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CURRENT TRANSPORT MECHANISMS OF ELECTROCHEMICALLY DEPOSITED CdS/CdTe HETEROJUNCTION

S. S. Ou and 0. M. STAFSUDD
Department of Electrical Engineering, University of California, U.S.A. Los Angeles, Los Angeles, CA 90024,

and B. M. BASOL
Monosolar Inc.. A Division of Monogram Industries, Inc., 8635 Aviation U.S.A. Blvd. Los Angeles, CA 90301,

(Received 1 May 1983; in revisedform

20 June 1983)

Abstract-The dark current transport mechanism in electrochemically deposited n-CdS/p-CdTe thin film heterojunctions is investigated. The forward current measured in the temperature range between 200 and 305K can be expressed as J,= J,,(T) exp (A V) and the reverse current can be expressed as
J, = - CV exp - CV[-,I(V, - Y)-1f2)]. The recombination-tunneling model. current mechanisms are consistent with a multi step

INTRODUCTION The potential for the utilization of CdS/CdTe heterojunctions for the terrestrial photovoltaic conversion of solar energy has long been recognized. CdTe has a direct band energy gap of about 1.45 eV and has high optical absorption coefficients. These properties make it very attractive as an absorber in a thin film solar cell. Low resistivity CdS, having an energy gap of 2.42 eV, is commonly used as a wide band gap window material in heterojunction cells. Moreover, both semiconductors can be fabricated by various thin film technologies. Several CdS/CdTe solar cells have been fabricated and characterized during the past few years. In 1972, Bonnet and Rabenhorst demonstrated the first all thin film CdS/CdTe heterojunction solar cell with an efficiency of about 5.4%[1]. Recently, all thin film CdSiCdTe solar cells prepared by close-spaced vapor sublimation[2], screen printing[3], and electrodeposition[4], showed efficiencies in excess of 8%. In order to further improve the performance of all thin film CdS/CdTe solar cells, a knowledge of the carrier transport mechanisms is essential. The purpose of this paper is to report on the current transport mechanisms for electrodeposited CdS/CdTe junctions. EXPERIMENTAL The details of the cathodic deposition process for CdS and CdTe films and the processing involved to make CdS/CdTe heterojunctions were described previously[4-61 and will not be repeated here. As a summary, the present device consisted of five layers. IT0 coated sodalime glass with a sheet resistance of 10 ohms/n served as the conductive substrate. CdS film was cathodically electroplated on the IT0 to a thickness of 500-1000 A. A 1.2-2pm thick layer of

CdTe was then deposited on the CdS film by using the same electrodeposition technique. After the formation of the heterojunction by heat treatment [6] the CdTe was briefly etched with bromine methanol and a gold layer was vacuum deposited on the CdTe film as the ohmic contact. CURRENT-VOLTAGECHARACTERISTICS The dark forward I-V characteristics of several cells were measured in the temperature range between 200 and 350K. Figure 1 shows a semilogarithmic plot of the forward I-V characteristics of a CdS/CdTe electrodeposited diode at various temperatures. The characteristics are roughly exponential

lo-, -2 10 10 N-10 3 210 2 ( -3 -

330%

_.

-4 -5 -6_ 10

lO-7 10 10
liOO,

-8

V (VOLTS) Fig. 1. The forward 21 bias dark I-V characteristics.

over five orders of magnitude. The small change in slope and magnitude over a substantial range of temperatures indicates a relatively temperature insensitive current transport mechanism. The forward currenttvoltage characteristics can be expressed by the empirical equation: J, = J,,(T) exp (A, v) (1)

fO. ;i
k
/

0 6
.

