Solar Cells, 24 (1988) 27 - 34 27

EFFICIENT THIN FILM CADMIUM TELLURIDE HETEROJUNCTION

SOLAR CELLS*

T. L. CHU, SHIRLEY S. CHU, K. D. HAN, Y. X. HAN, Y. H. LIU and

M. K. MANTRAVADI
Southern Methodist University, Dallas, T X 75275 (U.S.A.)
(Received November 16, 1987; accepted December 22, 1987)

Summary

A commonly used configuration of thin film cadmium telluride hetero-

junction solar cell is: ohmic contact/p-CdTe/TCS/SnO2 :F/glass where TCS is
a transparent conducting semiconductor. Its photovoltaic characteristics
depend on (i) the band gap energy, electron affinity, electrical conductivity,
lattice parameter and thermal expansion coefficient of the TCS (or the
window material), (ii) the resistivity of, and minority carrier diffusion length
in, p-CdTe, (iii) the cleanliness of the p-CdTe-TCS interface, and (iv) the
resistance of the contact to the p-CdTe. In this work, a Zn0.3Cd0.TS film
deposited by vacuum evaporation was used as the window material, the
resistivity of p-CdTe films, deposited by close-spaced sublimation was con-
trolled by adjusting the composition of the source material, and a p-HgTe
film, deposited by direct combination of the elements, was used as the
ohmic contact. The characteristics of the solar cells are discussed.

1. Introduction

Thin film cadmium telluride heterojunction solar cells have been under
investigation for many years. A commonly used configuration is: ohmic
contact/p-CdTe/TCS/SnO2 :F/glass, where TCS is a transparent conducting
semiconductor or the window. Its photovoltaic characteristics depend on (i)
the band gap energy, electron affinity, electrical conductivity, lattice param-
eter and thermal expansion coefficient of the window material, (ii) the
resistivity of, and minority carrier diffusion length in, p-CdTe, (iii) the clean-
liness of the p-CdTe-TCS interface, and (iv) the resistance of the contact to
the p-CdTe. Major difficulties associated with the fabrication of efficient
CdTe solar cells include the deposition of low resistivity p-CdTe films and
the formation of stable low-resistance contact to p-CdTe films. In spite of

*Paper presented at the 8th Photovoltaic Advanced Research and Development

Project Review Meeting, Denver, CO, U.S.A., November 15 - 18, 1987.

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

28

these difficulties, thin film CdS/CdTe solar cells with a conversion efficiency
of greater than 10% have been prepared by several authors [1 - 3].
In this work, a Zn0.3Cd0.TS film was used as the window material to
improve its optical transparency, the resistivity of p-CdTe films deposited by
the closed-spaced sublimation (CSS) process was controlled by using source
material of appropriate compositions, and a p-HgTe film was used as an
ohmic contact to p-CdTe films. Thin film CdTe solar cells with a conversion
efficiency of nearly 11% were prepared in this manner. The experimental
procedures and results are summarized in this paper.

