Journal of The Electrochemical Society, 153 共1兲 A1-A4 共2006兲 A1

0013-4651/2005/153共1兲/A1/4/$20.00 © The Electrochemical Society, Inc.

Effects of Bulk Photoconductivity on Photocurrent Action

Spectra of Molecular p-n Heterojunction Solar Cells
Oleg Shevaleevskiy,a,b,z Liudmila Larina,b Seung Yeop Myong,a and
Koeng Su Lima
a
Department of Electrical Engineering and Computer Science, Korea Advanced Institute of Science and
Technology, Daejeon 305-701, Korea
b
Institute of Biochemical Physics RAS, 119991 Moscow, Russia

We have investigated how bulk photoconductivity influences the photovoltaic parameters of zincphthalocyanine-fullerene
共ZnPc/C60兲 p-n heterojunction solar cells. The results indicate that the photocurrent action spectrum of a cell depends strongly on
the photoconductivity and spectral characteristics of each component material. We therefore propose a model that simulates the
action spectra of the short-circuit photocurrent in the molecular organic solar cells, and our model is based on the assumption that
the photocurrent action spectrum depends on the bulk layer photoconductivity.
© 2005 The Electrochemical Society. 关DOI: 10.1149/1.2126576兴 All rights reserved.

Manuscript submitted February 26, 2005; revised manuscript received June 30, 2005. Available electronically November 2, 2005.

Molecular organic photovoltaic devices based on p-type semi- Experimental

conductors, such as metal-phthalocyanines 共MPc where M = Zn,
Cu, TiO, or H2兲, have recently attracted great interest due to the
appearance of n-type fullerenes 共C60兲, which form photosensitive
p-n junctions with MPc.1-4 The efficiency of organic solar cells is
still lower compared to traditional solid-state devices.5 Initially, a
relatively large power conversion efficiency for a p-n junction or-
ganic photovoltaic cell based on p-type CuPc and n-type perylene
derivative was realized by Tang.6 Fullerenes were successfully ap-
plied in different constructions of molecular photovoltaic cells
for fabricating p-n heterojunctions,1,2 improvement of organic cell
performance by doping,7,8 and for manufacturing plastic-type solar
cells.9 Recently, a record efficiency of around 4% was reported
for p-i-n multilayer devices that used ZnPc and C60 modified mo-
lecular layers.10 However, the power conversion efficiency of any
molecular photovoltaic device is limited by poor charge carrier
mobility 共⬍1 cm2 /V s兲 and small exciton diffusion length 共LD
⬇ 10 nm兲 in organic layers.11,12 In condensed phthalocyanine lay-
ers, exciton diffusion length may depend on the fabrication condi-
tions, and the reported LD values vary from 10 to 30 nm for ZnPc7,13
and from 12 to 60 nm for CuPc films.14,15 The photoexcitations
created in the bulk of a thick molecular layer do not reach the
interface region of the p-n junction and therefore do not contribute
to the photocurrent of the device. Thus, the carrier production re-
gions are limited to the dimension of space-charge 共depletion兲 layers
that only extend over the film interfaces. Due to this the light illu-
mination produces two kinds of photoeffects: photoconductivity in
the bulk of the layer that decreases the cell serious resistance, and a
photovoltaic effect in the interface region resulting in the generation
of the photocurrent. Since Simon and Andre16 reported significant
information about photogenerated carriers at the p-n heterojunction,
various models have been proposed that simulated the photocurrent
of organic molecular solar cells.17-20 However, the role of bulk layer
photoconductivity is still being debated.
We assume that the spectral dependence of series resistance in
molecular organic cells should not be neglected because of its influ-
ence on the cell photocurrent. Normally, the thickness of a bulk
layer in organic solar cells several times exceeds the dimension of a
depletion layer. Hence, the series resistance can severely limit the
shape of photocurrent action spectrum and the conversion efficiency.
To prove this supposition, we report on the performance of fabri-
cated n-C60 /p-ZnPc solar cells. We also propose a theoretical model
that describes the behavior of photocurrent action spectra and effects
of the bulk layer photoconductivity.
z
E-mail: O_Chevale@Yahoo.com
Thin molecular layers were vacuum sublimated at a pressure of
10−6 Torr from resistively heated quartz crucibles using conven-
tional ZnPc and C60 共99.9% purity兲 powder purchased from Kodak
and MER Corp., respectively. Before the deposition, ZnPc powder
was predominantly recrystallized under argon ambient by train sub-
limation.
Figure 1 shows the arrangement of the fabricated p-n hetero-
junction solar cell produced by successive evaporation of C60
and ZnPc. First, we deposited n-C60 layers on Corning glass
substrates coated with indium tin oxide 共ITO兲 transparent front
electrodes. After deposition, the samples were kept under an ultra-
high vacuum of 10−7 Torr during 24 h to reduce the initial oxy-
gen content. Then, without exposure to air, the p-ZnPc layers were
successively evaporated. Finally, the coplanar gold 共Au兲 back
contacts with a thickness of 50nm and an area of 2 ⫻ 10 mm
were deposited on top of the device. Thus, we fabricated photo-
voltaic cells with a structure of ITO/n-C60 /p-ZnPc/Au. To provide
a comparative study of organic layer thickness on cell
performance, we have prepared three types of cells with the follow-
ing parameters: 共A兲 n-C60共80 nm兲/p-ZnPc 共120 nm兲, 共B兲 n-
C60共400 nm兲/p-ZnPc共400 nm兲, and 共C兲 n-C60共800 nm兲/p-
ZnPc共800 nm兲. With the same deposition conditions, single layers
of n-C60 and p-ZnPc were prepared on ITO substrates for the UV-
visible 共UV-vis兲 optical spectra and photoconductivity measure-
ments. Dark and photocurrent of single layers have been measured
at constant dc electrical field 共⬃105 V/cm兲 in sandwich cell con-
figuration between ITO front and Au back electrodes. Action spectra
of short-circuit photocurrent for C60 /ZnPc cells were recorded under
illumination from the ITO side. While measuring the photocurrent,
we appropriately filtered and calibrated irradiation from a 500W
xenon lamp through a monochromator to obtain a constant incident
photon intensity 共 PIN兲 of 10 ␮W/cm2 in the wavelengths of 360–
850 nm. A Shimadzu UV-3101 PC spectrophotometer was used to
record the optical absorption spectra. The current density–voltage
共J-V兲 characteristics were measured under illumination of a
15 mW/cm2 halogen lamp using an HP 1415B semiconductor pa-
rameter analyzer.
Results
The dark conductivity of the n-C60 layer 共␴D1兲 was measured
just after its deposition to prevent the oxygen doping, while the
p-ZnPc layer was exposed to air to induce the oxygen doping before
we measure its dark conductivity 共␴D2兲. Although the oxygen dop-
ing significantly reduces the ␴D1 value, it was reported that the
doping process lasts longer than the time needed to take our
measurements.21 In contrast, a short exposure to air initiates a
 JOURNAL OF APPLIED PHYSICS 98, 054311 共2006兲 共兲

