstruction, b) internal charge transfer, and/or c) external adsorbates. The latter leads to the presence of bound
surface polarization charges which also require internal and/or external compensation. From the perspective of Schottky diode fabrication, a
detailed understanding of these phenomena is important for the control of contact properties and device characteristics. We have investigated the
influence of surface polarity on the morphology and electrical properties of melt-grown (medium resistivity ~ 0.3 Ocm) and hydrothermally
grown (high resistivity ~ 300 Ocm) bulk ZnO single crystals. Atomic force microscopy showed the presence of monolayer-height triangular
shaped terracing and vacancies on the Zn-polar face of hydrothermal ZnO with no such features observed on the O-polar face. The electrical
properties of high resistivity ZnO, investigated through four point probe measurements and variable temperature Schottky diode characterisation,
were found to be significantly different when measured in air and under vacuum conditions. The surface conductivity was found to increase
significantly when measured in vacuum, indicating the presence of a surface conduction channel which is activated by the removal of
adsorbatesmost likely oxygen and water vapourfrom the ZnO surface. This well-known characteristic of ZnO has important consequences
for contacts, which are usually fabricated under vacuum but operated in air. Furthermore, valence band x-ray photoelectron spectroscopy (XPS)
revealed the presence of a significant electron accumulation layer on both the Zn-polar and O-polar faces in vacuum, which is not present in air
as indicated by scanning Kelvin probe microscopy. Variable emission angle XPS measurements revealed there is a significant coverage of
hydroxyl bonds on the Zn-polar and O-polar surfaces under ultra-high vacuum pumping. In light of this, it is surprising that very high quality Au,
Pt and silver oxide Schottky contacts, with ideality factors close to the image force controlled limit, were fabricated on the high resistivity
material without the need for any special surface treatments. While high quality silver oxide diodes, with barrier heights in excess of 1.0 eV, were
routinely achieved on the Zn-polar, O-polar and non-polar faces of both melt and hydrothermal ZnO, those on the Zn-polar face had consistently
higher barriers. The barrier height difference between diodes on the Zn-polar and O-polar faces was 200 meV for hydrothermal ZnO and 50 meV
for melt ZnO. The larger polarity effect for the high resistivity material is consistent with a model of spontaneous polarization induced surface
band bending.
4:00 PM L10.7
Polymer Schottky Contact on Polar ZnO Surfaces. Ryosuke Y. Gunji1, Masaki Nakano1, Atsushi Tsukazaki1, Akira Ohtomo1, Tomoteru

Fukumura1 and Masashi Kawasaki1,2; 1Institute for Materials Research, Tohoku University, Sendai, Japan; 2CREST, JST, Tokyo, Japan.
Schottky contacts have been made on ZnO surface using rare metals such as Au, Pt, and Ag. However, the junction properties are often found to
vary depending on the surface polarity and methods used for metal deposition and surface treatments. We have been studying Schottky junctions
with a conducting polymer, poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS), which is formed by simple spin-coating
technique. Good junction properties were reproducibly obtained for various n-type oxide semiconductors including the +c face of ZnO [1]. In
case of the -c face of ZnO, however, coating PEDOT:PSS solution resulted in interface reaction due to its acid nature and the higher reactivity of
the -c face than +c face. Such reaction has to be avoided since the surface of ZnO thin films is typically the -c face. Here we report on realization
of high quality Schottky junction composed of PEDOT:PSS and the -c face of ZnO by using silane-coupling agent. ZnO single crystals were
immersed into the diluted solution of the agent, and then PEDOT:PSS was spin-coated. The interface reaction was inhibited by the thin
molecular layer, which was formed spontaneously by silane-coupling reaction on the ZnO surface. Au contact electrode was deposited on
PEDOT:PSS by thermal evaporation. Circular mesa structures and ring-shaped Ohmic electrodes were formed by ion milling and electron-beam
evaporation with photolithography, respectively. Schottky junction properties were examined by current-voltage (I-V) and capacitance-voltage
(C-V) characteristics at room temperature. The I-V characteristic was well in accordance with thermionic emission model and extracted ideality
factor was nearly unity. From the C-V profile, donor concentration of the ZnO crystal was evaluated to be ~10 16 cm-3. Thus, this simple wet
process can be used for electrical evaluation of both +c and -c faces of ZnO. [1] M. Nakano et al., Extended Abstracts (The 54th Spring Meeting
2007) The Japan Society of Applied Physics and Related Societies, 29p-ZA-14
4:15 PM L10.8
Electrical Characterization of N+-implanted n-type ZnO Single Crystal: ZnO p-n Homojunction and Deep Level Defects. Qilin Gu1,
Xuemin Dai1, Chi-Chung Ling1, Shijie Xu1, Liwu Lu1, Gerhard Brauer2, Wolfgang Anwand2 and Wolfgang Skorupa2; 1Physics, The University
of Hong Kong, Hong Kong, China; 2Institut fr Ionenstrahlphysik und Materialforschung, Forschungszentrum Rossendorf, Dresden, Germany.
Unintentionally doped n-type ZnO single crystals were implanted by nitrogen ions with different fluences of 1013, 1014 and 1015 cm-2
respectively under accelerating voltage of 150 keV. The oxygen face was chosen for the implantation at a substrate temperature of 300C .
Electrical characterization techniques including current-voltage (I-V), capacitance-voltage (C-V), Deep Level Transient Spectroscopy (DLTS)
and double-correlation DLTS (DDLTS) were used for investigating all the as-implanted samples and control sample through Au/n-ZnO Schottky
diodes. DLTS results showed that N+ implantation with the fluence of 1013 cm-2 introduced one prominent electron trap EN1 at 0.95eV below
conduction band with trap concentration of 41015 cm-3 and capture cross section of 610-12 cm2 which was not observed in non-implanted
control sample. This implantation induced deep level was also observed in as-implanted ZnO samples with fluences of 10 14 and 1015 cm-2. ZnO
p-n homojunction was successfully fabricated due to the formation of p-type layer after 650C post-implantation annealing in air for 30 minutes.
DLTS measurements showed that the deep states in as-implanted samples still persisted after 650C annealing. However, it was found that E N1
finally disappeared after 750C thermal annealing through DLTS spectra. On the other hand, another electron trap with activation energy of
0.174 eV and capture cross section of 4.710-17 cm2 was detected in 750C-annealed p-n junction. Detailed properties of implantation induced
defects were discussed based on plentiful DLTS spectra. Moreover, a broad red luminescence peak centered at 620nm was observed in
low-temperature photoluminescence spectra of all the as-implanted samples, whereas absent in the non-implanted control sample. It was also
found that the red luminescence peak existed in 650C-annealed sample. As for 750C-annealed sample, there was no obvious red emission peak
and a strong green luminescence peak dominated the PL spectrum. Using multimode Brownian oscillator (MBO) model, the induced broadband
had a zero phonon wavelength coincided with the energy scheme of the transition between the detected 0.95eV deep level and the valance band.
Combined with first-principle calculation results, this EN1 deep level can be assigned to be oxygen vacancy (VO) which was predicted to be
located ~1 eV below conduction band.
4:30 PM L10.9
Influence of Monochromatic Illumination on Chemisorption Processes in ZnO. George C. Whitfield and Harry L. Tuller; Department of
Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts.
ZnO, as an n-type semiconducting metal oxide (SMO), exhibits a strong chemoresistive sensitivity to a variety of oxidizing and reducing gases.
[1] While SMO based sensors typically need to be heated to temperatures in excess of 300C to obtain reversible signal response, previous
studies have demonstrated sensor operation at room temperature upon illumination with visible and UV light. [2, 3] In the present work, the
effect of light on ZnO-based gas sensor performance is investigated, with particular attention toward the effect of varying wavelength. ZnO
photoconductance spectra are measured in environments of controlled temperature and atmosphere, and spectral characteristics are correlated to
sensor performance during monochromatic illumination. These experiments are used to gain insight into the density of electronic states at the
ZnO surface and their relation to chemisorption processes active during gas sensor operation. [1] M. Suchea et. al., Thin Solid Films 515,
551-554 (2006) [2] K. Anothainart et. al., Sensors and Actuators B 93, 580-584 (2003). [3] M. Law et. al., Angew. Chem. Int. Edit. 41,
2405-2408 (2002)

4:45 PM L10.10
Bilayered (MoOx/ ZnGaO / substrate) Nano-composite Structure Transparent Conducting Oxide with Improved Work Function. Titas
Dutta, Vikram Bhosle and Jagdish Narayan; North Carolina State University, Raleigh, North Carolina.
Research on transparent conducting oxides (TCOs) alternative to indium tin oxide (ITO) has attracted lot of attention due to the serious concern
related to the cost and chemical stability of indium oxide. ZnO doped with group III elements is a promising candidate because of its superior
stability in hydrogen environment, benign nature and relatively inexpensive supply. Ga doped ZnO films with electrical and optical properties
comparable to ITO can be grown on sapphire as well as inexpensive glass substrates. However, ZnO based TCO films suffer from low work
function (4.1 eV, compared to that of 4.8 eV for ITO), which is a critical parameter for device applications. We report here the growth of a
bilayered structure consisting of thin MoOx layer on Zn0.95Ga0.05O film for transparent electrode applications. The thin MoOx buffer layer
provides a higher work function, and superior surface and diffusion barrier characteristics without affecting the overall transmittance and sheet
resistance. The higher work function of the MoOx (~ 5.0 eV) is envisaged to improve the transport of the carriers across the heterojunction in the
device, thus, resulting in the increase in device efficiency. The films (MoOx, ZnGaO) and the heterostructures (MoOx / ZnGaO) have been
deposited using pulsed laser deposition (PLD). To understand the growth characteristics of the thin MoO x layer, films (few monolayers) were
grown on glass, sapphire and ZnGaO templates at different temperatures and oxygen partial pressure. The characteristics of the MoO x film and
the heterostructure have been investigated in detail using X-ray diffraction, TEM, X-ray photoelectron spectroscopy (XPS), and electrical and
optical property measurements. The thickness of MoOx layer was determined to be ~1.5 nm 0.5 nm which corresponds to 4 unit cells. The
thickness of the layer was carefully controlled by controlling the repetition rate and the number of pulses. One of the most important features of
this work is the 2-D growth of the MoOx film on the various templates as verified by XPS. The 2-D growth of the film leads to a uniform
coverage and a smooth surface, which are expected to be conducive to improve the device performance. In the MoOx film molybdenum exists in
Mo4+ , Mo5+ and Mo6+ oxidation states in a monoclinic phase. The MoOx films exhibited transmittance of more than 80% across the visible
region and a resistivity of the order of 10-3 O-cm. However, the overall transmittance and the resistivity are dictated by the thicker layer of
ZnGaO beneath the MoOx. Thus, the sheet resistance and the transmittance of the composite structure are close to that of ITO, albeit with
improved work function and diffusion barrier properties. Preliminary results of the performance of test devices based on these novel TCO layers
will be presented and the suitability of these layers for transparent electrode application will also be discussed.

Thursday Evening, November 29, 2007
8:00 PM
L11.1
Electrical and Electro-optical Investigations on the Polarization Coupling in Epitaxial Ferroelectric BTO/ZnO Heterostructures.
Matthias Brandt1, Holger Hochmuth1, Michael Lorenz1, Marius Grundmann1, Mathias Schubert2, Tino Hoffman2, Rao Voora2, Nurdin
Ashkenov1,3 and Jrgen Schubert4; 1Fakultt fr Physik und Geowissenschaften, Institut fr Experimentelle Physik II, Abteilung
Halbleiterphysik, Universitt Leipzig, Leipzig, Germany; 2Department of Electrical Engineering and Center for Materials Research and
Analysis, University of Nebraska-Lincoln, and Nebraska Center for Materials and Nanoscience, Lincoln, Nebraska; 3Present Address: Opteg
GmbH, Leipzig, Germany; 4Forschungszentrum Jlich GmbH, IBN 1-IT, D-52425 Jlich, Germany.
Ferroelectrics are a material class of increasing importance in electronics. A large number of electrical and electro-optical applications are
known, including ferroelectric switches, capacitors, non volatile memory elements, optical switches and thin film transistors. ZnO is an emerging
candidate for UV optoelectronic devices, especially due to its high exciton binding energy. While the polarization in ferroelectric materials is
switchable by external electric fields, wurtzite ZnO exhibits a permanent spontaneous polarization. However, publications concerning the effects
of polarization coupling in BTO/ZnO structures are sparse. Previously, polarization coupling effects have been observed by us in experiments on
Pt/BTO/ZnO/Pt structures on Si[1]. Asymmetric current-voltage (I-V), capacitance-voltage (C-V) and field dependent polarization P(E)
hysteresis loops were demonstrated. A change of more than 30% in capacitance could be detected depending on the direction of the bias sweep.
Lately, we have investigated the structural, morphological, electrical and electro-optical properties of structurally improved BTO/ZnO
heterojunctions grown on SrTiO3 (STO) substrates. BTO films of 800nm thickness have been grown on lattice matched STO substrates by
pulsed laser deposition (PLD). Two mechanisms for the fabrication of back contacts have been employed, STO:Nb substrates and 70nm thick

