Journal of Physics and Chemistry of Solids 66 (2005) 18681871

www.elsevier.com/locate/jpcs

Fabrication of p-CuGaS2/n-ZnO:Al heterojunction light-emitting

diode grown by metalorganic vapor phase epitaxy and
helicon-wave-excited-plasma sputtering methods
Shigefusa F. Chichibu *,1, Takuya Ohmori, Naoyuki Shibata,
Takahiro Koyama, Takeyoshi Onuma
Institute of Applied Physics and Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba, Ibaraki 305-8573, Japan

Abstract
Greenish-white electroluminescence (EL) was observed from the heterojunction light-emitting diodes (LEDs) composed of p-type (001)
CuGaS2 chalcopyrite semiconductor epilayers and preferentially (0001)-oriented polycrystalline n-type ZnO thin films. The CuGaS2 layers were
grown on a (001) GaP substrate by metalorganic vapor phase epitaxy and the ZnO films were deposited by the surface-damage-free helicon-waveexcited-plasma sputtering method. The n-ZnO/p-CuGaS2 LED structure was designed to enable an electron injection from the n-type wider band
gap material forming a TYPE-I heterojunction. The EL spectra exhibited emission peaks and bands between 1.6 and 2.5 eV, although their higher
energy portions were absorbed by the GaP substrate. Since the spectral lineshape resembled that of the photoluminescence from identical CuGaS2
epilayers, the EL was assigned to originate from p-CuGaS2.
q 2005 Elsevier Ltd. All rights reserved.
Keywords: A. Semiconductors; A. Metalorganic vapor phase epitaxy (MOVPE); B. Chalcopyrites compounds; B. Semiconducting ternary compounds; B. Lightemitting diodes

1. Introduction
The Cu(Al,Ga)(S,Se)2 multinary chalcopyrite (Ch) semiconductors [1,2] are promising candidates for the use in lightemitting devices operating in the visible and ultraviolet spectral
ranges, since the direct bandgap energies (Eg) of them range
from 1.7 eV (CuGaSe2) to 3.5 eV (CuAlS2). Among the Ch
compounds, CuGaS2 is a possible candidate for the use in green
light emitting diodes (LEDs), because its Eg is 2.48 eV at
300 K [3].
The fundamental problem in fabricating pn junction devices
using Cu(Al,Ga)(S,Se)2 compounds is that they exclusively
show p-type conductivity [1,2]. Due to this unipolar problem,
heterostructures combined with (Cd,Zn)(S,Se)-based IIVI
compounds, which tend to show n-type conductivity, have been

* Corresponding author. Tel.: C81 29 853 5022; fax: C81 29 853 5205.
E-mail address: optoelec@bk.tsukuba.ac.jp (S.F. Chichibu).
1
Also at: NICP, ERATO, Japan Science and Technology Agency, 4-1-8
Honcho, Kawaguchi 332-0012, Japan, and Photodynamics Research Center,
Institute of Physical and Chemical Research (RIKEN), Sendai 980-0868,
Japan.

0022-3697/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jpcs.2005.09.007

proposed [1,46] for the LED configuration. However,

intermixing between them, especially the Cu diffusion into
the IIVI layers during the epitaxial growth, and the latticemismatching hindered to obtain good LED performances.
Indeed, the electroluminescence (EL) peak energy of a
CuGaS2/ZnSe diode fabricated by liquid-phase epitaxy was
as low as 1.9 eV [5]. As a result of the elimination of the
intermixing by means of room-temperature vacuum evaporation of Al and ZnS onto the p-CuGaS2 bulk single crystals,
Kobayashi et al. have observed green EL at low temperature
from Al/ZnS/CuGaS2 metalinsulatorsemiconductor (MIS)
diodes [6] and Al/CuGaS2 Schottky diodes [7], in which
electrons have been injected from the Al electrode through the
MIS and Schottky junctions by tunneling. To improve the
electron injection efficiency using a pn junction, Honda et al.
[8] have grown P-doped p-CuGaS2 hetero-epitaxial films by
metalorganic vapor phase epitaxy (MOVPE) [9,10] on S-doped
n-GaP (GaP:S) substrate. However, the EL peak energy of the
LED was 2 eV and the spectrum did not exhibit emissions
energetically higher than 2.2 eV [11], because Eg of GaP
(2.26 eV) is lower than that of CuGaS2 (2.48 eV) [3] and they
are considered to form a TYPE-II heterojunction [12].
ZnO is one of the attracting compounds to inject electrons
into CuGaS2 forming a TYPE-I heterostructure, since its Eg is

