APPLIED PHYSICS LETTERS

VOLUME 85, NUMBER 19

8 NOVEMBER 2004

Greenish-white electroluminescence from p-type CuGaS2 heterojunction

diodes using n-type ZnO as an electron injector
S. F. Chichibu,a,b T. Ohmori, N. Shibata, T. Koyama, and T. Onuma
Institute of Applied Physics and Graduate School of Pure and Applied Sciences, University of Tsukuba,
1-1-1 Tennodai, Tsukuba 305-8573, Japan1

Received 2 June 2004; accepted 13 September 2004

Greenish-white electroluminescence EL was observed from p-type 001 CuGaS2 chalcopyrite
semiconductor epilayers grown on a 001 GaP substrate by metalorganic vapor phase epitaxy, due
to the electron injection from preferentially 0001-oriented polycrystalline n-type ZnO thin films
deposited by the surface-damage-free helicon-wave-excited-plasma sputtering method. The
structure was designed to enable the electron injection from n-type wide band gap partner for
p-CuGaS2 forming the ZnO / CuGaS2 TYPE-I heterojunction. The EL spectra exhibited emission
peaks and bands between 1.6 and 2.5 eV, although the higher energy portion was absorbed by the
GaP substrate. Since the spectral line shape resembled that of the photoluminescence from the
identical CuGaS2 epilayers, the EL was assigned to originate from p-CuGaS2. 2004 American
Institute of Physics. DOI: 10.1063/1.1818333
The CuAl, GaS , Se2 ternary chalcopyrite semiconductors and their alloys1,2 are promising candidates for lightemitting devices operating in the visible and ultraviolet spectral ranges, since the direct band gap energies Eg range
from 1.7 eV CuGaSe2 to 3.5 eV CuAlS2. Among these,
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 essential problem in fabricating pn junction devices
using CuAl, GaS , Se2 compounds is that they exclusively
show p-type conductivity.1,2 Due to this unipolar problem,
heterojunctions combined with Cd,ZnS,Se-based IIVI
compounds, which tend to show n-type conductivity, have
been proposed.1,4,5 However, intermixing between them, especially the Cu diffusion into the IIVI layers during the
epitaxial growth, and the lattice-mismatching hindered obtaining good LED performances. Indeed, emission peak energy of the CuGaS2 / ZnSe diode fabricated by liquid-phase
epitaxy was 1.9 eV.5 As a result of the elimination of the
intermixing by means of room-temperature vacuum evaporation of Al and ZnS on the p-CuGaS2 bulk single crystals,
Kobayashi et al. have observed green electroluminescence
EL at low temperature from Al/ ZnS / CuGaS2 metal
insulatorsemiconductor MIS diodes6 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 by the
use of a pn junction, Honda et al.8 have grown P-doped
p-CuGaS2 heteroepitaxial films by metalorganic vapor phase
epitaxy MOVPE9,10 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 The results may be due to the fact that Eg of GaP
2.26 eV is lower than that of CuGaS2 2.48 eV3 and they
are considered to form TYPE-II heterojunctions.10,12

ZnO is one of the attracting compounds to inject electrons efficiently into CuGaS2 forming TYPE-I heterostructure, since its Eg is 3.37 eV, electron affinity s is 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 c001 face of CuGaS2
epilayers811 grown on 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, the use of damage-free deposition techniques for
preferentially oriented polycrystalline n-ZnO thin films
might function for the present purpose.
In this letter, the observation of greenish-white EL is
reported for the heterojunction LEDs composed of
p-CuGaS2 active layers grown by MOVPE14 and Al-doped
n-ZnO ZnO:Al electron injector deposited by the surfacedamage-free
helicon-wave-excited-plasma
sputtering
HWPS15 methods.
A schematic cross-sectional drawing of the n-ZnO /
p-CuGaS2 heterostructure LEDs is shown in the inset of Fig.
1. They consisted of approximately 0.7-m-thick undoped
001 p-CuGaS2 epilayers grown on 001 GaP:S substrates,
50-nm-thick undoped n-ZnO interlayers, and 600-nm-thick
n+-ZnO : Al films. The undoped ZnO layer was inserted in

Author to whom correspondence should be addressed; electronic mail:

optoelec@bk.tsukuba.ac.jp
b
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 9800868, Japan.

FIG. 1. Typical currentvoltage I V characteristics at room temperature

of the n-ZnO / p-CuGaS2 heterojunction LEDs fabricated on the S-doped
n-GaP GaP:S substrate. Inset: The schematic drawing of the LED cross
section and the detection direction.