90.5

where A, is a constant which is independent of temperature. The index i = I, 2 refers to two voltage regions of each curve and J,(T) is the extrapolated intercept of the curve with the current axis. At applied biases above 0.65 V, the curves deviate from exponential behavior and indicate the effect of the series resistance. This effect is even more pronounced at lower temperatures due to the increased resistivity of the CdTe with decreasing temperature. Analysis of data for this report was carried out in regions where there was no effect of the series resistance. Table 1 shows the values of A, and Az at different temperatures along with the corresponding values of n which can be obtained by fitting the data to the standard diode equation: J, = .I,, exp (y V/nk T)
(2)

10

-ia

T (OK) Fig. 2. The dark current density vs temperature

It is observed from Table I that diode factors (n) required to fit the 1-V data to eqn (2) are close to and larger than 2 for the entire temperature range tested. Furthermore, there is a 90;, or more change in n value going from 207 to 338K. Values A, on the other hand, are insensitive to temperature change within experimental error. Therefore, the data is not consistent with eqn (2) but is consistent with eqn (1).

This indicates a tunneling mechanism for the entire range of temperatures. Figure 2 shows the temperature dependence of the current at constant voltage. The curve shows In I = UT + h V which indicates that the current transport mechanism is a multi-step recombination/ tunneling one as described by Riben and Feucht[7]. Figure 3 shows a plot of log .I,, vs temperature. The data fits well on straight lines, which agrees with this model. The typical dark reverse 1-V characteristics at different temperatures are shown in Fig. 4 for the

Table

I. Jo, n. A at various
Reglo o< v " 2) < 0.3

temperatures
ii1 volts A CC')

for electrodeposited

n-CdS/p-CdTe
Region 0.3 < " V < c2 0.6 A ("-'I volts

emperature (
338 334 329 321 302 306 297 291 283 212 263 251 243 233 219 207

JO (mA!cm

JO (rnA/Crn2)

K)

2.2x10 1.8x10-9 l.lxlfl 5*10-'" 2.9x10-" 2x10-10 1.3x10-~0 1X10-10 i.zxio-1' 2x10-'1 3X10-12 3x10-12 I.ixlf'2 ,.2x10-'3 3XIO-14 1x10-'4

-9

2.07 2.09

16.6 16.61 16.03 16.61 16.61 16 I6 16 15.50 16.61 16.8 16.3 16 IS 15.2 14.5

8.5x10-'0 7x10-10 5XlC'O 2.5~10-'~ 1.ox10-~0 8x10-l' bxlO-" 4.6x10-" I.ixlO-"

1.7 1.76 1.81 1.83 1.9 1.93 2.07

20.22 19.79 19.4R 19.79 19.71 19.65 18.85 18.35 18.98

-9

2.2 2.18 2.25 2.37 2.44 2.49 2.65 2.56 2.62 2.84 2.98 3.32 3.48 3.86

L.IJ
2.16

Area=O.OZcm J=Joexp(AV) or J=Joexp(qV/nkT)

CdSiCdTe heterojunctions

23

-11 10 0 -12 0 10 kc--I 200

-10 10 -

DEVICE AREA 0.02 CM

250

300 T (OK)

350

400 -11 10 0

Fig. 3. J,, vs temperature.

I -1.0 V (VOLTS) -2.0 _< b 3

lo-

-7_

Fig. 5. The reverse bias current I,/ V vs (V, - V)

.
-

7c
> .
L

lo-

349%

lo-!

-11 10
1

multistep tunneling is possible. In this model[7], the electrons first stepwise tunnel from the conduction band of the n-type semiconductor into the empty interband states which are located in the p-type semiconductor and subsequently recombine through a staircase of closely spaced states in the depletion region. Assuming that the electric field is constant in the depletion region, the concentration of the trapping states is high, the levels are uniformly distributed in both energy and space, and the tunneling probability of electrons between levels is as given by Franz[8], the forward current in the multi-step tunneling/recombination model can be expressed by:
(

0.6

0.6

0.7

0.8

Jf=BXN,exp[-aR~2(Vd-KV)]

(3)

(VD -v 1-/2~VOLTS-12)

