J. Php. D:Appl. Phys. 26 (1993) 1787-1792.

Printed in the UK

I I
I Growth and annealing of Culn,,,Ga,,,Se, 1
1 thinfilms
E Ahmedt, A E Hill, R D Pilkington and R D Tomlinson
Department of Electronic and Electrical Engineering, University of Salford,Sallord
M5 4WT,UK
Received 24 February 1993, in final form 17 June 1993

Abstract. Culno75G&25Se2(CIGS). a promising materlal for solar cell applications,

was produced in the form of thin films by the evaporation of pre-reacted
polycrystalline c GS material onto glass substrates. The deposits were
characterized using x-ray dinraction (XRD) and scanning electron m croscope
(SEM) techniques. They were found to have a strong preterred orien!at.on with tne
(112) plane parallel to the substrate. Results from energy dispersive analysis w:th
x-rays (EDAX) and Rutherford backscattering spectroscopy (RES) indicated that the
as-grown films were slightly deficient in selenium, otherwise the composition was
comparable w.th tne stan ng polycrystalline material. Electr;cal measurements
revealed both n- and p-type COndJClivIikS with surtace resist:v:ty values in the
range of lO-'-lO3 Q cm. A two-stage post-deposition heat treatment of tne films
was performed to improve tne composition and crystal structure and to optimize
the eledrica. properties. It was observed that the first annealing stage produced
an excelsentimprovement in the compos:tion of the films. An increase in tne film
grain size (to > 2 pm) was observed when the lilms were sLbsequently annealed
in a 9:l mixture of N2:Hz. StructJra. ana compositional characteristics are usea to
explain obsewed changes in electrical propenies.

1. Introduction
Considerable interest in copper temary and quatemary
semiconductor compounds has been stimulated by their
application in high-efficiency thin film photovoltaic
devices for use in both terrestrial and space environments
[ 1,21. Thin film solar cells based on a polycrystalline
Cu(In,Ga)Sez (CICS) absorber have proved to be
extremely stable and efficient; 15.4% efficient cells have
been reported for CuInSez (CIS) [3]. Copper gallium
&selenide (CGS)has also been investigated but to date
has shown less promise in stand-alone devices, with only
6% efficient solar cells having been fabricated 141.
Both single-crystal and thin film forms of CIS have
been extensively researched for over two decades due
to its distinctive properties [5] such as direct band
gap, high absorption coefficient (IO5 cm-'), moderate
surface recombinations velocities and radiation hardness
[61. Unfortunately, the energy band gap value of
approximately 1.02 eV (for thin film CIS) is smaller than
the theoretically optimum value of 1.5 eV for solar cells
[71.The band gap of thin film CuGaS@ is of the order
I .68eV and therefore, by partially substituting gallium
for indium, the band gap can be adjusted to this optimum
value [SI. The resultant CuInt-,GaxSe2 (CIGS) can have
any band gap value between 1.02 and 1.68 eV. More
t Permanent address: Physics Department, B Z University,
Multan. Pakistan.
than 16% efficient CIGS solar cells have recently been
reported [3].
Post-deposition heat treatments can considerably
improve the properties of thin films and hence the
parameters of photovoltaic devices based on these
films [9]. Good cell performance has been shown to
be related to the stoichiometry and structure of the
absorber material [IO]. Current studies on chalcopyrite
thin film CIGS deposition techniques have involved
flash evaporation 1111, elemental co-evaporation 1121,
laser ablation 1131, molecular beam epitaxy 1141 and
sputtering 1151. It has been observed that films
grown on substrates at room temperature are amorphous
while films deposited at temperatures above 500 K
are polycrystalline with a (1 12) preferred orientation
[16]. It has been shown that films produced by the
above techniques nearly always require post-deposition
annealing to optimize the film properties. Mooney et a1
[ 171 performed a systematic study and used rapid thermal
annealing for recrystallization of co-evaporated CIS.
Enhanced grain growth was observed in polycrystalline
CIS using this technique [MI.Laude eta1 [I91illustrated
the synthesis of polycrystalline films of CIS by laser
irradiation of vacuum evaporated multi-layer sandwiches
of Cu, In and Se. They observed no phases other than
the desired chalcopyrite.
This paper reports the growth, compositional,
structural and electrical properties of CuIno,,sG~.&ez
thin films prepared by the flash evaporation technique.

