Thin-film solar converters based on the p-Cu₁.₈S/n-CdTe surface-barrier structure
A surface-barrier structure with the transparent p-Cu₁.₈S component was used to make thin-film polycrystalline n-CdTe-based solar converters. Cadmium telluride was grown on CdSe substrates using the quasi-closed volume technique through a graded-gap CdSexTe₁₋x interlayer. A multilayer p-Cu₁.₈S/n-CdT...
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Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
2015
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irk-123456789-1207362017-06-13T03:03:14Z Thin-film solar converters based on the p-Cu₁.₈S/n-CdTe surface-barrier structure Bobrenko, Yu.N. Pavelets, S.Yu. Semikina, T.V. Stadnyk, O.A. Sheremetova, G.I. Yaroshenko, M.V. A surface-barrier structure with the transparent p-Cu₁.₈S component was used to make thin-film polycrystalline n-CdTe-based solar converters. Cadmium telluride was grown on CdSe substrates using the quasi-closed volume technique through a graded-gap CdSexTe₁₋x interlayer. A multilayer p-Cu₁.₈S/n-CdTe/n-CdSe/Мо structure was prepared. It makes it possible to increase the degree of structural perfection of thin photosensitive n-CdTe layers without application of additional high-temperature treatments, as well as to obtain an ohmic back contact without some additional doping of CdTe. The quantum efficiency spectra and critical parameters of solar converters have been presented. The prospects for application of polycrystalline n-CdTe in solar power engineering have been discussed. 2015 Article Thin-film solar converters based on the p-Cu₁.₈S/n-CdTe surface-barrier structure / Yu.N. Bobrenko, S.Yu. Pavelets, T.V. Semikina, O.A. Stadnyk, G.I. Sheremetova, M.V. Yaroshenko // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2015. — Т. 18, № 1. — С. 101-105. — Бібліогр.: 15 назв. — англ. 1560-8034 DOI: 10.15407/spqeo18.01.101 PACS 73.20.At, 73.40.Kp, 84.60.Jt http://dspace.nbuv.gov.ua/handle/123456789/120736 en Semiconductor Physics Quantum Electronics & Optoelectronics Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
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A surface-barrier structure with the transparent p-Cu₁.₈S component was used to make thin-film polycrystalline n-CdTe-based solar converters. Cadmium telluride was grown on CdSe substrates using the quasi-closed volume technique through a graded-gap CdSexTe₁₋x interlayer. A multilayer p-Cu₁.₈S/n-CdTe/n-CdSe/Мо structure was prepared. It makes it possible to increase the degree of structural perfection of thin photosensitive n-CdTe layers without application of additional high-temperature treatments, as well as to obtain an ohmic back contact without some additional doping of CdTe. The quantum efficiency spectra and critical parameters of solar converters have been presented. The prospects for application of polycrystalline n-CdTe in solar power engineering have been discussed. |
| format |
Article |
| author |
Bobrenko, Yu.N. Pavelets, S.Yu. Semikina, T.V. Stadnyk, O.A. Sheremetova, G.I. Yaroshenko, M.V. |
| spellingShingle |
Bobrenko, Yu.N. Pavelets, S.Yu. Semikina, T.V. Stadnyk, O.A. Sheremetova, G.I. Yaroshenko, M.V. Thin-film solar converters based on the p-Cu₁.₈S/n-CdTe surface-barrier structure Semiconductor Physics Quantum Electronics & Optoelectronics |
| author_facet |
Bobrenko, Yu.N. Pavelets, S.Yu. Semikina, T.V. Stadnyk, O.A. Sheremetova, G.I. Yaroshenko, M.V. |
| author_sort |
Bobrenko, Yu.N. |
| title |
Thin-film solar converters based on the p-Cu₁.₈S/n-CdTe surface-barrier structure |
| title_short |
Thin-film solar converters based on the p-Cu₁.₈S/n-CdTe surface-barrier structure |
| title_full |
Thin-film solar converters based on the p-Cu₁.₈S/n-CdTe surface-barrier structure |
| title_fullStr |
Thin-film solar converters based on the p-Cu₁.₈S/n-CdTe surface-barrier structure |
| title_full_unstemmed |
Thin-film solar converters based on the p-Cu₁.₈S/n-CdTe surface-barrier structure |
| title_sort |
thin-film solar converters based on the p-cu₁.₈s/n-cdte surface-barrier structure |
| publisher |
Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
| publishDate |
2015 |
| url |
http://dspace.nbuv.gov.ua/handle/123456789/120736 |
| citation_txt |
Thin-film solar converters based on the p-Cu₁.₈S/n-CdTe surface-barrier structure / Yu.N. Bobrenko, S.Yu. Pavelets, T.V. Semikina, O.A. Stadnyk, G.I. Sheremetova, M.V. Yaroshenko // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2015. — Т. 18, № 1. — С. 101-105. — Бібліогр.: 15 назв. — англ. |
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Semiconductor Physics Quantum Electronics & Optoelectronics |
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Semiconductor Physics, Quantum Electronics & Optoelectronics, 2015. V. 18, N 1. P. 101-105.
