EFFECT OF CdS ANNEALING IN (CdCI, + CdS) ATMOSPHERE ON CdTe CELLS

Sung Chan Park, Byung Wook Han, Jin Hyung Ahn, Byung Tae Ahn, and *Donghwan Kim
Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology,
373-1
Koosung-dong, 'Yusung-gu, Taejon 305-701, Korea
*Department of Materials Science and Engineering, Korea University, Anham-dong, Sunbuk-gu, Seoul,
Korea

ABSTRACT
source in a closed carbon boat in the form of a (CdCI2 +
CdS) mixed powder. The effects of (CdCI, + CdS)
To increase graintreatment
size, solution-grown
CdSand
films
on the optical
photovoltaic properties of
were annealed at 560C in a (CdCI, + CdS) atmosphere,
CdTe cells were investigated.
instead of CdCI, only environment. CdS was used to
prevent the evaporation of CdS from the films.
EXPERIMENTAL
After 5 PRODUCDURE
min annealing, the grain size increased from 10 nm to
100 nm and the surface morphology
CdS filmswas
were
very
prepared
smooth by chemical bath
and densely packed. The
deposition
optical transmittance
process from solutions
was
containing cadmium
greatly improved nearacetate
E,, compared
and thiourea.
to that Substrate
of CdS films
materials were ITOannealed at 400C for coated
30 min corning
in H2. The
glass
efficiency
and un-doped
of the
ZnO-coated corning
CdTe solar cell was improved
glass. Uniform
by fabricating
CdS films
with
on the
ITO/glass
CdS
were obtained
layer annealed in a (CdCI,+CdS)
when the pHatmosphere.
value of solution
The
was 12. 200 nm thick CdS
increase of the efficiency
films was
weremainly
annealed
due in
to athe
closed
inlcrease
carbon boat at 560C in
Ar with
of fill factor, which might be due to the decrease
of a (CdCI, + CdS) powder.
defects at CdTe bulk and the
CdTe
CdSiCdTe
cells consist
interface.
of carbon/CdTe/CdS/ITOiglass
and its structure can be found in the literature[-/]. CdTe
films were deposited by close-spaced sublimation (CSS)
method. Screen printed CdTe layers were used as a
INTRODUCTION
CSS source. CSS CdTe films were prepared by
the source
layer have
in 10 Torr He. The source
In the efficient sublimating
CdTe solar cells,
CdS films
temperature
and such
substrate
temperature were 650C and
been deposited by several
techniques
as spray
pyrolysis, vacuum evaporation,
6OO0C, respectively.
and chemicalThe
bath
Cd content in the CdTe film
deposition (CBD) [l-31.
grown
Chu by
et CSS
al. was
reported
48% and
a solar
the bulk resistivity of CdTe
R.cm. The cells,
active by
area of CdTe cell was W x
efficiency of 15.8% inwas
the3x104
Sn0,iCdSiCdTe
depositing CBD CdS and annealing the films in H, 141. L =I x 0.5 cm2.
0-7803-3767-0/97/$10.00
0characteristic
1997
26th
IEEE
PVSC;
Sept.
30-0ct.
53
13,1997;
Anaheim,
CA
the
CdCI,
However,
grains
sequentially
method
coating
in
photovoltaic
the
grain
quality
Totreatment,
treatment
tofor
was
and
CdS
prevent
of
the
size
carried
the
film,
aCdCI,
ofproperties
CdS
deposited
rough
CdS
of
purpose
the
can
we
film
followed
resulting
saturated
CdS
by
substrate.
surface.
loss
cause
employed
Velectrode
using
surface
dispersive
which
scanning
films
Keithley
Chemical
light
force
film
annealed
was
CdTe
of
of
CdS
by
The
because
applying
in
CdTe
mist
solution
light
were
was
CdS
microscopy
film
It
aannealing.
roughness
loss
The
the
crystal
electron
current
composition
CdS
was
in
is
measured
controlled
from
cells.
generator
x-ray
investigated
critically
source
most
H,
irreproducible
essential
powder
and
the
used
[5,6].
aCdS
has
was
thin
spectroscopy
structure
source
(AFM).
make
quadity
commonl'y
of
microscopy
for
The
was
by
film
very
as
measured
or
CdS
was
by
However,
coating
four
pirt-holes
electrical
depends
coating
to
tungsten
aspin
by
and
using
during
The
small
films
analyzed
vapor
of
increase
and
x-ray
point
used
nanovoltmeter.
electrical
(SEM),
by
of
(EDS).
the
on
of
fixed
were
microstructure
lamp.
solar
probe
diffraction
ohmic
by
silicon
analyzed
respectively.
at
The
energy
The
simulator
method
resistivity
contact.
100
illuminated
intensity
pyranometer
An
mW/cm2.
by
(XRD)
of
In-Ag
using
atomic
of
CdS
The
and
of
of
I-and
CdS