0022-3727/93!101787+06$07.50 @ 1993 IOP Publishing Lld 1787

E Ahmed et a/
This thin film deposition method is well known and very
convenient for deposition of alloys and compounds in
which dissociation would normally be a problem. We
have recently demonstrated [ 111 that thin films of CIOs
with compositions close to the starting material can be
produced by this simple and straightforward technique.
Particular emphasis has been given to the effects of
post-deposition heat treatments on the film properties
and we have shown that a two-stage annealing process
can be used to improve the composition, grain size and
electrical properties.
2. Sample preparation and experimental
Thin CuIn0,,~Ga&3e~films were deposited by flash
evaporation using an apparatus developed at Salford
[ZO]. The fine grain (150-2.50 pm) starting material
was made by repeated grinding and sieving of polycrys-
talline C U I ~ , , , ~ ~ G Q . ~prepared
$ ~ ~ , using 99.999% pure
constituent elements, which had previously been etched
and cleaned. Preparation details have been given pre-
viously [ l l ] and will not be repeated here.
Both flat tungsten strip and molybdenum twin
chimney boats were used as the evaporation source.
The temperature of the source was varied between
900°C and 13OO"C,as measured by a Pt-646 Rh/Pt-
30% Rh thermocouple placed directly below the source.
A precise measure of the source temperature was
established using an optical pyrometer, as reported in
our previous paper [l 11. The continuous feeding of fine
grain CIGS onto the hot source was established by means
of a motor-controlled vibrating hopper and a specially
designed feeder tube. A source-to-substrate distance of
12 cm and a measured pressure better than lo-' Torr
were found to be optimum for successful growth of
CIGS thin films. Films were deposited onto ultrasonically
cleaned Corning 7059 glass substrates, the temperature
of which was varied between room temperature and
200°C.
Three different annealing regimes were adopted,
henceforth referred to as regime 1, regime 2 and regime 3
consisting of 1, annealing in vacuum; 2, annealing in an
ambient gas of a 9:1 mixture of Nz:H2; and 3, annealing
in a selenium atmosphere. Post-deposition annealing
experiments were carried out in a sealed glass ampoule,
whose shape allowed the sample and the selenium to be
separate. The influence of various temperatures in the
range 200°C to 500°C was investigated.
The structural properties of the as-deposited and
annealed films were investigated by SEM and XRD, using
Cu Ka radiation. The composition was evaluated using
EDAX and was cross checked by RBS. The electrical
parameters, including resistivity and conductivity type,
were determined by the four-point and hot-pint probe
techniques respectively.
1788
0 ,
90U 1000 il00 1200 1300 DQ
SOURCE TEMPERATURE ("C)
Figure 1. The effect of source temperature on the
CulnlGaSe2film composition.
3. Results and discussion
To orepare homogeneous and stoichiometric thin
films- b; the flash evaporation technique, the source
temperature must be controlled carefully and should be
high enough to evaporate all the constituent elements. A
systematic study of the effect of the source temperature
on the composition of CIGS thin films was carried out and
the results are summarized in figure 1. It is evident that
the films deposited at source temperatures < 1050°C
were deficient in copper, whereas, at approximately
1300"C, the copper content in the films was comparable
to that of the starting material. At temperatures >
1100°C analysis revealed a slight excess of indium
and a small deficiency of selenium. This selenium
deficiency was probably due to its higher vapour
pressure. Under our experimental conditions, a source
temperature of approximately 1300 "C (measured by the
source thermocouple) was found to be the minimum
evaporation temperature for successful deposition of
CIGS thin films with a composition comparable to that
of the starting material. Films in the thickness range
6000-13000 A were prepared.
Figure 2 shows the CIGS compositional triangle with
data for as-grown and annealed samples. The as-grown
samples, produced at a source temperature of 1300"C,
(labelled 'a' in figure 2) were always slightly rich in
indium and deficient in selenium. Apart from these
deviations, the values for copper and gallium (within
the measurement error of 4%) are very close to those
of the starting material composition. Dramatic changes
in atomic composition resulted when the samples were
exposed to specific post-deposition heat treatments.
Annealing of samples using regime 1 (labelled 'b') and
regime 2 (labelled 'e') showed no appreciable change
in the composition. Other authors have reported partial
loss of selenium after annealing in vacuum 1211. Our
measurements did not confirm this, as a very small
selenium loss could not be detected, due to the accuracy
of the EDAX technique (i4%). When annealing the films
at a temperature of 300°C in a selenium atmosphere,
an improvement in the composition (labelled 'c') was