0003-6951/2004/8519/4403/3/$22.00
4403
2004 American Institute of Physics
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4404

Appl. Phys. Lett., Vol. 85, No. 19, 8 November 2004

order to raise the conduction band energy. Au and Al were

used as ohmic contacts to p-CuGaS2 and n+-ZnO : Al, respectively. The Al electrode area was 0.0125 cm2.
The CuGaS2 epilayers were grown at 600 C using a
vertical quartz reactor MOVPE apparatus scPD-Z1M.10,14
Details of the growth conditions and structural and optical
properties of CuGaS2 epilayers will be found
elsewhere.3,10,12,14 Since the accumulated carriers at the
CuGaS2 / GaP interface made the conventional Hall measurement difficult, the net acceptor concentrations in the CuGaS2
epilayers, NA ND, where NA and ND are acceptor and donor
concentrations, respectively, were measured by capacitance
voltage measurement to be 0.7 1.0 1017 cm3. 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 2 in. diameter were placed on the movable multitarget holder, which enabled one to deposit the films without
interruption. 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 configuration15 enabled depositing thin films
softly due to the elimination of plasma bombardment of the
GaP substrate. The rf power, Vt, and deposition pressure
were 300 W, 300 V, and 0.15 Pa, respectively. The gas
composition and deposition temperature were pure Ar and
350 C for the undoped ZnO interlayers and Ar: O2 = 12: 1
and 325 C for the ZnO:Al films, respectively. The electron
concentration, mobility, and resistivity of the ZnO:Al films
were separately measured using a single film on glass substrates to be 5 1018 cm3, 3.6 cm2 V s, and 0.34 cm, respectively. The electron concentration in the undoped ZnO
was similarly estimated to be approximately 1018 cm3.
The EL was observed from the top of the device, as
shown in the inset of Fig. 1. The emission was dispersed by
a 67 cm focal length grating monochromator and the signal
was detected phase-sensitively by a GaAs:Cs photomultiplier. For comparison, photoluminescence 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.
Typical currentvoltage I V characteristics of
n-ZnO / p-CuGaS2 LEDs at 300 K is shown in Fig. 1. The
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 Figs. 2a and 2b,
respectively, where Eg of ZnO, CuGaS2, and GaP were taken
as 3.37, 2.48, and 2.26 eV and s values of them were taken
as 4.1,13 4.1,12 and 4.0 eV, respectively. The work functions
M of Al and Au were taken as Al = 4.3 eV and Au
= 5.1 eV. The Fermi level EF in p-CuGaS2 was calculated to
be 0.14 eV above the valence band EV using the values of
NA ND = 1 1017 cm3 and the effective density of states
Nv = 2.05 1019 cm3, which is calculated from the hole effective mass16 mh = 0.69m0, where m0 is the electron mass.
The EF position in undoped and Al-doped ZnO layers was
taken on the conduction band EC, since their ND values
nearly agreed with the Mott density in ZnO being 3.3
1018 cm3.17

Chichibu et al.

FIG. 2. a Band alignment of the Al/ n-ZnO / p-CuGaS2 / Au LED under

thermal equilibrium and b band alignment of the LED structure vertically
below the Al electrode see the inset in Fig. 1.

As shown in Fig. 1, the forward current I f seemed to

have an onset voltage approximately 2 V, which nearly
agreed with the diffusion voltage for the conduction band, as
shown in Fig. 2a. The depletion layer is considered to be
formed mostly in p-CuGaS2, since NA ND in CuGaS2 is one
order of magnitude lower than ND in ZnO. Therefore, I f is
considered to be dominated by electron injection from
n-ZnO into p-CuGaS2 and subsequent recombination, because the valence band discontinuity EV = 0.89 eV is considered to act as a hole diffusion barrier. However, the ideality factor 1 V was greater than 15, which implies 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 1.1 102 A / cm2 resistance was 57 k, which is
due also to the high series resistance in the 0.7-m-thick
p-CuGaS2 laterally conducting thin layers, as shown in the
inset in Fig. 1.
Although the LED showed a rectifying property, the reverse current Ir began to increase around 6 V, and the rectification ratios, which are defined as I f / Ir, were as small as
36, 19, and 9.1 for 4, 6, and 8 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 later in the EL and PL spectra of
CuGaS2, 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. The
interdiffusion of Cu and Zn into ZnO and CuGaS2, respectively, is also probable, since ZnO films were deposited at
325 350 C. Note that the intermixing between
CuAl, GaS , Se2 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. 3a. Typical current density was
1.6 A / cm2. The spectral shape of the EL seemed to extend to
the higher energy while the rest part remained unchanged as
the temperature was decreased from 293 to 90 K, as shown

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Chichibu et al.