Charge transport in hydrogenated boron-doped nanocrystalline

silicon-silicon carbide alloys
Seung Yeop Myong,a兲 Oleg Shevaleevskiy, and Koeng Su Lim
Department of Electrical Engineering and Computer Science, Korea Advanced Institute of Science and
Technology (KAIST), 373-1 Guseong-dong, Yuseong-gu, Daejeon 305-701, Republic of Korea
Shinsuke Miyajima and Makoto Konagai
Department of Physical Electronics, Tokyo Institute of Technology (TIT), 2-12-1 O-okayama, Meguro-ku,
Tokyo 152-8552, Japan
共Received 25 January 2005; accepted 28 July 2005; published online 9 September 2005兲
We have investigated the carrier transport mechanism of mixed-phased hydrogenated boron-doped
nanocrystalline silicon–silicon carbide alloy 共p-nc-Si-SiC: H兲 films. From temperature-dependent
dark conductivity measurements, we found that the p-nc-Si-SiC: H alloys have two different carrier
transport mechanisms: one is the thermally activated hopping between neighboring crystallites near
the room-temperature region and the other is the band tail hopping below 150 K. © 2005 American
Institute of Physics. 关DOI: 10.1063/1.2037871兴

I. INTRODUCTION p-a-SiC: H window layer.6 Due to the natural hydrogen treat-

Thin films of hydrogenated amorphous silicon 共a-
Si: H兲 and silicon carbide 共a-SiC: H兲 have attracted consid-
erable research interest mainly due to their potential applica-
tions in electronics, optical devices, and window layers in
photovoltaic thin-film solar cells. To achieve a high-
efficiency thin-film solar cell, a window layer should have a
high electrical conductivity and a wide optical band gap. Due
to the incorporation of carbon atoms, a-SiC: H has a wider
band gap than a-Si: H. However, the incorporated carbon
atoms limit the electrical conductivity of a-SiC: H.
We can improve the electrical conductivity of a-SiC: H
by an impurity doping. However, the impurity doping re-
duces the optical band gap of films. In recent years, one
promising way to incorporate a wide band gap and a high
conductivity has been proposed by producing the mixed-
phase structure consisting of microcrystalline 共␮c − 兲 or
nanocrystalline 共nc-兲 Si grains embedded in a-Si: H network.
We firstly reported on the preparation of hydrogenated boron
共B兲-doped nc-Si–SiC:H 共p-nc-Si− SiC: H兲 alloy films con-
taining nc-Si grains embedded in a-SiC: H matrix via the
photodecomposition of C2H4.1 Its optical transmittance is
mainly governed by the a-SiC: H matrix, while nc-Si grains
are responsible for the effective transport of charge carriers.2
This p-nc-Si− SiC: H alloy has a higher electrical con-
ductivity, optical transmittivity, carrier mobility, and doping
efficiency than the conventional undiluted p-a-SiC: H. Based
on the deposition of p-nc-Si− SiC: H alloy,1–4 H2-diluted
p-a-SiC: H buffer layers of p-i-n-type a-Si: H or protocrys-
talline silicon 共pc-Si:H兲 solar cells were prepared.5–8 We
found that the natural hydrogen treatment—etching the de-
fective undiluted p-a-SiC: H window layer and improving
order in the window layer—takes place just before the highly
conductive, low absorption, and well-ordered H2-diluted
p-a-SiC: H buffer layer deposition onto the undiluted
FAX: ⫹82-42-869-8530; electronic mail: myongsy@kaist.ac.kr
a兲
ment, we can effectively reduce the recombination at the p / i
interface, resulting in dramatic improvement of all solar cell
parameters.
The B doping of nc-Si–SiC:H alloys considerably en-
hances their dark conductivity 共␴D兲. At the same time, the
doping level may influence the degree of the structural dis-
order, film crystallinity, and defect density distribution. Vari-
ous carrier transport mechanisms have been reported for a-
Si: H,9–11 ␮c-Si: H,12,13 and nc-C:H films.14 In this paper, we
investigated the electric transport of p-nc-Si− SiC: H alloys.
II. EXPERIMENT
Films were deposited by the Hg-sensitized photoassisted
chemical-vapor deposition 共photo-CVD兲 technique using the
mixture of SiH4, H2, B2H6, and C2H4 reactant gases. A low-
pressure Hg lamp with resonance lines of 184.9 and 253.7nm
was used as an UV light source to dissociate the mixture
gases. In all depositions, the hydrogen dilution ratio
共H2 / SiH4兲, ethylene gas flow ratio 共C2H4 / SiH4兲, chamber
pressure, substrate temperature, and Hg bath temperature
were kept at 20, 0.07, 0.46 Torr, at 250 and 20 °C, respec-
tively. We deposited about 150–170-nm-thick films on Corn-
ing 7059 glass substrates with varying boron doping ratio
共B2H6 / SiH4兲 from 1000 to 8000 ppm.
We performed Raman spectroscopy and dynamic force
microscopy 共DFM兲 to inspect the structural change of the
films. Raman spectra were measured by using JASCO Corp.,
NRS-1000 system. The wavelength of Ar laser is 532 nm.
We used phase-modulated spectroscopic ellipsometer 共Jobin
Yvon, UNISEL兲 in order to measure the film thickness and
absorption coefficient. We measured the direct current 共dc兲
␴D via coplanar Al contacts 共gap:1 mm兲 formed by thermal
evaporation. The temperature dependence of ␴D was mea-
sured using a closed-cycle He cryostat with a proportional-
integral-derivative 共PID兲 temperature controller. Since ␴D
measurements performed in a coplanar configuration are sen-
sitive to the presence of surface adsorbates,15 we maintained

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 JOURNAL OF APPLIED PHYSICS 99, 033520 共2006兲

A cubic phase of C3N4 synthesized in the diamond-anvil cell

L. C. Minga兲 and P. Zinin
Hawaii Institute of Geophysics and Planetology, University of Hawaii at Manoa, Honolulu, Hawaii, 96822
Y. Meng
HPCAT, APS, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439
X. R. Liu and S. M. Hong
Laboratory of High Pressure Physics, Southwest Jiaotong University, Chengdu, Sichuan, China 610031
Y. Xie
Structure Research Laboratory and Department of Chemistry,
University of Science and Technology of China, Hefei, Anhui, China 230026
共Received 1 September 2005; accepted 15 December 2005; published online 14 February 2006兲
A cubic phase of C3N4 was discovered. It was recovered at ambient conditions from the
graphite-like C3N4 共g-C3N4兲 phase subjected to pressures between 21 and 38 GPa in a
diamond-anvil cell, laser heated to temperatures between 1600 and 3000 K. The x-ray-diffraction
data of the phase are best explained by a cubic unit cell with the lattice parameters a
= 3.878± 0.001 Å. With an assumption of 1 molecule/ unit cell 共Z = 1兲 for the cubic phase, the molar
volume of the cubic phase is 35.126 cm3 / mol and the density is 2.62 g / cm3. The density of the
cubic phase is less than that which was predicted for the high-pressure phases but is 12% denser
than the low-pressure graphitic phase 共␳ = 2.336 g / cm3兲. The cubic phase has not been predicted
theoretically and represents an unknown structure in C3N4. © 2006 American Institute of Physics.
关DOI: 10.1063/1.2168567兴