- %CU
Figure 2 The effectof annealing (various regimes) on the CulnIGaSe film composition.
always observed. It can be clearly seen that the resulting
film composition is approaching that of the source
material 025%. In+Ga 25%, Se 50%) from which
solar cells with 10.5% efficiency have been fabricated
1221. When samples were subjected to a higher
temperature anneal (500°C) in a selenium atmosphere,
the Se:Cu:(In+Ga) ratio changed with an increase in the
percentage of selenium and a corresponding decrease in
the percentages of copper and indiumlgallium (labelled
*a').
The RBS technique is very useful for observing the
surface composition as well as the homogeneity of the
films. The RBS spectra also gives information regarding
the film thickness. This technique makes use of a
2 MeV He+ ion beam from a Van de Graaff generator
in conjunction with a multi-channel energy analyser
with a resolution of 5 kelr per channel. Figure 3
shows the difference between the RBS spectra of CIGS
thin films before and after annealing in selenium at
300°C. Results were analysed using specialist computer
software yielding aata on the sample thickness and
surface mposition. A small peak at channel energy
346 indicated an indium excess on the surface of the
as-grown material; this is in good agreement with our
E D A ~results. After annealing it can be clearly seen
that the excess surface indium has diffused into the film,
resulting in the removal of the indium peak in the RBS
spectrum. The homogeneity of the film is also improved
as shown by the smoothing of the top plateau of the
spectrum. The film thickness is related to the number of
channels across which the spectrum is recorded. Figure 3
Teveals that, after annealing, the film has increased in
thickness from 5850 A to 6500 A. This is a well-known
e m t [23], attributed to incorporation ,of selenium in
vacancies existing within the as-grown fiims. This
effect was repeatedly observed in a number of samples
annealed under the same condihons. Bulk compositional
analysis can be achieved using this techniqw*butthe thin
film has to be of a thickness (< 2OCh A$ whereby
Growth of Culno.75Gao&e2thin films
Reported CIS cell
efficiencies [23]
-
I Cu
I
A5-grown
. . . .. Annealed in Se
i CQQ
CHANNELNUMBER
Figure 3. Rutherford backscattering spectra of (-)
as-grown and (. .. .. .) selenium annealed thin film
Culn/GaSe2.
the individual peaks can be resolved, the error in the
measurements can then be reduced to approximately
0.2%. For thicker films the RBS peaks overlap and the
measurement error is increased to approximately 10%
[241.
In order to determine the smcture of both as-
grown and annealed CIGS samples, x-ray diffraction
analysis was carried out and the observed spectra are
shown in figure 4. It is evident from the spectrum
of the as-grown film that the (112) diffraction line
dominates heavily. After annealing the film at 300°C in
a selenium atmosphere, we observe a small increase of
the other CIGS diffraction lines, which could be attributed
to relaxation in the preferred orientation of the film
structure. This indicates that the flash evaporated film
has a preferred growth direction, the (112) plane being
parallel to the substrate. For annealing temperatures
above 400°C. *the films were highly stressed, which
resulted in them peeling away from the substrate,
therefore it was difficult to obtain diffraction spectra for
1789
E Ahmed et a/

,
y , ,, ,
" I I , " , , ,, ,
Figure 4. The XRD spectra of as-grown and annealed
(under S e at 300°C)CIGS thin films.

