Solar Energy Materials

and Solar Cells

ELSEVIER Solar Energy Materials and Solar Cells 46 (1997) 323-331

n-ZnSe/p-ZnTe/n-CdSe tandem solar cells

P. Gashin*, A. Focsha, T. Potlog, A.V. Simashkevich, V. Leondar
Semiconductor Physics Department, State University of Moldova, 60 Mateevieh str., MD 2009 Kishinau,
Moldova
Received 5 October 1995; received in revised form 1 February 1997

Abstract

A monolithic, three-terminal tandem structure n-ZnSe/p-ZnTe/n-CdSe was fabricated by

successive epitaxial growth from the vapor phase of ZnTe and CdSe thin layers on ZnSe single
crystals. At 300K and AM1.5 the following photoelectric parameters were obtained:
Is¢ =4.3mA/cm 2, Voc =0.98V, ff=0.75, r I =4.0% for the ZnSe/ZnTe devices and
12.8 mA/cm 2, 0.80 V, 0.53, 6.8%, respectively, for the ZnTe/CdSe devices. The photosensitivity
of the tandem structures covers the visible region of spectrum from 0.47 to 0.86 lam. The
open-circuit voltage is 1.78 V, with a total conversion efficiency 10.8%.

Keywords." Thin layers; Single crystals; Tandem structure

1. Introduction

Wide-gap I I - V I compounds present a special interest for solar energy conversion

due to their high photosensitivity, direct optical transitions and high values of
absorption coefficient ( ,-~ 104 c m - i) in the visible region of spectrum. These proper-
ties make it possible to use thin films with the thickness of a few microns for solar cell
fabrication. At the same time the photovoltaic conversion efficiencies of solar cells
based on such I I - V I compounds as ZnSe, ZnTe and CdSe do not exceed 10% [1-4].
However, they could be used as elements in tandem cell systems consisting of two or
more junctions based on compounds with different band gaps. In this case the total
conversion efficiency increases.

* Corresponding author. Tel.: (373.2)240666; fax: (373.2) 240655; e-mail: gashin@cinf.usm.md

0927-0248/97/$17.00 © 1997 Elsevier Science B.V. All rights reserved

PIt S0927-0248(96)00015-9
324 P. Gashin et al./Solar Energy Materials and Solar Cells 46 (1997) 323-331

This paper illustrates the results of fabrication, structure, and photoelectrical

properties examination of the tandem structure n-ZnSe/p-ZnTe/n-CdSe. A short
communication on this topic was published in Ref. [5].

2. Samplepreparation
The use of a monolithic structure is one of the methods for making tandem cell
systems. In our case such a structure has been obtained by successive epitaxial growth
of ZnTe and CdSe layers onto ZnSe single-crystal substrates oriented in the [1 1 0]
direction. These substrates were cleaved directly before the deposition of ZnTe layers.
It was used an epitaxial method employing a transport reaction and resublimation in
an open system in reduction atmosphere. The remaining gas pressure was
2 x 10- 5 Torr. Polycrystalline CdSe and ZnTe were used as evaporation material. The

Table 1
The summary of heterojunction preparation conditions and the electrical parameters of ZnTe and CdSe
layers

Layer Source Substr. Doping source Concentration Mobility

T~(°C) Tc(°C) Ta(°C) (cm- 3) (cm2/V s)

p-ZnTe 820 630 380 (2.1M.3) x 1017 53-87

n-CdSe 810 650 320 2.4 x 1017 460

h~
1

2.67
Z~e l
ZnTe I

2 3
a) b)
Fig. 1. n-ZnSe/p-ZnTe/n-CdSe tandem structure: (a) schematic diagram; (b) energy diagram.
 P. Gashin et al./Solar Energy Materials and Solar Cells 46 (1997) 323 331 325