I. INTRODUCTION II. EXPERIMENTAL METHODS

The prediction by Liu and Cohen1 of the existence of a
␤-C3N4 phase with a bulk modulus and hardness similar to
diamond has fostered significant research efforts to synthe-
size this material 共see review papers2–4兲 Various reports
claim the synthesis of carbon nitride C3N4: however, “none
of the studies provide a comprehensive characterization of a
single phase material.”3 The data on the synthesis of dense
C3N4 phases reported by different authors to date “have yet
to present unambiguous evidence for the crystallization of
carbon nitrides with the proposed structures.”4 It was also
argued from chemical considerations that “extensive network
with C–N single bonding has never been documented and
only very local C–N bonds are known as in amino acids.”5
Recent studies of the phase transformation of the turbo-
stratic carbon nitride 共t-CN兲 under high pressure and tem-
perature showed that at 4.7 GPa, the thermal decomposition
of t-CN starts at 990 K and forms a disordered graphite. With
a pressure increase up to 17.8 GPa, the onset temperature of
the decomposition increases to 1850 K, and the process is
accompanied by the formation of diamond.6 It was con-
cluded that the low-compressibility forms of carbon nitride
could not be obtained in a large volume press at pressures up
to 20 GPa and temperatures up to 2100 K.
In this study, we present evidence for an unquenchable
high-pressure phase at a pressure above 20 GPa and at tem-
perature above 1600 K, which converts into a cubic phase
upon the decompression to ambient conditions.
a兲
Electronic mail: ming@soest.hawaii.edu
The pressure- and temperature-induced phase transfor-
mation of C3N4 was studied up to 38 GPa using laser-heated
diamond-anvil cells and angle-dispersive powder x-ray dif-
fraction 共ADXD兲 at Advanced Photon Source 共APS兲, Ar-
gonne National Laboratory. A Mao-Bell-type diamond anvil
cell 共DAC兲 and a symmetrical DAC were used in this study.
Each cell has a pair of type I brilliant-cut diamond anvils of
0.25–0.3 carat and a culet of 350–500 ␮m. A stainless-steel,
fully hardened 250-␮m-thick gasket was first indented to
40 ␮m, and then a hole of 90–130 ␮m in diameter was
drilled, which served as the sample chamber. The experi-
ments were performed using a monochromatic synchrotron-
radiation source 共␭ = 0.3876 or 0.46047 Å兲 at the 16-IDB
beamline of the High Pressure Collaborative Access Team
共HPCAT兲 facility at the Advanced Photon Source 共APS兲. The
monochromatic x-ray beam was focused down to 30
⫻ 30 ␮m2, using multilayer bimorph mirrors in a
Kickpatrick-Baez configuration, similar to that described ear-
lier for the GeoSoilEnviroConsortium for Advanced Radia-
tion Studies 共GSECARS兲 facility.7 Diffraction images were
recorded for 30–300 s with an on-line image-plate fast-scan
detector and were integrated and corrected for distortions
using FIT2D software.8 The distance between the sample and
the charge-coupled device 共CCD兲 detector was either
347.964 mm 共for ␭ = 0.38760 Å兲 or 347.818 mm 共for ␭
= 0.46047 Å兲. Pressure was determined off line by the ruby
fluorescent method and also by the internal NaCl using the
diffraction peak 共200兲 with the established equation of state.9
To achieve high-pressure and high-temperature condi-
tions, the sample in a diamond-anvil cell was heated by a

0021-8979/2006/99共3兲/033520/6/$23.00 99, 033520-1 © 2006 American Institute of Physics

 Diamond & Related Materials 15 (2006) 1405 – 1411
www.elsevier.com/locate/diamond

Combined FIB technique with acoustic microscopy to detect steel–DLC

interface defects
Karin Bernland a, Bernd Köhler a, Pavel V. Zinin b,*, Dong Fei c, Douglas A. Rebinsky c
a
Fraunhofer IZFP-D, 01326 Dresden, Germany
b
School of Ocean and Earth Science and Technology, University of Hawaii, Honolulu, HI 96822, USA
c
Technical Center, Caterpillar Inc., Peoria, IL 61656, USA

Received 18 March 2005; received in revised form 1 September 2005; accepted 25 October 2005
Available online 4 January 2006

Abstract

In this work, focused ion beam (FIB) technique was employed to characterize subsurface defects in chromium-containing DLC (Cr-DLC)
coatings. Subsurface defects as small as one micron were successfully detected in a flat Cr-DLC coated steel coupon by scanning acoustic
microscopy (SAM). The nature of the subsurface defects in the coating was investigated by repeated FIB milling and a scanning electron
microscopy (SEM) imaging technique where element analysis was done by Energy Dispersive X-ray spectroscopy (EDX). It has been found that
defects are located mostly at the DLC steel interface. A model for the bump-like defects is proposed based on the SAM, EDX and FIB
measurements. Model is that of a dilamination/void between Cr layer and steel substrate. The existence of these defects at the interface leads to the
defects visible on the surface of the DLC coating; bumps or pits which are larger in diameter compared to the subsurface defects.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Acoustic microscopy; Focused ion beam; Subsurface defects; Diamond-like carbon

1. Introduction microscopy (SEM) can give this information, both techniques

DLC (diamond-like-carbon) coatings have been widely used
in tribological applications because of their distinct tribological
properties such as high wear, pitting and scuffing resistance,
and low friction [1 –6]. DLC coatings are typically produced
using physical vapor deposition (PVD) processes. Defects
including voids, scratches, flaking, cracks, and macroparticles
often occur in the coating, both at and below the surface. These
defects can adversely affect the performance of the coating,
leading to unpredicted premature failure of the coated
component. To our knowledge defects at the DCL coating/
steel interface have not been investigated.
Acoustic microscopy studies conducted with a high-
frequency (1 GHz) acoustic microscope showed that most of
the defects are located 2 –3 Am below the top surface of the
coatings [7,8]. However, acoustic microscopy cannot deter-
mine the exact size, depth, and composition of the defects.
While conventional optical microscopy or scanning electron
* Corresponding author.
E-mail address: zinin@soest.hawaii.edu (P.V. Zinin).
0925-9635/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.diamond.2005.10.070
have the limitation in that only surface defects can be
examined. The purpose of this paper is to characterize the
subsurface defects (location of the defect and its composition)
in chromium-containing DLC (Cr-DLC) coated components by
using a focused ion beam technique FIB/SEM imaging system
and scanning acoustic microscopy (SAM). An ion sputtering
process was applied from above the specimen to do fine
milling of the coating. The specimen was then imaged with
high resolution by SEM. With repeated sputtering and imaging,
the 3-D microstructure of the coating was examined without
removing or repositioning the specimen. We demonstrated that
a combination of the FIB/SEM and SAM techniques is a
powerful tool for studying defects at the DLC/steel interface.
2. Deposition process
The Cr-DLC coating was produced in Caterpillar’s in-house
closed-field unbalanced magnetron sputtering system
(CFUMS). The CFUMS is a 1/4 industrial scale chamber.
The system incorporates two opposing rectangular cathodes
each having a Cr target with a purity of 99.95%. Argon (Ar) is
 Diamond & Related Materials 15 (2006) 1405 – 1411
www.elsevier.com/locate/diamond