scattering and the decrease of bulk defects. Since the

transparency
was strongly depended on the annealing
RESULT AND DISCUSSION
time and CdCI, amount, the concentration of bulk defects
within grains
Fig. 1 shows the SEM micrographs
of theseemed
CdS a main factor.
films: (a) as-deposited, (b) annealed at 400C for 30 min
in H,, (c) annealed at 560C for5 min in CdCI, only
atmosphere and (d) annealed at 560C for 5 min in a
L
(CdCI, + CdS) atmosphere. The grain size of the CdS
film annealed at 400C for 30 min in H, is similar to that n
of the as-deposited film. The CdS film annealed in a
CdCI, atmosphere shows large grains and many voids.
The voids formed by the evaporation of CdS from the
CdS film. On the other hand, the CdS film annealed in a
(CdCI, + CdS) atmosphere shows large grain and a
densely packed morphology. No voids or pinholes
appear in the film. The grain size increased from about
10 nm to about 100 nm after annealing at 560C for 5
min in (CdCI, + CdS) atmosphere. The as-deposited film
had a rough surface with 29 nm rms roughness by AFM.
300 400 500 600 700 800
But the CdS film annealed in a (CdCI, + CdS)
atmosphere had a smoother surface with 15
nm rms
Wavelength
(nm)
roughness. The large grain size and smooth surface
Fig.to2.improve
Opticalthe
transmission
spectra of
should be useful
CdSlCdTe interface
andCdS films: (a)
as-deposited
and
(b)
(CdCI,
+
CdS)
annealed.
the CdTe film uniformity.
Fig. 3 shows the electrical resistivity of CdS films
as a function of annealing time at 560% in a (CdCI, +
CdS) atmosphere. As the annealing time increases up to
5 min, the resistivity increases from 50 Q.cm to 200
Q cm. Then the resistivity slightly decreases with further

increase in the annealing time. To understand the

resistivity variation with annealing times, we have
analyzed the composition of the CdS films. The
composition fo as-deposited film was [S]/[Cd] = 0.78

Fig. 3. Electrical resistivity of CdS films as a function

532
deposited,
transmittance
the
Fig.improved
(d)
CdS
improved
CdS)
near
be
decrease
(CdCI,
films.
atmosphere.
500
1. SEM
by
nm
(b)
+annealing
Note
annealing
by
wavelength,
micrographs
of
CdS)
might
H,
using
grain
that
Since
annealed,
annealed.
be
time
the
this
boundary
CdS
related
solar
solar
of
transmittance
at
film.
film
CdS
(c)
560C
spectra
efficiency
scattering,
to
at
films:
CdCI,
The
several
560C
inimprovement
has
annealed,
a(a)
Annealing
near
(CdCI,
in
ais
factors
assurface
broad
aexpected
E,
(CdCI,
+is
and
of
CdS)
peak
time
such
greatly
+toatmosphere.
(minute)
as 5c!
.>cEA0 .- .Fig.
2of
shows
the
optical
transmission
0E
5-t
10
15
20
spectra
25
30
of
the
fn
102;
/a,
-.
,.,,I.,.,.,,,
h

