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Solar Cells, 23 (1988) 31 48

- 31

THIN FILM CADMIUM T E L L U R I D E SOLAR CELLS BY TWO


CHEMICAL VAPOR DEPOSITION TECHNIQUES

T L. CHU
Electrical Engineering Department, Southern Methodist Umverszty, Dallas, T X 75275
(U.S.A.)
(Accepted September 17, 1987)

Summary

Cadmium telluride (CdTe) has long been recognized as a promising thin


film photovoltaic material. In this work, polycrystallme p-CdTe films have
been deposited by two chemical vapor deposition techniques, namely the
combination of vapors of elements (CVE) and close-spaced sublimation
(CSS). The CVE technique is more flexible m controlling the composition
of deposited films while the CSS technique can provide very high deposition
rates. The resistivity of p-CdTe films deposited by the CVE and CSS tech-
niques can be controlled b y intrinsic (cadmium vacancies) or extrinsm
(arsenic or antimony) doping, and the lowest resistivity obtainable is about
200 ~ cm. Both front-wall (CdTe/TCS/glass) and back-wall (TCS/CdTe/sub-
strate) cells have been prepared. The back-wall cells are less efficient because
of the high and irreproducible p-CdTe--substrate interface resistance. The
CSS technique is superior to the CVE technique because of its simplicity
and high deposition rates; however, the cleaning of the substrate in s i t u is
more difficult. The interface cleanliness is an important factor determining
the electrical and photovoltaic characteristics of the heterojunction. Hetero-
junction CdS/CdTe solar cells of area 1 cm 2 with conversion efficiencies
higher than 10% have been prepared and junction properties characterized.

1. Introduction

It is generally recognized that cadmium telluride (CdTe), a direct-gap


semiconductor with a room temperature band gap energy of 1.50 eV, is a
promising thin film photovoltaic material. Because of its sharp optical
absorption edge and large absorption coefficients, solar radiation with
energy in excess of the energy gap is essentially all absorbed within 1 - 2
pm of the surface, and a relatively short minority carrier diffusion length
in the material can be tolerated. CdTe films axe not suitable for efficient
homojunction cells. The first thin film CdTe heterojunction solar cell has the
configuration Cu2Te/CdTe, prepared in a manner similar to Cu2S/CdS solar

0379-6787/88/$3.50 Elsevier Sequoia/Printed in The Netherlands


32

cells, t e an n-type film of resistivity about 10 ~ cm, vapor-deposited on


a molybdenum or glass substrate, was treated with a cuprous salt solution
to form the heterojunction. Solar radiation is incident on the Cu2Te side and
is nearly all absorbed by the CdTe. Conversion efflciencies of about 6%
have been obtained [1]. The deposition of relatively low-resistivity n-CdTe
films and the formation of low-resistance ohmm contacts to these films are
relatively simple; however, the Cu2Te/CdTe solar cells are unstable due to
the high diffusivlty of copper in CdTe. Subsequent work was directed to the
use of a large band gap high conductivity semiconductor, usually referred to
as transparent conducting semiconductor (TCS), as the heterojunction
partner. Since essentially all known TCSs are n type, p-type CdTe must be
used as the absorber. The problems associated with the use of p-CdTe films
are well known: the difficulty of depositing high conductivity films owing
to self-compensation and the difficulty of forming low-resistance ohmic
contacts owing to the large work function of p-CdTe.
Cadmium sulfide has been the most c o m m o n l y used heterojunction
partner for p-CdTe because of its large electron affinity (4.5 eV compared
with 4.28 eV for CdTe), a reasonable optmal transparency (a band gap
energy 0.9 eV higher than that for CdTe), an ability to mimmize the surface
recombination and the ease of depositing low-resistivity films. The CdS/-
CdTe structure has been investigated by many investigators using p-CdTe
films deposited by various techniques such as close-spaced chemmal
transport [2], sintering [3], electrodeposltmn [4, 5] etc.
In this work, device-quality p-CdTe films have been deposited by two
chemical vapor deposition (CVD) techmques namely, the direct combination
of vapors of the elements (CVE) and close-spaced sublimatmn (CSS), with
emphasis on the control of resistivity of CdTe films. Their structural, electri-
cal and photovoltaic propertms have been characterized and the results are
summarized m this paper.