Combined FIB technique with acoustic microscopy to detect steel–DLC

interface defects
Karin Bernland a, Bernd Köhler a, Pavel V. Zinin b,*, Dong Fei c, Douglas A. Rebinsky c
a
Fraunhofer IZFP-D, 01326 Dresden, Germany
b
School of Ocean and Earth Science and Technology, University of Hawaii, Honolulu, HI 96822, USA
c
Technical Center, Caterpillar Inc., Peoria, IL 61656, USA

Received 18 March 2005; received in revised form 1 September 2005; accepted 25 October 2005
Available online 4 January 2006

Abstract

In this work, focused ion beam (FIB) technique was employed to characterize subsurface defects in chromium-containing DLC (Cr-DLC)
coatings. Subsurface defects as small as one micron were successfully detected in a flat Cr-DLC coated steel coupon by scanning acoustic
microscopy (SAM). The nature of the subsurface defects in the coating was investigated by repeated FIB milling and a scanning electron
microscopy (SEM) imaging technique where element analysis was done by Energy Dispersive X-ray spectroscopy (EDX). It has been found that
defects are located mostly at the DLC steel interface. A model for the bump-like defects is proposed based on the SAM, EDX and FIB
measurements. Model is that of a dilamination/void between Cr layer and steel substrate. The existence of these defects at the interface leads to the
defects visible on the surface of the DLC coating; bumps or pits which are larger in diameter compared to the subsurface defects.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Acoustic microscopy; Focused ion beam; Subsurface defects; Diamond-like carbon

1. Introduction microscopy (SEM) can give this information, both techniques

DLC (diamond-like-carbon) coatings have been widely used
in tribological applications because of their distinct tribological
properties such as high wear, pitting and scuffing resistance,
and low friction [1 –6]. DLC coatings are typically produced
using physical vapor deposition (PVD) processes. Defects
including voids, scratches, flaking, cracks, and macroparticles
often occur in the coating, both at and below the surface. These
defects can adversely affect the performance of the coating,
leading to unpredicted premature failure of the coated
component. To our knowledge defects at the DCL coating/
steel interface have not been investigated.
Acoustic microscopy studies conducted with a high-
frequency (1 GHz) acoustic microscope showed that most of
the defects are located 2 –3 Am below the top surface of the
coatings [7,8]. However, acoustic microscopy cannot deter-
mine the exact size, depth, and composition of the defects.
While conventional optical microscopy or scanning electron
* Corresponding author.
E-mail address: zinin@soest.hawaii.edu (P.V. Zinin).
0925-9635/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.diamond.2005.10.070
have the limitation in that only surface defects can be
examined. The purpose of this paper is to characterize the
subsurface defects (location of the defect and its composition)
in chromium-containing DLC (Cr-DLC) coated components by
using a focused ion beam technique FIB/SEM imaging system
and scanning acoustic microscopy (SAM). An ion sputtering
process was applied from above the specimen to do fine
milling of the coating. The specimen was then imaged with
high resolution by SEM. With repeated sputtering and imaging,
the 3-D microstructure of the coating was examined without
removing or repositioning the specimen. We demonstrated that
a combination of the FIB/SEM and SAM techniques is a
powerful tool for studying defects at the DLC/steel interface.
2. Deposition process
The Cr-DLC coating was produced in Caterpillar’s in-house
closed-field unbalanced magnetron sputtering system
(CFUMS). The CFUMS is a 1/4 industrial scale chamber.
The system incorporates two opposing rectangular cathodes
each having a Cr target with a purity of 99.95%. Argon (Ar) is
ISSN 0020-1685, Inorganic Materials, 2006, Vol. 42, No. 5, pp. 528–531. © Pleiades Publishing, Inc., 2006.
Original Russian Text © A.V. Shlyakhtina, I.V. Kolbanev, O.K. Karyagina, 2006, published in Neorganicheskie Materialy, 2006, Vol. 42, No. 5, pp. 587–590.

Effect of Heterovalent Substitution

on the Electrical Conductivity of (Yb1 – xMx)2Ti2O7
(M = Ca, Ba; x = 0, 0.05, 0.1)
A. V. Shlyakhtinaa, I. V. Kolbaneva, O. K. Karyaginab
aSemenov Institute of Chemical Physics, Russian Academy of Sciences,
ul. Kosygina 4, Moscow, 119991 Russia
b Emanuel Institute of Biochemical Physics, Russian Academy of Sciences,
ul. Kosygina 4, Moscow, 119991 Russia
e-mail: annash@chph.ras.ru
Received December 8, 2005

Abstract—(Yb1 – xëax)2Ti2O7 and (Yb1 – xBax)2Ti2O7 (x = 0, 0.05, 0.1) have been synthesized using hydroxide
coprecipitation and mechanical activation of oxide mixtures, and their electrical conductivity has been mea-
sured from 350 to 1000°C. The pyrochlore titanate (Yb0.9Ca0.1)2Ti2O7 synthesized at 1400°C from a mechani-
cally activated oxide mixture has the highest conductivity, ~0.1 S/cm at 1000°C, among the oxygen-ion-con-
ducting pyrochlores studied so far. The (Yb0.95Ca0.05)2Ti2O7 and (Yb0.9Ca0.1)2Ti2O7 samples prepared by react-
ing coprecipitated powder mixtures at 1400°C have a lower conductivity, as do the (Yb1 – xBax)2Ti2O7 (x = 0.05,
0.1) samples prepared using mechanical activation.
DOI: 10.1134/S0020168506050141

INTRODUCTION In this paper, we report the synthesis of

The (Gd1 – xCax)2Ti2O7 (x = 0.1) pyrochlore titanate
was reported to possess high ionic conductivity, ~5 ×
10–2 S/cm at 1000°C [1]. Gd2(Ti1 – xZrx)2O7 disordered
pyrochlores (1000°C ionic conductivity of ~1 ×
10−2 S/cm) [2, 3] and Gd 2((GaSb)1 − xZrx)2O7 [4] were
also shown to be good high-temperature oxygen-ion
conductors. Recently, the family of pyrochlore-like titan-
ates with high ionic conductivity has been extended
owing to the synthesis of new materials with the general
stoichiometry Ln2 + xTi2 – xO7 – x/2 (Ln = Dy–Lu, x =
0−0.44) (LANTIOX) [5–11]. Among these materials,
the highest ionic conductivity, ~5 × 10–3 to 10–2 S/cm at
740°C, is offered by Ln2Ti2O7 and Ln2 + xTi2 – xO7 – x/2
with x = 0.096 synthesized at 1600–1670°C [5–11].
The high-temperature ionic conductivity of Yb2Ti2O7
(~5 × 10–3 to 10–2 S/cm at 740°C) prepared through
mechanical activation or hydroxide coprecipitation fol-
lowed by firing at 1600°C was studied in detail by
Shlyakhtina et al. [5–7] and Abrantes et al. [10, 11].
As reported by Kramer and Tuller [1], heterovalent
substitution of calcium for gadolinium in the pyro-
chlore titanate Gd2Ti2O7 ((Gd1 – xCax)2Ti2O7 , x = 0.1)
increases its ionic conductivity by three orders of mag-
nitude: from 2 × 10–5 to 2 × 10–2 S/cm at 740°C. It is
reasonable to expect that calcium doping will also
cause a significant increase in the ionic conductivity of
Yb2Ti2O7 .
(Yb1 − xCax)2Ti2O7 and (Yb1 – xBax)2Ti2O7 (x = 0, 0.05,
0.1) samples using coprecipitation or mechanical acti-
vation and their electrical conductivity.
EXPERIMENTAL
(Yb1 – xCax)2Ti2O7 (x = 0.05, 0.1) samples were pre-
pared via coprecipitation of Yb(III), Ca(II), and Ti(IV)
hydroxides with NH4OH and (NH4)2CO3 at pH 10.4
from appropriate chloride solutions. A sulfate test for
Ca2+ in the mother solution showed that all of the cal-
cium was precipitated. The precipitate was separated
from the solution by centrifugation and then washed
several times with water until free of chloride ions.
Next, the precipitate was dried at 105°C for 24 h. After
prefiring at 650°C for 2 h, the resultant powder was
pressed at 10 MPa into disks 10 mm in diameter and
2 mm in thickness, which were sintered at 1400°C for
4 h and then furnace-cooled.
We also used mechanical activation of Yb2O3 +
TiO2 , CaO + Yb2O3 + TiO2 , and Yb2O3 + TiO2 + BaO2
mixtures in an eccentric vibratory mill [12] to prepare
Yb2Ti2O7, (Yb1 – xCax)2Ti2O7 , and (Yb1 – xBax)2Ti2O7 (x =
0.05, 0.1) samples. It is well known that mechanical
activation of starting mixtures allows one to vary the
structural perfection and, accordingly, the conductivity
of the resulting mixed oxides [13, 14]. After mechani-
cal activation, the mixtures were pressed at 26 MPa into