2. Zinc cadmium sulfide as the window material

Cadmium sulfide is the most c o m m o n l y used window material for thin

film CdTe solar cells because of its reasonable optical transparency and the
ease of depositing low resistivity films. Further, the electron affinity of CdS
(4.5 eV) is higher than that of CdTe (4.28 eV), and there is no spike in the
conduction band to impede the transport of minority carriers from the p-
CdTe to the TCS. However, the band gap energy of CdS is only 2.42 eV, and
0.1 m of CdS film will absorb 36% of the incident radiation with energy
greater than the band gap energy. Thus, a larger band gap window material
is more desirable as long as its electron affinity is higher than that of CdTe.
Although ZnS with a band gap of 3.6 eV is n o t a suitable window material
because of its low electron affinity (3.9 eV), ZnS and CdS form a continuous
series of solid solutions. The composition of the solid solution may be
optimized with respect to the band gap energy and electron affinity. For
example, the addition of up to 35% ZnS to CdS results in no energy spike in
the conduction band of the CdTe/Zn0.3sCd0.6sS heterojunction, and the
band gap energy of the TCS is increased by about 0.4 eV. The deposition of
ZnxCdl_ xS films by the simultaneous evaporation of ZnS and CdS has been
reported by several investigators [4- 6]. Lattice parameter and band gap
energy of the solid solution have been f o u n d to change almost linearly with
composition, and electrical resistivity increases from less than 1 ~ cm to
more than 10 l° ~2 cm as x increases from zero to unity.
The evaporation technique was also used in this work for the deposition
of high conductivity Zn~ C d l - ~ S films. The source containers were made of
graphite and were placed inside independently controlled tantalum heaters.
The ZnS and CdS crucibles were maintained at 1 0 0 0 - 1100 °C and 8 0 0 -
900 °C respectively, depending on the composition desired. The substrate
was maintained at about 200 °C using ELH lamps as heaters. The deposited
films were usually 0 . 1 - 0.3 pm thick and showed no structural features
under a scanning electron microscope. The grain size is estimated to be
100 - 300 A. Because of the small thicknesses of the Zn~Cdl _~S films, the
X-ray diffraction technique can n o t be used to determine the composition of
the films. Since the band gap energy of ZnxCdl_~S films is essentially a
linear function of composition, the measurement of optical transmission
 29

5
E
u
Q
¢2)
4

¢.)

c~
w
1

I . . . ~ [
2.4 2.6 2.8 3.0 3.2
ENERGYOF PHOTONS, eV
Fig. 1. Optical a b s o r p t i o n o f a Z n x C d l _ x S film d e p o s i t e d o n a C o r n i n g 7 0 5 9 glass sub-
strate.

characteristics of Z n x C d I _ x S films was used to determine their composition.

Z n x C d l - x S is a direct band gap material, the square of the absorption coef-
ficient ~ is a linear function of the p h o t o n energy, and the extrapolation of
this straight line to ~ = 0 yields the band gap energy. Several compositions of
ZnxCdl_ xS films with band gap energy of 2.75 - 2.95 eV have been prepared,
and their optical absorption has been measured on a Cary 17 spectrophotom-
eter. Figure 1 shows the ~2 vs. E plot near the band edge of a ZnxCdl_xS
sample, and an optical band gap of 2.75 eV was deduced, corresponding to
approximately Zn0.2aCd0.72S.
The undoped films in the composition range Zn0.2sCd0.TsS and Zn0.4-
Cd0.6S have a room temperature resistivity of about 104 ~2 cm, Hall mobility
of 45 cm 2 V-1 s-1 and carrier concentration of ( 1 - 2 ) × 1013 cm -3. The
resistivity of Zn~Cdl_~S films may be reduced to 1 - 10 ~ cm by using
aluminum as a dopant. The room temperature Hall mobility in these films is
(10 - 15) cm 2 V-1 s-1 , corresponding to carrier concentrations in the range
8 × 1016 to 2 × 10 iv cm -a.

3. Resistivity control o f p-CdTe films

The deposition of CdTe films by the close,spaced sublimation tech-

nique is based on the reversible dissociation of CdTe at high temperatures,
and the apparatus and procedure of this process have been described previ-
ously [3]. One major problem in the fabrication of thin film CdTe solar cells
is the deposition of low resistivity CdTe films. When CdTe films are depos-
30

ited onto the surface of heated substrates by the direct recombination of the
vapor of the elements in a gas flow system, the resistivity of the film may be
controlled, to a limited extent, by intrinsic doping (using a cadmium-
deficient reaction mixture) or extrinsic doping (adding AsH3 or PH3 to the
reaction mixture), and p-CdTe films with a resistivity of about 200 ~ cm can
be deposited [7]. Similar techniques have been applied to the resistivity con-
trol of CSS CdTe films by using source materials of appropriate composition,
since the CSS process provides a direct transport of each c o m p o n e n t of the
source material to the substrate. The CSS technique involves several inter-
related parameters: the temperatures of the source and the substrate, the
separation between the source and the substrate, the nature of the atmo-
sphere and the pressure in the reaction tube, and the composition of the
source material. For example, the pressure in the reaction tube is important
in determining the rate of deposition, since the dissociation pressure of CdTe
depends exponentially on temperature. At a given source temperature, the
sublimation rate increases rapidly as the pressure in the reaction tube is
reduced from the atmospheric pressure. At too low pressures, e.g. 1 Torr,
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 be-
tween the source temperature, the gas pressure and the deposition rate. The
results of m a n y experiments suggest that a helium pressure of 30 Torr, a
source-to-substrate separation of 0.1 cm, a source temperature of 700 °C and
a substrate temperature of 600 °C are suitable for the CSS process. Thus, the
composition of the source material remains as the only important parameter.
The CdTe source material was prepared by the direct combination of
the elements with different degrees of cadmium deficiency or a stoichio-
metric mixture containing varied concentrations of a dopant, such as arsenic
or antimony. Under the sublimation conditions described above, the elec-
trical resistivity of CSS CdTe films depends strongly on the concentration
of the dopant or cadmium vacancies in the source material. Figure 2 shows