2. CdTe films by combination of vapors of elements

The depomtion of CdTe films by the direct combmation of cadmium


and tellurium vapors on the substrate surface in a gas flow system is based
on the following reaction:
2Cd(g) + Te2(g ) , 2CdTe(s) (1)
The homogeneity region of CdTe may be as high as 1 at.% on both the
cadmium-rich and tellurium-rich sides of the stoichiometric composition.
The direct combination of elemental cadmium and tellurium vapors at the
surface of the substrate at 950 C has been used for the deposition of CdTe
laser windows up to 15 cm 2 in area and 2 mm in thickness [6]; the high
substrate temperature was reqtured to yield windows with a good micro-
structure and high deposition rates. The CVE technique has the advantage
that the stoichiometry of deposited films and the dopant concentration
and distribution in the deposit can be precisely controlled.
33

T h e r e a c t i o n in eqn. (1) is chemically reversible and is c h a r a c t e r i z e d


b y a stability c o n s t a n t KCdTe(T) at a given t e m p e r a t u r e u n d e r equilibrium
conditions:
gCdTe(T) = ( P c d O ) ( P T e 2 0) 1/2

w h e r e pcd and PTe2 are the e q u f l i b r m m partial pressures o f cadmium and


Te2 respectively at t e m p e r a t u r e T. T h e s t a b d i t y c o n s t a n t o f C d T e in the
t e m p e r a t u r e range 500 - 800 C is s h o w n m Fig. 1. At a given t e m p e r a t u r e ,
the equilibrium v a p o r pressures o f the e l e m e n t s are appreciably higher t h a n
t h e dissociation pressure o f CdTe. When a r e a c t i o n m i x t u r e contains
c a d m i u m and Te2 at partial pressures Pcd and pTe 2 respectively, t h e deposi-
t i o n o f C d T e takes place if Pcd(PTe,)I/2 > Kcdwe(T) at the substrate t e m p e r a -
ture. Since t h e e l e m e n t s are soluble in CdTe, the c o m p o s i t i o n o f t h e deposi-
t e d film d e p e n d s o n t h e t e l l u r i u m - t o , c a d m i u m m o l a r ratio m the r e a c t i o n
mixture.

TEMPERATURE, C
800 700 600 500
I

10-5

10-6 _

10-7

~ lO-s

i0 "9

I
9 10 11 12 13
IOOO/T K-1
Fig. 1. The stability constant of CdTe in the temperature range 500 - 800 C.

2.1. The depos~tzon process


T h e a p p a r a t u s for the d e p o s i t i o n o f C d T e films and the t e m p e r a t u r e
profile o f the f u r n a c e are shown schematically m Fig. 2. A c a d m i u m con-
tainer, a t e l l u r i u m c o n t a i n e r and t h e substrate were placed in a fused-silica
r e a c t i o n t u b e in a m u l t i z o n e f u r n a c e with each z o n e separately h e a t e d and
c o n t r o l l e d . H y d r o g e n or helium was used to carry c a d m i u m and tellurium
vapors to t h e surface o f t h e h e a t e d substrate (alumina, t u n g s t e n - c o a t e d
graphite etc.) w h e r e t h e y c o m b i n e t o d e p o s i t CdTe. T h e d e p o s i t i o n rate
o f C d T e films is d e t e r m i n e d b y the partial pressures o f c a d m i u m and
34

'
Ci i I TO
E](}IAUST
"%- II~ J SUBSTRATE i
Cd / I I

SEVEN ZONE FURNACE


.

~oo

H 2 PH 3 AsH3H 2 H 2 700

() SHUT-OFF VALVE 600 no


Q METERING VALVE

f -- 500
A,B,C,D,E FLOWMETERS
TEMPERATURE PROFILE

Fig 2 Schematic dmgram of the apparatus for the deposition of CdTe films

tellurmm in the reactmn mixture and by the substrate temperature; the


observed rates were in qualitative agreement with those calculated from the
stability constants of CdTe shown in Fig. 2.
CdTe films deposited on ceramic or coated graphite substrates under a
wide range of conditions are tightly adherent to the substrates. The initial
stage of depomtion involves the formation of isolated crystallites of random
shape and size. Further deposition of CdTe results m the coalescence of all
adjacent crystallites producmg a continuous film. The average grain raze
in the resulting films depends strongly on the substrate temperature. Figure
3 shows the scanning electron micrograph of the surface of a typical film
of thickness about 20 #m depomted at 550 C in which many grains have
well<ieveloped faces. The deposited films are essentially polycrystalline from
X-ray diffraction examinations [7]. The composition of many films has
been determined by the electron mmroprobe technique. Unless the tel-
lurium-to-cadmium molar ratio in the reaction mixture deviates appreciably
from unity, all films have been found to be essentially stoichiometric within
the experimental error. (The experimental error is relatively large because
of the surface roughness.) The dependence of the stoichiometry of the
film on the composition of the reaction mixture becomes more apparent
from electrical measurements.