528
ISSN 0020-1685, Inorganic Materials, 2006, Vol. 42, No. 5, pp. 528–531. © Pleiades Publishing, Inc., 2006.
Original Russian Text © A.V. Shlyakhtina, I.V. Kolbanev, O.K. Karyagina, 2006, published in Neorganicheskie Materialy, 2006, Vol. 42, No. 5, pp. 587–590.

Effect of Heterovalent Substitution

on the Electrical Conductivity of (Yb1 – xMx)2Ti2O7
(M = Ca, Ba; x = 0, 0.05, 0.1)
A. V. Shlyakhtinaa, I. V. Kolbaneva, O. K. Karyaginab
aSemenov Institute of Chemical Physics, Russian Academy of Sciences,
ul. Kosygina 4, Moscow, 119991 Russia
b Emanuel Institute of Biochemical Physics, Russian Academy of Sciences,
ul. Kosygina 4, Moscow, 119991 Russia
e-mail: annash@chph.ras.ru
Received December 8, 2005

Abstract—(Yb1 – xëax)2Ti2O7 and (Yb1 – xBax)2Ti2O7 (x = 0, 0.05, 0.1) have been synthesized using hydroxide
coprecipitation and mechanical activation of oxide mixtures, and their electrical conductivity has been mea-
sured from 350 to 1000°C. The pyrochlore titanate (Yb0.9Ca0.1)2Ti2O7 synthesized at 1400°C from a mechani-
cally activated oxide mixture has the highest conductivity, ~0.1 S/cm at 1000°C, among the oxygen-ion-con-
ducting pyrochlores studied so far. The (Yb0.95Ca0.05)2Ti2O7 and (Yb0.9Ca0.1)2Ti2O7 samples prepared by react-
ing coprecipitated powder mixtures at 1400°C have a lower conductivity, as do the (Yb1 – xBax)2Ti2O7 (x = 0.05,
0.1) samples prepared using mechanical activation.
DOI: 10.1134/S0020168506050141

INTRODUCTION In this paper, we report the synthesis of

The (Gd1 – xCax)2Ti2O7 (x = 0.1) pyrochlore titanate
was reported to possess high ionic conductivity, ~5 ×
10–2 S/cm at 1000°C [1]. Gd2(Ti1 – xZrx)2O7 disordered
pyrochlores (1000°C ionic conductivity of ~1 ×
10−2 S/cm) [2, 3] and Gd 2((GaSb)1 − xZrx)2O7 [4] were
also shown to be good high-temperature oxygen-ion
conductors. Recently, the family of pyrochlore-like titan-
ates with high ionic conductivity has been extended
owing to the synthesis of new materials with the general
stoichiometry Ln2 + xTi2 – xO7 – x/2 (Ln = Dy–Lu, x =
0−0.44) (LANTIOX) [5–11]. Among these materials,
the highest ionic conductivity, ~5 × 10–3 to 10–2 S/cm at
740°C, is offered by Ln2Ti2O7 and Ln2 + xTi2 – xO7 – x/2
with x = 0.096 synthesized at 1600–1670°C [5–11].
The high-temperature ionic conductivity of Yb2Ti2O7
(~5 × 10–3 to 10–2 S/cm at 740°C) prepared through
mechanical activation or hydroxide coprecipitation fol-
lowed by firing at 1600°C was studied in detail by
Shlyakhtina et al. [5–7] and Abrantes et al. [10, 11].
As reported by Kramer and Tuller [1], heterovalent
substitution of calcium for gadolinium in the pyro-
chlore titanate Gd2Ti2O7 ((Gd1 – xCax)2Ti2O7 , x = 0.1)
increases its ionic conductivity by three orders of mag-
nitude: from 2 × 10–5 to 2 × 10–2 S/cm at 740°C. It is
reasonable to expect that calcium doping will also
cause a significant increase in the ionic conductivity of
Yb2Ti2O7 .
(Yb1 − xCax)2Ti2O7 and (Yb1 – xBax)2Ti2O7 (x = 0, 0.05,
0.1) samples using coprecipitation or mechanical acti-
vation and their electrical conductivity.
EXPERIMENTAL
(Yb1 – xCax)2Ti2O7 (x = 0.05, 0.1) samples were pre-
pared via coprecipitation of Yb(III), Ca(II), and Ti(IV)
hydroxides with NH4OH and (NH4)2CO3 at pH 10.4
from appropriate chloride solutions. A sulfate test for
Ca2+ in the mother solution showed that all of the cal-
cium was precipitated. The precipitate was separated
from the solution by centrifugation and then washed
several times with water until free of chloride ions.
Next, the precipitate was dried at 105°C for 24 h. After
prefiring at 650°C for 2 h, the resultant powder was
pressed at 10 MPa into disks 10 mm in diameter and
2 mm in thickness, which were sintered at 1400°C for
4 h and then furnace-cooled.
We also used mechanical activation of Yb2O3 +
TiO2 , CaO + Yb2O3 + TiO2 , and Yb2O3 + TiO2 + BaO2
mixtures in an eccentric vibratory mill [12] to prepare
Yb2Ti2O7, (Yb1 – xCax)2Ti2O7 , and (Yb1 – xBax)2Ti2O7 (x =
0.05, 0.1) samples. It is well known that mechanical
activation of starting mixtures allows one to vary the
structural perfection and, accordingly, the conductivity
of the resulting mixed oxides [13, 14]. After mechani-
cal activation, the mixtures were pressed at 26 MPa into