S.F. Chichibu et al. / Journal of Physics and Chemistry of Solids 66 (2005) 18681871

3.37 eV, electron affinity cs is approximately the same as that

of CuGaS2 being 4.1 eV [12,13], and it can be doped heavily
n-type with Ga or Al. Although wurtzite ZnO cannot be grown
epitaxially on the (001) face of CuGaS2 epilayers [811] grown
on a (001) GaP substrate, the roles of ZnO in the proposed
ZnO/CuGaS2 heterostructure are to carry and inject electrons
from the Al electrode to p-CuGaS2. Therefore, polycrystalline
ZnO thin films might function for the present purpose, provided
that the films are deposited by certain surface damage-free
deposition techniques.
In this article, the observation of greenish-white EL is
reported for the heterojunction LEDs composed of p-CuGaS2
active layers grown by MOVPE [14] and Al-doped n-ZnO
(ZnO:Al) electron injector deposited by the surface-damagefree helicon-wave-excited-plasma sputtering (HWPS) [15]
methods.

2. Experiment
A schematic cross-sectional drawing of the n-ZnO/pCuGaS2 heterostructure LEDs is shown in Fig. 1(a). They
consisted of approximately 0.7-mm-thick undoped (001)
p-CuGaS2 epilayers grown on (001) GaP:S substrates, 50nm-thick undoped n-ZnO interlayers, and 600-nm-thick nCZnO:Al films. Au and Al were used as ohmic contacts to
p-CuGaS2 and nC-ZnO:Al, respectively. The Al electrode area
was 0.0125 cm2.
The CuGaS2 epilayers were grown at 873 K using a vertical
quartz reactor MOVPE apparatus (scPD-Z1M) [10,14]. Details
observation
dierction

(a)
Al

Au

(~5x1018cm-3)

n+-ZnO:Al
undoped n-ZnO
p-CuGaS2 (1x1017cm-3)
n-GaP:S (3x1017cm-3)

1869

of the growth conditions and structural and optical properties of

CuGaS2 epilayers will be found elsewhere [3,10,13,14]. Since
the accumulated carriers at the CuGaS2/GaP interface made the
conventional Hall measurement difficult, the net acceptor
concentrations in the CuGaS2 epilayers, NAKND, where NA
and ND are acceptor and donor concentrations, respectively,
were measured by capacitancevoltage measurement to be
0.71.0!1017 cmK3. After growing CuGaS2, the samples
were transferred from the MOVPE reactor to the HWPS
chamber in the air. Therefore, surface oxides such as CuO and
GaO were removed by etching using a solution composed of
HF:HNO3:H2OZ1:1:4 [16].
The undoped and Al-doped preferentially (0001)-oriented
polycrystalline ZnO films were deposited using the HWPS
apparatus (Sanyu SVC-700PHW). Details of the HWPS system
have been given in the previous reports [15]. A 99.999%-pure
undoped ZnO and an Al2O3-doped (2 wt%) 99.99%-pure ZnO
targets (51-mm diam.) were placed on the movable multiple
target holder, which enabled to deposit the films without the
interface exposure to the air. The HWP excited in a quartz tube
from the 99.9995%-pure Ar/99.99995%-pure O2 mixture was
introduced into the chamber by the weak magnetic field
gradient, and the velocity of Ar cations onto the targets was
accelerated by the negative dc bias (Vt) applied on back of the
holders. Our configuration [15] enabled depositing thin films
softly due to the elimination of plasma bombardment of the
epilayer surface. The rf power, Vt, and deposition pressure were
300 W, K300 V, and 0.15 Pa, respectively. The gas composition and deposition temperature were pure Ar and 623 K for
the undoped ZnO interlayers and Ar:O2Z12:1 and 598 K for
the ZnO:Al layers, respectively. The electron concentration,
mobility, and resistivity of the ZnO:Al films were measured
using a single film on glass substrates to be 5!1018 cmK3,
3.6 cm2/V s, and 0.34 Ucm, respectively. The electron concentration in the undoped ZnO was similarly estimated to be
approximately 1018 cmK3.
The EL was observed from the top of the device, as shown
in Fig. 1(a). The emission was dispersed by a 67-cm-focallength grating monochromator and the signal was detected
phase-sensitively by a GaAs:Cs photomultiplier. For comparison, photoluminescence (PL) spectra of the CuGaS2 epilayers
and GaP:S substrate were measured using the 325.0 nm line of
a cw HeCd laser (2 mW) as an excitation source.