2.2. Electrical properties


Empirically, we may determine the compomtion of the reaction
m~xture required for the deposition of stoichiometric CdTe films. When the
tellurium-to-cadmium molar ratio m the reaction mixture m increased
shghtly (less than 1%), the deposit becomes p type, and n-type CdTe results
35

Fig. 3. Scanning electron micrograph of the surface of a typical CdTe film deposited at
550 C.

when the tellurium-to-cadmium ratio is reduced slightly (cadmium vacancies


and tellurium vacancies are acceptors and donors respectively). This transi-
tion from p-type to n-type CdTe occurs over a very narrow range of the
tellurium-to-cadmium molar ratio in the reaction mixture.
Nearly stoichiometric p-type and n-type CdTe were deposited on
alumina substrates and used for resistivity and Hall measurements by the
van der Pauw technique. Ohmic contacts to the n-type film were made
by evaporating indium to the four corners of the specimen through a metal
mask followed by annealing in a hydrogen atmosphere. Ohmic contacts to
the p-CdTe film were made by etching the surface with a solution of H N O ~
K2Cr207 followed by evaporating gold onto the surface and annealing in
hydrogen. Nearly stoichiometric p- and n-CdTe films have a high lateral
resistivity at room temperature (about 104 ~2 cm). The carrier concentra-
tions deduced from lateral resistivities and Hall mobilities are of the order
of 1014 cm -3. The resistivity decreases and the carrier concentration
increases exponentially with temperature. The resistivity-temperature and
carrier concentration-temperature relations for nearly stoichiometric n-type
and p-type films are shown in Fig. 4. The activation energy in both n- and
p-type films is about 1.5 eV, suggesting that the activation energy is related
to the conduction process across the grain boundaries.

2.3. Doping
The electrical resistivity of p-CdTe films may be controlled by either
mtrinsic doping (varying the tellurium-to-cadmium molar ratio in the reac-
tion mixture) or extrinsic doping (the addition of AsH3 or PH 3 to the
reaction mixture). Tungsten-coated graphite was used as the substrate for
the doping experiments. (The use of graphite as a substrate cannot yield
36

TEMPERATURE, C
125 i00 50 25

1016f

10-2

a~

15 'i,// 10_3
~10 )
io -4

I0 Iz I0 -5

4j ' ) t
26 30 34
I
02
I
04
I
06
I
08
I
l0
IO00/T, K-I VOLTAGE, VOLTS

Fig 4. E l e c t r i c a l r e s i s t i v i t y a n d c a r r i e r c o n c e n t r a t i o n m n e a r l y s t o m h m m e t r i c n- a n d
p - C d T e films o n a l u m i n a s u b s t r a t e s as a f u n c t i o n of t e m p e r a t u r e - - - , p type,------,
n type
Fig. 5. T h e c u r r e n t - v o l t a g e characteristics of an Au/p-CdTe/W/graphlte structure

n-CdTe films owing to the incorporation of carbon into CdTe films and
carbon behaves as an acceptor m CdTe [8].)
The electrical resistivity of p-CdTe films was measured m the thickness
direction. Ohmic contacts to p-type CdTe films were formed by electro-
less gold plating at about 100 C to form Au/p-CdTe/W/graphite structures.
Owing to the large work function of p-CdTe, the p-CdTe-W interface is
always rectifying. An example of the current-voltage characteristics of an
Au/p-CdTe/W graphite structure is shown in Fig. 5. By forward biasing the
CdTe/substrate junction at high voltages, the current-voltage relation
is linear due mainly to the series resistance associated with the resistance of
CdTe, and its slope may be used to deduce the upper hmit of the resistivity
of the CdTe films (the Au/CdTe resistance is assumed to be small). The
resistivity of CdTe films in the thickness direction may be different from the
lateral resistivity owing to grain boundary effects. This is particularly true
m high resistivity films, smce the potential barrier across the gram
boundaries contributes to the lateral resistivity and this contribution
decreases with increasing carrier concentration in the film. At sufficiently
high carrier concentrations, the potential barrier at gram boundaries becomes
negligible, and the van der Pauw measurements provide the average resisti-
vity of the grains. However, the resistivity measured in the thickness
direction of the film consists of contributions from the columnar grams and
grain boundaries. Their relative importance depends on the carrier concentra-
tion in the grains and the chemical and structural properties of the gram
boundaries. If the grain boundaries have a lower impedance due to such
37