528
 Solid State Ionics 177 (2006) 1149 – 1155
www.elsevier.com/locate/ssi

Synthesis and electrical transport properties of

Lu2+xTi2−xO7−x/2 oxide-ion conductors
A.V. Shlyakhtina a,⁎, J.C.C. Abrantes b , A.V. Levchenko c , A.V. Knot'ko d ,
O.K. Karyagina e , L.G. Shcherbakova a
a
Semenov Institute of Chemical Physics RAS, Kosygina str. 4, 119991 Moscow, Russia
b
Polytechnic Institute of Viana do Castelo, ESTG, 4900 Viana do Castelo, Portugal
c
Institute of Problems of Chemical Physics RAS, Chernogolovka, 142432 Moscow reg., Russia
d
Moscow State University, Chemical Department, Leninskie gory, 119992, Russia
e
Emanuel Institute of Biochemical Physics RAS, Kosygina str. 4, 119991 Moscow, Russia
Received 24 November 2005; accepted 12 April 2006

Abstract

The Lu2+xTi2−xO7−x/2 (x = 0; 0.052; 0.096; 0.286; 0.44; 0.63; 33.3–49 mol% Lu2O3) nanoceramics with partly disordered pyrochlore-type
structure are prepared by sintering freeze-dried powders obtained by a co-precipitation technique with 1600 °C annealing. Similar to pyrochlore-
like compositions in the zirconate system, some of the new titanates are good oxide-ion conductors in air. The new solid-state electrolytes have
oxide-ion conductivity in the interval of 1.0 × 10− 3 – 2.5 × 10− 3 S/cm at 740 °C in air. This value of conductivity is comparable with that of ZrO2/
Y2O3 ceramics. The conductivity of Lu2+xTi2−xO7−x/2 depends on the chemical composition. The highest ionic conductivity is exhibited by nearly
stoichiometric Lu2+xTi2−xO7−x/2 (x = 0.096; 35.5 mol% Lu2O3) material containing ∼ 4.8 at.% LuTi anti-site defects.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Disordered pyrochlore; Anti-site defect; Oxide-ion conductor

1. Introduction
Many solid-state electrolytes have a crystal structure of the
fluorite type, CaF2. Fast oxide- or fluorine-ionic transport in
these structures is usually related to presence of numerous
anionic vacancies. High oxide-ion conductivity, according to
the vacancy mechanism, has been shown to exist in the cubic
phases of ZrO2 (9 mol% Y2O3, Sc2O3), CeO2, ThO2 and δ-
Bi2O3 [1,2].
Double pyrochlore-like oxides Ln2M2O7 (Ln-rare-earth
elements, M = Hf, Zr, Ti) are very close structurally to oxy-
gen-deficient fluorites. Ln2M2O7 often demonstrate a tendency
to order–disorder (pyrochlore–fluorite) transformation at ele-
vated temperatures. Order–disorder phase transitions of this
type are known for Gd2Hf2O7 (TP→F = 2150 °C) and Tb2Hf2O7
⁎ Corresponding author. Tel.: +7 495 137 83 03; fax: +7 495 242 02 53.
E-mail addresses: annash@chph.ras.ru, annashl@inbox.ru
(A.V. Shlyakhtina).
0167-2738/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.ssi.2006.04.022
(TP→F = 2350 °C) [3]. As for the zirconates, the pyrochlore–
fluorite transformations exist in Nd2Zr2O7, Sm2Zr2O7 (TP→F =
2000 °C), and Gd2Zr2O7 (TP→F = 1530 °C) [4]. It was found that
the pyrochlore–fluorite transformations greatly influence their
oxide-ion conduction properties, so the high-temperature modi-
fications possess pronounced ionic conductivity while pure
electronic transport dominate in the low-temperature ones.
It is also known that the structural type of Ln2Zr2O7 (Ln-
rare-earth elements) compounds is clearly defined by the Ln-
element in its formula. The existence of pyrochlore-type struc-
tures was shown for the rare-earth zirconates with Ln = La–Sm,
whereas the zirconates with Ln = Tb–Lu have fluorite-type
structures. Sm2Zr2O7, Eu2Zr2O7, and Gd2Zr2O7 are located near
the phase boundary between the pyrochlores and the fluorites.
One of these compounds (Eu2Zr2O7) is known to possess the
highest oxide-ion conductivity in the series, σ = 8.3 × 10− 3 S/cm
at 800 °C [5].
Among rare-earth titanates, some Ln2Ti2O7 pyrochlore
compositions have already proved their ability for oxide-ion
Materials Science Forum Vols. 514-516 (2006) pp. 422-426
online at http://www.scientific.net
© (2006) Trans Tech Publications, Switzerland

New Oxide-Ion Conductors Ln2+xTi2-xO7-x/2

(Ln = Dy – Lu; x=0.096)

A. V. Shlyakhtina1,a, J.C.C. Abrantes2,b, A.V. Levchenko3, c , S. Yu.

Stefanovich4,d, A.V. Knot,ko4, d , L.L. Larina 5, e
1
Semenov Institute of Chemical Physics RAS; Kosygina str., 4, 119991, Moscow, Russia;
2
Polytechnic Institute of Viana do Castelo, ESTG, 4900 Viana do Castelo, Portugal;
3
Institute of Problems of Chemical Physics RAS; Chernogolovka, Moscow reg., 142432,
Russia;
4
Moscow State University, Chemical Department; Leninskie gory, 119992, Russia;
5
Emanuel Institute of Biochemical Physics RAS; Kosygina str., 4, 119991, Moscow,
Russia
a b c
annash@chph.ras.ru, jabrantes@estg.ipvc.pt, lyuq@icp.ac.ru

Keywords: electrolyte, ionic conductivity, ion blocking, disordered pyrochlore

Abstract. New oxide-ion conductors Ln2+xTi2-xO7-x/2 (Ln = Dy-Lu, x = 0.096; 35.5 mol. % Ln2O3·
64.5 mol.% TiO2)-LANTIOX with a disordered pyrochlore structure are obtained by coprecipitation
with next thermal annealing at 1600ºC. Their ionic conductivity in air at 740°C attains 5·10-3 S/cm
for Ln2.096Ti1.904O6.952 (Ln= Lu, Yb), 10-3 S/cm for Ln2,096Ti1,904O6,952 (Ln=Tm, Er, Ho) and 10-
4
S/cm for Dy2,096Ti1,904O6,952 due to the presence of defects in both the cation and anion sublattices.
The materials contain ~4.8-10.6% LnTi anti-site defects. Ln2.096Ti1.904O6.952 ceramics are shown to
be stable in the temperature range of 1400 to 1700ºC. 1400ºC-samples Ln2+xTi2-xO7-x/2 have lower
ionic conductivity then 1600ºC and 1690ºC samples.