epitaxy of CdSe layers was accomplished in a short time after the recharge of the
reactor with the evaporating materials. The doping of ZnTe with As and of CdSe with
In was carried out during their growth. The impurity atoms move to the mixture zone
due to the concentration gradient. Then they were transported in the form of atomic
flux to the deposition zone.
The thicknesses of ZnTe and CdSe layers were 6-12 and 4-10 gm, respectively. The
ZnSe single-crystal substrates with the thickness of 200-250 gm were previously
annealed in liquid Zn and the electron concentration was (1-5)x 1017 cm 3 with
a mobility of 470-500 cmZ/V s. The preparation conditions and the electrical para-
meters of ZnTe and CdSe layers are given in Table 1. The tandem solar cells obtained
in this way have a planar n - p - n structure (Fig. 1). Au and In were deposited by
vacuum evaporation to make ohmic contacts for ZnTe and CdSe, respectively. The In
contacts for ZnSe were alloyed at 400°C, and their contact area did not exceed
1-3 mm 2 which make ~> 10% of the whole substrate surface. This contact system
allowed us to connect the whole structure in series (contacts 1-3) as well as each cell to
a separate load (contacts 1 2 or 2-3).

3. Results

3.1. Structural investigations

The investigations of surface topography and crystalline structure of ZnTe and

CdSe thin films as well as the n-ZnSe/p-ZnTe/n-CdSe tandem system interfaces were
carried out using metallography, electron diffraction, scanning electron microscopy,
electron-beam-induced current, and electron probe microanalysis.
The pictures obtained with the help of an optical microscope and electron diffrac-
tion micrographs reveal a cubic modification of crystallites in ZnTe and CdSe
epitaxial layers with growth direction [1 1 0]. It is seen from Fig. 2a that typical ZnTe
and CdSe films are homogeneous in thickness and the ZnSe/ZnTe and ZnTe/CdSe
interfaces are represented by straight lines. The distribution of Cd and Zn atoms and
of electron-beam-induced current obtained by means of scanning electron microscopy
is given in Fig. 2b. The qualitative distribution of Cd atoms on the cleaved surface of
the tandem structure (in C d t ~c 1 characteristic X-rays) is proportional to the density of
light points on this picture. One can see that Cd atoms are observed only in the region
of CdSe layer. The distribution of Zn atoms and of the electron-beam-induced current
at the passing of the electron probe along a line perpendicular to the heterojunctions
interfaces is shown also in this picture. It is seen that the concentration of Zn atoms
decreases to "zero" in the CdSe layer. Similar results were obtained for the distribu-
tion of Se and Te atoms.
These results allow to conclude that the mutual diffusion of elements during the
deposition of ZnTe on ZnSe crystals and the following epitaxial growth of CdSe layers
on the surface of ZnTe films does not occur in the limits of the range of X-ray
generation region which is about of 2-3 ~tm. The oscillogram of electron-beam-
induced current in CdSe/ZnTe and ZnTe/ZnSe heterojunctions is presented in Fig. 2b
326 P. Gashin et al./Solar Energy Materials and Solar Cells 46 (1997) 323-331

Fig. 2. (a) Microphotography of n-ZnSe/p-ZnTe/n-CdSe tandem structure interface. (b) The distribution
of Zn and Cd atom concentration of cleaved surface of the tandem structure n-ZnSe/p-ZnTe/n-CdSe
combined with the electron-beam-induced current signal.
 P. Gashin et al./Solar Energy Materials and Solar Cells 46 (1997) 323 331 327

also. The direction of the current for each junction is opposite due to the n p-n
structure of the cell. One can see that the position of maximum values of the induced
current coincides with the heterojunctions interfaces.
The minority carrier diffusion length L was determined from the dependence of the
electron-beam-induced current on the coordinate. It was obtained that for ZnTe
epitaxial layers L, = 0.57~0.81 ~tm, for CdSe epitaxial layers L p = 0.62 0.71 Bm and
for ZnSe crystals Lp -- 0.78 0.85 [am.

3.2. Electrical properties.

The ZnSe/ZnTe/CdSe tandem structure consists of two heterojunctions:

ZnSe/ZnTe and ZnTe/CdSe (Fig. 1, contacts 1-2 and 2-3 respectively). The cur-
rent-voltage and capacitance voltage characteristics for each separate junction have
been measured.
In darkness, the forward current in the temperature range 77~,00 K for both the
junctions exponentially depends on applied voltage according to the usual relation

I=I0 [ exp ~ - 1 , ] (1)

where A is the diode factor. The pre-exponential current (Io) varies rapidly with
temperature according to

I0=I0oexp [ -- k r J " (2)

The reverse characteristics showed a power-law variation: I ~ V m with "m" changing

with applied bias.
The capacitance voltage measurements of both ZnSe/ZnTe and ZnTe/CdSe het-
erojunction showed a linear variation of C-2 vs. voltage. The capacitance depends
weakly on the frequency of the measuring signal. The summary of electric parameters
of the ZnSe/ZnTe/CdSe tandem structure is given in Table 2.