The composition of the CdS film. annealed

. . I .for. 5, rriin
. , was
* .
[S]/[Cd] = 0.85. Therefore, theI,
resistivity
change
with
, , , ,
the
annealing time might be due to CdS stoichiometry
change.
Fig. 4 shows the SEM micrographs of the CdTe
films prepared by CSS process on the CdS; films
annealed (a) at 400C for 30 min in H, and (b) at 560C
for 5 min in a (CdCI, + CdS) atmosphere. The CdTe film
deposited on the (CdCI, + CdS) annealed CdlS film
shows larger grains compared to the CdTe film deposited
on the H, annealed CdS film. The larger grain size of
CdTe film is due to the larger grain size of CdS
substrate. The CdTe film in fig. 4(b) had a stronger (1
11)
preferred orientation than the CdTe film in fig
0.0 0.2 0.4 0.6 0.8 1.0
4(a).

, , I , , , ~

2
1
.
.
.
.
. (V)
Bias voltage
. fabricated
Fig. 5. The dark J-V curves of the CdTe cells
with the CdS films annealed in H, and in a (CdCI,+CdS)
.
atmosphere.
.
Fig. 6 shows the illuminated J-V curve of the CdTe
cells. The cell efficiency of CdTe cells with
the 400C H2
(C
while that
annealed
of CdTe
CdS cells
6.5%,
film is
with
56OoC, (CdCI, + CdS) annealed CdS film is 7.8%.
dC By
(CdCI, + CdS) treatment, the fill factor increased
significantly from 0.49 to 0.58, while the I,
Vac did not
change. The J,, increased a little. The increase of fill
+C from
factor is due to the decrease of series resistance
8.4 R.cm to 6.6 R.cm. The reduced series resistance
dS
might result from the decrease of defects in the CdTe
bulk and at the CdS/CdTe interface caused )a
by the
Fig. 4. SEM micrographs
of
CSS
CdTe
films
increase of CdTe grain size and the smoother
deposited on CdS films, which are annealed
(a) interface
at
CdS/CdTe
morphology.
nn
400C for 30 min in H, and (b) at 560C for 5 min in a
ea 0
(CdCI, + CdS) atmosphere.
1
ed
Fig. 5 shows the dark J-V curves of the CdTe cells
*
fabricated with the CdS films annealed at 400C: in H,
H,w
annealed
and at 560C for 5 min in a (CdCl,+CdS) atmosphere. No
CdS
film areCdCI,
2.1 and
1.3, respectively,
the biason
additional
treatment
which usuallyatperformed
w-10....
H, 0.3
annealed
CdS
film
and
the
533
CdS/CdTe
conducted.
of
voltage
recombination
compared
The
concentrations
CdTe
treatment.
formation
(CdCI,+CdS)
probable
bulk
V.cells
to
When
are
is
The
that
treatment
reason
avoided
greatly
current
the
to
diade
results
atin
improve
the
bias
annealed
Fig.
is
the
factors
by
reduced
in
CdS/CdTe
is
that
also
voltage
CdTe
(CdCI,+CdS)
6.
the
significantly
junction
Illuminated
the
show
CdS
of
cell
CdTe
by
interface
0(CdCI,+CdS)
is
recombination
film
the
that
the
100
with
cell
properties
below
treatment.
CdTe
and
(CdCI,+CdS)
200
the
H,
with
I-V
reduced,
with
0.2
cells
and
300
pinhole
treatment.
curves
aannealed
V,
in
400
(CdCI,
was
defect
with
the
500
of
Bias
the
+CdTe
600
CdS)
CdS
voltage
7cells
film.
annealed
(mV)
with H,