Fig. 4. The reverse bias dark I-V characteristics. preavalanche breakdown regions. For lower voltages (V < 0.5 V) the current is a linear function of the voltage while at higher voltages, the current is proportional to V. Figure 5 shows the variation of the reverse current I,/ V vs (V, - V) where Vd is the build-in voltage determined by the C-V measurements.
DISCUSSION

with LY = (rr/4h)(m,~,/N,)~ where N, is the density of tunneling/recombination centers, X is the transmission coefficient for electrons to cross the interface, K = [l + (tpNJtnNd)-1, m, is the effective mass of the electron t,, cP are the dielectric constants of CdS and CdTe respectively, N,, Nd are the net ionized charge density on each side, and R is the number of steps required to traverse the depletion region. The above equation can also be expressed as:
J/ = Jo, exp (BT) exp (AKV) (4)

A carrier concentration on the order of IO-1 0E9cm 3 is necessary for the band-to-band tunneling. The measured ionized change density in electrodeposited CdTe is on the order of lOI cm 3 and is therefore too low to allow simple tunneling through the potential barrier at the junction. But

where B represents the temperature dependence introduced by change of Vd with temperature. For forward bias, a value of 0.07 was calculated for the empirical coefficient B using Fig. 3. A room temperature value of N, = 2.7 x 1016/cm3 was determined from 10 Hz capacitance-voltage character-

24 istics. /PI,,=- 0.

s. s. ou

Pi

(il.

I lm,,, c = 9.6~,,and K = I was assumed and the number of tunneling steps was calculated from Eqn (3) to be about 69 (for A = 16.5) and 40 (for A = 19) for region No. I (V < 0.3 V) and NO. 2 (b > 0.3 V) respectively. This means that 40 to 69 steps are required to traverse the depletion region. The number of steps is in reasonably good agreement results previously published by other with authors[9. IO]. The existence of two straight lines above room temperature as seen in Fig. I may result from nonuniform distribution of trap levels in the space charge region under forward bias condition. The temperature dependence of J,, can result either from L,,or BXN, terms of eqn (3). Several authors attributed the linear variation of log I with T in GeGaAs[7], CdS,:Cu$ [ I I] and lTO/Si [ 121 heterojunctions to a linear increase in V,, with decreasing temperature. Figure 6 shows the results of capacitance-voltage measurements at various temperatures for our device. In all the curves the I/c vs bias behavior is a straight line, indicating an abrupt junction. The change in slope at higher reverse bias is attributed to the uncovering of a deep level. It can be observed that. unlike other work, although V,, decreases with increasing temperatures at temperatures lower than 273K. it increases with increasing temperatures at higher temperatures. Thus, although the multistep recombination/tunneling model may explain the forward I-V characteristics of electrodeposited CdSiCdTe heterojunctions, substantial disagreement exists as to the dependence of V,, on temperature at temperatures higher than 273 K. This disagreement is probably due to the interface states. Although Donnelly and Milnes[ 131 considered the case in abrupt heterojunction including the interface states, they did not explicitly describe the effect of interface states on v<, in terms of temperature. However, it is known that the temperature affects the
60 224K

carrier concentration. the Fermi level and thus !I,,.In addition. the temperature dependence of the forward current is not necessarily related to lx;,. In the preavalanche breakdown region. the behavior of the reverse current can also be explained hy a multi-step tunneling/recombination model. The transport mechanism is Zener electrons tunneling from CdTe valence band to CdS conduction band. The equation for reverse current is:

where IT, is a barrier corresponding step and

to one tunneling

From the experimental values. we found i. = 5.X. The barrier between steps is about 2 x IO eV and IO steps are required. This large number of steps has also discovered in Cu$CdS solar cells[ I I]. due to the high &,, t A& value. The trap density h, required for the multistep tunneling can also be obtained from:

J,
Iy

exp (i( I,, -

I)