conductive SrRuO3 between the substrate and the BTO layer. Further, ZnO top electrodes of 400nm thickness and 2 mm diameter were grown
by PLD. Ohmic front contacts have been realized by DC sputtered Au pads with 1 mm diameter. Pt contacts have been DC sputtered instead of
the ZnO for comparison. Superior structural properties were observed in comparison to the polycrystalline structures obtained on Si substrates. A
very good (001) and (0002) alignment has been observed for the BTO and ZnO layers respectively. The leakage current could be reduced by 4
orders of magnitude in comparison to the previous structures. The influence of persistent photocurrents has been investigated. Depending on the
time the sample was kept in darkness, the leakage currents could be reduced by another order of magnitude. This allowed the direct observation
of the ferroelectric switching currents of the BTO, which could be used to determine the coercive field in BTO and the spontaneous polarization
in ZnO. A detailed model analysis of the electrical switching behaviour will be given. [1] N. Ashkenov, M. Schubert, E. Twerdowski, B. N.
Mbenkum, H. Hochmuth, M. Lorenz, H. v. Wenckstern, W. Grill, and M. Grundmann, Thin Solid Films 486, 153-157 (2005)
L11.2
Metal-Catalyst-Free and Surface-Roughness-Assisted Selective Area Growth of Zinc Oxide Nanowires by Thermal Evaporation. Shu-Te
Ho, Hsin-Yu Lin and Heh-Nan Lin; Materials Science and Engineering, National Tsing Hua University, Hsinchu, Taiwan.
We report an effective growth method which can approach selective area growth of zinc oxide nanowires without the employment of metal
catalyst. This can exclude effectively metal catalyst as a residual contamination from the Schottky junction or optical resonator. The PMMA film
of thickness 50 nm spin-coated on two types of substrates, Si (100) and a-sapphire, was used as a resist layer for fabrication of the selective area
patterns, microsquare and nanogroove arrays, by using e-beam lithography and atomic force microscopy nanomechining, respectively. The Si
and sapphire substrates were immersed for 15 s in a solution of potassium hydroxide (KOH, 1M) and sodium hydroxide (NaOH, 1M),
respectively, and then these arrays were selectively etched. Root-mean-square roughness measurements inside the etched region by using
contact-AFM shown a little difference compared with roughness values of the bare substrates. The growth of ZnO nanowires was performed in
furnace system with gas flow of mixed O2 and Ar in which the temperatures of substrate zone were set as 620 C for Si and 580 C for sapphire.
However, the surface-roughness-assisted growth mechanism of ZnO nanowires has been opaque to our knowledge and it could be due to the
increase of vacancy sites on etched surface within Langmuir adsorption as assisted heteronucleation of vapor or liquid zinc on substrate surface.
L11.3
Homoepitaxial ZnO-Layers Grown in 2D-Growth Mode by MOVPE. Soren Heinze, A. Krtschil, J. Blaesing, A. Dadgar, T. Hempel, J.
Christen and A. Krost; Institute of Experimental Physics, Otto-von-Guericke-University, Magdeburg, Germany.
The II-VI semiconductor ZnO offers a tremendous potential for optoelectronic devices in the blue and near ultraviolet spectral regime due to its
wide direct band gap of 3.4 eV and the large excitonic binding energy of 60 meV. In contrast to GaN large and inexpensive ZnO substrates are
available and therefore homoepitaxial growth of ZnO-layers should be possible. In contrast to heteroepitaxial growth, homoepitaxial grown
layers are expected to have a significantly lower number of structural defects due to advantages as perfect lattice and thermal expansion match.
However, most of the work in recent years has been performed on heteroepitaxial growth of ZnO layers. For the purpose of homoepitaxial
growth the substrates were annealed in a rapid thermal-annealer for 15 minutes at 1100C in a box with ZnO powder and oxygen atmosphere.
Annealing under these conditions leads to atomically flat surfaces on a large scale area. On such pretreated substrates we have grown high
quality ZnO layers by MOVPE. A systematic variation of growth conditions like VI/II-ratio, growth temperature and reactor pressure finally
resultes in atomically flat surfaces grown under a 2D-growth mode. Here, we present our latest results on the morphological and structural
properties of these layers.
L11.4
Transparent Thin-film Transistors with ZnO Active Layer Fabricated by RF Magnetron Sputtering Method. Woo-Seok Cheong, Chi-Sun
Hwang, Sang-Hee Ko Park, Jaeheon Shin, Chun-Won Byun, Doo-Hee Cho, Minki Ryu, Shinhyuk Yang, Sung Min Yoon, Jeong-Ik Lee, Hye
Yong Chu and Kyoung Ik Cho; Electronics telecommunications Research & Institute, Daejeon, South Korea.
Zinc oxide(ZnO) is very interesting material for practical applications because of its high transparency in the visible light and simultaneously
high electrical conductivity. In this study, transparent thin-film transistors(TTFTs) with active channel of zinc oxide were fabricated, where zinc
oxide thin films were prepared by RF(radio frequence) magnetron sputtering on glass substrates. ZnO films could be made diffrently under the
condition of different working pressures, gas ratios (oxygen/oxygen+argon) and rf plasma powers. For our analysis on device properties, as well
as bottom-gated structrues (inverted staggered, inverted coplanar), top-gated structures (staggered, coplanar) were used with changing active
deposition conditions. The microstructures of films and devices were investigated by transmission electron microscopy (TEM), X-ray diffraction
(XRD), FIB(focused ion beam) scanning electron microscopy (SEM) and atomic force microscopy (AFM). From the analysis of microstructures,
ZnO films without oxygen gas were similar to the structure zone model (SZM), while other films (with oxygen gas) were shown a similar
morphological evolution with each other. At the condition with high kinetic energy, the Rrms was reachied the lowest value, 0.36nm at 100nm

(film thickness). The optical transmittance at 550nm was around 80% or higher for most films. In general, current-voltage (I-V) properties
measured through the gate showed that the channel was n-type, and Ion/Ioff ratio was more than 106, where the channel mobility had the values
of 0.06 ~2.0 cm-2V-1s-1. The trend of transmittance and XRD was closely related with the device properties. The high peak intensity in XRD
resulted in the high off current, while the device with low stressed active films did in the high on current.
L11.5
Donor Doping of ZnO with Group VII Elements. Joachim Sann1, Niklas Volbers1, Stefan Lautenschlaeger1, Swen Graubner1, Felizitas
Eylert1, Melanie Pinnisch1, Kay Potzger2 and Bruno K. Meyer1; 11st Physics Institute, University of Giessen, Giessen, Hessen, Germany;
2Institute of Ion Beam Physics and Materials Research, Forschungszentrum Rossendorf, Dresden, Germany.
In order to produce ZnO-based devices not only p-type doping, but also controlled n-type doping is essential. For the group VII elements F, Cl,
Br, I substituting O neither their donor levels nor their influence on Photoluminescence spectra have been intensely studied. In this work we
doped ZnO single crystals with F, Cl, Br or I by diffusion through the surface and by ion implantation with fluences of about 10 14 ions/cm2. The
samples have been investigated by low temperature and temperature dependent Photoluminescence, and Hall measurements have been
performed in the van-der-Pauw configuration. We will give an assignment between dopant and PL-recombinations and determine the respective
donor binding energies. First results on CVD-grown in-situ doped samples will be shown.
L11.6
Optical Properties of Nanoporous ZnO Structures. Waitz Thomas2, Michael Tiemann2, Joachim Sann1, Jan E. Stehr1, Peter J. Klar1, Bruno
K. Meyer1, Swantje Horst3 and Sangam Chatterjee3; 11st Physics Institute, University of Giessen, Giessen, Hessen, Germany; 2Institute of
Inorganic and Analytical Chemistry, Justus Liebig University, Giessen, Germany; 3Faculty of Physics and Material Sciences Center, Philipps-
University, Marburg, Germany.
We report the synthesis of nanoporous ZnO, which exhibits a periodically ordered, uniform pore system with crystalline pore walls. The
crystalline structure is investigated by X-ray diffraction, transmission electron microscopy, and selected area electron diffraction. The large
specific surface area and the uniformity of the pore system are confirmed by nitrogen physisorption. Raman spectroscopy along with
low-temperature continuous-wave and time-resolved photoluminescence measurements confirm the high degree of crystallinity and give insight
into defects participating in the radiative recombination processes. The band edge and near band edge luminescence are dominant in the entire
spectral range from 2 to 3.4 eV, the deep recombinations in the visible spectral range being almost five orders of magnitude lower in intensity.
Individual recombinations can be assigned to specific extrinsic impurities, i.e. gallium and hydrogen. The I8 recombination line appears to be
significantly broadened compared to bulk samples. The broadening is attributed to different local environments of gallium donors situated at the
surface or in the interior of the pore walls. This reflects the enhanced surface-to-volume ratio. The dynamics of the recombination processes are
compared with corresponding bulk reference samples.
L11.7
Gas Sensing Properties of Porous ZnO Nano-Platelet Films. Amandeep Saluja2, Seth Hubbard1, Jie Pan3, Lei Kerr3, Eunjung Cho4 and
Dimitris Pavlidis4; 1Department of Physics, Rochester Institute of Technology, Rochester, New York; 2Microelectronics Engineering
Department, Rochester Institute of Technology, Rochester, New York; 3Department of Paper and Chemical Engineering, Miami University,
Oxford, Ohio; 4Department of High Frequency Electronics, Technische Universitt Darmstadt, Darmstadt, Darmstadt, Germany.
Solid state chemical sensors are gaining popularity and finding extensive use in process control, environmental monitoring and residential safety.
ZnO, a semiconducting metal oxide, has attracted great interest over the years due to its sensitivity to a variety of gases. Nanostructured sensing
materials, such as nanowires, nanotubes and quantum dots offer an inherently high surface area, thus reducing operating temperatures and
increasing sensitivity to low concentrations of analytes. In this work, various ZnO nanostructures were synthesized and tested as chemical
sensors. Initial ZnO nanoparticles were prepared by a simple solution chemical process. The as-prepared ZnO thin films were characterized by
Secondary Electron Microscopy (SEM) and BET Sorptometer. SEM images demonstrate that the particles have uniform diameter of about 15 nm
and are aligned to form plate-like nanostructures. The surface area obtained from BET measurement is 21.5 m2/g with 50% of the pore diameters
in the range of 20 to 80 nm. The gas sensor platforms consisted of Pt inter-digitated fingers with a spacing of 10 m. The sensor platform was
dip-coated with ZnO nano-platelets suspended in terpineol to form a uniform film. Sensing was performed in a closed quartz chamber and the
flow of gases was regulated using calibrated mass flow controllers. For all experiments, the carrier gas was high purity N 2 and dry industrial air
was used after exposure to recover the sensors to their initial state. The sensitivity [(R air-Rgas)/(Rair)] was measured for different concentrations
of the analytes and values in excess 80% for 60ppm of H2 gas were observed at room temperature. High sensitivity of the sensor at low
temperatures is attributed to both the increased surface area of the porous ZnO nano-platelets and the presence of a Pt catalyst. Measurements at
higher temperatures (150 C) show even higher sensitivities, near 96% for a 20 ppm H2 concentration. Short response and recovery times of

about 200 seconds were observed for these ZnO nano-platelets. The sensitivity for CO gas was also measured and found to be about near 90%
for 80 ppm at operating temperatures of 200 C. The sensors depict incomplete recovery of resistance at room temperature for both H 2 and CO
gases. This effect is possibly due to the traces of elemental Zn in the material, which were not oxidized at the time of recovery. However, this
effect was not observed at higher temperatures. Gas sensor design and sensor platforms will be optimized for nano-structured materials and a
detailed study on the effect of different operating parameters such as temperature, inter electrode spacing, gas concentration and material
properties (ZnO nanorod arrays, plates and wires) on gas sensitivity will be presented. The sensing mechanism of each type of gas will be
correlated to the nanomaterials properties. Sensitivity of the ZnO nanostructures to other sensing gases such as NH 3 and C2H5OH will be
presented.
L11.8
Annealing Studies on Arsenic Implanted Zinc Oxide. Niklas Volbers1, Stefan Lautenschlaeger1, Joachim Sann1, Shengqiang Zhou2, Kay
Potzger2, Frank Bertram3, Andre Krtschil3, Jrgen Christen3, Alois Krost3, Holger Wenckstern4, Marius Grundmann4 and Bruno K. Meyer1;
11stPhysics Institute, University of Giessen, Giessen, Hessen, Germany; 2Institute of Ion Beam Physics and Materials Research,
Forschungszentrum Rossendorf, Dresden, Germany; 3Institute of Experimental Physics, Otto-von-Guericke-University, Magdeburg, Germany;
4Institute for Experimental Physics, University of Leipzig, Leipzig, Germany.
Arsenic is considered a possible acceptor in in ZnO and as such it is a possible dopant to achieve p-type conductivity. Ion implantation provides
an accurate and reproducable method to incorporate this dopant into ZnO crystals. In the presented work, high quality ZnO crystals were
implanted with 75As ions, using implantation doses of 1016 atoms/cm2. The crystals were then annealed at temperatures of up to 1100 C.
Dynamic secondary ion mass spectrometry shows the evolution of the implanted ions in the films and the corresponding motion of residual
impurities. For the electrical characterisation, Hall effect, scanning capacitance microscopy, CV and admittance measurements were performed.
In addition, the optical properties were investigated by observing the photoluminescence and cathodoluminescence.
L11.9
Preparation of a Dominant (002) Orientation ZnO Nano-rod by Electrodeposition and its Optical Properties. Chia-Feng Chang1,
Tsung-Ying Liu1, Chen-Feng Huang1, Tsing-Hai Wang2, Shi-Ping Teng2 and Jiann-Ruey Chen1; 1material science and engineering, national
tsing hua university, Hsinchu,, Taiwan; 2Dept. Engineering and System Science, National Tsing Hua University, Hsinchu, Taiwan.
In this paper, ZnO nano-rods with a dominant (0 0 2) orientation were obtained by chemical electrodeposition on ITO glass substrates at lower
temperature under constant current. Our results showed that the grain size and aspect ratio of the ZnO nano-rods are strongly vulnerable with
some parameters such as current density, deposition time and temperature of the reaction bath. Results from XRD suggest that the moiety of (0 0
2) orientation increases when the applied current density decreases. The XPS analysis shows a Zn/O ratio between 0.5~1, which is in good
agreement with its stoichiometry. In addition, the ZnO nano-rods are composed mostly of hexagonal columns, which is confirmed by SEM
analysis. Furthermore, a band gap of 3.3 eV of ZnO is obtained from photoluminescence spectra.
L11.10
Optical SHG for ZnO Films with Different Morphology Stimulated by UV-laser Thermotreatment. Kazimierz J. Plucinski1, V.
Kapustianyk2 and I. V. Kityk3; 1Electronics, Military University of Technology, Warsaw, Poland; 2Scientific-Technical and Educational Centre
of Low Temperature Studies,, Univ. of Lviv, Lviv, Ukraine; 3Institute of Physics, J. Dlugosz University, Czestochowa, Poland.
We have discovered substantial influence of the ZnO grain sizes on the output second harmonic generation stimulated by nanosecond pulses of
371 nm nitrogen laser during simultaneous superposition of the electrostatic electric field with electric strength about 2 kV/cm. To explore an
influence of film morphology on the second order optical susceptibility we have explored the films prepared by electron sputtering with average
grain sizes about 1000 nm and films synthesized by rf-magnetron sputtering on the two different substrates - glass and amorphous quartz with
average grain sizes about 137 nm and 29 nm, respectively. Comparing the UV-induced optical second harmonic generation for the ZnO films
with different grain sizes we came to a conclusion that the samples with nanorods are characterised by substantially larger second order
susceptibility (up to 5.7 pm/V at 1064 nm fundamental wavelength) compared to those for the films with smaller grain sizes (1.5 pm/V). This
may be due to fact that UV-illumination deals only effectively with simultaneous electric filed treatment enhancing the second order optical
susceptibility. A correlation between the temperature of local laser thermo-heating and the output optical second harmonic generation may
indicate on principal role of the local thermal expansion in the observed output second harmonic generation.
L11.11
Ultraviolet Luminescence in Epitaxial Phosphorus-Doped ZnO Thin Films. Xiaoqing Pan1, Arnold Allenic1, Wei Guo1, Yanbin Chen1,