3.3. Photoelectrical properties

The photoelectrical properties of the ZnSe/ZnTe/CdSe tandem structure were

investigated by illumination through the wide gap ZnSe substrate. The optical
transmission of these substrates in the sensitivity region of ZnTe/CdSe heterojunction
(2 = 0.56-0.86 Jam) is 62-69%. Thus, the photo-generation of non-equilibrium carriers
occurs both in ZnSe/ZnTe and in ZnTe/CdSe heterojunctions. The photons with the
energies hv ~ 2.26 eV generate non-equilibrium charge carriers in ZnSe/ZnTe junc-
tion as well as photons with hv <<,2.26 eV passing through the ZnTe/CdSe interface
and create electron-hole pairs there.
The spectral photosensitivity distribution in the case of separate connection of the
ZnSe/ZnTe and ZnTe/CdSe junction (contact 1-2 and 2-3, respectively) in the tandem
structure is given in Fig. 3. It is seen that the photosensitivity of the typical tandem
328 P. Gashin et al./Solar Energy Materials and Solar Cells 46 (1997) 323-331

Table 2
The electric parameters of the ZnSe/ZnTe/CdSe tandem structure

Heterojunction W~(0) (lain) Io (A/cm2) A m VD (V) AEa (eV)

ZnSe/ZnTe 1.2 6 x 10-13 2.0 5.1 1.2 0.66

ZnTe/CdSe 0.2 6 × 10-10 1.9 2.7 0.9 0.62

Note: Wd(0), zero bias junction width; VD,diffusion potential, A is measured at 300 K; m is measured in the
interval 1 10V.

100
#
~, ).(~')
v

a)
4o

2o

I I i I I

0.5 0.6
).(~,)
0.7 0.8 0.9

Fig. 3. The spectral photosensitivity distribution of n-ZnSe/p-ZnTe/n-CdSe tandem structure: (a) ZnSe/
ZnTe heterojunction; (b) ZnTe/CdSe heterojunction; (c) nZnSe/pZnTe/nCdSe tandem structure connected
in series.

structure covers the region of spectrum from 0.47 to 0.86 ~tm. In the case of junction
connection in series (contacts 1-3) the signal polarity change in the spectral distribu-
tion is observed due to the fact that the Z n S e / Z n T e and Z n T e / C d S e junctions
generated p h o t o v o l t a g e of opposite sign (Fig. 3c). This is also observed distinctly in
the oscillogram of the electron- beam-induced current (Fig. 2b). This effect m a y be
used for the fabrication of optical pyrometers [6].
As usual, the short-circuit current Isc in both junctions increases proportionally to
the light intensity and the open circuit voltage Voc tends to saturation in conformity
with the expression

Vo~AkTlnIIr ] (3)
- e Too + 1 '
 P. Gashin et al./Solar Energy Materials and Solar Cells 46 (1997) 323 331 329

12 b)

I
¢;

a)
4

i I
0 0.2 0.4 0.6 0.8 V

Fig. 4. The load characteristics of n-ZnSe/p-ZnTe/n-CdSe tandem structure at 300 K and illumination
80 mW/cm2: (a) ZnSe/ZnTe; (b) ZnTe/CdSe.