0.14
(b)

Current (mA)

0.12

3. Results and discussion

0.10 S=0.0125 cm2

0.08
0.06
0.04
0.02
0.00
-0.02
-8

-6

-4

-2 0
2
Voltage (V)

Fig. 1. (a) Schematic drawing of the cross-section and the detection direction of
the n-ZnO/p-CuGaS2 heterojunction LEDs fabricated on the S-doped n-GaP
(GaP:S) and (b) typical IV characteristics of the LEDs at room temperature.

Representative currentvoltage (IV) characteristics of the

n-ZnO/p-CuGaS2 LEDs at 300 K is shown in Fig. 1(b).
Corresponding energy band diagrams of the LEDs along the
current-flow direction and along the cross-section below the Al
electrode under thermal equilibrium are drawn in Fig. 2(a) and
(b), respectively, where Eg of ZnO, CuGaS2, and GaP are taken
as 3.37, 2.48, and 2.26 eV and cs values of them are taken as
4.1 [13], 4.1 [12], and 4.0 eV, respectively. The work functions
(FM) of Al and Au are taken as FAlZ4.3 eV and FAuZ5.1 eV.
The Fermi level EF in p-CuGaS2 is calculated to be 0.14 eV
above the valence band Ev using the values of NAKNDZ1!

S.F. Chichibu et al. / Journal of Physics and Chemistry of Solids 66 (2005) 18681871

1017 cmK3 and the effective density of states NvZ2.05!

1019 cmK3, which is calculated from the hole effective mass
[17] mhZ0.69m0, where m0 is the electron mass. The EF
position in undoped and Al-doped ZnO layers is taken on the
conduction band Ec, since their ND values nearly agreed with
the Mott density in ZnO being 3.3!1018 cmK3 [18].
As shown in Fig. 1(b), the forward current If had an onset
voltage approximately 2 V, which nearly agreed with the
diffusion voltage for the conduction band, as shown in
Fig. 2(a). The depletion layer is considered to be formed
mostly in p-CuGaS2, since NAKND in CuGaS2 is one order of
magnitude lower than ND in ZnO. Therefore, If is dominated by
the electron injection from n-ZnO into p-CuGaS2 (and
subsequent recombination), because the valence band discontinuity (DEvZ0.89 eV) is considered to act as a hole
diffusion barrier. However, the ideality factor (!1 V) was
approximately 1317, implying the presence of certain current
barriers and recombination channels, and possible electron
tunneling at the uncontrolled interface between ZnO and
CuGaS2, as depicted by crosses in Fig. 2. Note that the forward
current density at 8 V was as low as 1.1!10K2 A/cm2
(resistance was 57 kU), which is due also to the high series
resistance of laterally conducting p-CuGaS2 thin layers, as
shown in the inset in Fig. 1(a).
Although the LED showed a rectifying property, the reverse
current Ir began to increase around K6 V, and the rectification
ratios (defined as If/Ir) were as small as 36, 19, and 9.1 for G4,
G6, and G8 V, respectively. Since the depletion layer expands
in the low carrier concentration CuGaS2 layer under reverse
bias, Ir is considered to be mainly dominated by the tunneling
of valence electrons of CuGaS2 into the ZnO conduction band
through deep defect levels, which will be shown in the EL and
PL spectra of CuGaS2 later, as well as certain recombination
currents through the interface. The formation of these
unwanted interfacial states/barriers is probable, since the
junction was made ex-situ and the n-ZnO layers are
polycrystalline materials. It should also be noted that

Wavelength (nm)
800
EL Intensity (arb. units)

Fig. 2. (a) Band alignment of the Al/n-ZnO/p-CuGaS2/Au LEDs under thermal

equilibrium and (b) band alignment of the LED structure vertically below the
Al electrode (Fig. 1(a)).