Yong Che2, Zhendong Hu2 and Bing Liu2; 1The University of Michigan, Ann Arbor, Michigan; 2IMRA America, Inc., Ann Arbor, Michigan.
Whether ZnO can compete with GaN for optoelectronic applications will depend on our ability to fabricate robust p-type material. We will show
that while good p-type conductivity can be observed in P-doped ZnO, the near band edge (NBE) luminescence is strongly degraded by the high
density of doping-induced defects. In a more general effort to improve on the NBE luminescence of P-doped ZnO and reduce the minority carrier
concentration, we have used oxygen plasma-assisted pulsed laser deposition to grow P-doped ZnO films epitaxially on both (0001) sapphire and
(0001) ZnO substrates. The oxygen plasma provides oxygen-rich growth conditions. We find that a new ultraviolet luminescence band at 3.1162
eV (at 12.5 K) appears in ZnO films doped with phosphorus. The transition was studied by excitation-intensity and temperature-dependent
photoluminescence measurements, and assigned to a donor-acceptor (DA) transition. The behavior and characteristics of the DA band will be
presented and the activation energy of the acceptor estimated as a function of the phosphorus concentration in the film. The microscopic origin of
the phosphorus acceptor will be discussed in the light of our transmission electron microscopy studies.
L11.12
Colloidal Synthesis of Optically Active ZnO/ZnS Core/Shell Nanocrystals. Krishnaprasad Sankar1, Brian A Akins1, Tosifa A Memon1, Shin
T. Bowers1,2, Gennady A Smolyakov1 and Marek Osinski1; 1Center for High Technology Materials, University of New Mexico, Albuquerque,
New Mexico; 2Present address: Division of Engineering, Brown University, Providence, Rhode Island.
Recent advances in colloidal nanomaterials have produced a new class of fluorescent labels by conjugating monodisperse semiconductor
nanocrystals with biospecies (antibodies, enzymes, oligonucleotides, etc.). These biofunctionalized nanocrystals provide important advantages
over conventional organic dyes: their emission wavelength can be continuously tuned to achieve a range of colors by changing the particle size,
and a single light source can simultaneously excite all the different-sized nanocrystals, therefore allowing for simultaneous imaging of different
colors. Additionally, semiconductor nanocrystals enable long-time, in-situ cell imaging due to 100-fold greater stability against photobleaching.
Moreover, the characteristic optical property of blinking provides readily distinguished emission from individual nanocrystals compared to
aggregates, or multimeric assemblies. Importantly, by defining the behavior of individual protein assemblies, it is now possible to resolve a
detailed picture of cellular trafficking and molecular processing events that have been previously unappreciated, but are critical to developing
new insight into biological processes, including receptor trafficking or vesicle recycling. However, colloidal nanocrystals reported to date are not
optimized for in vivo studies. In addition the requirements associated with the quality of in vivo imaging data, such as minimal nonspecific
deposition and retention of luminescent properties over a sufficiently long time, the most fundamental is: nanocrystals must not be harmful to the
investigated cells. This fundamental requirement has so far received relatively little attention, perhaps due to the pioneering character of all
nanocrystal imaging studies at this stage. A survey of the materials used to date as components of colloidal quantum dots resembles more a
catalog of poisons and carcinogens than desirable non-invasive tools. ZnO nanocrystals possess a number of properties making them very
attractive for optical applications, such as wide bandgap, large exciton binding energy, radiation hardness, and strong surface-defect-related
green emission. As such, they are of interest as potential high-speed nanophosphors for conversion of UV light into visible emission in UV LEDs
and laser diodes. Gas and chemical sensors, electro- and photoluminescent devices, solar energy conversion, and transparent UV-protection films
can be named as potential applications of ZnO nanocrystals. Being a non-toxic substance, ZnO is a very attractive material for biomedical
applications. When doped with various other materials, the wide bandgap of ZnO could be used to get a wide spectral range of narrow emission
lines. In this paper, we report on colloidal synthesis of ZnO/ZnS core/shell nanocrystals and their characterization by TEM, EDS, and steady
state UV-VIS optical absorption and photoluminescence spectroscopies.
L11.13
Sputter Deposition of ZnO Layers at High Substrate Temperatures. Angelika Polity1, Sebastian Eisermann1, Joachim Sann1, Swen
Graubner1, Stefan Lautenschlaeger1, Niklas Volbers1, Andre Krtschil2, Alois Krost2 and Bruno K. Meyer1; 11st Physics Institute, University of
Giessen, Giessen, Hessen, Germany; 2Institute for Experimental Physics, Otto-von-Guericke-University, Magdeburg, Germany.
Pure ZnO and nitrogen doped ZnO thin films have been prepared on sapphire, gallium nitride films, and zinc oxide substrates at substrate
temperatures up to 750 C by radio-frequency (RF) sputtering. A pure ZnO ceramic target was used in pure argon, in a mixture of argon and
oxygen or in a mixture of argon, oxygen and nitrogen. By optimizing the sputter parameters, such as sputtering power, temperature of the
substrate or Ar/O2/N2 sputtering gas ratios, high quality films were obtained. The thin film crystallinity and surface morphology has been
investigated with X-ray diffraction (XRD), atomic force (AFM) and scanning electron microscopy (SEM). Optical properties have been
examined by measuring optical transmission and photoluminescence (PL) spectra. Hall and Scanning Capacitance Microscopy (SCM)
measurements were carried out to check electric properties. Secondary Ion Mass Spectrometry (SIMS) measurements have been performed to
determine the distribution of nitrogen in the doped layers. To conclude, the ZnO film crystallinity greatly increases with increasing substrate
temperatures and the layer surfaces become smoother. High quality ZnO layers could be deposited on epi-ready zinc oxide substrates which was
proven by PL measurements. Nitrogen was successfully incorporated into the layers, but homogeneous p-type conductivity has not been
achieved, p-type domains could be observed at the grain boundaries.

L11.14
Transient Gain Spectroscopy of ZnO Epilayers After Multiphoton Pumping. Christoph Lange2, Sangam Chatterjee2, Stefan
Lautenschlaeger1 and Bruno K. Meyer1; 11. Physics Institute, Justus-Liebig-University, Giessen, Germany; 2Faculty of Physics and Material
Sciences Center, Philipps-University, Marburg, Germany.
ZnO layers of about 100 nm thickness were grown heteroepitaxially on three different substrates, i.e. GaN, sapphire, and sapphire/MgO in the
same growth run by chemical vapor deposition. Transient gain measurements using transmission pump-probe spectroscopy at room temperature
are performed on all three ZnO epilayers. Results are obtained for direct, one photon pumping and multiphoton pumping at different wavelength.
The differences between the results on the three samples as well as between the two types of measurements are presented and discussed.
L11.15
Defects in Bulk ZnO Studied by Time-resolved Photoluminescence. Michael A. Reshchikov, Physics Department, Virginia Commonwealth
University, Richmond, Virginia.
In spite of considerable attention to defect-related broad photoluminescence (PL) bands in ZnO, the origin of the deep-level defects in this
semiconductor remains uncertain and transitions causing these bands are not well identified. The analysis of defect-related PL in ZnO is
complicated by the fact that PL bands from different defects have similar shapes and positions or essentially overlap. Time-resolved PL enables
one to resolve PL bands related to different defects and determine types of optical transitions. Unintentionally doped bulk ZnO samples were
grown by hydrothermal method in Tokyo Denpa Co. Ltd. (Japan) and MTI Corporation. At low temperatures the PL spectrum contained a very
broad band with the peak position observed between 2.0 and 2.4 eV, depending on excitation intensity. Evolution of the PL spectrum after a pulse
excitation revealed that the broad band is composed of an orange (OL) and green (GL) luminescence bands having maxima at 1.96 and 2.4 eV,
respectively. The GL band dominated at times up to 1 ms and then disappeared. The OL band decayed as approximately t -1 over a wide time
interval, and its spectrum could be recorded even 24 hours after the excitation source was switched off. The slow nonexponential decay of the
OL band is attributed to transitions from shallow donors to a deep acceptor (donor-acceptor pair transitions). The ionization energy of the
acceptor has been determined as 0.5-0.6 eV from the quenching of the OL band at temperatures above 230 K. Large Stokes shift and nearly
Gaussian shape of the OL band are explained in a model accounting for strong electron-phonon coupling.
L11.16
Magneto Properties of Nano-crystalline Co-doped ZnO Thin Films. Christoph Knies1, Swen Graubner1, Jan E. Stehr1, Matthias Elm1, Detlev
M. Hofmann1, Peter J. Klar1, Nikolai Romanov2 and Bruno K. Meyer1; 11st Physics Institute, Justus-Liebig-University, Giessen, Germany; 2A.
F. Ioffe Institute, St. Petersburg, Russian Federation.
Co doped ZnO is an interesting material for room temperature spintronic applications. Nano-crystalline ZnO samples doped with Co were
synthesized by a wet-chemical synthesis using dip coating for the film formation. Samples with Co contents up to 30% can be synthesized. The
as grown films are of a low conductivity. The carrier concentration of the films can be increased by several orders of magnitude up to about 10 19
cm-3 by controlled annealing in Zn vapor. The magnetic properties of the samples were investigated by temperature and magnetic-field
dependent circular dichroism (MCD) measurements as well as magneto-transport measurements. Our results indicate a transition from
paramagnetic to macroscopic ferromagnetic behavior which is caused by the annealing procedure. Currently, we verify whether the
ferromagnetic like properties of ZnCoO are mediated by carriers or by a non-random Co distribution within the sample. The somewhat similar
synthesis approach of K. R. Kittilstved et al. [Appl. Phys. Lett. 89, 062510 (2006)] yielded comparable results.
L11.17
A Study of High Quality Al-doped ZnO Thin Films Grown at Low Temperature by Pulsed Laser Deposition. Ram K Gupta1, K. Ghosh1,
S. R Mishra2 and P. K Kahol1; 1Physics, Astronomy and Materials Science, Missouri State University, Springfield, Missouri; 2physics, the
university of memphis, memphis, Tennessee.
Highly conducting and transparent Al-doped ZnO (AZO) thin films, which are oriented along c-axis and have wurtzite structure, were grown on
quartz substrate at low temperature by pulsed laser deposition. The techniques of x-ray diffraction (XRD), Raman spectroscopy, atomic force
microscopy (AFM), optical transmission spectroscopy (OTS), electrical resistivity, and Hall Effect were used to study the effect of growth
temperature and oxygen pressure on the structural, electrical transport, and optical properties of these films. The optical transparency in all the
films is high and does not change much with oxygen pressure and growth temperature. However, electrical parameters such as resistivity, carrier
concentration, and mobility strongly depend on both oxygen pressure and growth temperature. The temperature dependence resistivity

measurement indicates semiconducting behavior of all the films. A detailed study indicates that the films which are highly conducting and
transparent correspond to an optimum temperature of 200 0C and an oxygen pressure of 5 10-7 bar. Higher transmittance of the AZO films
compared with pure ZnO and ITO and comparable mobility make us to suggest that Al-doped ZnO is an excellent material for optoelectronic
applications.
L11.18
Thermoelectric Measurements on Artifically Structured ZnO Epitaxial Layers. Gert Homm, Joerg Teubert, Stefan Lautenschlaeger,
Thorsten Henning, Peter J. Klar and Bruno K. Meyer; 1st Physics Institute, Justus-Liebig-University, Giessen, Germany.
ZnO layers of about 1000 nm thickness were grown homoepitaxially on ZnO substrates by chemical vapor deposition. The layers are n-type with
electron concentrations of about 1017 cm-3. Stripes of the as grown samples were artifically structured by photolithography. The patterns consist
of regular arrays of holes with different spacings and hole diameters. The patterns were transferred either by wet-chemical etching or by
ion-beam etching. The Seebeck coefficient is measured in the temperature range of 80 K to 300 K. The influence of the artificial structuring on
the thermodynamic figure of merit is discussed.
L11.19
Visible Luminescence of Rare Earth Ions Doped Amorphous Zinc Oxide Thin Films Grown by Sputtering Technique. Wojciech M
Jadwisienczak1, Ajay S Vemuru1, Aurangzeb Khan2 and Martin E Kordesch2; 1School of EECS, Ohio University, Athens, Ohio; 2Department of
Physics and Astronomy, Ohio University, Athens, Ohio.
We report on the luminescence of rare earth (RE) (Sm, Tb, Er, Tm) ions doped ZnO films grown by the radio frequency magnetron sputtering
technique. Samples were insitu doped with selected RE ions without any intentional co-dopants and deposited on silicon or quartz substrates at
low temperature. The as-grown samples morphology was amorphous as was confirmed by the X-ray analysis. RE-doped a-ZnO films were
investigated by optical transmission in the ultraviolet-visible spectral range, Raman scattering, photoluminescence (PL) and
cathodoluminescence (CL) spectroscopes at 11 K and 300 K. In general, CL spectra of as-grown RE-doped a-ZnO films show characteristic
emission lines due to 4f-shell transitions of RE3+ ions without any host background. Optical excitation of a-ZnO doped with a single RE species,
using above the bandgap excitation resulted in strong host emission overlapped with RE3+ emission bands. PL of a-ZnO co-doped with Sm, Er
and Tm produces strong white light emission easily detected by naked eye. Using collected data we discuss the possibility of sensitization of RE
ions using nano-crystals embedded in a-ZnO matrix for white light emitting phosphor applications.
L11.20
Observation of Room Temperature Ferromagnetism in Ga:ZnO - A Transition Metal Free Transparent Ferromagnetic Conductor.
Vikram Bhosle and Jagdish Narayan; Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina.
We report the observation of room temperature ferromagnetism (RTFM) in group III element (e.g. Ga, Al) doped ZnO. The major emphasis is
placed on the defect characterization through detailed structural, chemical, electrical and magnetic property measurements in order to understand
the origin of RTFM observed in this system. The ZnO films with varying Ga concentration (1-7 at%) were grown on (0001) sapphire using
pulsed laser deposition (PLD). The detailed structural characterization of the films was performed using X-ray diffraction and transmission
electron microscopy (TEM). The chemical concentration and purity of the films was verified by using x-ray photoelectron spectroscopy (XPS).
The magnetic properties of the films were measured with a vibrating sample magnetometer (VSM) from Quantum Design. The magnetic
behavior observed in ZnO is attributed to the concentration of oxygen vacancies which act as F-centers. The electrons trapped in these F-centers
tend to get easily polarized under the influence of the magnetic field thus leading to the magnetization of the film. It is also surmised that the
degenerate electrons present in the films further aid in the magnetization process by facilitating the transfer of moment from one polarized center
(F-center) to another. The role of oxygen vacancies was established unequivocally from the experiments performed as a function of oxygen
partial pressure during film deposition and the annealing experiments in air (~ 650 oC). It was observed that the magnetization could be
systematically varied by varying the oxygen vacancy concentration in the film. The dependence of magnetic properties with vacancy
concentration in ZnGaO films has been complemented with electrical resistivity measurements and Hall measurements. However, it was
observed that the presence of Ga is also necessary to instigate the magnetic behavior in this system and has been related to the donor
characteristics of the dopant and its complex interaction with the oxygen vacancies. This is the first time ferromagnetic behavior has been
observed in Ga:ZnO system. These results help us to understand the cause of ferromagnetism in ZnO doped with elements having fully filled
d-orbitals. The situation might be completely different in case of transition metal doped ZnO, however, these results suggest a need to take a
closer look into the role of vacancies in those samples as well. The most important implication of this work is the use of ZnGaO films for the
realization of transparent spintronics in addition to the large pool of applications for this very interesting system.