nm. the
The spectral
junction response
recombination
Fig 7600
shows
of thecurrent
CdTe at low bias
cells. Thecondition
CdTe cellwas
fabricated
significantly
with the
reduced
CdS film
by the (CdCI, + CdS)
annealed intreatment.
a (CdCI, +The
CdS)
CdTe
atmosphere
cell efficiency
shows higher
increased to 7.8%
spectral response
by annealing
between
in a500
(CdCI,+CdS),
and 600 nm while
than the
the cell
CdTe cell with
annealed
CdSinfilm
6.5%. Thethat
increase of
with the the
CdS H,
film
annealed
H,. showed
It is expected
from
the transmission
efficiency
spectra
is mainly
of CdSdue
film(Fig.
to the increase
2) and the
of fill factor
spectral response of CdSICdTe
caused
cell,bythe
smaller
J,, should
series resistance.
increase significantly. However, the increase of J,, in
the
cell(fig.
6) is small because the absolute value REFERENCE
of the
series resistance is large(6.6 R.cm). The main
S. Albright,
B. Ackerman,
and J. F. Jordan,
IEEE
component of the series
resistance
was the lateral
[I]
37,Electron
1990, pp.
434.
resistance of IT0 film.
Trans.
Devices
I

T. Anthony, A. L. Fahrenbruch, M. Deters, and

[2] R.
Appl.
H.pp.
Bube,
Phys.
57, J.
1985,
400.
Chu, C. Ferekides,
[3]C.T.Q.L.Wu,
S.
Chu,
S.
J.
Proc. lEEE Photovoltaic
Britt, andSpecialists
C. Wang,
IEEE, NewYork, 1991, pp. Conf.,
952.

a,

0) C

0
a, B L
lyL0

a, n
u)

Chu, C. Ferekides, C.T.Q.L.Wu,

Chu,
J.
S.
S.
[4]
Britt
C.7608.
Wang,
70,
1991,
J. and
Appl.
pp.
Phys.
[5] B. E. McCandless
Proc.of
Hegedus,
S.22nd
and
S.
lEEE Photovoltaic Specialisfs
IEEE, New York,
Conf.,
1991, pp. 967-972.

Lo I I I . I. I). . *J
500 600 700 800 900

[6] G. C. Morris
Proc.of
and S.23nd
K. Das,
/E
Wavelength (nm)
Photovoltaic
Specialists1993,
Conf.,
IEEE, Louisville,

pp. 469-474.
Fig. 7. Relative spectral response of CdS/CdTe cell with
H, annealed CdS and (CdCI, + CdS) annealed CdS.

J.
[7] G.Y. Chung, S.C. Park, K. Cho, and B.T. Ahn,
1995, Appl.
pp 5493-5498.
PhyS., 78,
It is known that the CdSICdTe cell with the CdCI, treated
CdS film shows higher spectral response
near
500
nm et al.,
Solar
[a] Energy
N. Nakayama
Materials
and
because of the CdCI, treatment prevent the
formation
of
35, 1994, pp.
Solarcells
271-278.
CdS,.,Te, in the CdS film during CSS process [9,10].
However, the reduced interface defect density
by
Mat.[9]
Res.
W. larger
Symp.
Song
Proc.
al.,
426,
1996,et
pp.
CdTe grain size and smoother CdSICdTe interface
331-336.
morphology can be another reason of the spectral
534
response
applied
powder.
from
was
of
CdS)
the
obtained.
greatly
To
about
atmosphere,
CdS/CdTe
prevent
CdS
After
[IO]
increase
10
vapor
improved
T.
The
annealing
nmthe
cell
Takamoto,
to
the
optical
source
near
CONCLUSIONS
loss
about
also
near
grain
500
at
of
as
transmittance
improved
100
E,
T.
nm.
560C
size
CdS
aTechnical
and
Agui,
form
nmfrom
of
and
the
for
between
of
CdS
H.Kurita,
CdS
smoother
quantum
5(CdCI,
Digest
min
film
of
film,
Miyazaki,
500
CdS
inincreases
efficiency
+of
and
surface
awe
nm
films
CdS)
(CdGI2
9nd
Mand
1996,
121-122.
ohmori,
PVSEC,
+ pp.