factors as dopant segregation, the measured resistance is contributed mainly


by the grain boundaries. Similarly, the grains contribute mainly to the
measured resistance when the grain boundaries are of high impedance.
The resistivity of p-CdTe films on W/graphite substrates may be con-
trolled by using reaction mixtures containing tellurium-to-cadmium molar
ratios higher than those required to yield stoichiometric CdTe. Figure 6
shows the resistivity of p-CdTe films deposited at 580 C as a function of the
tellurium-to-cadmium molar ratio in the reaction mixture. The room tem-
perature resistivity of nearly stoichiometric p-CdTe deposited at 580 C
is about 104 ~2 cm. As the cadmium partial pressure m the reaction mixture
is reduced, the resistivity of the film first decreases owing to the increased
cadmium vacancy concentration and reaches a minimum, about 200 ~2 cm,
at a tellurium-to-cadmium molar ratio of about 1.15. A lower resistivity is
obtainable at higher substrate temperatures owing to the higher defect
concentration. As the cadmium partial pressure in the reaction mixture is
further reduced, the resistivity increases presumably owing to the formation
of defect complexes or self-compensation. At larger tellurium-to-cadmium
molar ratios, the deposited films may have a resistivity as high as l 0 s ~2 cm.
It should be pointed out that owing to the use of a gas flow system, a large
change in the tellurium-to-cadmium molar ratio in the reaction mixture
results in only a small change in the composition of deposited CdTe films,
less than the accuracy of the electron microprobe analysis. Also, no com-
positional lnhomogeneities were detected across the films by the electron
microprobe analysis.
The electrical resistivity of p-type CdTe films may also be controlled by
the addition of dopants (AsH 3 or PH3) to the reaction mixture during the
deposition process. Using a reaction mixture with a composition required
to yield nearly stoichiometric films, the effects of the addition of AsH 3

09 |0 11 L2 1.3 14 ! 2 3 4 5
TelCd RATIOIN REACTIONMIX]IJRE AsH3/Cd RATIO X IO3

F i g . 6. E l e c t r i c a l r e s i s t i v i t y o f p - C d T e f'drrm as a f u n c t i o n of the tellurium-to-cadmium


m o l a r r a t i o i n the reaction m i x t u r e .

Fig. 7. Electrical resistivity o f p-CdTe films as a f u n c t i o n o f t h e a r s i n e - t o - c a d m i u m m o l a r


ratio m the reaction mixture.
38

on the resistivity of CdTe films is shown in Fig. 7. When the AsH 3 concentra-
tion in the reaction mixture is gradually increased, the resistivity of the film
decreases, and a mlmmum, at about 200 ~2 cm, occurs at an AsH3-to-
cadmium molar ratio of about 2 10 -3. The resistivity increases at higher
AsH 3 concentratmns presumably owing to the interaction of the dopant
with the native defects.

2 4 . Optical p r o p e r t i e s
CdTe fll,ms were deposited on Corning 7059 glass substrates at 540-
550 C. Nearly stoichiometric tellurium-deficient (n type of m m l m u m
resistivity) and cadmium<leficient (p type of minimum resistivity) films
were obtained by adjusting the tellurium-to-cadmium molar ratio in the
reaction mixture. The deposited films were mechanically pohshed with
alumina and their optical absorption at room temperature was measured
using a Varian Model Cary 17 spectrophotometer. Figure 8 shows a plot of
a2 (a is the absorption coefficient) of a nearly stoichiometric CdTe film
vs. photon energy. The extrapolation of the linear portion of the plot to
the energy axis ymlds an optical band gap of 1.50 eV for the fundamental
absorption, essentially the same as the band gap of single-crystal CdTe.
The a2 vs. p h o t o n energy plots for tellurium- and cadmium<teficient CdTe
films also yield the same band gap.

20

~15
c~

~10

?
/
/
/,//
II/" /
I I I
48 1 19 1 50 l 51 05 10 1
POSITION, MICROMETERS
PHOTON ENERGY, eV

Fig. 8 Optical absorption data of a nearly stoichiometric CdTe film.


Fig. 9. The electron-beam-reduced current-beam position relation for the determination
of effective intragrain diffusion length in a p-CdTe film.
39

2.5. Minority carner d,ffuszon length


The effective lntragrain minority carrier diffusion length in several
cadmium<leficient and arsenic<loped CdTe films on W/graphite substrates
has been measured by the scanned electron-beam-induced current method
in an ETEC Autoscan scanning electron microscope [7]. Figure 9 shows
an induced current-beam position relation for a p-CdTe film, where the
effective intragrain diffusion length is about 2 m, considerably higher than
that in n-CdTe films.