L11.21
Multiphonon Raman Scattering and Optical Properties of ZnMnO Ternary Alloy. Sandra Liliana Dussan1, Pijush Bhattacharya2, Kousik
Samanta1 and Ram S Katiyar1; 1Physics, University of Puerto Rico, San Juan, Puerto Rico; 2Physics, Fisk University, Nashville, Tennessee.
The field of Spintronics is generating much interest due to its potential to conserve energy in a wide range of applications, such as spin valves,
non-volatile memory devices, and quantum computation. The 3d transition metal (Mn, Co, Ni, Cu, etc.) doped II-VI compound semiconductor,
ZnO is the most promising dilute magnetic semiconductor (DMS) for the spintronic applications. In this work we have carried out the lattice
dynamical and optical bandgap studies of Mn substituted ZnO by micro-Raman scattering and optical transmission spectra. Apart from the first
order Raman modes of ZnO and Zn1-xMnxO (x = 0, 0.01, 0.03, 0.05, and 0.10) at 99.9, 381, 438.5, 573, and 584 cm-1 corresponding to E2low,
A1TO, E2high, A1LO, and E1LO, respectively, we observed five addition optical modes at 327 (I1), 332 (I2), 482 (I3), 525 (I4), and 680 (I5)
cm-1, where I1 and I5 is present only in 10% Mn substituted ZnO sample. The modes I2, I3, and I4 are assigned as multi-phonon scattering
considering the two phonon processes in the disorder lattice due to Mn doping and these are identified as (E2high - E2low), (A1TO + E2low),
and (E2high + E2low) respectively. To identify the additional modes, I1 and I5, we have carried out Raman measurements on ZnMn2O4 target
and compare the spectra with 10% Mn doped ZnO; and we found that these two additional modes originated from the precipitation of spinal
secondary phase ZnMn2O4 in 10% Mn doped ZnO. The crystalline grain sizes of 1, 3, 5, and 10% Mn substituted ZnO samples were calculated
by phonon confinement model as 31.8, 18.3, 15.9, and 14.1 nm, respectively. The optical band gap was found to increase from 3.27 eV to 3.41
eV with Mn concentration and additional broad sub-bandgap absorption was found around 3 eV with higher Mn content.
L11.22
Blue Luminescence in ZnO Films Grown of by Peroxide MBE. Vitaliy Avrutin1, Mikhail A. Reshchikov2, Natalia Izyumskaya1, Ryoko
Shimada1 and Hadis Morkoc1,2; 1Electrical Engineering, Virginia Commonwealth University, Richmond, Virginia; 2Physics Department,
Virginia Commonwealth University, Richmond, Virginia.
Interest in ZnO is due to its potential applications to blue-ultraviolet light emission. Because of precise control over the deposition parameters,
molecular beam epitaxy (MBE) is widely employed for ZnO thin films. However, relatively low temperature of the growth by MBE may result
in formation of a variety of native defects and complexes. Photoluminescence (PL) is a well suited for studying point defects. Low-temperature
PL spectrum of undoped ZnO contains numerous excitonic sharp lines and a defect-related broad band in the yellow/green part of the spectrum.
In addition, occasionally a blue band peaking at about 3.1 eV is observed [1]. We observed such a broad band in a set of ZnO films grown by
MBE using H2O2 oxygen source on a-plane sapphire. This band was observed for a wide range of oxygen-to-zinc ratio. In contrast, however, no
blue band was observed when an RF plasma source was used for oxygen in the same chamber under similar conditions. The PL spectrum in the
peroxide grown samples contained a sharp and intense line at 3.360 eV, assigned to an exciton bound to a shallow donor, and phonon replicas as
well as a blue-UV band at 2.85 -3.15 eV and a yellow band at 2.13-2.30 eV in different samples under varying excitation conditions. The
well-defined blue band had a Gaussian shape with a full width at half maximum of 0.22-0.30 eV. The salient features of this band are (i) strong
shift to higher energies (up to 150 meV) with the band narrowing (from 0.30 to 0.22 eV) when the excitation power density varied from 10-5 to
100 W/cm2 ;(ii) a strong red shift (~ 150 meV) with increasing temperature from 10 to 180 K. The blue-UV band intensity decreased by a factor
of 103 with increasing temperature from 10 to 250 K, disappearing at room temperature. The yellow band blue-shifted by ~ 150 meV both with
increasing excitation intensity at 10 K and temperature from 10 to 300 K at a low excitation intensity. These effects can be explained with
band-to-band and band-to-acceptor transitions in the presence of potential fluctuations rather than donor-acceptor pair transitions involving
unknown shallow acceptors. The potential fluctuations might be due to the presence of hydroxyl groups when H2O2 is used. [1] B. Kumar et al.,
Appl. Phys. Lett. 89, 141901 (2006).
L11.23
MOCVD Growth of GaN and InGaN on ZnO as a Sacrificial Substrate. Nola Li1, Shen-Jie Wang1, Eun-Hyun Park1, Zhe Chuan Feng1,2,
Adriana Valencia3, Jeff Nause3 and Ian Ferguson1,3,4; 1School of Electrical and Computer Engineering, Georgia Institute of Technology, Atlanta,
Georgia; 2Graduate Institute of Electro-Optical Engineering and Department of Electrical Engineering, National Taiwan University, Taipei,
Taiwan; 3CERMET Inc, Atlanta, Georgia; 4School of Material Science Engineering, Georgia Institute of Technology, Atlanta, Georgia.
ZnO has been considered as a substrate for epitaxial growth of III nitrides due to its close lattice and stacking order match. There have been some
reports of the growth of GaN based materials on ZnO substrates by Molecular Beam Epitaxy (MBE). Here, we will report the In0.18Ga0.82N
epitaxial layer on lattice-matched ZnO substrates by metal-organic chemical vapor deposition (MOCVD). In addition, the variation of In
incorporation in the InGaN films were controlled well on ZnO substrates under different growth temperatures. The high-resolution X-ray
diffraction has confirmed the epitaxial growth of InGaN film on ZnO substrates. In this talk, the optical and structural characterization of InGaN
epilayer on ZnO substrates were performed by using photoluminescence (PL), optical transmission, and atomic force microscopy (AFM).
However, it is well known that there is high reactivity between ZnO and GaN during the high temperature growth, such as with MOCVD.

Secondary ion mass spectrometry (SIMS) has revealed Zn and O diffusion occurring at the interface. The mechanisms of epitaxial growth and
inter-diffusion between InGaN and ZnO substrates will be discussed. The use of ZnO will also act as a sacrificial substrate that will lead to a thin
nitride film leading to higher external quantum efficiency devices, simple low cost fabrication, and high product yield with high brightness.
L11.24
Erbium Environment in ZnO:Er Polycrystalline Fibers Produced by Electrospinning. Danilo Mustafa1, Ji Wu2, Jeffery L. Coffer2 and
Leandro R. Tessler1; 1Instituto de Fsica "Gleb Wataghin", Unicamp, Campinas, SP, Brazil; 2Deparment of Chemistry, Texas Christian
University, Fort Worth, Texas.
Erbium-doped polycrystalline ZnO fibers were prepared by electrospinning. Organo-metallic Zn and Er (0.5, 1.0 and 2.0 % Er/Zn ratio)
precursors dissolved in methanol, DI water and acetic acid were forced through a syringe needle. An electric field of 20 kV over 16 cm was used
to promote the growth of fibers from the needle to a rotating drum. The resulting material consisted of entangled fibers with 0.5 to 1 m typical
diameter. The as-prepared samples present faint Er3+ luminescence at 1.5 m when excited by the 488 nm line of an Ar+ laser. This
luminescence intensity increases up to 25 times when the samples are annealed for 30 min at 500 C in air. The effect of annealing over the Er
environment was determined by EXAFS measurements at the Er L3 edge. In all as-prepared samples Er is coordinated to 8 1 oxygen atoms at
up to 0.236 0.001 nm interatomic separation. After annealing the coordination is reduced to 5.9 0.6 and the atomic separation becomes 0.230
0.001 nm. This is comparable to Er2O3 where the coordination is 6 and the first neighbor distance is 0.226 0.002 nm. The overcoordination
in the as-prepared samples is consistent with the Er L3 edge at 8361.7 0.5 eV compared to 8360.2 0.5 eV in the annealed samples and 8359.9
0.5 eV in Er2O3. In conclusion, the annealing of electrospun ZnO:Er fibers makes the Er environment more similar to that of Er 2O3 increasing
the luminescence efficiency.
L11.25
Diblock Copolymer Reverse Micelles as Nanoscale Reactors for Zinc Oxide Nanoparticles. Cleva W Ow-Yang, Osman el-Atwani, Taner
Aytun and Omer Faruk Mutaf; Materials Science & Engineering, Sabanci University, Istanbul, Turkey.
Their potential for blue-light source applications underscores the technological attraction of ZnO nanoparticles. However, the degree of
blue-shift in their absorption edge scales with particle size, so the narrow bandwidth requirement places a strict demand for monodispersity in the
nanoparticle population size distribution. Thus in the last decade, the use of diblock copolymer micelles in the synthesis of different metallic and
semiconductor nanoparticles has become increasingly common, in part because the yield is reasonably monodisperse. In the study that we are
presenting, zinc oxide nanoparticles were synthesized inside polystyrene-b-poly2vinlpyridine (PS-b-P2VP) micelles in toluene using zinc acetate
and tetra methyl ammonium hydroxide (TMAH) as reactants. The UV-visible absorption spectra of the solutions showed a peak with an onset
around 340 nm, indicating the presence of ZnO nanoparticles. Comparison with reference solutions also suggests the presence of zinc oxide in
the material system. To prove that these did indeed form inside the micelles, the system was extensively studied by phase and topographical
imaging using tapping mode atomic force microscopy, by dynamic light scattering, and by high angle annular dark field imaging in a scanning
transmission electron microscope, and these results would be presented as well.
L11.26
UV Assisted Surface Cleaning and Electrical Characterization of Zinc Oxide Nanowire Field Effect Transistor. Ved P Verma1, Hoonha
Jeon2, Sookhyun Hwang2, Minhyon Jeon2 and Wonbong Choi1; 1Mechanical and Materials Engineering, Florida International University,
Miami, Florida; 2Department of Nano Systems Engineering, Inje University, Gimhae, South Korea.
Electrical characteristics of zinc oxide nanowire (ZNW) field-effect transistors (FETs) are investigated at high temperature and vacuum
conditions. Ultraviolet (UV) light stimulated oxygen desorption from the active channel improves the device performance of ZNW-FETs. Results
show that charge transport in single ZNW depends on its surface environmental conditions. UV irradiation assisted with high temperature and
vacuum condition, removes absorbed oxygen from the surface of nanowire and the current values increase upto 400 nA from 50 nA at a bias
voltage of 2 V. ZNW-FETs fabricated in this study exhibits a mobility of ~ 4.10 cm2/V.s and high on-off ratio of ~ 104.
L11.27
The Horizontal Growth of ZnO Nanowires on Si and Sapphire Substrates. Jian Shi1, Qingkai Yu2, Shin-Shem Pei2 and Hao Li1; 1University
of Missouri-Columbia, Columbia, Missouri; 2University of Houston, Houston, Texas.
Straight and curled horizontally aligned ZnO nanowires (NWs) were achieved using a chemical vapor deposition method on a-plane sapphire,
c-plane sapphire, and (111) silicon substrates. Scanning electron microscopy (SEM) reveals that straight ZnO NWs preferred to align along

different orientations on different substrates. No wavy structure was observed on the straight aligned ZnO NWs. The orientations of these ZnO
NWs were primarily affected by metal catalysts density and the substrates. In addition, curled ZnO NWs, similar to nanorings, were also
observed sticking on some of the substrates. These unique ZnO NWs horizontally grown on substrates may provide unique advantages for
fabricating network nanodevices that can be integrated directly by the silicon technology.
L11.28
Cathodoluminescence Study of Carrier Diffusion in ZnO. Matthew Ronald Phillips1, Dominique Drouin2, Victoria Anne Coleman3, Jodie
Bradby4 and Chennupati Jagadish4; 1Microstructural Analysis Unit, University of Technology, Sydney, Sydney, New South Wales, Australia;
2Universit de Sherbrooke, Sherbrooke, Quebec, Canada; 3Department of Materials Chemistry, Uppsala University, Uppsala, Sweden;
4Department of Electronic Materials Engineering, The Australian National University, Canberra, Australian Capital Territory, Australia.
Scanning cathodoluminescence (CL) imaging of dislocation contrast has been used to investigate carrier diffusion in ZnO. The experiments were
conducted on the oxygen face of high quality c-axis n-type (~ 1 x 10-17 cm-3) ZnO single crystals purchased from Cermet, Inc. Non-radiative
dislocations were introduced around pits created using a 4.3 um spherical indenter with maximum loads of 100 and 200 mN. An injected carrier
volume approaching a point source was achieved by using an ultra low excitation voltage (1 - 3 kV) with a < 2 nm electron probe diameter.
Under these conditions the electron probe can be considered to be purely diffusive and consequently carrier behavior can be investigated at high
spatial resolution using scanning CL microscopy. Carrier diffusion was modeled under the injection conditions using normalized depth and radial
total electron energy loss profiles calculated using Monte Carlo simulations. The recombination length (L) was estimated by measuring the CL
contrast, C(r), around isolated dislocations at normal incidence to the ZnO surface. CL intensity line profiles measured across these dislocations
were analyzed using C(r) ~ exp(-r/L), where r is the distance of the electron probe from the dislocation core. From these measurements the
carrier diffusion length in ZnO was estimated to be around 100 nm.
L11.29
Microstructural Study of Zinc Oxide Nanocrystals and their Photoelectric Application. Jun Guo1, Yong Hu2, Ting Mei2 and Tim White1;
1MaterialScience and Engineering, Nanyang Technological University, Singapore, Singapore; 2Electrical and Electronic Engineering, Nanyang
Technologoical University, Singapore, Singapore.
In recent years, chemically synthesized colloidal nanocrystals were found to exhibit many attractive advantages in physical properties (e.g.
size-tunable optoelectronic characteristics), versatile solution process ability, and low fabrication cost. Nanostructure materials like nanocrystals
with dimensions down to nanometer scale, such as quantum dots (QDs), are fundamentally preferred gain material for fabricating low
dimensional devices, benefiting from quantum effects. Colloidal synthesis is an economical and efficient approach providing nanocrystal
materials with tunable size to meet emission wavelength requirements. In the field of photonics, colloidal quantum dots based materials have the
opportunity for exploitation in diverse applications such as biolabeling, photovoltaics, electroluminescence, etc. In this work, the synthesis of
ZnO, In2O3 and Ga2O3 (1-3 nm) semiconductor nanocrystal materials were investigated and their photoelectric properties were measured.
X-ray powder diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray
photoelectron spectrometry (XPS), and photoluminescence (PL) spectroscopy were used to characterize the nanocrystals obtained. The PL shows
a strong blue-shift because of small dimension effect, and other results show that oxide nanocrystals were fabricated successfully in certain
condition and the morphology of the samples varied with synthesis condition. The relations between property and structure were analyzed for
further improvement of the process. A light-emitting device was fabricated based on the experimental results. Through this work, an economical,
efficient technological platform based on colloidal synthesis will be developed for the fabrication of oxide semiconductor nanocrystal gain
materials, and UV light emitting devices.
L11.30
Synthesis of Assembled ZnO Structures by Precipitation Method in Aqueous Media. Selene Sepulveda-Guzman1, Elder de la Rosa1,2, B.
Reeja-Jayan1,3, Miguel Ramirez1, Domingo Ferrer1, Xiaoxia Gao4 and Miguel Jose-Yacaman1,4; 1Chemical Engineering, The University of
Texas, Austin, Texas; 2Centro de Investigacin en Optica, Leon, Guanajuato, Mexico; 3Electrical and Computer Engineering, The University of
Texas, Austin, Texas; 4Texas Materials Institute, The University of Texas, Austin, Texas.
The design of structures by the assembly of nanoparticles have received great attention during the last years due to their different properties from
those of the single nanoparticles. In addition, the process of assembly allows the study of several growth parameters, such as nucleation, that are
difficult to elucidate in single particles. A wide range of methods have been developed to assembly ZnO nanoparticles in complex structures
such as spheres, flower-like and web-like agglomerates. However, the synthesis of these structures usually requires two or more steps in order to
obtain the assembly. In this work we present a one-step synthetic method to obtain assembled ZnO structures by precipitation in aqueous media.
The morphology of the ZnO assemblies was studied by Scanning electron microscopy (SEM). Snowflake-like and flower-like morphologies can