~ lfi4 .

/ i I I I I
i017 1018 I0I? I0~
CONCENTRATIONOF $b IN CdTe SOURCEMAIERIAL, CM"3

F i g . 2. E f f e c t o f d o p a n t concentration in the source material on the resistivity o f C S S

CdTe films.
 31

the resistivity of deposited CSS p-CdTe films as a function of the antimony

concentration in the source material. The lowest antimony concentration in
the CdTe source material prepared was 1017 cm -3, approximately 10 ppm,
and the room temperature resistivity of the CSS CdTe films was higher than
104 ~2 cm. As the antimony concentration in the CdTe source increases, the
resistivity of CSS CdTe film decreases, reaching a minimum of about 200
cm at an antimony concentration of 1019 cm -3. Further increases in the anti-
m o n y concentration in the source material increases the resistivity of CdTe
films because of self,compensation or other defect interactions. The resistiv-
ity of CSS CdTe films may also be controlled by using cadmium-deficient
source material, as shown in Fig. 3. The dependence of the resistivity of CSS
CdTe films on the cadmium deficiency in the source material is similar to
that on the concentration of antimony in the source material.

~10 3
m
_E

-~I02

I I I I
1018 1019
Concentration of Cd Vacancies in CclTe Source Material, cm"3
Fig. 3. Effect of the c a d m i u m vacancy c o n c e n t r a t i o n in the source material on the resis-
tivity of CSS CdTe films.

4. Ohmic contacts to p-CdTe films

The formation of a stable, reproducible, low-resistance contact to thin

films of p-CdTe is a well-recognized problem associated with the fabrication
of efficient solar cells. Various approaches to form contacts to CdTe have
recently been reviewed [8, 9]. The fabrication of ohmic contacts to CdTe is
strongly dependent on obtaining sufficient carrier density in the material.
Acceptor levels greater than 1017 c m -3 are easily obtained in single-crystal
CdTe but are very difficult to obtain for polycrystalline material. Conse-
quently, contacts with a specific resistivity of about 0.2 ~2 c m 2, which is
adequate for efficient solar cells,can be obtained readily with single crystals
but not with polycrystalline CdTe. The best approach to form low-resistance
contacts to p-CdTe films is probably to use contact materials with a higher
32

electron affinity than p-CdTe (× ~ 5.6 - 5.7 eV). HgTe (X = 5.9 eV) has been
used successfully as low-resistance contacts to p-type single-crystal cadmium
telluride and cadmium mercury telluride, p-type CdTe single crystals of 10 -
15 ~ cm resistivity were first etched in a Br2-CH3OH solution and then
coated with a layer of HgTe 100 pm thick by close spacing isothermal depo-
sition at 550 °C for 20 h. The room temperature specific resistance of this
contact is about 0.1 ~ cm 2 [10].
The use of HgTe as an ohmic contact to p-CdTe films has been investi-
gated in this work. HgTe is thermally unstable; its dissociation pressure in
the temperature range 300 - 500 °C is shown in Fig. 4 (the dissociation pres-
sure of CdTe is included for comparison). The relatively high pressure of
mercury over HgTe, about 1 Torr at 300 °C, suggests that the deposition of
HgTe on CdTe should be carried out at as low a temperature as possible to
minimize the diffusion of mercury along grain boundaries in CdTe and the
interdiffusion between CdTe and HgTe [11]. HgTe is a semimetal; however,
mercury and tellurium vacancies are acceptors and donors respectively. It is
essential to use p-HgTe as the contact to p-CdTe. The deposition of HgTe
films was carried out by the combination of the vapors of the elements in a
gas flow system. This reaction has been used for the epitaxial growth of
HgTe films on CdTe substrates at 470 °C [12]. The apparatus used for the
deposition of HgTe films is shown schematically in Fig. 5. A mercury con-
talner and a tellurium container, both made of fused silica, and the sub-
strate (p-CdTe/SnO2 :F/glass) were placed in a fused silica reaction tube in a
multizone furnace with each zone separately heated and controlled. Since
the vapor pressure of the elements varies exponentially with temperature,
the temperatures of the mercury and Te2 containers must be accurately
controlled. Hydrogen or helium was used to carry mercury and Te2 vapors