3. CdTe films by close-spaced sublimation

The deposition of CdTe films by the CSS technique is based on the


reversible dissociation of CdTe at high temperatures:
2CdTe(s) ~ 2Cd(g) + Te2(g)
A CdTe source and a substrate are separated by a small distance, and the
source is maintained at a higher temperature than the substrate. The source
CdTe dissociates into its elements which recombine on the substrate surface
depositing CdTe films. Since the deposition process involves the direct
combination of the elements, the CSS techmque is also considered as a
CVD process. The CSS technique is similar to the epitaxial growth of III-V
compounds by the close-spaced chemical vapor transport technique devel-
oped during the 1960s [9], except that no transport agent is used. When
the spacing between the source and substrate is less than a few per cent
of the dimension of the substrate, then the material transport conditions
are largely independent of conditions elsewhere in the system. The close
spacing of source and substrate also provides direct transport of each
component of the source across the space. The CSS technique has been used
for epitaxial growth of CdTe [10, 11] and has recently been applied to
the deposition of polycrystalline CdTe films [2, 11, 12]. However, the
control of the resistivity of CSS CdTe films has not been mvestigated in
detail.

3.1. The deposttion process


The apparatus used for the deposition of p-CdTe films by the CSS
technique, similar to that used by others [9], is shown schematically in
Fig. 10. The substrate and source, separated by about 1 mm and supported
by appropriate holders, were enclosed in a controlled atmosphere in a
fused-silica tube provided with gas inlet and outlet tubes. They were main-
tained at desired temperatures by using quartz lamps, and therrnocouples
inserted into the holders were used to control their temperatures. The
source material was prepared by the direct combination of the elements
with different degrees of cadmium defmiency or from a stoichiometric
mixture containing varied concentrations of a dopant such as arsenic or
antimony. Coming 7059 glass or SnO2:F/glass were used as substrates.
40

QUARTZ LAMP

TttERMOCOUPLE

Fig. 10 Schematm diagram of the apparatus for the depomtlon of p-CdTe films by the
CSS technique.

The CSS technique, though simple m principle, involves several inter-


related parameters such as the temperatures of the source and the substrate,
the separahon between the source and the substrate, the nature of the
atmosphere and the pressure in the reaction tube, the composition of the
source material etc. For example, the pressure in the reaction t ube m
i m p o r t a n t m determining the rate of deposition since the dissociation
pressure o f CdTe depends exponentially on temperature. At a given source
temperature, the sublimation rate increases rapidly as the pressure in the
reaction tu b e is reduced from the atmospheric pressure. At t oo low pres-
sures, 1 T o r t for example, the mean free path of the gaseous species in
the reaction tube increases, and the condensation process is no longer
limited to the space between the substrate and the source material. Thus,
a compromise must be made between the source temperature, the gas
pressure and the deposition rate. The results of m any experiments suggest
that, using the apparatus shown in Fig. 10, a helium pressure of 30 Tort,
a source-substrate separation of 0.1 cm and a source-substrate t em perat ure
difference of 100 C are suitable for the CSS process. Thus the substrate
t e m p er atu r e and the composition of the source material remain as the
i m p o r t a n t process parameters.
The deposition rate of CSS CdTe films depends strongly on the
substrate temperature, as shown in Fig. 11, where the source t e m p e r a t u r e
was 100 C above the substrate temperature in all cases. The rate mcreases
from ab o u t 0.6 pm rain -1 at 500 C to about 10 #m min -1 at 600 C. The
logarithm of the depomtlon rate is a linear f u n c h o n of the reciprocal tem-
perature m kelvms, and the slope of this linear plot yields an activation
energy o f a b o u t 1.58 eV, similar to the band gap energy of CdTe, indicating
that the dissociation of the source material is the rate-determining step.

3.2. Microstructure
The microstructure of CSS CdTe films m strongly affected by the sub-
strate temperature. Figure 12 shows the scanning electron mlcrographs of
41

100 -

~ 5o

lO

05
I I
1 m15 1 Z 125 1 3
1000/I, K-I

Fig. 11. Effects of substrate temperature on the depositlon rate of C d T e films by the C S S
techmque

(a) (b)
Fig. 12 Scanning electron micrographs of C S S C d T e films deposited at (a) 500 C and
(b) 6 0 0 C.

the surface of films deposited at 500 and 600 C. The grain size increases
from less than 1 pm in films deposited at 500 C to 3-5 pm in films
deposited at 600 C. The hlms deposited at higher temperatures also
consisted of grains with well-developed faces.
42