be obtained by changing the temperature. Possible mechanism that explain the change in the morphology by the reaction temperature will be
discussed. The crystalline structure of the samples was analyzed by X-ray diffraction and HRTEM. STEM analysis was done to study the
morphology and the mass distribution of the elements of the assembly. The optical properties of the resulting structures were determinated by
photoluminescence (PL). The results indicate that the ZnO structures present UV and visible emissions upon excitation at 350 nm. According to
the XPS analysis, the ZnO assemblies obtained at lower temperature present excess of Zn of 4% that generates the yellow emission band.
L11.31
Electrical and Optical Studies on Bandgap Modified MgxZn1-xO Transparent Thin Films. Wei Wei1, Chunming Jin1, Jagdish Narayan1
and Roger Narayan2; 1Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina; 2Joint Department of
Biomedical Engineering, University of North Carolina at Chapel Hill and North Carolina State University, Chapel Hill, North Carolina.
Doped zinc oxide thin films have received considerable scientific interest in recent years due to their excellent electrical and optical properties.
For example, zinc oxide and magnesium oxide can form MgxZn1-xO alloys, which exhibit tunable bandgap values. At low magnesium
concentrations, MgxZn1-xO has a wurtzite structure with a bandgap varying from 3.4 eV (x=0) to 4.3 eV (x=0.36). The hexagonal phase
MgxZn1-xO alloy can be epitaxially grown on sapphire substrates by means of domain matching epitaxy (DME) theory. Unlike insulating cubic
phase (x > 0.5) alloys, hexagonal MgxZn1-xO alloys tend to exhibit semiconducting behavior. Due to their relatively small bandgap values,
hexagonal MgxZn1-xO alloys can easily be n-type doped. For example, group V element-doped MgxZn1-xO alloys are transparent conducting
oxides that can be optically transparent in the tunable wavelength regime. In this report, the structural, electrical and optical properties of
gallium-doped MgxZn1-xO films were examined. High-quality gallium-doped MgxZn1-xO (x=0.05, 0.1, and 0.15) films were epitaxially grown
on c-plane sapphire substrates at 700oC. Gallium dopant concentrations of 0.5%, 1%, 3% were included in this study. The film thickness values
for these materials were determined to be ~500-700 nm. The structural properties of gallium-doped MgxZn1-xO films were investigated using
transmission electron microscopy and X-ray diffraction, and the electrical properties were investigated using four-probe resistance measurements
and Hall effect measurements. The resistance measurements were obtained as a function of temperature from room temperature to 15 K. The
resistivity varied from 10-4 ohm cm-1 to 10-2 ohm cm-1 with increasing magnesium concentration for a given gallium concentration. Hall effect
measurements were performed in the van der Pauw configuration at room temperature. These measurements revealed that the carrier
concentration was reduced from 1020 cm-3 to 1017 cm-3 as the magnesium concentration was increased. The optical properties were
investigated using absorption, transmission and photoluminescence studies. The absorption and transmission spectra revealed a bandgap shift.
The bandgap energy was also calculated by fitting the absorption spectrum. These materials are considered to be promising candidates for
several opto-electronic devices, including flat panel displays, UV light emitting diodes, and solar cells.
L11.32
Top-gate ZnO-based TFTs and Circuits by RF Sputtering. Shahrukh Akbar Khan, Abbas Jamshidi-Roudbari and Miltiadis Hatalis; Electrical
Engineering, Lehigh University, Bethlehem, Pennsylvania.
ZnO-based thin film transistors (TFTs) have gained considerable attention due to their excellent material properties including wide-bandgap,
intrinsic n-type conductivity, optical transparency and relatively high field effect mobility. Furthermore, low-temperature processing capability
and compatibility with established IC processing techniques of such oxide TFTs provide very attractive alternative to conventional Si-based
TFTs and may render possible fully integrated active-matrix display devices. This work emphasizes room temperature deposition and fabrication
of top-gated staggered structure ZnO-TFTs and integration of ZnO-TFT based simple logic circuits. We synthesized ZnO thin films by RF
sputtering in an Ar/oxygen ambience with no intentional heating of the substrates. The electrical, optical and structural properties of the ZnO thin
films can be well-controlled by altering process parameters such as RF power density and relative oxygen partial pressure. Typical deposition
was carried out at a chamber pressure of 15 mTorr, Ar/oxygen flow rates of 15 sccm/1 sccm and RF power density of 3W/cm2. The resistivity of
the as-deposited films was between 10E4-10E6 ?-cm with high optical transparency (>80%) in the visible spectrum and minimal surface
roughness as detected by high-resolution AFM imaging. Gated van der Pauw and Kelvin-bridge structures were lithographically patterned to
asses ZnO channel resistance. In the completed devices, a dual-stack (Ta2O5/SiO2) dielectric layer was effective in suppressing gate-leakage
current below 10 pA and enabled depletion-mode ZnO-TFT operation exhibiting hard saturation. A Ti/Au metallization scheme was adopted to
provide good ohmic contact to ZnO. TFTs retained well-behaved transfer characteristics down to a channel length of 4 m with on/off drain
current ratio exceeding 10E5, threshold voltage between -15 V to -5 V and inverse sub-threshold slope of around 1.75 V/decade. The TFTs
however, suffered from polarity dependent gate-bias hysteresis due to trap-states at the channel-dielectric interface. This undesirable effect is
found to be eliminated by a post-fabrication thermal annealing in a forming gas ambience. This treatment also reduces the threshold voltage
variations and resulting TFTs scale well with varying drain bias and W/L ratios. ZnO-TFTs with different device configurations were also
fabricated to address fringe electric field effects beyond device edges and sidewall effects associated with source/drain resistance. Finally, to
demonstrate the viability of ZnO-based device integration, simple circuits such as inverters and pseudo-logic circuits are designed, fabricated and
tested.

L11.33
Abstract Withdrawn
L11.34
Abstract Withdrawn
L11.35
Structural and Field Emission Properties of Selectively-Grown ZnO Nanorod Arrays by Solution Method. Ahsan Ul haq Qurashi, Yoon
Bong Hahn, Sang Hoon Kim and Jin Hwan Kim; School of Semiconductor and Chemical Engineering, Chonbuk National University, Jeonju,
jeoklabukto, South Korea.
We have demonstrated a novel and scalable solution method for the growth of high-quality and uniform ZnO nanorod arrays. The growth
location and shape of nanorods were defined by lithography precisely. Growth of bunch-like nanorod arrays with excellent long-range order has
been observed when the pattern size was kept as 2x2 m2, and 500x500 nm2 respectively. The successful synthesis of periodic individual, or
two nanorods was achieved by decreasing pattern size to sub 100x100 nm2. The diameter and length of nanorods were found to be 70~80 and
800 ~ 1,000 nm, respectively. Structural analysis revealed that the as-grown nanorods are single crystalline in nature and grown along c-axis
direction. The photoluminescence studies of nanorods showed a sharp ultra violet emission at a wavelength of ~381 nm and a broad deep-level
visible emission at ~580 nm. Field emission current density (J) versus macroscopic field (E) measurements showed that the emission current
density of ZnO nanorods is high as 0.052 mA/cm2 at the field of 3.2 V/micrometer and the turn-on field, a field where the emission current
density can be districted from the background noise, is about 2.85 V/micrometer m.
L11.36
Enhanced Mode of ZnO Field Effect Nanobiosensor. Sang Yeol Lee1, Kyung Ah Jeon2, Minsoo Sohn3, Kyunghwa Yoo3, A Mi Choi4 and
Hyo Il Jung4; 1Center for Energy Materials, Korea Institute of Science and Technology, Seoul, South Korea; 22Department of Electrical and
Electronic Engineering, Yonsei University, Seoul, South Korea; 3Department of Physics, Yonsei University, Seoul, South Korea; 44School of
Mechanical Engineering, Yonsei University, Seoul, South Korea.
ZnO nanowires (NWs) were fabricated on p-Si (100) substrates by the thermal evaporation and oxidation of metallic zinc powder without the
presence of any metal catalyst or additives. Scanning electron microscopy (SEM) images indicate that the diameters of ZnO NWs were from 40
to 50 nm and the average length was longer than 2 m. We have fabricated nanobiosensors based on ZnO NW field effect transistors and report
the chemical sensitivity of ZnO NWs. The surface of ZnO nanobiosensor has been functionalized with biotin. ZnO nanobiosensor can be easily
detected streptavidin binding. The electrical property of ZnO nanobiosensor showed enhanced mode depending on the surface treatment of
functionalization for the detection of streptavidin and biotin binding.
L11.37
Valence Band Structure of ZnO and MgxZn1-xO. R. Schmidt-Grund1, C. Sturm1, M. Schubert2, N. Ashkenov1, B. Rheinlaender1, D.
Faltermeier3, H. Hochmuth1, A. Rahm1, J. Blaesig4, C. Bundesmann5, J. Zuniga-Perez6, T. Chavdarov1, M. Lorenz1 and M. Grundmann1;
1Institut fr Experimentelle Physik II, Semiconductor Physics, Universtt Leipzig, Leipzig, Germany; 2Department of Electrical Engineering,
University of Nebraska, Lincoln, Nebraska; 3Physikalisches Institut, Universitt Stuttgart, Stuttgart, Germany; 4FNW/IEP/AHE, Otto-von-
Guericke Universitt Magdeburg, Magdeburg, Germany; 5Leibniz-Institut fr Oberflchenmodifizierung e.V., Leipzig, Germany;
6CRHEA-CNRS, Valbonne, France.
In recent years, much attention has been devoted to study the optical properties of ZnO. Beyond these, the band-gap near band-to-band
transitions and the related excitonic contributions are of specially interest because their relevance for optoelectronic applications. For wurtzite-
structure ZnO and MgZnO, due to the spin-orbit and crystal-field interaction, the topmost valence band is split into three subbands with different
symmetries. The band-to-band transitions involving these bands and the lowest conduction band have different selection rules for coupling with
light polarised parallel or perpendicular to the wurtzite-structure optical axis. So far, the order of the G-point valence bands (G 7-G9-G7 or
G9-G7-G7) is still a question under debate.
We present an attempt to clear up the valence band order of ZnO and MgxZn1-xO thin films grown using pulsed laser deposition on sapphire
substrates. The analysis is based on the sign and the value of the spin-orbit and crystal-field splitting energies. We have varied these parameters
upon strain-variation, variation of the unit-cell volume, and by cation replacement (Zn with Mg). The found dependencies have been compared
with theoretical predictions. The strain variation was provoked by utilising the temperature dependence of the lattice mismatch between the films
and the substrates, by using different oriented sapphire substrates (c-, r-, and m-plane), and by variation of the thin film thickness. A variation of

the unit-cell volume was induced by temperature variation as well as by changing the Mg content in the mixed crystals.
The spin-orbit and crystal-field splitting energies have been calculated applying the quasi-cubic model for the three band-gap near band-to-band
transition energies. The latter have been obtained by means of model analysis of spectroscopic ellipsometry data for temperatures between 5 K
and 800 K. The structural properties of the thin films have been investigated using X-ray diffraction measurements (XRD), even in dependence
on the temperature. From the XRD data, the lattice constants, the unit-cell volume, and the strain-tensor elements have been calculated. Using
kp perturbation theory, the effect of the strain on the spin-orbit and crystal-field splitting energies was taken into consideration.
From these investigations we have found very strong hints for the valence band order of ZnO thin films to be G 7-G9-G7 at room temperature.
L11.38
Solution-phase Synthesis of ZnO Nanoparticles: Nucleation Kinetics. Geonel Rodriguez-Gattorno and Gerko Oskam; Applied Physics,
CINVESTAV - IPN, Merida, Yucatan, Mexico.
Solution processing has been shown to be a suitable method to prepare ZnO nanoparticles allowing a large degree of control over the particle
size and size distribution. ZnO nanoparticles are generally prepared from a non-aqueous solvent such as alkanols by reacting a dissolved Zn-salt
with a source of hydroxide such as NaOH or even H2O. The synthesis can be divided in four steps: precursor formation, nucleation, growth, and
aging (aggregation and coarsening). The relative rates of the different processes determine the properties of the final product. Extensive work has
been published on the coarsening kinetics of ZnO nanoparticles, but very few papers deal with the kinetics of the nucleation process. In this
paper, we present results on the nucleation, growth and aging kinetics for the synthesis of ZnO nanoparticles from the system ZnCl 2, NaOH, and
H2O in ethanol, as a function of reactant concentration. The reaction kinetics are found to be a strong function of their respective concentrations.
For the syntesis of ZnO from 1 mM ZnCl2 and 1 - 2 mM NaOH, the nucleation of ZnO is very slow at relatively low water concentration (20 -
50 mM), while the nucleation and growth rates increase with higher water concentration. The coarsening kinetics are found to be essentially
independent of water concentration. At a fixed, low water concentration, a time period is observed where only nucleation of ZnO nanoparticles
occurs, and the growth and coarsening rates are negligible. In this regime, the nucleation rate was found to be proportional to the ZnCl 2
concentration (maintaining the ratio [ZnCl2]:[NaOH:[H2O] a constant). At sufficiently high water concentrations (> 100 mM), the nucleation and
growth kinetics are very fast, and mainly coarsening is observed. In this case, it is found that the ZnO formation reaction is only completed if the
[ZnCl2]:[NaOH] = 1:2; it can be concluded that at lower concentrations of NaOH, water cannot react with the additional ZnCl 2 to form ZnO. The
results are discussed in terms of two mechanisms, involving the kinetics of precursor formation and the dependence of the nucleation rate on the
supersaturation.
SESSION L12: ZnO Thin Film Devices

Chair: Takafumi Yao
Friday Morning, November 30, 2007
8:30 AM L12.1
Advanced Zinc Oxide Based Devices for the Next generation of Thin Film Transistors and Solar Cells. Rodrigo Ferrao de Paiva Martins1,2,
Leandro Raniero1, Pedro Miguel Candido Barquinha2,1, Luis MN Pereira1,2, Goncalo P. Goncalves2,1 and Elvira Maria Correia Fortunato2,1;
1CEMOP, Uninova, Caparica, Portugal; 2CENIMAT I3N, FCTUNL, Caparica, Portugal.
The recent application of wide band gap oxide semiconductors to transparent thin film transistors (TTFTs) is making a fast and growing
(r)evolution on the contemporary solid-state electronics. In this paper we present recent results obtained using polycrystalline and amorphous
oxide semiconductors, like zinc oxide, indium zinc oxide gallium indium zinc oxide and gallium tin zinc oxide produced by rf sputtering at room
temperature used in TTFT and heterojunction p-type crystalline silicon and n-type oxide semiconductor solar cells with efficiencies above 14%.
The TTFT work in the enhancement mode and exhibit excellent saturation drain currents with on-off ratios exceeding 107 and on voltages raging
from 0.1 V to 8 Volts. The optical transmittance data in the visible range reveals average transmittance of the entire devices higher than 80 %,
including the glass substrate. Channel mobilitys are also quite respectable, with some devices presenting values higher than 30 cm2/Vs, even
without any annealing or other post deposition improvement processes. The high performances presented by these TTFTs, associated to high
electron mobility, at least two orders of magnitude higher than that of conventional amorphous silicon TFTs and a low threshold voltage, opens
new doors for applications in flexible, wearable, disposable portable electronics as well as battery-powered applications.