Introduction
Oxygen-ion conductors are the subject of extensive studies as potentially attractive solid electrolytes
for use in high-temperature fuel cells, oxygen sensors for the automobile industry, and oxygen-ion-
conducting membranes for catalytic synthesis [1].
In 2003, a new family of ion-conducting pyrochlores with the general formula Ln2+xTi2-xO7-x/2 (Ln =
Tm-Lu; x = 0-0.63; 33.3-49 mol% Ln2O3) was discovered [2, 3]. The high-temperature phases of
the stoichiometric compounds Ln2Ti2O7 (Ln = Tm-Lu) have a distorted pyrochlore structure, form at
1600-1670ºC, i.e., near their melting points (1670ºC for Lu2Ti2O7, 1690ºC for Yb2Ti2O7 and
Tm2Ti2O7), and at 740ºC have an ionic conductivity of 10-3 to 10-2 S/cm. Ion-conducting
nonstoichiometric Lu2+xTi2-xO7-x/2(x = 0.052-0.63; 34.5- 49 mol% Lu2O3) were sintered in a broader
temperature range : 1400-1700ºC [3].
According to the Ln2O3 –TiO2 (Ln = Tm-Lu) phase diagrams, the compounds Ln2Ti2O7 in these
systems have broad homogeneity ranges, from 33.3 to 50 mol % Ln2O3 [3,4]. The phase diagrams of
the Er2O3 –TiO2, Ho2O3 –TiO2, and Dy2O3 –TiO2 systems differ from those of Ln2O3 –TiO2 with
Ln = Tm-Lu [4], however the pyrochlore phases of Ln2Ti2O7 in the former systems have 33.3-50
mol% homogeneity ranges when Ln is Er or Ho. Dy2O3-TiO2 system has narrower homogeneity
range of pyrochlore Dy2Ti2O7.
In this paper, we report the synthesis and electrical conductivity of Ln2+xTi2-xO7-x/2 (Ln = Dy-Lu, x =
0.096) materials (compositions falling within the homogeneity range of Ln2Ti2O7).
 Solid State Ionics 178 (2007) 59 – 66
www.elsevier.com/locate/ssi

Effect of non-stoichiometry and synthesis temperature on the structure and

conductivity of Ln2+xM2−xO7−x/2 (Ln = Sm–Gd; M = Zr, Hf; x = 0–0.286) ☆
A.V. Shlyakhtina a,⁎, A.V. Knotko b , M.V. Boguslavskii b , S.Yu. Stefanovich b ,
I.V. Kolbanev a , L.L. Larina c , L.G. Shcherbakova a
a
Semenov Institute of Chemical Physics, Russian Academy of Sciences, Kosygina str. 4, 119991 Moscow, Russia
b
Department of Chemistry, Moscow State University, Leninskie gory, 119992 Moscow, Russia
c
Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, Kosygina str. 4, 119991 Moscow, Russia
Received 31 May 2005; received in revised form 19 July 2006; accepted 2 November 2006

Abstract

The effect of non-stoichiometry on the crystal structure and total conductivity of Ln2+xZr2−xO7−x/2 (Ln = Sm–Gd; x = 0–0.286) was investigated.
The intensity of the pyrochlore superlattice reflections from Ln2+xZr2−xO7−x/2 is shown to decrease with increasing Ln concentration. Within the
homogeneity range of the pyrochlore phase of Ln2+xZr2−xO7−x/2 (Ln = Sm–Gd), the activation energy of high-temperature conduction in samples
prepared by 1600 °C sintering of mechanically activated oxide mixtures (Ln2O3 and ZrO2) is ∼ 0.87–1.04 eV. The highest conductivity among the
Ln2+xZr2−xO7−x/2 (Ln = Sm–Gd) materials is offered by stoichiometric Ln2Zr2O7 samples with a pyrochlore structure, which contain 5–8.1% LnZr +
ZrLn anti-structure pairs, except for Gd2Zr2O7 (∼ 22%). The crystal structure of Ln2+xHf2−xO7−x/2 (Ln = Sm–Gd) is investigated after sintering at
1000–1670 °C. The compounds Ln2.096Hf1.904O6.9 (Ln = Eu, Gd) prepared by 1200 °C sintering of mechanically activated oxides (Ln2O3 and HfO2)
undergo a fluorite-type to pyrochlore phase transition above 1200 °C. The conductivity of Gd2Hf2O7 and Sm2.096Hf1.904O6.952 sintered at 1600 °C
seems to be ionic above 780 °C, with an activation energy of 0.77 and 0.82 eV, respectively. In this work, using mechanical activation of starting
mixtures, the conductivity of the Ln2+xHf2−xO7−x/2 (Ln = Sm–Gd) hafnates was raised close to the level of Ln2+xZr2−xO7−x/2 (Ln = Sm–Gd). The
hafnates synthesized by the procedure in question are similar in structural disorder to Ln2+xZr2−xO7−x/2 (Ln = Sm–Gd), and the disorder ensures high
oxygen ion mobility and, accordingly, significant high-temperature conductivity.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Pyrochlore; Fluorite; Oxide-ion conductor; Ceramics

1. Introduction
Pyrochlore oxides have recently been the subject of extensive
studies as potentially attractive dielectric materials [1], catalysts,
solid electrolytes [2,3] and radiation absorbers [4]. The Gd2Zr2O7,
Sm2Zr2O7, Gd2Hf2O7 and Sm2Hf2O7 pyrochlores are known to
undergo a high-temperature (1530–2400 °C) order–disorder
(pyrochlore–fluorite) phase transition, which is, typically accom-
panied by a sharp rise in ionic conductivity [5–8]. Very recently, the
Ln2Ti2O7 (Ln = Tm–Lu) pyrochlores have also been found to
undergo a high-temperature order–disorder transformation [9–11].
☆ systems, ∼ 26–40 mol% Ln2O3 in Ln2±xZr2−±xO7±x/2 (Ln = Sm–
Presented at the 15th Int. Conf. on Solid State Ionics, July 17–22, 2005,
Baden-Baden, Germany.
⁎ Corresponding author.
E-mail address: annashl@inbox.ru (A.V. Shlyakhtina).
0167-2738/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.ssi.2006.11.001
Among the rare-earth titanates, zirconates and hafnates with the
pyrochlore structure, the highest temperatures of the pyrochlore–
fluorite phase transition are observed for the hafnates. The ionic
conductivity of these pyrochlores can be increased by thermal
treatment or appropriate doping. In particular, a high ionic
conductivity was found in Gd2(Ti1−xZrx)2O7 with x ≥ 0.4 [12]
and (Gd1−xCax)2Ti2O7 with x = 0.1 [13].
The Ln2O3–ZrO2, Ln2O3–HfO2 (Ln = Sm–Gd) and Ln2O3–
TiO2 (Ln = Dy–Lu) phase diagrams are similar in that each of
them has a significant range of pyrochlore-like solid solutions.
At 1600 °C, the homogeneity range of the pyrochlore phase is
33.3–49 mol% Ln2O3 in the Ln2+xTi2−xO7−x/2 (Ln = Ho–Lu)
Gd), and ∼ 30–40 mol% Ln2O3 in Ln2+xHf2−xO7−x/2 (Ln = Sm–
Gd). Most of these pyrochlore solid solutions can be regarded as
doped Ln2M2O7 (M = Ti, Zr, Hf) pyrochlores, i.e., solid
 Materials Research Bulletin 42 (2007) 742–752
www.elsevier.com/locate/matresbu