TEMPERATURE, °C
500 400 300

100~~' ~ I ' II

10-2

~- 104

10-8 I I "F. N 1 r t x
1.2 1,4 1.6
10001 T, °K-1
F i g . 4. D i s s o c i a t i o n pressure of HgTe in the temperature r a n g e 3 0 0 - 5 0 0 °C.
 33

®i
®~ , I
•
TO
L~"AU S T

SEVEN ZONE FUIINACE

A, B, C, D MASsFLOWCONTROLLERS
t
(~ SRUT-OFFVALVE
Fig. 5. Schematic diagram of the apparatus for the deposition of HgTe films by direct
combination of the elements.

to the substrate surface. The important process parameters are the substrate
temperature, and the composition and flow rate of the reaction mixture.
Although the substrate temperature is an important factor determining the
deposition rate of HgTe, it is essential to use as low a substrate temperature
as possible. The composition of the reaction mixture, i.e. the [Te2]/[Hg]
ratio, determines the conductivity t y p e of the HgTe films. The [Te2]/[Hg]
ratio required to produce p-type HgTe films depends on the substrate
temperature because of the decreasing sticking coefficient of mercury with
increasing temperature.
A series of experiments have been carried o u t for the deposition of
HgTe films. A substrate temperature of 400 °C was used in the initial experi-
ments; tightly adherent p-type films were obtained at rates of 0.3 - 0.5 gm
min -1 using [Te2]/[Hg] ratios of 1 - 1.2. Films 3 - 5/~m thick had a sheet
resistance of 50 - 80 ~2/[3. However, shunting occurred in most cases, and
the substrate temperature was subsequently reduced. At lower substrate
temperatures, such as 300 °C, the deposition rate was significantly reduced,
and lower [Te2]/[Hg] molar ratios must be used to yield p-type films
because of the higher sticking coefficient of mercury. Further, the sheet
resistance of deposited films also increased. The lowest temperature at
which adherent films can be obtained is 2 7 5 - 300 °C. The composition of
the films was confirmed by X-ray diffraction. At 275 °C, shunting does n o t
occur as frequently as at higher temperatures.

5. Photovoltaic characteristics

Many solar cells of the configuration p-HgTe/p-CdTe/Zn0.3Cd0.TS/

SnO2 :F/glass have been prepared. The best solar cell of I cm 2 area prepared
thus far had a conversion efficiency of 10.84% under illumination with ELH
lamps equivalent to air mass 1 conditions; its open~ircuit voltage, short-
circuit current density and fill factor are 0.78 V, 23.4 m A c m -2 and 59.4%
34

1
AREA: c m ~
Voc: 0 . 7 8 V \
Jsc: 23.4rnA/cm2 \
FF: 59.4% \
lO E:E: 10.84'b /

0.2
I
0.4
L
0.6
|1
0.8
VOLTAGE,VOLTS
Fig. 6. Illuminated characteristics of a p-HgTe/p-CdTe/Zno.3Cd0.TS/SnO2:F/glass solar
cell.

respectively (Fig. 6). It is believed that the conversion efficiency can be

improved by optimizing all processing steps, particularly by using a more
transparent window.

Acknowledgment

This work was supported by the Solar Energy Research Institute under
subcontract XL-5-05039-1.

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