these samples. Figures 5(a)-(c) shown SEM micrographs

of the as-grown and annealed films. The as-grown
CIGS film has a rough porous nature with an average
grain size of the order 2000 A.
When these as-grown
CIGS films were annealed in a Nz:Hz atmosphere at
temperatures ranging between 250 "C and 400"C, the
microstructure changed considerably and large grains
of the order 1 'pm in size were found to result at a
temperature of 300°C. Grain growth to ahout 2 p m
was observed for samples annealed first in a selenium
atmosphere at 300 "C and then subsequently annealed
in an ambient gas of 9:l mixture of NZ:H2at 300°C.
It is anticipated that, with further optimization of the
annealing regime, that is temperature and time, larger
Figure 5. SEM micrographs of GIGS thin film: ( a ) as-grown;
grains such as those observed in figure 5(c) could be ( b )annealed in N2:H2at 300°C:and (c) annealed in Se at
grown reproducibly. 300°C followed an anneal in N2:H2(9:l) at 300°C.
The resistivity and conductivity type of both as-
grown and annealed CIGS films were measured by four- (i) Post-deposition heat treatments at temperatures
point and hot-point probe techniques respectively. It was not exceeding 300 "C,in vacuum, resulted in no change
found that the resistivity values of the as-deposited films to the conductivity type. The resistivity values either
were in the range of 10-l-lO'Q cm and both n- and p- remained constant or showed very small variations. A
type conductivities were observed. As we have reported change in conductivity type from p- to n-type is usually
recently [ll], the conductivity type can be related to attributed to selenium loss. Under our experimental
the various defect levels present in the films. Detailed conditions no selenium loss was observed.
analysis of post-deposition heat treatments was carried (ii) As-deposited samples, annealed in an atmosphere
out to identify the reason for the existence of n-type of 9:l mixture of Nz:H2 again showed no change in the
conductivity. On the basis of these studies, the following conductivity type. However, an appreciable change in
effects were observed. the resistivity was noted. This is attributed to increase

1790

ANNEALING T E M P E R A T U R E Pcr
Figure 6. Variation of resistivily as a function of annealing
temperature for films annealed in Se.
in grain size.
(iii) Annealing in selenium atmospheres always
changed the conductivity from n- to p-type. Consider-
able variation in resistivity was also observed.
From these preliminary experiments, the relationship
between resistivity and annealing temperatures (under a
Se atmosphere) was deduced, figure 6. The as-grown n-
type film (deposited at a substrate temperature of 200°C)
had a resistivity value of 12.2 S2 cm. After annealing
in selenium at temperatures up to 300°C, the resistivity
decreases and a change in conductivity from n- to p-type
is observed. This can be attributed to improvements in
both crystallinity and grain size. At low temperatures,
a relatively large spacing between crystallites offers
a high resistive path to the movement of charge
carriers. The increased growth of the crystallites at
higher annealing temperatures should ideally decrease
the number of grain boundaries and therefore decrease
the resistivity. However, when the films were
subjected to a high-temperature (> 300°C) anneal,the
resistivity increased very sharply, and at 500°C it
attained a value of 1.32 x lo2 S2 cm. This increase
could be explained by considering the deviations from
stoichiometry of the film. As described earlier, high-
temperature anneals (500°C) result in damage to the
fiIms and therefore both composition and crystallinity
are degraded. Another possible explanation for the
observed increase in resistivity relies on experimental
evidence that copper is the most mobile species within
copper ternary compounds [25]. It is proposed that, at
temperatures of the order 350°C. copper migrates to the
grain boundaries, resulting in an increase in the number
of intrinsic defects ( N A ) within each grain, causing a
decrease in resistivity. Above 350°C. grain growth
occurs, which reduces the number of grain boundaries
so that some of the copper migrates back into the grains
and reduces the overall population of intrinsic defects
( N A ) . This consequently increases the resistivity.
Growth of Culno.,5G%,25Se2
thin films
4. Conclusions
CuIno,75Gao,25Sezthin films have been successfully
grown on glass substrates using a simple and Iow-
cost flash evaporation technique. High-quality polycrys-
talline films with a strong (1 12) preferred orientation and
compositions n e a to that of the starting material have
been produced at source temperatures of about 1300°C.
Both n- and p-type conductivities were observed The
observed n-type conductivity in the as-grown films has
been attributed to the existence of a selenium deficiency.
Post-deposition heat treatments in various ambients
have resulted in an improvement of both composition
and grain size. A two-stage annealing process
involving an initial anneal in selenium (to optimize the
composition) followed by a second anneal in a Nz:H*
atmosphere (to increase the grain size) has been shown to
be beneficial. The annealing of our samples under high-
vacuum conditions may have resulted in a very slight
loss of selenium but this was not observed.
This initial study has shown that, by using an
optimized annealing procedure, thin films of CIGS with
the desired structure and properties can be prepared.
It is believed that, by further optimizing the annealing
regime, large grains of CIGS can be grown, which will
be advantageous in the production of solar cells based
on this material. Work is continuing with the intention
of producing photovoltaic devices based on these films.
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