the n-ZnO films were deposited 10 years after the growth of

CuGaS2 epilayers. The inter-diffusion of Cu and Zn into ZnO
and CuGaS2, respectively, is also probable, since ZnO films
were deposited at 598623 K. Note that the intermixing
between Cu(Al,Ga)(S,Se)2 epilayers and GaAs or GaP
substrates has been indicated by X-ray photoelectron spectroscopy method [12].
In spite of these obstacles, the LEDs exhibited visible,
yellowish-orange EL bands between 1.6 and 2.26 eV at 293 K,
as shown in Fig. 3(a). Typical current density was 1.6 A/cm2.
The EL band seemed to extend in the higher energy side while
the rest part remained unchanged as the temperature was
decreased from 293 to 90 K, as shown in Fig. 3(a). Since the
higher cut-off energies corresponded to Eg of GaP, some of the
higher energy portion of the EL from CuGaS2 may be absorbed
by the substrate. Conversely, the emissions lower than Eg of GaP
are guided in the substrate and they may be efficiently extracted
from the device, leading to their stronger EL intensities.
EL spectra of the LEDs at 90 K are shown in Fig. 3(b). For
comparison, PL spectra of the CuGaS2 epilayer, which was cut
from the same wafer used for LED #1, and GaP:S substrate
measured at 77 K are also shown. As shown, the spectral
lineshape of the EL band higher than 2.2 eV resembled that of
the PL from CuGaS2. Also, the near-band-edge EL peak was
remarkable at 2.42.5 eV in the magnified spectrum. Conversely, the GaP:S substrate exhibited PL bands at 2.03 and
1.75 eV only, and the polycrystalline ZnO did not exhibit any
700

(a)

600

500

EL
90K

Eg(GaP)

230K
293K
1.6

1.8

2.0

2.2

2.4

2.6

Photon Energy (eV)

Wavelength (nm)
800

600

700

(b)
Intensity (arb. units)

1870

EL #2 (70K)
23mA, 19V

GaP:S
PL(77K)

500
EL #1 (90K)
20mA, 19V

CuGaS2
PL(77K)
x25

1.6

1.8

2.0

2.2

2.4

2.6

Photon Energy (eV)

Fig. 3. (a) EL spectra of the ZnO/CuGaS2 LED as a function of temperature and
(b) EL spectra of two ZnO/CuGaS2 LEDs at 70 and 90 K. PL spectra of the
identical CuGaS2 epilayer and the GaP:S substrate measured at 77 K are also
shown for comparison.

S.F. Chichibu et al. / Journal of Physics and Chemistry of Solids 66 (2005) 18681871

PL. From these experimental facts, the observed EL bands are

assigned to originate from the CuGaS2 layers. The color of the
EL from LED #2 was seen as greenish, due to the enhanced
emissions between 2.3 and 2.4 eV. It should be noted that the
EL spectra at 90 K contained an EL band at 2.05 eV and the
lower-energy tail down to 1.6 eV. Some of them are considered
to originate from the GaP:S substrate, since the EL from
CuGaS2 is absorbed by GaP, as discussed for Fig. 3(a), and the
electrons injected from ZnO into CuGaS2 might overflow into
the underlying GaP due to the bandgap difference and the
electric field, as shown in Fig. 2(b).
4. Conclusion
Greenish-white EL was observed from the p-type (001)
CuGaS2 epilayers due to the electron injection from the n-type
preferentially (0001)-oriented polycrystalline ZnO films deposited by the HWPS technique. The currentvoltage and EL
characteristics of the junction were consistent with the model that
ZnO/CuGaS2 forms the TYPE-I heterostructure. Further
improvements in the qualities, increase in the layer thickness,
and proper control of the hole concentration in p-CuGaS2
epilayers are necessary to improve the LED performances.
Acknowledgements
The authors would like to thank Professor S. Shirakata and
Professor H. Nakanishi for fruitful discussions. Continuous
encouragement of Professor K. Sato, Professor T. Irie,
Professor T. Sota and Professor F. Hasegawa is gratefully
acknowledged. They would like to thank Trichemical
Laboratory and Sanyu Denshi Corporation for continuous
encouragements. This work was supported in part by the 21st
Century COE program Promotion of Creative Interdisciplinary Materials Science for Novel Functions and Grant-in-Aid
for Scientific Research Nos. 15656080 and 16360146 under
MEXT, Japan.

1871

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