8:45 AM L12.2
ZnO Based Transparent Thin Film Transistor with GZO Electrode and HfO Dielectrics. Sang Yeol Lee, Center for Energy Materials,
Korea Institute of Science and Technology, Seoul, South Korea.
Transparent thin film transistor (TTFT) with ZnO channel layer has been fabricated and characterized. As grown n-type ZnO channel layer,
HfO2 dielectric layer and Ga doped ZnO transparent electrode have been adopted to implement transparent thin film transistor. Pulsed laser
deposition and RF magnetron sputtering system have been used to fabricate thin films. Investigation on ohmic contact property between Ga
doped ZnO transparent electrode and ZnO channel layer is presented with the variation of energy bandgap for the application of ZnO
semiconducting devices. Electrical and optical properties of TTFT show on-off ratio of higher than 105 and transparency of higher than about
80%, respectively.
9:00 AM L12.3
The Effects of Various Circumstances for GIZO Thin Film Transistors. Sun Il Kim, Chang jeong Kim, Jae Chul Park, Ihun Song, Jae Chul
Lee, Eun Ha Lee and Young Soo Park; Semiconductor Device Lab., SAIT, Yongin-si, Gyeonggi-do, South Korea.
In this study, we investigated the effects of various circumstances, especially the plasma and humidity, for Ga2O3-In2O3-ZnO (GIZO) TFT.
Before the TFT is passivated, the active surface of bottom gated GIZO TFT is exposed to the plasma and wet solution in conventional process.
Especially, the source/drain metal etching process delivers the plasma damage on the surface of GIZO active layer. When the GIZO TFT was
exposed in SF6, Ar and O2 plasma for metal dry etching, a significant change in Ids-Vgs curve was observed. The off current increased
dramatically and the threshold voltage shifted negatively. It is considered because the oxygen vacancy is generated and the carrier concentration
increases in surface of active layer by ion bombardment. However, the off current and threshold voltage recovered as time was going. The
recovery time is longer in Ar plasma than SF6 or O2 plasma. For the effect of water vapor, the GIZO TFT is left in humidity of 80 %. The off
current and threshold voltage is changed and the recovery is observed like the exposure in plasma. It is considered because the absorption of OH-
radical generates the carriers in the active surface due to the bond break of Zn, Ga, In and oxygen.
9:15 AM L12.4
Hysteresis Problem in ZnO Electronic Devices. Hyunjin Ji1, Jaewoo Lee1, Hyeyeon Ryu1, Daehyun Kim1, Gyutae Kim1 and Honyun Lee2;
1Korea University, Seoul, South Korea; 2LG electronics, Seoul, South Korea.
Zinc oxide (ZnO) has drawn much attention because of their interesting semiconducting properties as a transparent device to visible lights with a
wide band-gap energy, 3.37eV. In fabricating ZnO TFT (thin film transistor) devices, the easy sputtering process can facilitate the formation of
thin film as a TFT on a plastic flexible substrate with a rather high mobility and a high on/off ratio over 10 5. But the stability problems such as
reproducibility or hysteresis became crucial for the practical application together with the recipe of enhancing the mobility. Voltage-current
characteristics of ZnO devices showed different behaviors under the floating gate or well-defined gate voltages as shown in Fig 1. When
measuring the current, the voltages were swept from zero to a positive maximum then to a negative maximum and returned to zero. The current
level for the sweeping-up stages was smaller than the case for the sweeping-down stages. The hysteresis in the voltage-current characteristics
was significant, attributed to the existence of traps in the gate side and the channel side close to an insulator-semiconductor interface. In the case
of the floating gate configuration, the charges in the insulator side traps were maintained so that the polarization of the dielectric (gate insulator)
is determined by the initial charge density (electron) of the gate insulator sides. The dielectric polarization can influence on the effective gate
voltage owing to the additional dipole field. The gate effect increased as the increase of drain voltage (Vds) can induce the migration of the
initial charges from the semiconductor. Based on the assumption of constant charges the gate bias will change, resulting in the positive curvature
of Vds characteristics different from the conventional FETs(field effect transistors). The changes of the gate effects can be verified by measuring
the variation of the capacitance between the gate and the source with the different drain voltages. The voltage-current characteristics as sweeping
the gate voltage showed the opposite direction in the hysteresis different from the output characteristics, which can be explained by the variation
of the threshold voltage as Vgs increase. The hysteresis was also found in individual ZnO nanowire FETs. Voltage-current characteristics in a
suspended configuration of a ZnO nanowire FET can verify the effect of gate dielectric material to the hysteresis. Pulsed bias was observed to
decrease the hysteresis curves, which can be explained by the reduced charging in the traps. The specific conduction mechanism will be
discussed together with the experimental proofs.
9:30 AM L12.5
Solution Processed Doped ZnO-based Thin Film Transistors. Sunho Jeong, Sul Lee, Youngmin Jeong, Dongjo Kim and Jooho Moon;
Department of Materials Science and Engineering, Yonsei University, Seoul, South Korea.
Channel layers of thin-film transistors (TFT) have been generally fabricated by vacuum deposition methods. However, recent years have seem a

growing interest in realizing TFTs based on solution-processable semiconducting materials for the applications in which low-cost and
low-temperature manufacturing is demanded. ZnO-based semiconducting oxides receive a recent spotlight as a new channel material alternative
to conventional Si-based materials and organic semiconducting materials. We have developed solution-processble Sn doped ZnO-based
semiconductor materials by sol-gel chemical reactions. The precursor solution was spin-cast to form a uniform crack-free dense channel layer of
the thickness ~ 100 nm. Stable sol-gel precursor solutions were obtained by controlling the composition of solvents and stabilizers, and their
influences on electrical performance of the transistors were demonstrated by measuring electrical parameters such as off-current, on-current,
mobility, and threshold voltage. Microstructure and crystallization behavior of the doped ZnO films were investigated by SEM, XRD, and
TG/DTA. For improving an electrical performance of the transistors, in addition, Sn doping concentrations varied from 5 to 40 mol% and XPS
surface analysis was performed to understand the role of Sn doping. The mobility values of the device heat-treated at 350 - 500 C are 0.1 - 0.5
cm2/Vs and on/off current ratio is 103 - 105. Furthermore, this sol-gel derived semiconducting oxide precursors are easily adopted for direct-
writing method such as ink-jet printing. We have also demonstrated the TFTs based on the ink-jet printed doped ZnO.
10:15 AM L12.6
ZnO Thin Film, Device, and Circuit Fabrication Using Low Temperature CVD Processes. Devin A. Mourey1,3, Jie Sun2,3, Dalong Zhao2,3,
Shelby F. Nelson4, David H. Levy4, Diane Freeman4 and Thomas N. Jackson2,3; 1Materials Science and Engineering, Penn State University,
State College, Pennsylvania; 2Electrical Engineering, Penn State University, State College, Pennsylvania; 3Center for Thin Film Devices and
Materials Research Institute, State College, Pennsylvania; 4Eastman Kodak Company, Rochester, New York.
ZnO and similar metal oxides have recently received a high level of interest as a result of their wide bandgap, high transparency, and good
electrical transport. [1] We report transparent, boron-doped, ZnO films on glass substrates by plasma enhanced chemical vapor deposition
(PECVD) at 200oC. A ~350nm boron-doped ZnO film showed a minimum resistivity of 4 x 10-4 O?cm with transmission >85% over the entire
visible spectrum. Diethyl zinc (DEZ) [Zn(C2H5)2], carbon dioxide (CO2), and triethylboron (TEB) precursors are used to form the heavily doped
zinc oxide film. The maximum free electron concentration, determined by Hall Effect measurement, was 10 21/cm3 with a corresponding mobility
of 13.5 cm2/V?s. SEM, AFM, XRD, and photoluminescence were done to understand film morphology and crystalline orientation and to
correlate materials properties to electrical transport in these films. A comparison was done between doped and intrinsic ZnO films, and
relationships between film structure and electrical transport were observed. In addition, undoped ZnO deposited by PECVD was compared to an
atmospheric pressure chemical vapor deposition process at the same substrate temperature of 200 oC. The two deposition techniques studied have
differing crystalline texture and grain structure. Thin film transistors (TFTs) were fabricated and evaluated from both the PECVD and the
atmospheric CVD processes. Top contact TFTs were formed on glass with sputtered indium tin oxide or Cr patterned to form the gates, a
CVD-based aluminum oxide dielectric, and aluminum source and drain contacts formed by lift off. The zinc oxide and aluminum oxide layers
were isolated by a wet etching process. TFTs fabricated using either PECVD or atmospheric CVD had field effect mobility >10 cm 2/V?s. The
atmospheric CVD process devices were highly uniform with threshold voltage <7 V, and subthreshold slope <0.5 V. Despite the potential
advantages of high mobility metal oxide TFTs, few reports have investigated the use of zinc oxide or related materials in circuits. Ofuji, et al,
recently reported a 5-stage indium gallium zinc oxide ring oscillator with propagation delay of less than 240 ns at 18V.[2] We have fabricated
7-stage ring oscillators using ZnO deposited by PECVD or atmospheric CVD. Circuits using PECVD ZnO showed relatively slow dynamic
response compared to the atmospheric CVD process. Circuits using atmospheric process CVD ZnO had propagation delays <100 ns/stage and
oscillation frequencies >1MHz at a supply voltage of 32 V and represent the fastest ZnO circuits reported to date. [1] Ozgur, U. et al. Journal of
Applied Physics 98, 041031 (2005). [2] Masato Ofuji, Katsumi Abe, et al., IEEE EDL, Vol. 28, No.4, April 2007
10:30 AM L12.7
Properties of ZnO/ZnS Mixed Thin Films Grown by Atomic Layer Deposition Method for the TTFT Applications. Sunyeol Jeon1,
Seokhwan Bang1, Seungjun Lee1, Semyung Kwon1, Wooho Jeong1, Inhoe Kim1, Hyeongtag Jeon1, Ho Jung Chang2 and Hyung-ho Park3;
1Division of Materials Science and Engineering, Hanyang University, Seoul, South Korea; 2Dankook University, Cheonan, South Korea; 3Yonsei
University, Seoul, South Korea.
Compound thin films can exhibit a widely tunable range of physical and electrical properties by varying the ratio of the composition. Atomic
layer deposition (ALD) technique is one of methods to grow various compound films because of its basic characteristics of sequential and
self-limiting surface reactions. In this study, ZnO/ZnS mixed thin films were grown with a traveling wave type ALD system in order to fabricate
the active channel layer of the transparent thin-film transistors (TTFT) for the next generation display device. The ZnO thin films grown by ALD
with H2O are too conductive to act as channel layers. In contrast to the ZnO ALD films, ZnS ALD films exhibited the semi-insulating properties
due to their low carrier densities. For this reason, we grew the thin films with ZnO/ZnS mixed and/or lamellar structures from alternate reactions
of ZnO and ZnS growths. The precursor used was Zn(C2H5)2, and reactant gases for ZnO and ZnS were H2O and H2S, respectively. The
deposition rates of the ZnO and ZnS films were approximately 1.9 and 2.1 /cycle, respectively. The composition ratio of thin films was
controlled by the number of ZnO and ZnS cycles. The chemical, physical, and electrical properties of these thin films were evaluated to be used
as channel layers for a TTFT structure. We analyzed chemical bond states of the thin films with X-ray photoelectron spectroscopy (XPS). Auger

electron spectroscopy (AES) was used to analyze the chemical composition and impurity contents. The crystallinity of the thin films was
characterized by X-ray diffraction (XRD). The interface morphology and thicknesses of these thin films were determined by using
high-resolution transmission electron microscopy (HRTEM). We examined the electrical characteristics by the hall effect measurement,
capacitance-voltage (C-V) measurement, and current-voltage (I-V) analysis with a capacitor structure, and the proper carrier density ranges of
1012 ~ 1015 cm-3 depending on the compositional variations were observed.
10:45 AM L12.8
Stability of Transparent Zinc Tin Oxide Transistors Under Irradiation with Visible Light. Patrick Goerrn, Marcus Lehnhardt, Thomas
Riedl and Wolfgang Kowalsky; Institut fr Hochfrequenztechnik, TU Braunschweig, Braunschweig, Germany.
Amorphous thin film transistors (TFTs) are widely used as switching devices for active matrix displays due to the possibility of large scale
integration on glass substrates. To date, the material of choice has been amorphous hydrogenated silicon (a-Si:H). On the other hand, amorphous
oxide semiconductors containing post-transition-metal cations like zinc tin oxide (ZTO) exhibit field-effect mobilities one order of magnitude
larger. Moreover, the stability of zinc tin oxide TFTs against bias stress can be superior compared to amorphous silicon TFTs. After 1000 hours
of bias stress with V_GS=V_DS=10V and I_DS=188uA, which is 2 orders of magnitude higher than the current needed for a pixel, we see a
shift of the threshold voltage as low as 320 mV. This long term stability plays a pivotal role for analog applications like active matrix organic
light emitting diode (OLED)displays, because a change of the characteristic of the TFTs concomitantly leads to a modification of the individual
pixel brightness. In addition, wide band gap oxide semiconductors like ZTO are highly transparent in the visible part of the spectrum. Thus ZTO
TFTs allow for the realization of applications beyond reach of a-Si:H e.g. active-matrix, bottom-emitting OLED displays with high filling factors
or even entirely transparent active-matrix displays. Of course, these applications require a low photosensitivity of the transparent TFTs. For
oxide TFTs very little is known about the influence of visible light irradiation. Owing to the wide band gap (larger than 3 eV), fundamental
absorption of visible light can be neglected. Nevertheless, due to the amorphous structure a significant contribution of defect states to the
absorption is expected. The variation of the characteristics of transparent zinc tin oxide thin film transistors under illumination of visible light has
been studied using light sources with different wavelength and intensity. Upon illumination a decrease of threshold voltage, field effect mobility
and an increase of the off current were observed. All these effects have been found to be reversible. The temporal dependence of the change of
these device parameters has been researched. Typical time scales are on the order of tens of hours. The effect of composition and processing
temperature on the device photosensitivity has been investigated. At a typical display brightness (below 1000 cd/m2) the shift of the threshold
voltage was found to be the dominating effect and is typically smaller than 2000 mV, even for illumination with blue light (470 nm). The results
of our investigations allow an estimate of the applicability of ZTO TFTs as OLED drivers in transparent displays concerning shelf-life and
stability against bias stress, illumination and temperature.
11:00 AM L12.9
Abstract Withdrawn
11:15 AM L12.10
Pulsed Laser Deposition of ZnOxTe1-x Thin Films and Application to p+-Si/ZnOTe/n-ZnO Heterojunction Diodes. Weiming Wang, Willie
Bowen, Shihchun Lin, Sarah Spanninga and Jamie Phillips; The University of Michigan, Ann arbor, Michigan.
Wide bandgap semiconductors based on ZnO and related II-VI oxide alloys are attractive for several device applications including light emitters
and detectors operating in the visible/ultraviolet spectral region, and transparent electronics. Research and development efforts on alloys related
to ZnO have predominantly focused on the mixed cation materials CdZnO, MgZnO, and BeZnO. Mixed anion alloys related to ZnO may also
provide the ability to tune semiconductor bandgap energy in the visible and ultraviolet spectral region, but are much less understood. Alloys of
ZnTeO may be of particular interest due the bandstructure of ZnTe and intrinsic p-type properties. ZnTe has a direct bandgap at 2.29eV,
corresponding to the green optical wavelength, and predicted large bandgap bowing analogous to the GaAsN alloy. Furthermore, ZnTe has
shown the ability for controllable p-type doping by nitrogen with hole concentrations of up to 1020 cm-3. In this work, we report on the
deposition of ZnOTe thin films by pulsed laser deposition. Thin films were deposited on sapphire, GaAs substrates and Si substrates using a
pulsed excimer laser, ZnTe target, and varying ambients of oxygen, nitrogen, and high vacuum. X-ray diffraction measurements indicate the
preferential formation of zinc-blend thin films similar to ZnTe, with higher oxygen pressures resulting in degraded crystal structure rather than
the formation of a wurtzite structure similar to ZnO. The optical bandgap energy shows a strong dependence on oxygen partial pressure, ranging
from the ZnTe bandgap of 2.3eV for deposition under high vacuum to greater than 3.1eV for deposition at 100mTorr oxygen partial pressure.
XPS measurements indicate a preferential formation of TeOx for high oxygen partial pressure. The variable bandgap energy of the ZnTeO thin
films is attractive for a variety of optoelectronic devices, including solar cells. These thin films were applied to n-ZnO/ZnO xTe1-x/p+-Si
heterojunctions, and demonstrate strong diode rectifying behavior and optical response in the visible spectral region. The electrical and optical
characteristics of these heterojunction diodes will be presented.