Appl. Phys. Lett., Vol. 85, No. 19, 8 November 2004

4405

In summary, greenish-white EL was observed from

p-type 001 CuGaS2 epilayers grown by MOVPE due to the
electron injection from the n-type preferentially 0001oriented polycrystalline ZnO films deposited by the HWPS
technique. The junction was considered to form 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.
The authors would like to thank Professor S. Shirakata
and Professor H. Nakanishi for fruitful discussions. They
would like to thank Trichemical Laboratory and Sanyu Denshi Corporation for continuous encouragement. 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.
1

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.

in Fig. 3a. Since the higher cut-off energies corresponded

to Eg of the GaP substrate, the higher energy portion of the
EL from CuGaS2 is considered to be absorbed by the substrate. Conversely, the emissions lower than Eg of GaP are
considered to be guided in the substrate and they may be
efficiently extracted from the device, leading to their stronger
EL intensities. EL spectra of two LEDs at 90 K are shown in
Fig. 3b. 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. Obviously, the spectral line shape of the EL higher than 2.2 eV
resembled that of the PL from CuGaS2, and the near-bandedge EL peak was remarkable at 2.4 2.5 eV in the magnified spectrum. Conversely, the GaP:S substrate exhibited PL
bands at 2.03 and 1.75 eV, and ZnO did not exhibit any PL.
From these experimental facts, the observed EL bands at
least those higher than 2.2 eV 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. 3a, and the electrons
injected from ZnO into CuGaS2 can overflow into the underlying GaP due to the band gap difference and the electric
field, as shown in Fig. 2b.

J. L. Shay and J. H. Wernick, Ternary Chalcopyrite Semiconductors:

Growth, Electronic Properties, and Applications Pergamon, Oxford,
1975.
2
Ternary and Multinary Compounds in the 21st Century, edited by T. Matsumoto, T. Takizawa, S. Shirakata, T. Wada, and N. Yamamoto Institute
of Pure and Applied Physics Books, 2001, Vol. 1, ISBN4-900526-16-9.
3
S. Shirakata and S. Chichibu, J. Appl. Phys. 87, 3793 2000.
4
S. Wagner, J. Appl. Phys. 45, 246 1974.
5
N. Yamamoto, T. Takayama, and B. R. Pamplin, Prog. Cryst. Growth
Charact. 10, 235 1985.
6
S. Kobayashi, Y. Moriyama, and F. Kaneko, Jpn. J. Appl. Phys., Part 2 30,
L1747 1991.
7
S. Kobayashi, Y. Moriyama, and F. Kaneko, Jpn. J. Appl. Phys., Part 2 31,
L1606 1992.
8
T. Honda, H. Otoma, K. Hara, J. Yoshino, and H. Kukimoto, Jpn. J. Appl.
Phys., Part 2 32, L560 1993; T. Honda, K. Hara, J. Yoshino, and H.
Kukimoto, Inst. Phys. Conf. Ser. 152, 373 1998.
9
K. Hara, T. Kojima, and H. Kukimoto, Jpn. J. Appl. Phys., Part 2 26,
L1107 1987; H. Kukimoto, Jpn. J. Appl. Phys., Part 1 323, 10 1993.
10
Results of MOVPE growth of CuAl, Ga, InS , Se2 by the present authors have been summarized in S. Chichibu, S. Shirakata, S. Isomura, and
H. Nakanishi, Jpn. J. Appl. Phys., Part 1 36, 1703 1997; S. F. Chichibu,
Y. Harada, M. Sugiyama, and H. Nakanishi, J. Phys. Chem. Solids 64,
1481 2003.
11
T. Honda, K. Hara, J. Yoshino, and H. Kukimoto, J. Phys. Chem. Solids
64, 2001 2003.
12
M. Sugiyama, H. Nakanishi, and S. F. Chichibu, Jpn. J. Appl. Phys., Part
2 40, L428 2001.
13
H. Hosono private communication.
14
S. Chichibu, S. Shirakata, M. Uchida, Y. Harada, T. Wakiyama, S. Matsumoto, H. Higuchi, and S. Isomura, Jpn. J. Appl. Phys., Part 1 34, 3991
1995.
15
K. Yamaya, Y. Yamaki, H. Nakanishi, and S. Chichibu, Appl. Phys. Lett.
72, 235 1998; S. F. Chichibu, T. Yoshida, T. Onuma, and H. Nakanishi,
J. Appl. Phys. 91, 874 2002.
16
P. W. Yu, D. L. Dowing, and Y. S. Park, J. Appl. Phys. 45, 5283 1974.
17
Introduction to Nitride Semiconductor Blue Lasers and Light Emitting
Diodes, edited by S. Nakamura and S. F. Chichibu Taylor and Francis,
London, 2000, p. 164.

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