3.3. Electrical propertLes


T h e electrical resistivity o f CSS p-CdTe films d e p e n d s o n the substrate
t e m p e r a t u r e and the c o m p o s i t i o n o f the source material. Since the CSS
process provides direct t r a n s p o r t o f each c o m p o n e n t of the source material
to the substrate, the resistivity of p-CdTe films m a y be c o n t r o l l e d b y usmg
d o p e d or c a d m i u m - d e f i c i e n t source material
The e f f e c t o f the substrate t e m p e r a t u r e o n the electrical resistivity o f
the CSS p-CdTe films on SnO::F/glass substrates m a y be illustrated b y a
series o f e x p e r i m e n t s using a source material c o n t a i n i n g 5 1018 a n t i m o n y
a t o m s per c e n t l m e t r e c u b e d and a s o u r c e - s u b s t r a t e t e m p e r a t u r e d i f f e r e n c e
o f 100 C. T h e electrical resistivity of CSS CdTe films m the thickness
d i r e c t i o n was m e a s u r e d in the same m a n n e r as for the CVE CdTe films. T h e
resistivity o f CSS C d T e films has been f o u n d to d e p e n d strongly o n the
substrate (source) t e m p e r a t u r e , as s h o w n in Fig. 13. It decreases rapidly
with Increasing t e m p e r a t u r e . T h e lower resistivity at higher substrate tem-
p e r a t u r e s could be related to t h e m o r e efficient i n c o r p o r a t i o n of a n t i m o n y
into C d T e films.
At a given substrate t e m p e r a t u r e , t h e electrical resistivity of CSS
p - C d T e films d e p e n d s strongly o n the c o n c e n t r a t i o n o f the d o p a n t in the
source material. Figure 14 shows the resistivity o f p-CdTe films d e p o s i t e d
at 6 0 0 C as a f u n c t i o n o f t h e a n t i m o n y c o n c e n t r a t i o n in the source material.
T h e lowest a n t i m o n y c o n c e n t r a t i o n in the C d T e source material p r e p a r e d
was 1017 cm -3, a p p r o x ~ n a t e l y 10 p p m , and the r o o m t e m p e r a t u r e resisti-
vity o f the CSS CdTe films was higher t h a n 104 EL cm. As the a n t i m o n y
c o n c e n t r a t i o n in the CdTe source increases, the resistivity o f the CSS C d T e
film decreases, reaching a m i n i m u m o f a b o u t 200 ~2 cm at an a n t i m o n y
c o n c e n t r a t i o n o f 1019 cm -3. F u r t h e r increases in the a n t i m o n y c o n c e n t r a -
t i o n in the source material increases the resistivity o f C d T e films owing to

lO4

4,000

o 3.000
i0 ~
>

2,000

1,0CC
lo 2
I I I i I I , J i I ,
SO0 540 580 1017 1018 1019 1020
SUBSTRATE TEMPERATURE, C CONCENTRATION OF Sb IN CdTe 50~RCE MATERIAL, CM -3

Fig 13. Effects of substrate temperature on the reslstlvity of CdTe films by the CSS
technique.

Fig. 14 Effects of d o p a n t c o n c e n t r a t l o n in source material on the reslstivlty of CdTe


films by the CSS technique.
43

~
V
103

10TM 10 l g

Concenlratlon of Cd Vacancies In CoTe Source Material, cm "3

Fig. 15. Effects of cadmium vacancy concentration in source material on the resistivity
of CdTe films by the CSS technique.

s e l f - c o m p e n s a t i o n or other defect interactions. A t a n t i m o n y c o n c e n t r a t i o n s


o f 1020 cm -3 or higher, no uniform adherent films c o u l d be obtained.
The resistivity o f CSS CdTe films may also be controlled by using
cadmium-deficient source material, as s h o w n in Fig. 15. The CSS CdTe
films were d e p o s i t e d at 6 0 0 C using the same c o n d i t i o n s as for a n t i m o n y -
d o p e d source material. The d e p e n d e n c e o f the resistivity o f CSS CdTe
films o n the c a d m i u m - d e f i c i e n c y in the source material is similar to that of
CVE CdTe films o n the tellurium-to-cadmium molar ratio in the reaction
mixture. While the resistivity o f CSS CdTe films may be controlled w i t h i n
a limited range by extrinsic or intrinsic doping, the CSS process is n o t as
flexible as the CVE process.

4. P h o t o v o l t a i c characteristics

Thin film CdTe h e t e r o j u n c t i o n solar cells may be classified into t w o


categories i.e., back-wall cells and front-wall cells, as illustrated in Fig. 16
[ 1 3 ] . B o t h t y p e s o f cells have been prepared in this work.