25

23
v

21

19 I I I I I I I I
.6 2.0 ~.4 2.8 3.2
Eg 1 (eV)

Fig. 5. The calculated dependence of the efficiency of a two-component tandem structure on the band gap
of the top cell at constant Eg of the lower material.

w h e r e If is the photocurrent. The current-voltage load characteristics of ZnSe/ZnTe

and ZnTe/CdSe heterojunctions at 300 K and illumination of 80 mW/cm 2 are given in
Fig. 4. The theoretical dependence of the efficiency of a two-component tandem
structure on the band gap Eg of the top cell for constant Eg = 1.7 eV for the lower
material (CdSe in our case) for AM1.5 was calculated (Fig. 5) according to the method
proposed in Refs. [7, 8]. The calculations were carried out for tandem solar cells each
element of which is functioning on its individual load, i.e. in calculations the criterion
of the equality of photocurrents flowing through narrow gap and wide gap elements is
not taken into account. It is seen that the optimum value of the top cell band gap is
330 P. Gashin et al./Solar Energy Materials and Solar Cells 46 (1997) 323 331

Table 3
The photoelectric parameters of the ZnSe/ZnTe/CdSe tandem structure (at AMI.5 illumination and
T = 300 K)r003n

Parameter ZnSe/ZnTe ZnTe/CdSe Z n S e - Z n T e CdSe

tandem
Tandem Separate Tandem Separate

Vo¢ (V) 0.98 1.20 0.80 0.82 1.78

ls~ (mA/cm 2) 4.3 9.3 12.8 14.1
ff 0.75 0.58 0.53 0.50
Efficiency(%) 4.0 8.1 6.8 7.2 10.8
Calculated efficiency (%) 12 19 24.8

2.4-2.6 eV, which is in accordance with Eg for ZnSe (2.67 eV) and ZnTe (2.26 eV). The
calculated value of the efficiencies are 24.8% for the ZnSe-ZnTe-CdSe tandem
structure, 19% for ZnTe-CdSe heterojunction and 12% for the ZnSe-ZnTe hetero-
junction. The obtained efficiency values are the theoretical limits, at the calculations of
which the losses on series and leakage resistances of p-n junction were not taken into
account, as well as losses due to reflection from the surface and its shadowing by the
contacts. The photoelectrical parameters determined for each heterojunction and the
tandem structure in the whole are summarized in Table 3.
The data obtained by means of contacts 1-2 and 2-3 (see Fig. la) for each
heterojunction as a component of the tandem structure are given in Table 3 in the
column "tandem". The results for ZnSe/ZnTe and ZnTe/CdSe heterojunctions fab-
ricated independent from one another are presented in the column "separate". The
tandem summary efficiency and open-circuit voltage were calculated by addition of
respective data measured in two separate circuits (contacts 1-2 and 2-3).

4. Conclusions

It must be noted that these results are obtained for unoptimised structures without
antireflection coatings and can be improved by reducing both current and voltage
losses, and by the appropriate choice of component heterojunction thickness and
doping level. The observed signal polarity change in the spectral distribution of the
photosensitivity of the ZnSe-ZnTe-CdSe tandem structure may be used for the
fabrication of optical pyrometers.
The efficiency of the investigated tandem structure at AM1.5 conditions is 10.8%
while the calculated efficiency for n-ZnSe/p-ZnTe/n-CdSe tandem structure is 24.8%.

Acknowledgements

The authors are grateful to Dr. P. Ketrush for useful discussions of results and
fruitful collaboration.
 P. Gashin et al./Solar Energy Materials and Solar Cells 46 (1997) 323 331 33t

References

[1] P.A. Gashin, A.V. Simashkevich, Phys. Stat. Sol. A 19 (1973) 615.
[2] P. Gashin, A. Simashkevich, D. Sherban, Sov. Semicond. Phys. 12 (1978) 180.
[3] F. Buch, A. Fahrenbruch, R.H. Bube, J. Appl. Phys. 48 (1977) 1596.
[4] S.A. Ringel, A.W. Smith, J. Appl. Phys. 70 (1991) 881.
[5] P. Gashin, G. Dvornic, M. Kagan, T. Liubashevskaia, A. Simashkevich, A. Focsha, Soy. J. Technol
Phys. Lett. 8 (1982) 930.
[6] M.J. Hampshire, T.I. Pritchard, R.D. Tomlinson, C. Hackney, J. Phys. E: Sci. Instr. 3 (1970) 185.
[7] J.J. Lofersky, Proc. 12th IEEE Photovoltaic Spec. Conf., Baton Rouge, LA, 1976, p. 957.
[8] V.M. Andreev, O.O. Iventieva, E.P. Romanova, V.S. Iuferov, Soy. J. Technol. Phys. 53 (1983) 2025.