Order–disorder phase transitions and high-temperature oxide ion

conductivity of Er2+xTi2xO7d (x = 0, 0.096)
A.V. Shlyakhtina a,*, A.V. Levchenko b, J.C.C. Abrantes c, V.Yu. Bychkov a,
V.N. Korchak a, V.A. Rassulov d, L.L. Larina e, O.K. Karyagina e, L.G. Shcherbakova a
a
Semenov Institute of Chemical Physics, Russian Academy of Sciences, ul. Kosygina 4, Moscow 119991, Russia
b
Institute of Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow Region 142432, Russia
c
UIDM, ESTG, Instituto Politecnico de Viana do Castelo, Apartado 574, 4901-908 Viana do Castelo, Portugal
d
All-Russia Research Institute of Mineral Resources, Staromonetnyi per. 31, Moscow 119017, Russia
e
Emanuel Institute of Biochemical Physics, Russian Academy of Sciences, ul. Kosygina 4, Moscow 119991, Russia
Received 24 January 2006; received in revised form 9 June 2006; accepted 19 July 2006
Available online 22 August 2006

Abstract
The Er2+xTi2xO7d (x = 0.096; 35.5 mol% Er2O3) solid solution and the stoichiometric pyrochlore-structured compound
Er2Ti2O7 (x = 0; 33.3 mol% Er2O3) are characterized by X-ray diffraction (phase analysis and Rietveld method), thermal analysis
and optical spectroscopy. Both oxides were synthesized by thermal sintering of co-precipitated powders. The synthesis study was
performed in the temperature range 650–1690 8C. The amorphous phase exists below 700 8C. The crystallization of the ordered
pyrochlore phase (P) in the range 800–1000 8C is accompanied by oxygen release. The ordered pyrochlore phase (P) exists in the
range 10001200 8C. Heat-treatment at T  1600 8C leads to the formation of an oxide ion-conducting phase with a distorted
pyrochlore structure (P2) and an ionic conductivity of about 103 S/cm at 740 8C. Complex impedance spectra are used to
separately assess the bulk and grain-boundary conductivity of the samples. At 700 8C and oxygen pressures above 1010 Pa, the
Er2+xTi2xO7d (x = 0, 0.096) samples are purely ionic conductors.
# 2006 Elsevier Ltd. All rights reserved.

Keywords: A. Ceramics; A. Oxides; B. Chemical synthesis; C. Electrochemical measurements; C. Impedance spectroscopy

1. Introduction

A2B2O7 pyrochlore-structured oxides have recently been the subject of intense attention owing to their unusual
electrical, magnetic, dielectric, optical and catalytic properties [1–3], which make them attractive materials for solid
oxide fuel cells, oxygen sensors, thermistors, resistors and switches. High-temperature oxide-ion conduction has been
recently found in Ca-doped Gd2Ti2O7 [4] and disordered Gd2(Ti1xZrx)2O7 and Y2(Ti1xZrx)2O7 pyrochlores [5,6].
Ionic conduction in the zirconate titanates is due to the formation of Frenkel defects in their oxygen sublattice,
accompanied by anti-site cation disordering [7]. Since reducing the difference in ionic radius between the A and B
cations in the pyrochlore structure favours cation disordering, Yb2Ti2O7 and Lu2Ti2O7 are likely to have disordered

* Corresponding author. Tel.: +7 495 137 83 03; fax: +7 495 242 02 53.
E-mail addresses: annashl@inbox.ru, annashl@mail.ru (A.V. Shlyakhtina).

0025-5408/$ – see front matter # 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.materresbull.2006.07.011
 Journal of Microbiological Methods 69 (2007) 353 – 357
www.elsevier.com/locate/jmicmeth

Novel insoluble dye-labeled substrates for screening

inulin-degrading microorganisms
Leonid N. Ten a , Wan-Taek Im b , Zubair Aslam b , Luidmila Larina c , Sung-Taik Lee b,⁎
a
Department of Biology & Medicinal Science, Pai Chai University, 14 Yeonja-1-Gil, Seo-Gu, Daejeon, 302-735, Republic of Korea
b
Department of Biological Sciences, Korea Advanced Institute of Science and Technology, 373-1, Guseong-dong, Yuseong-gu, Daejeon 305-701, Republic of Korea
c
Institute of Biochemical Physics, Kosigin st. 4, 119991 Moscow, Russia
Received 22 August 2006; accepted 6 February 2007
Available online 28 February 2007

Abstract

Inulin hydrogels were used to prepare insoluble colored substrates for screening of inulin-degrading microorganisms. Methycrylated inulin,
synthesized with glycidyl methacrylate, was crossed-linked by free radical polymerization producing an insoluble hydrogel. The inulin hydrogels
were colored with one of three covalent dyes (Reactive blue 4, Reactive orange 14, Reactive red 120). The efficacy of the colored inulin hydrogels
was determined by comparing their performance to insoluble, colored amylose, xylan and HE-cellulose in screening assays. Novel substrates
(alone or in combination with other insoluble colored substrates) were successfully used for screening inulin-degrading microorganisms from
sludge samples. Selected strains were identified using 16S rDNA gene partial sequencing; all of them belong to the genus Bacillus.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Insoluble colored substrates; Inulin; Inulin-degrading microorganisms

1. Introduction internal hydrolysis of this polyfructan by microbial endoinuli-

Microorganisms are the most convenient sources for
production of polysaccharide-degrading enzymes such as
amylase, xylanase and inulinase (Chaudhary et al., 1997;
Pandey et al., 1999). The most widely used plate screening
methods for the detection of polysaccharide- and protein-
degrading microorganisms are based on the use of insoluble
dye-labeled substrates (Caplan and Fahey, 1982; Safarik, 1987;
Lee and Lee, 1997; Ruijssenaars and Hartmans, 2001).
Combinations of insoluble substrates, each individually col-
ored, allow simultaneous screening for multiple polysaccharide-
and/or protein-degrading activities (Ten et al., 2004, 2005).
However, existing methods for synthesis of these substrates are
not acceptable for low molecular weight polysaccharides such
as inulin that consists of linear chains of β-(2,1)-linked
fructofuranose molecules (Van Loo et al., 1995). Inulin is one
of the main sources for production of functional sweeteners;
⁎ Corresponding author. Department of Biological Sciences, Korea Advanced
Institute of Science and Technology, 373-1 Kuseong-Dong, Yuseong-Gu,
Daejeon 305-701, Republic of Korea. Tel: +82 42 869 2617; fax: +82 42 863
5617.
E-mail address: e_stlee@kaist.ac.kr (S.-T. Lee).
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doi:10.1016/j.mimet.2007.02.007
nase yields inulo-oligosaccharides that possess various health-
promoting properties (Yun, 1996; Kim et al., 1997; Sangeetha
et al., 2005). Selection of endoinulinase-producing microorgan-
isms as sources of the enzyme is necessary for industrial
production of functional food ingredients. It can be achieved
straightforwardly at primary screening only by using insoluble
colored inulins. Taking into account the abovementioned
limitations of existing methods a new approach is required to
synthesize these practically important substrates.
The aims of this study are: (i) to design a novel method for
production of insoluble diversely colored inulin hydrogels, and
(ii) to use the resulting substrates for screening of inulin-
degrading microorganisms.
2. Materials and methods
2.1. Chemicals
Reactive orange 14, Reactive red 120, inulin from chicory root,
Cibacron blue 3GA, ammonium persulfate, N,N,N′,N′-tetra-
methylethylenediamine (TMEDA), 4-dimethylaminopyridine,
and N,N-dimethylformamide (DMF, HPLC grade) were