doi: 10.15407/ spqeo18.01.101
© 2015, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
101
PACS 73.20.At, 73.40.Kp, 84.60.Jt
Thin-film solar converters based on the p-Cu1.8S/n-CdTe
surface-barrier structure
Yu.N. Bobrenko, S.Yu. Pavelets, T.V. Semikina, O.A. Stadnyk, G.I. Sheremetova, M.V. Yaroshenko
V. Lashkaryov Institute of Semiconductor Physics, NAS of Ukraine
41, prospect Nauky, 03028 Kyiv, Ukraine
Phone: 38(044) 525-61-52; e-mail: pavelets@voliacable.com
Abstract. A surface-barrier structure with the transparent p-Cu1.8S component was used
to make thin-film polycrystalline n-CdTe-based solar converters. Cadmium telluride was
grown on CdSe substrates using the quasi-closed volume technique through a graded-gap
CdSexTe1x interlayer. A multilayer p-Cu1.8S/n-CdTe/n-CdSe/Мо structure was prepared.
It makes it possible to increase the degree of structural perfection of thin photosensitive
n-CdTe layers without application of additional high-temperature treatments, as well as
to obtain an ohmic back contact without some additional doping of CdTe. The quantum
efficiency spectra and critical parameters of solar converters have been presented. The
prospects for application of polycrystalline n-CdTe in solar power engineering have been
discussed.
Keywords: solar converter, cadmium telluride, copper chalcogenide, graded-gap layer,
surface-barrier structure.
Manuscript received 04.09.14; revised version received 10.12.14; accepted for
publication 19.02.15; published online 26.02.15.
1. Introduction
The developments of thin-film solar converters (SC)
have reached the stage of mass manufacturing
application. The most competitive SC are those made of
amorphous silicon (а-Si:H), cadmium sulfide-telluride
CdS-CdTe and copper-indium (or copper-gallium)
diselenide CdS-Сu(In, Ga)Se2. The efficiency η of
laboratory patterns of the above SC reaches 10, 16 and
18%, respectively.
The advantages of CdTe-based SC [1-7] are their
effectiveness, possibility of making SC on flexible
substrates (high specific power) and high radiation
resistance. A thin CdS layer in an efficient n-CdS/p-
CdTe structure is non-photoactive and serves as a wide-
gap window. The polycrystalline p-CdTe acts as a
photosensitive SC component.
The results obtained using the single crystal n-
CdTe are less impressive (efficiency up to 9% only
[8, 9]). Since the optimal p-type wide-gap window for n-
CdTe is not known, only the possibility of Schottky
barrier diode application was discussed in literature. The
small achievements are related to bad parameters of the
corresponding barrier structures. In addition (when
dealing with polycrystalline layers), a drawback of
metal-semiconductor contacts is complexity of obtaining
a continuous thin metal film on a relief surface of
polycrystalline semiconductor.
New prospects for the development of barrier
structures are related to the existence of an effective
match with n-type IIVI semiconductors, namely,
digenite p-Cu1.8S (stable strongly degenerate
modification of copper chalcogenide) [10-13]. The
advantages of using p-Cu1.8S instead of metal in surface-
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2015. V. 18, N 1. P. 101-105.
doi: 10.15407/ spqeo18.01.101
© 2015, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
102
barrier photoconverters are related with the rather high
work function (~5.5 eV) and possibility of growing
nanometer (~10 nm) Cu1.8S film on the surface of
polycrystalline IIVI layers.
In this work, we report on fabrication of
Cu1.8S/CdTe SC (based on polycrystalline n-CdTe) and
studying its main properties.
2. Fabrication of polycrystalline solar converters
The main requirements for polycrystalline CdTe layers
serving as the photosensitive part of SC are as follows:
1. The layers must be textured, with crystallites of
optimal sizes, thus making it possible to minimize
current losses at intercrystallite interlayers of the
polycrystalline layer. To improve the structural
properties of р-CdTe, manufacturing technology
for СdS-CdTe SC must include a high-temperature
“chloride” treatment. It results in crystallite growth
as well as promotes diffusion of Te and Cu
acceptor impurities into the CdTe layer [1, 4].
2. The layers must have a reliable ohmic back contact.
The molybdenum back electrode is coated with Te
and Cu films before CdTe layer deposition on it to
improve ohmic contact to polycrystalline p-CdTe.
3. The layers must be sufficiently low-resistant. To
meet this requirement for polycrystalline CdTe
layers, doping with the corresponding impurity has
to be made. In this case, one has to take into
account difficult-to-control predominant diffusion
of foreign impurity over the intercrystallite
interlayers. This process impairs reproducibility of
manufacturing technology for solar cells and may
lead to degradation of their properties. To illustrate,
one of the main mechanisms of degradation of р-
CdTe based SC is copper diffusion into the region
of СdS-CdTe heteroboundary from the back
electrode [4]. Indium diffusion from CdS into the
р-CdTe layer results in reduction of the solar cell
efficiency [1].