11:30 AM L12.11
High-current-density CuOx/InZnOx Thin Film Diodes for Application to Cross-point Resistive Memory. Bo Soo Kang1, Myoung-Jae
Lee1, Genrikh Stefanovich1, Wen Xu Xianyu1, Ki Hwan Kim1, Seung Eon Ahn1, Chang Bum Lee1, Youngsoo Park1 and Bae Ho Park2,1;
1Semiconductor Device Lab., Samsung Advanced Institute of Technology, Yongin-si, Gyeonggi-do, South Korea; 2Department of Physics,
Konkuk University, Seoul, South Korea.
Recently, there has been a growing need for high performance diode as resistive memory devices emerge with cross-point one diode one resistor
(1D1R) structure. The 1D1R structure is a promising building block for 3 dimensional stack memory devices. A diode is a key switch element in
cross-point structure which prevents misreading through unexpected circuitous paths. Oxide-based diodes are considered as new candidates for
3D stack structure since it is formidable to use epitaxial silicon-based p-n diodes due to high processing temperatures, significant costs, and
formation of silicide on metallic layers. High forward current density, high forward/reverse current ratio, and low processing temperature are
important requirements of thin film diodes for application to high density stack memory. We fabricated CuO x/InZnOx thin film heterojunction
diode on platinized silicon substrate by RF-sputtering at room temperature. No Schottky contact was formed when Pt and W were used as
electrode materials for p-type CuOx and n-type InZnOx respectively. The diode showed good rectifying characteristics at room temperature: a
rectifying ratio of >105 at 1.25 V, a forward current density of >104 A/cm2, an ideality factor less than 2. The diode also exhibited a fast
response to pulse signals. Turn-on and turn-off transient responses were stabilized within a few tens of nanoseconds in response to a square pulse
signal with amplitude of 0.85 V and width of 300 ns.
11:45 AM L12.12
Performance and Stability of ZnO TFTs with SiO2, SiN and AlN Insulators. Maria M De Souza1, Richard B. Cross1, Divine Ngwashi1,
Suhas Jejurikar2 and K. P. Adhi2; 1Emerging Technologies Research Centre, De Montfort University, Leicester, United Kingdom; 2Dept of
Physics, University of Pune, Pune, Maharashtra, India.
ZnO can be deposited at low cost over large areas and at relatively low (or room) temperature, suggesting good compatibility with flexible
substrate materials for display applications. It offers the potential of at least 10 times higher mobility in comparison to a:si TFTs. Little is known
however, about the extent of instability mechanisms in ZnO TFTs with various insulators. In this work we will describe (A) Instability
mechanisms of ZnO TFTs fabricated via RF magnetron sputtering with silicon dioxide and silicon nitride as insulators. Temporary shifts in
threshold as a result of gate bias stress are found to arise due to fast interface states at the insulator boundary. In comparison to silicon dioxide,
silicon nitride gives a better performance both in terms of stability and transistor parametrics. Under AFM it is found that the growth of ZnO on
the two insulators results in different topographies. The shape of the ZnO grains on top of SiN are elongated as opposed to the conical shape
demonstrated by the material grown on to SiO2. The overall surface roughness of ZnO/SiO2 is also greater than that of the ZnO/SiN stack. This
may be explained by the differences in the lattices at the interface between the ZnO and SiN/SiO2 layers, which contributes to the disparities in
the performance of the two sets of devices. (B) Performance and instability mechanisms of ZnO TFTs with AlN as insulator. In comparison to
silicon nitride or oxide, the lattice constants (a= 3.1 A and c = 4.98 A) of AlN are more closely matched with ZnO 3.249, 5.201. The AlN
was deposited via pulse laser deposition and the ZnO via RF sputtering. Devices with excellent electrical characteristics were obtained. The
performance and stability of these transistors will also be presented at the conference.
SESSION L13: ZnO Defects and Surfaces

Chair: David Norton
Friday Afternoon, November 30, 2007
1:30 PM L13.1
Gas Phase Synthesis of Zinc Oxide Nanocrystals and Their Surface Modification Using Small and Large Acidic Ligands. Sankhanilay
Roy Chowdhury1,3, Moazzam Ali1,3, Daniela Sudfeld2,3 and Markus Winterer1,3; 1Faculty of Engineering, University Duisburg-Essen,
Duisburg, Germany; 2Faculty of Physics, University Duisburg-Essen, Duisburg, Germany; 3CeNIDE, University Duisburg-Essen, Duisburg,
Germany.
Zinc oxide nanocrystals are synthesized using the chemical vapor synthesis (CVS) technique. Diethylzinc is used as zinc precursor. Synthesized
zinc oxide nanocrystals are characterized by X-ray diffraction (XRD), nitrogen adsorption and desorption, transmission electron microscopy

(TEM) and dynamic laser scattering. As-synthesized zinc oxide has a primary particle size of about 10 nm and an isoelectric point at pH 9.5. The
surface of zinc oxide nanocrystals can be modified using short chain organic acids like formic acid and glycine as well as using low molecular
weight polyacrylic acid (PAA). The isoelectric point shifts towards acidic pH when glycine is used as surface modifier whereas it shifts towards
basic pH with formic acid. The use of PAA generates a very high value of zeta potential over the range of pH studied in these experiments and
thereby eliminates the isoelectric point.
1:45 PM L13.2
Molecular Adhesion Mechanisms on Single Crystalline, Hydroxide Stabilized ZnO(0001) Surfaces. Markus Valtiner1 and Guido
Grundmeier2,1; 1Christian Doppler Laboratory for Polymer/Metal Interfaces, Max Planck Institute fr Eisenforschung, Dsseldorf, Germany;
2Technical and Macromolecular Chemistry, University of Paderborn, Paderborn, Germany.
A combined approach of single molecule adhesion studies by means of AFM and of DFT studies, which provides a deeper understanding of the
mechanisms of molecular adhesion of organic macromolecules on metal oxides, will be presented. First, the design of suitable model surfaces
will be discussed. The main focus is the preparation and characterisation of ZnO surfaces that are comparable with the inevitable idealisations of
a theoretical treatment. Therefore, different ambient atmosphere approaches were developed for the preparation of clean, non-reconstructed,
single crystalline ZnO(0001) surfaces. Depending on the preparation technique, atomically flat terraces with a width of 100 nm up to several
micrometers were observed using an atomic force microscope (AFM). The obtained surface structures were further characterized by means of
angle resolved X-ray photoelectron spectroscopy (AR-XPS), time-of-flight secondary ion mass spectroscopy (ToF-SIMS), Auger electron
spectroscopy (AES) and low-energy electron diffraction (LEED) measurements. Based on these results it can be shown, that the obtained
surfaces are, in contrast to surfaces prepared under UHV condition, stabilised by the adsorption of a monolayer of hydroxides. Secondly, it will
be demonstrated that these developed surfaces are suitable to study molecular adhesion in electrolytes as these surfaces are very well defined.
Moreover, the surface structure of the used model surfaces turned out to be extremely stable in electrolyte solutions. The stability of the surfaces
under the respective ambient conditions will be demonstrated and single molecules desorption events by means of single molecule AFM
spectroscopy will be discussed. The main advantage of this setup is, that single molecule desorption events on these specially prepared surfaces
are closely comparable with the idealisations of the theoretical modelling. Consequently the theoretical modelling, within the framework of the
density functional approach, will be discussed and compared with the obtained experimental results.
2:00 PM L13.3
Abstract Withdrawn
2:15 PM L13.4
Abstract Withdrawn
2:30 PM L13.5
Cathodoluminescence Study of Polish Induced Luminescence in Single Crystal ZnO. Esther Alarcon-Llado1,2, Frank Bertram1, Juergen
Christen1, Lluis Artus2, Buguo Wang3 and Michael Callahan4; 1Institute of Experimental Physics, Otto-von-Guericke-University, Magdeburg,
Germany; 2Institut Jaume Almera, CSIC, Barcelona, Catalunya, Spain; 3Solid State Scientific Corporation, Hollis, New Hampshire;
4Optoelectronic Technology Branch, Air Force Research Laboratory, Hanscom AFB, Massachusetts.
ZnO is a wide band-gap material with growing interest because of its advantageous physical properties. However, no-reproducible p-type doping
has been obtained so far. One of the main reasons is the high residual intrinsic defect concentration which is still not completely understood. The
dominant defect-related luminescence of undoped ZnO is the well-known green (GL) and the yellow luminescence (YL) band. The origin of
these bands in ZnO is still controversial. Copper impurities, oxygen vacancies and zinc interstitial defects are the potential candidates to be
responsible for the GL band. On the other hand, the YL luminescence is hardly believed to be originated by Li impurities [1]. In this work we
investigate the luminescence in bulk, single crystal ZnO by means of spatially resolved cathodoluminescence (CL) spectroscopy. The sample
was grown by the hydrothermal method and post-growth rapid thermal annealed at 950oC under continuous O2 flow for 10s. A mechanical
polishing process was performed on a surface perpendicular to the c-plane to remove the surface layer of the bulk crystal. SE images of the
polished surface show a flat, mirror like surface with some parallel running scratches. CL measurements at T = 5 K were carried out at the
polished surface perpendicular to the c-plane of the bulk crystal right after the mechanical polishing process. Without polishing no CL intensity
had been observed. The optical spectrum of ZnO bulk material is usually characterized by intense luminescence intensity with rich structure of
excitonic lines. Up to 20 emission lines are listed so far [2]. Nevertheless, the sample under study shows only a weak luminescence intensity
mainly influenced by the polishing of the surface. The lateral averaged CL spectrum shows dominating near band edge (NBE) luminescence and
a broad defect band around 2.2 eV. The NBE is dominated by the bound exciton line I6 (3.360 eV). In addition, the free exciton X (3.375 eV) as

well as the bound excitons I0 (3.370 eV), I9 (3.356 eV) and I10 (3.352 eV) are visible. A strong correlation between the CL intensity of the
excitonic lines and the morphology is observed. The NBE luminescence strongly quenches at the position of the scratches. No spectral shift is
observed while approaching these marks. It is worth noting that even in the regions without any features on the SE image, monochromatic CL
images show dark lines running through. These lines mark the position of already removed scratches and cracks from the top surface indicating a
long range/distant acting damage of the scratches. In contrast, a complementary behavior is observed for the defect-related luminescence band.
This defect band shows its highest normalized intensity at the scratches. This correlation suggests that the mechanical polish process induces a
new radiative recombination channel. REFERENCES [1] T.M. Borseth et al., Appl. Phys. Lett. 89, 262112 (2006) [2] B.K. Meyer et al., Phys.
Stat. Sol. (b) 241, 231 (2004)
2:45 PM L13.6
Dynamic of Dislocations in Plastically Deformed ZnO. Ichiro Yonenaga, Haruhiko Koizumi, Yutaka Ohno and Toshinori Taishi; Institute for
Materials Research, Tohoku University, Sendai, Japan.
Knowledge on the dislocation characters and dynamical properties is essentially important as a basis for the control of dislocation generation and
deformation during crystal growth and device processing. Recently, ZnO oxide semiconductor is expected for UV light-emitting device and is
supposed for dislocations to be introduced easier than rival materials as GaN and SiC. However, up to now, far less is known on the dynamic and
optical properties of dislocations in ZnO except a limited number of papers on nano-indentation. This paper reports first results of the direct
measurement of mechanical strength of ZnO single crystals at elevated temperatures. Specimens prepared from bulk single-crystals h-ZnO,
purchased from Goodwill (Russia), were deformed by means of uni-axial compressive deformation at elevated temperatures. The yield stress of
ZnO in the temperature range 650 ~ 850 degree C is around 10 ~ 15 MPa, i.e. much easily deformed even at low temperatures in comparison
with those of GaN and SiC. From the analysis of the temperature dependence of the yield stress, the activation energy for dislocation motion in
ZnO is estimated to be 0.8- 1 eV.
3:30 PM L13.7
Zn Vacancies and Electrical Isolation of MBE-ZnO by O Irradiation. Asier Zubiaga1, Filip Tuomisto1, Victoria A. Coleman2 and
Chennupati Jagadish2; 1Laboratory of Physics, Helsinki University of Technology, TKK Espoo, Finland; 2Department of Electronic Materials
Engineering, The Australian National University, Canberra, Australian Capital Territory, Australia.
Ion implantation processes can be of interest for p-type doping or electrical isolation of ZnO based devices but the ion-induced damage should
first be better understood. Structural, optical, electrical and magnetic properties in ZnO exposed to irradiation with energetic particles have
recently been under study. It has been observed that the electrical properties of ZnO re quite resistant to particle radiation, and the irradiation
induced defects anneal at low temperatures. ZnO remains crystalline even after high ion irradiation doses [1]. We have studied nominally
undoped and Al-doped (concentrations 21018, 51018 and 11019 cm-3) ZnO single-crystal epilayers grown on a-plane sapphire by plasma
assisted molecular beam epitaxy. Defect induced isolation was introduced by implantation with 2 MeV O + ions at room temperature. This
incident beam energy was chosen to ensure that both the maximum damage peak and the O ions were placed within the sapphire substrate.
Different implantation doses were used ranging from 41012 to 11017 cm-2. The electrical isolation was measured in situ during the
implantation with In-Ga Ohmic contacts. Slow positron Doppler Broadening technique was used to study zinc vacancy related defects introduced
during the implantation process. We show that the dominant defects detected by positrons are Zn vacancies that are introduced at a rate of about
2000 cm-1 at low and moderate fluences, and that vacancy clusters are formed at the highest irradiation fluences. The Zn vacancies are a likely
cause for the isolation, while the vacancy clusters are possibly related to the loss of resistivity observed at the highest fluences. [1] S. O.
Kucheyev, J. S. Williams, C. Jagadish and J. Zou, Phys. Rev. B 67, 94115 (2003).
3:45 PM L13.8
Micro-Raman and Resonant Raman Scattering in Homoepitaxial- grown ZnO. Axel Hoffmann1, M. R. Wagner1, U. Haboeck1, P. Zimmer1,
J. Sann2, S. Lautenschlaeger1 and B. K. Meyer2; 1Inst. f. Fstkoerperphysik, TU Berlin, Berlin, Germany; 21 Physikalisches Institut, Justus Liebig
University, Giessen, Germany.
The homoepitaxial growth of zinc oxide reveals some unexpected difficulties. Although there should not be a noticeable thermal or lattice
mismatch we found a strong dependence on growth properties and substrate preparation. Micro-Raman on-plane spectra of ZnO epilayers and
substrates indicate highly oriented films of excellent crystal quality. In cross-section Raman measurements a radical change of the spectra is
observed supporting the assumption that the c-axis of the films is rotated during the growth procedure. However, the existence of different
growth domains is apparent and might be the reason for a slight internal strain variation observable by the shift of the nonpolar E2 mode of the
host lattice. From these findings we draw conclusions concerning the influence of sample preparation, in particular surface effects of the
substrates. Resonant Raman scattering in ZnO at low temperatures is performed to investigate the influence of exciton phonon interactions such