.j -=cr!V,,/~

(7)

where (I is CdTe lattice constant. and w tound a value of N, = 2.1 x IOcm . The experimental linear vartation of In ./, with 7 is shown in Fig. 7. Assuming that the energy band gap of CdTe changes linearlv with temperature L:4 = &, ~ cT. and I?, is a constant with temperature.
-7
10
_

t/
,l ,J

,/-3v / /
10

,/-2v /A( ./I,/

\
i

49 ,/:/ ,,,/;c-_~; , ,// /;; / / , ,,.P _ / .d ,A , ,/ ,/, /r,/ /4 :,.I

c
L -

z10-l
-l( 10

,i/ /
2 0 300

,,

Y,
AREA 0.02 CM 2

DEVICE

-1 10
V (VOLTS)

310

320 T (K)

330

340

3 0

CdSiCdTe heterojunctions
we have:

25

Monogram Industries (Contract No. 4-44252&57241). In addition, the authors thank Mr. E. Tseng and Dr. R. L. Rod &J,)= -(V,-V)- l/&E , I+

(8)

of Monosolar Inc., for their contributions to this project. The authors, would also like to thank Mr. M. Jansen for useful discussions. REFERENCES 1. D. Bonnet and H. Rabenhorst, Proc. 9th IEEE Photo voltaic Spec. Conf., p. 129, IEEE, New York (1972). 2. Y. S. Tyan and E. A. Perez-Albuerne, Proc. 16th IEEE Photovoltaic Spec. Conf., p. 794, IEEE, New York (1982). 3. H. Uda, H. Matsumoto, Y. Komatsu, A. Nakano and S. Ikegami, Proc. 16th IEEE Photovoltaic Spec. Conf., p. 801, IEEE, New York (1982). 4. B. M. Basal, E. S. Tseng, R. L. Rod, S. Ou and 0. M. Stafsudd, Proc. 16th., IEEE Photoaoltaic Spec. Conj:, p. 805, IEEE, New York (1982). 5. M. P. R. Panicker, M. Knaster and F. A. Kroger, J. Electrochem. Sot. 125, 566 (1978). 6. B. M. Basol, E. S. Tseng and R. L. Rod., U.S. Patent 4, 388, 483 (1983). 7. A. R. Riben and D. L. Feucht, ht. J. Electron. 20, 583 (1966). 8. W. Franz, Hbd. Phys., XVII, 155 (1956). 9. E. I. Adirovich, Y. M. Yuabov, G. R. Yagudaev, Phys. Stat. Sol. (a) 6, 311 (1971). IO. K. W. Mitchell, A. L. Fahrenbruch and R. H. Bube, J. Appl. Phys. 48, 4365 (1977). 11. S. Martinuzzi, 0. Mallem, Phys. Status Solidi (a) 16, 339, (I 973). 12. N. S. Chang and J. R. Sites, J. Appl. Phys. 49, 4833 (1978). 13. J. P. Donnelly and A. G. Milnes, Proc. IEE 113, 1468 (1966). 14. B. M. Basal, R. L. Rod and E. S. Tseing, Proc. 4th E. C. Photoaoltaic Solar Energy Conference p. 719, Italy (1982).

with c = 4.5 x 10 4eV/C for CdTe. By using Fig. 7, we find d In J,/dT 3 x 10m4 at - 2V. This value is very small compared to our experimental finding of 0.83. This indicates that E, is not a constant with respect to the temperature. Assuming E, is a function of temperature, we have a(Egp + A E,)(dE,/dT) s 0.085 which is consistent with Adirovich et ul.[13] value of 0.017.
CONCLUSION

conclude, the 1-V characteristics of eiectrodeposited CdS/CdTe heterojunction shows that the tunneling is a predominant current transport mechanism between 200 and 350K. Previous work on CdS/CdTe heterojunctions indicated that the current transport mechanism was tunneling below 300K and generation/recombination above 300K [lo, 141. This mechanism was found to be dominant under forward as well as the reverse bias conditions. Present work on all thin film devices indicated tunneling is applicable in both temperature ranges. This indicates that these devices have a higher density of defects/traps in the depletion region that are effective tunneling centers.
To Acknowledgement-The authors wish to acknowledge the support of this reasearch by Monosolar, Inc. a division of