OHMIC CONTACT

11
ITO or CdS, 0 3 - 0 5 ,urn
p-COTe,5 - ].5 ,urn

CdS or CdZnS, n 1 - O.2 ,urn

p-COTe, 10 - ~ .om SnO2 F, 0.3-0.5,urn

Sb, 0 2 - O 5 ~Jm GLASS

W/GRAPHITE OR GRAPHITE
Ill
BACKWALL CELL FROHTWALL CELL

Fig. 16. The back-wall and front-wall configurations of thin film CdTe hetero]unction
solar cells.
44

4 1 Back-wall cells
In back-wall cells, the p-CdTe film and the TCS are deposited succes-
mvely on the substrate The major problem of this approach is the lack of
a reproducible stable low-resistance ohmm contact to p-CdTe films. Because
o f them large work function, c o m m o n metals cannot form a barrierless
c on tact with p-CdTe. The c ont a c t resmtance may be reduced by lowering
the barrier height or decreasing its thmkness. A substantial increase in the
tunneling current may be obtained by creating a region of high carrier
concentration under the cont act either through alloy regrowth or in-dif-
fusion of a suitable d o p a n t provided by the cont act material. G roup Ib
dopants (copper, silver and gold) are unsmtable because of their high dlf-
fusiwty at the temperatures used for the deposition of CdTe films. The use
of a n t i m o n y was f ound to reduce the interface resistance in some cases;
however, the results were n o t reproducible.
Using Sb/W/graphite as substrates, solar cells were prepared by the
successive deposition of (1) 15 - 20 pm of p-CdTe of resistivity about 200 Yt
cm by CVE, (2) 0.3 - 0.5 #m of ITO by 1on-beam sputtering, and (3) silver
grid contact, 10 lines per centlmetre, by vacuum evaporatmn. The best
cells o f area 1 cm 2 have an (AM) mr mass 1 efficiency of about 8.2% under
simulated AM 1 conditions, as shown m Fig. 17. The perform ance of the
back-wall cells appears to be limited by the p-CdTe-substrate interface
resistance.

4.2 F r o n t - w a l l cells
In the front-wall configuration, the TCS film IS first deposited on
a glass substrate, followed by the depomtion of the p-CdTe film and the
ohmic contact. The advantage of this approach is t hat the contact is form ed

16--

i
02 04 06 08
VOLTAGE, VOLTS
Fig. 17. Cu~cent-voltage chaxacteristms o f a back-wall cell o f the conflguration I T O /
p - C d T e / W / g r a p h i t e u n d e r l l l u n m n a t l o n w i t h E L H lamps equivalent t o A M 1 conditions'
cell area, 1 c m 2, Voc = 0 74 V, Jsc = 17.4 m A c m - 2 , fill f a c t o r , 6 3 . 5 % ; e f f i c i e n c y , 8 2%
45

as the last step of the fabrication process and is not subjected to further
heat treatment, thus eliminating the p-CdTe-substrate interface resistance
problem encountered m the back-wall configuration.
Several TCSs are suitable as the heterojunction partner from electron
affinity considerations and the use of CdS is emphasized m this work. The
substrate has the configuration CdS/SnO2:F/glass. Fluorine-doped SnO:
films were deposited by CVD and CdS films were deposited by vacuum
evaporation. The sheet resistance of CdS/SnO::F films is usually 8 - 1 0
~2/D. The p-type CdTe films were deposited on the substrates by CVE and
CSS.
The CVE technique has the advantages that in a gas flow system the
surface of the substrate can be etched zn s i t u and that low-resistivity (200
~2 cm or less) p-CdTe can be readily deposited through non-stolchiometry
or extrinsic doping. However, reasonably high rates (0.3- 0.4 /~m m m - ' )
can only be obtained at relatively high temperatures, for example, 550 C.
Further, CVE CdTe films consist of large grains, and films of thickness
1 5 - 20 pm axe requtred to eliminate pinhole problems. Because of the
long deposition time at relatively high temperatures, chemical reactmn
between CdS and CdTe at the interface is likely. Many front-wall solar
cells have been prepared from CVE CdTe film using copper-doped graphite
as the ohmic contact to p-CdTe [14]. The best solar cells of area 1 cm 2
have an AM 1 efficiency of about 9.8%, as shown in Fig. 18. An electron-
beam-induced current examination suggested that the maximum response
is about 0.3 #m mto CdTe, possibly owing to the interface reaction resulting
from the large t e m p e r a t u r e - t i m e product during the deposition of CdTe.
In the CSS technique the control of the surface cleanhness of the
substrate and source material by in s z t u etchmg is more difficult. The impor-
tance of surface cleanhness is apparent from the dark current-voltage