as the deformation potential for non-polar optical phonons and the Frhlich interaction for polar LO phonons are discussed. The magnitude of
the of the resonance enhancement for the 2 E1 ( LO ) Raman mode is found to vary in dependence for resonantly excited free and bound exciton
complex. Theses results are discussed in terms of different coupling strengths of the Frhlich interaction with neutral and ionized bound exciton
complexes. In addition the recombination and decay dynamics of bound exciton complexes, their phonon replica and resonantly enhanced
Raman modes will be presented and discussed considering scattering via real excitations versus virtual states.
4:00 PM L13.9
Optical Spectroscopy of A-plane ZnO Epilayers and Heterostructures Grown on R-plane Sapphire Substrates by MBE. Christian
Morhain1, Bassirou Lo2, Monique Teisseire-Doninelli1, Jean-Michel Chauveau1,3, Borge Vinter1,3 and Martin Albrecht4; 1CRHEA-CNRS,
Valbonne Sophia Antipolis, France; 2Universit Cheikh Anta Diop, Dakar, Senegal; 3Physics Dept, University of Nice-Sophia Antipolis, Nice,
France; 4Institut fr Kristallzchtung, Berlin, Germany.
MBE growth of ZnO on R-plane oriented sapphire substrates results in fully A-plane oriented epilayers. A key advantage of such a non-polar
orientation is that it leads to quantum well heterostructures showing no built-in electric field, and hence excitons having large binding energies
(no e-h separation by the electric field). With the aim of identifying the specific properties of A-plane ZnO films, these were investigated by
detailed optical spectroscopy, carried out by means of reflectivity, temperature-dependent photoluminescence (PL), selective PL as well as
cathodoluminescence (CL). The main results are: -(i) The luminescence emission is strongly linearly polarised for free exciton lines (>95%) as
well as for defect-related emissions. -(ii) The strain state in the samples is high as testified by the ~ 20 meV shift towards UV of all free excitons
as compared to C-plane oriented samples. This property holds even for 1m thick samples. -(iii) The lowest energy exciton (A) has a greater
oscillator strength than the B exciton, unlike c-oriented samples. -(iv) The nature of the main bound exciton emission as well as the chemical
origin of the involved defects are determined by SPL. -(v) A new band, not detected in c-oriented layers, is observed in the energy range of the
1st phonon replica of (A). The origin of this line could be unambiguously identified as the recombination of electron-hole pairs decorating basal
stacking faults from the comparison of TEM plane views and cathodoluminescence mapping carried out on thin TEM-prepared samples. -(vi) A
strain gradient is observed along the growth direction, which is particularly well evidenced on step wet-etched samples. This can result in an
energy shift of the band gap by several meV and has to be taken into account for a proper analysis of the optical spectra. Relaxation mechanisms
and residual strain are explored using ZnMgO buffer layers with Mg contents up to 40%.
4:15 PM L13.10
Electrical Characterization of Defects in ZnO Grown by Pulsed-laser Deposition. Holger vonWenckstern1, F. D. Auret2, W. E. Meyer2, P. J.
Janse van Rensburg2, G. Biehne1, H. Hochmuth1, M. Lorenz1 and M. Grundmann1; 1Institut fr Experimentelle Physik II, Semiconductor
Physics, Universtt Leipzig, Leipzig, Germany; 2Physics Department, University of Pretoria, Pretoria, South Africa.
The properties of the wide band-gap II-VI semiconductor ZnO make this material interesting for applications in UV optoelectronics. Defects
have crucial impact on the performance of devices. Although the defects in bulk-grown ZnO have been studied in some detail [1], much less is
known about the defects present in ZnO grown by pulsed-laser deposition (PLD).
We employed deep level transient spectroscopy (DLTS) and thermal admittance spectroscopy (TAS) to investigate the defect states in as-grown
ZnO PLD thin films and the impact of annealing (2h, 750C) in either oxygen, nitrogen and vacuum on the defect spectrum. For that, high
quality Pd/ZnO Schottky diodes were evaporated through a shadow mask on the Zn-face of the samples. A n ++ ZnO:Al layer is used as ohmic
back contact and results in low series resistances between about 50 and 200 Ohm [2].
Four shallow defects with levels at 28 meV, 60 meV, 100 meV and 140 meV below the conduction band minimum Ec, respectively are revealed
by TAS and DLTS. The 100 meV defect displayed metastable behavior: annealing under reverse bias at temperatures of above 130 K introduces
this defect while annealing under zero bias above 110 K removes it. We have determined, and will discuss, the complete introduction and
removal kinetics of this defect. Using high resolution Laplace DLTS we found that close to the commonly observed defect E3 (about 300 meV
below Ec) another close lying peak labeled E3(with a level at 370 meV below Ec) is observed. While the concentration of E3 did not show
pronounced changes during annealing, the defect E3 is strongly diminished for nitrogen or vacuum annealing, respectively.
Irradiating the Schottky diodes with a white LED at 4 K creates a defect with a level at 50 meV below Ec. However, now the 60 meV peak is
diminished. This behavior is only observed for diodes prepared on as-grown or oxygen treated samples. Annealing at temperatures above 120 K
removes the 50 meV defect and the 60 meV peak is reintroduced.
[1] F. D. Auret, S. A. Goodman, M. J. Legodi, W. E. Meyer, and D. C. Look, Appl. Phys. Lett. 80, 1340 (2002).
[2] H. von Wenckstern, G. Biehne, R. A. Rahman, H. Hochmuth, M. Lorenz, and M. Grundmann, Appl. Phys. Lett. 88, 092102 (2006).
4:30 PM L13.11
Characterization of Mid-gap Defect Level in ZnO by High Resolution X-ray Photoelectron Spectroscopy Using Synchrotron Radiation.
Naoki Ohashi1, Yutaka Adachi1, Takeo Ohsawa2, Isao Sakaguchi1, Haruki Ryoken1, Hideki Yoshikawa2, Shigenori Ueda2, Hajime Haneda3 and

Keisuke Kobayashi2; 1Optoelectronics Group, National Institute for Materials Science, Tsukuba, Ibaraki, Japan; 2Beam Line Station, National
Institute for Materials Science, Tsukuba, Ibaraki, Japan; 3Sensor Materials Center, National Institute for Materials Science, Tsukuba, Japan.
In the present study, we investigated electronic structure of ZnO films and bulk crystals by X-ray photoelectron spectroscopy (XPS). In
particular, we obtained XPS spectra of ZnO using a synchrotron radiation (SR) having high photon energy, 6 keV. Extremely high photon flux
utilized by using the SR enables very high resolution and signal/noise ratio, and elongated escape depth of photoelectron by using the high
energy incident beam enables us to observe bulk electronic structure. In this paper, we concentrate on detection of mid-gap state in ZnO, which is
critical to the charge compensation phenomena. Moreover, we discuss effects of crystalline polarity on formation of the mid gap state from the
result of XPS measurement for the single crystalline ZnO with various polarization. Samples were commercially available bulk ZnO single
crystals grown by a hydrothermal method or a chemical vapor transport method, ZnO thin films prepared by a pulsed laser deposition method,
ZnO thick films prepared by a liquid phase epitaxy method, and ZnO ceramics prepared by an ordinary ceramic synthesis process. Here, the thin
and thick film samples includes pure ZnO, (Zn,Mg)O alloy, and Al-doped ZnO, and the film crystals were hoepitaxially grown on ZnO single
crystals or heteroepitaxially grown on sapphire or zirconia substrates. Some of these samples were irradiated by ion beam to introduce impurity
or to create defects caused by the irradiation damage. The high resolution XPS measurements were performed at the BL15XU beam line
constructed in the SPring-8 and the platform for experiments has been collaborated between SPring-8/JAEA (Japan Atomic Energy Agency),
SPring-8/JASRI (Japan Synchrotron Radiation Research Institute) and HiSOR (Hiroshima Synchrotron Radiation Center, Hiroshima University).
The XPS spectra were taken at room temperature using a Scienta SES-2002 electron energy analyzer with a total energy resolution of 270 meV
or higher. The excitation energy was fixed to 6 keV and the inelastic mean free paths of photoelectrons at the kinetic energy of 6 keV range
between 5 to 15 nm, which is almost 5 - 10 times larger than those at 1 keV. That enables us to investigate intrinsic electronic structures into the
bulk. The pesence of defect/impurity level in mid-gap was clearly detected by the XPS measurement. For example, density of state of the
mid-gap state in the Al-doped ZnO films varied with the condition of thermal treatment and the mid-gap state corresponding to the acceptor state
was found in ZnO after ion beam irradiation. It is also notable that profile of XPS spectra obtained from (0 0 0 1), (0 0 0 -1), (1 1 -2 0) and (1 0
-1 0) face disagreed to one another, indicating that permanent polarization of ZnO lattice affects to the electronic state of ZnO. In particular, XPS
spectra of valence band region were sensitive to the crystalline orientation. The detailed interpretation of the variation of XPS spectra will be
discussed at the symposium.
4:45 PM L13.12
Effect of Ga doping on Luminescence in ZnO. Michael A. Reshchikov1, Junqing Xie2, Brian Hertog2 and Andrei Osinsky2; 1Physics
Department, Virginia Commonwealth University, Richmond, Virginia; 2SVT Associates, Inc., Eden Prairie, Minnesota.
In spite of impressive achievements in growth of high-quality ZnO, point defects in this semiconductor are not well understood. In particular,
assignments of the broad bands in the yellow-green part of the photoluminescence (PL) spectrum of undoped and doped ZnO remain highly
controversial. In this work we analyze in detail the yellow luminescence (YL) band having a maximum at about 2.2 eV at 10 K in undoped and
Ga-doped ZnO films grown on sapphire substrate. The YL band is attributed to transitions from the shallow GaZn donor to a deep acceptor
having an energy level about 0.7 eV above the top of the valence band. The activation energy of the YL-related acceptor is close to the 2-/-
energy level of the isolated zinc vacancy (VZn) in ZnO (0.8 eV) predicted from the first-principles calculations [1]. It is also likely that the
acceptor responsible for the YL band is not an isolated VZn but a complex defect such as V ZnGaZn. The intensity of the YL band decreased
several orders of magnitude with Ga doping, in agreement with the above assignments. The shift of the YL band maximum with increasing
excitation intensity at 10 K is negligible in undoped layers but reaches 0.1 eV in Ga-doped ones. With time delay after a pulse excitation, the YL
band shifted to lower energies in Ga-doped ZnO. The noticeable shifts of the YL band with excitation intensity and with time delay are attributed
to manifestation of potential fluctuations created by random distribution of impurities in Ga-doped ZnO. [1] A. F. Kohan, G. Ceder, D. Morgan,
and C. G. Van de Walle, Phys. Rev. B 61, 15019 (2000).
The Materials Research Society restricts the use of member, volunteer and staff contact information, including all email addresses. This applies
to all published materials from MRS and information on the MRS website. Contact information may not be used for solicitations, announcements
or similar messages unless the sender can prove that the recipient has requested such items. Please contact info@mrs.org with questions.
Materials Research Society: 506 Keystone Drive, Warrendale, PA, 15086-7537, USA
Phone: 724.779.3003 Fax: 724.779.8313 Contact Us: info@mrs.org 1995-2015
Web Site Development by The Berndt Group

Mrs

Hochgeladen von

Dokumentinformationen

Copyright

Verfügbare Formate

Dieses Dokument teilen

Dokument teilen oder einbetten

Freigabeoptionen

Stufen Sie dieses Dokument als nützlich ein?

Sind diese Inhalte unangemessen?

Copyright:

Verfügbare Formate

Mrs

Hochgeladen von

Copyright:

Verfügbare Formate

Abstracts: Symposium L: Zinc Oxide and Related Materials http://www.mrs.

Symposium L: Zinc Oxide and Related Materials

David P. Norton Chennupati Jagadish

Irina Buyanova Gyu-Chul Yi

Proceedings to be published online

SESSION L1: ZnO Nanowires for Applications

1 of 72 Tuesday 29 December 2015 04:27 PM

2 of 72 Tuesday 29 December 2015 04:27 PM

3 of 72 Tuesday 29 December 2015 04:27 PM

optical properties of the ZnO core.

4 of 72 Tuesday 29 December 2015 04:27 PM

SESSION L2: ZnO Nanowire Synthesis and Properties

5 of 72 Tuesday 29 December 2015 04:27 PM

6 of 72 Tuesday 29 December 2015 04:27 PM

7 of 72 Tuesday 29 December 2015 04:27 PM

8 of 72 Tuesday 29 December 2015 04:27 PM

9 of 72 Tuesday 29 December 2015 04:27 PM

SESSION L3: ZnO Doping and Defects

10 of 72 Tuesday 29 December 2015 04:27 PM

11 of 72 Tuesday 29 December 2015 04:27 PM

12 of 72 Tuesday 29 December 2015 04:27 PM

de Fisica Aplicada i Electromagnetisme, Universitat de Valncia, Valencia, Spain.

13 of 72 Tuesday 29 December 2015 04:27 PM

SESSION L4: ZnO Crystal Growth and Properties

14 of 72 Tuesday 29 December 2015 04:27 PM

15 of 72 Tuesday 29 December 2015 04:27 PM

16 of 72 Tuesday 29 December 2015 04:27 PM

17 of 72 Tuesday 29 December 2015 04:27 PM

SESSION L5: Poster Session

18 of 72 Tuesday 29 December 2015 04:27 PM

19 of 72 Tuesday 29 December 2015 04:27 PM

20 of 72 Tuesday 29 December 2015 04:27 PM

21 of 72 Tuesday 29 December 2015 04:27 PM

22 of 72 Tuesday 29 December 2015 04:27 PM

23 of 72 Tuesday 29 December 2015 04:27 PM

24 of 72 Tuesday 29 December 2015 04:27 PM

25 of 72 Tuesday 29 December 2015 04:27 PM

26 of 72 Tuesday 29 December 2015 04:27 PM

SESSION L6: Magnetically Doped ZnO

27 of 72 Tuesday 29 December 2015 04:27 PM

28 of 72 Tuesday 29 December 2015 04:27 PM

29 of 72 Tuesday 29 December 2015 04:27 PM

30 of 72 Tuesday 29 December 2015 04:27 PM

SESSION L7: P-type Doping

31 of 72 Tuesday 29 December 2015 04:27 PM

32 of 72 Tuesday 29 December 2015 04:27 PM

33 of 72 Tuesday 29 December 2015 04:27 PM

SESSION L8: Poster Session

34 of 72 Tuesday 29 December 2015 04:27 PM

35 of 72 Tuesday 29 December 2015 04:27 PM

36 of 72 Tuesday 29 December 2015 04:27 PM

37 of 72 Tuesday 29 December 2015 04:27 PM

38 of 72 Tuesday 29 December 2015 04:27 PM

39 of 72 Tuesday 29 December 2015 04:27 PM

40 of 72 Tuesday 29 December 2015 04:27 PM

2Coordination Engineering Labortory, Kogakuin University, Tokyo, Japan.

41 of 72 Tuesday 29 December 2015 04:27 PM

42 of 72 Tuesday 29 December 2015 04:27 PM

University of Nebraska, Lincoln, Nebraska; 3Leibniz-Institut fr Oberflchenmodifizierung e.V., Leipzig, Germany.

43 of 72 Tuesday 29 December 2015 04:27 PM

SESSION L9: Epitaxial Growth of ZnO

44 of 72 Tuesday 29 December 2015 04:27 PM

45 of 72 Tuesday 29 December 2015 04:27 PM

46 of 72 Tuesday 29 December 2015 04:27 PM