~, 24

.~ 20

~ 16
m

I I
0.2 04 06 08
VOLTAGE,VOLTS
Fig. 18. CuzTent-voltage characteristics o l a front-wail cell o f the conflguratlon C:Cu
(ohmic contact)/p-CdTe(CVE)/CdS/SnO2:F/glass under illumination with E L H lamps
equivRlent to AM 1 conditions: Voc = 0 . 7 2 V; Jse = 2 4 . 0 m A c m - 2 ; fill f a c t o r , 5 7 . 0 % ;
efficiency, 9 85%.
46

characteristics of CdTe/CdS heterojunctions. Figure 19 shows the dark


forward characteristics at various temperatures of a typical CdTe/CdS
heterojunctlon when the substrate-source material assembly was
heated in a reducing atmosphere prior to the deposition of CdTe. The
diode quality factor varies from 1.6 to 1.7 at a forward bias lower than
about 0.6 V and is essentially independent of temperature. The saturation
current density vs. reciprocal temperature in the temperature range 2 6 8 -
348 K yields an activatmn energy of 0.72 eV. The slope of the J - V charac-
teristics of this CdTe/CdS heterojunction is essentially temperature indepen-
dent, suggesting that the interface recombination process plays an important
role in the current transport across the junction. Figure 20 shows the dark
forward characteristms at various temperatures of a CdTe/CdS hetero-
junction where no in s t t u etching was used. The saturation current density
is considerably higher than that shown in Fig. 19. At temperatures above
298 K, the J - V characteristics may be described by a thermally activated
recombination. However, the saturation current density at low temperatures
is essentmlly independent of temperature, indicating that the tunneling
of carners into interface states is a d o m i n a n t current transport mechanism.

ln-2

/ :
10-3 .:'/

~4r ~1i: I i i
- 5 " : J :
7//I / -
t/ ~.,'_~..-%~/
A,_"d2/ ~J/ ~ : , Q:

(.~
l0 i.-/ ," .." / ~n ~ #

/: /:
/.
10-
':,W/-"
10 -9 V/,: ,
02
~
04
,
06
~ ~
08
L_
0] 02 03 0_4 05
VOLTAGE, VOLTS VOLTAGE, VOLTS
F~g. 19. Dark c u r r e n t - v o l t a g e c h a r a c t e r i s t i c s o f a C d T e / C d S heterojunction (with in situ
etching) a t various temperatures.
Fig. 20. Dark c u r r e n t - v o l t a g e characteristics of a C d T e / C d S heterojunction (without
in s i t u etching) at various temperatures.
47

!'"l"*'l'"'l""i .... I .... I .... I .... I"'~

~ 10p

i
-2
2
-~,,,I . . . . I , , , , h , , , h , , , h , , , h , , , i , , , , I , J
0 02 04 0_6
VOLTAGE. VOLTS

Fig. 21. C u r r e n t - v o l t a g e characteristics of a front-wall cell of the configuration C:Cu/-


p-CdTe(CSS)/CdS/SnO2:F/gI~u~ under global AM 1.5 conditions: area, 1.222 cm 2, Vo =
0.7484 V; Jar = 22.21 m A crn-2; fill factor, 0.6339; efficiency, 10.5%.

The deposition rate of p-CdTe films by the CSS technique is consider-


ably higher than that by the CVE technique, and 3 - 4 min are sufficient to
form the solar cell structure. The short duration required in the deposition
of p-CdTe films greatly reduces the interaction between CdTe and CdS,
and solar cells with efficiencies higher than 10% have been obtained. Figure
21 shows the illuminated current-voltage characteristics of a p~dTe(CSS)/-
CdS/SnO2:F/glass solar cell of area 1.2 cm 2 under global AM 1.5 conditions
measured at the Solar Energy Research Institute. The open-circuit voltage,
short-circuit current density and fill factor are 0.748 V, 22.2 mA cm -2
and 63.4% respectively, corresponding to a conversion efficiency of 10.5%.
The use of other TCSs and better controlled ohmic contact to p-CdTe
will be reported in future communications.

5. Conclusion

C a d m m m telluride has been shown to be a promising thin film photo-


voltaic material for terrestrial power generation. CdS/CdTe heterojunction
solar cells with conversion efficiencies higher than 10% have been demon-
strated. Further improvements in the conversion efficiency of thin film
CdTe solar cells can be expected by optimizing the TCS, the thickness of
the p-CdTe film, the ohmic contact to p-CdTe etc.

Acknowledgments

This work was supported by the Solar Energy Research Institute


under Subcontract XL-5-05039-1.
48

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