In our work, we study the possibility to solve the
above-mentioned problems for n-CdТе by its epitaxial
growing on orienting polycrystalline n-CdSe substrates.
A graded-gap CdSexTe1x interlayer was grown to
exclude the mechanism of formation of structural defects
related to a mismatch between the CdSe and CdТе
lattice parameters.
Using the quasi-closed volume technique, the
graded-gap CdSe layer and n-CdТе were sequentially
deposited, in the common technological cycle, onto the
Mo-metallized glass-ceramic substrates. Molybdenum
serves as the reliable ohmic electrode to the CdSe layer.
So, CdТе growing on the Мо-CdSe substrate through a
graded-gap interlayer solves the problem of obtaining
ohmic contact to photosensitive polycrystalline n-CdТе
layer without additional doping. Growing n-CdТе on the
orienting n-CdSe substrates through a graded-gap
interlayer solves also the problem of obtaining textured
(with optimal crystallite sizes) photosensitive n-CdТе
layers without additional high-temperature treatment of
the multilayer SC structure.
Fig. 1 presents the results of investigation of
specimen surfaces performed with a scanning probe
microscope NanoScope IIIa Dimension 3000
TM
(Digital
Instruments, USA) using atomic force microscopy
(AFM) in the periodic contact mode. The silicon probes
with nominal tip radius of 10 nm were used in
measurements.
a
b
c
Fig. 1. AFM patterns of surface fragments of CdTe specimens
grown on different substrates: a) Mo-metallized glass-
ceramics, b) Мо/CdSe, c) Мо/CdSexTe1–x /CdSe.
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2015. V. 18, N 1. P. 101-105.
doi: 10.15407/ spqeo18.01.101
© 2015, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
103
We studied the surfaces of CdTe specimens grown
on different substrates. In the case of Mo-metallized
glass-ceramic substrate for CdTe (Fig. 1а), the
characteristic crystallite size is 1.4 m (standard
deviation of 0.425 m). The large to little ratio is
sufficiently high: 2.455/0.698. For the Мо/CdSe/CdTe
structure (Fig. 1b), the average grain size is essentially
larger: 6.7 m. The large to little ratio decreased to
8.06/5.31 m. For a CdTe specimen on the Мо/CdSe
substrate with a graded-gap x1xTeCdSe interlayer of
about 100 nm (Fig. 1c), the surface character changed.
The crystallites demonstrate a trend to formation of a
plateau of about 13 m with growth terraces.
The above results testify that it is possible to obtain
a sufficiently perfect thin CdTe film of an optimal
thickness (1…2 m) with large crystallites without
additional high-temperature treatment of the structure.
To make SC, a barrier-forming layer of p-type
copper sulfide (its stable modification Cu1.8S) was
deposited on CdTe surface using the vacuum sputtering.
The SC structure has the attributes of the surface-barrier
one: electric field is practically completely concentrated
in n-CdТе owing to sharp doping asymmetry in the
contacting materials (the hole concentration in Cu1.8S
р = 321cm105 ). The total structure thickness is
4…5 m, while that of the graded-gap layer is
100…200 nm. The SC series resistance is determined by
the resistances of the CdSe and CdTe layers, which
thicknesses are 3…4 and 1.5 m, respectively. The
structure is illuminated from the side of the transparent
component of copper sulfide Cu1.8S, thickness of which
was 20…30 nm.
It is possible to obtain sufficiently low-resistant
polycrystalline CdSe layers without additional doping
with a foreign impurity. It is known [14] that one can
vary the concentration of free charge carriers within
wide limits in the specimens obtained by regulating the
concentration of intrinsic defects of crystal lattice when
changing the manufacturing conditions for CdSe crystals
(as opposed to CdТе). The concentration of majority
charge carriers in polycrystalline CdSe crystals grown
without additional doping with a foreign impurity was
316cm102...1 . It was sufficient for keeping the series
resistance of the structure within admissible limits.
The situation with CdTe is more complicated. One
cannot obtain CdTe layers with the electron concentration
n > 313cm10 by using the quasi-close volume technique.
The effect of intergrowth of donor-type point defects from
the CdSe substrate to n-CdТе through a developing
graded-gap interlayer (which is characteristic of ZnS and
ZnSe [10, 12]) was not observed in the multilayer
structures under investigation. The electron concentration
did not exceed 314cm10 , which is obviously not enough
for efficient operation of SC.
So, additional doping of SC with a foreign impurity
is required to ensure the use of n-CdТе layers. In this
work, CdTe was doped with indium in the course of
growing to determine the potential of n-CdТе-based SC.
3. Experimental results
Fig. 2 presents the energy band diagram of the system p-
Cu1.8S/n-CdTe/n-CdSe/Мо SC. A reliable ohmic contact
of the CdSe layer with Mo-metallized glass-ceramic
substrate (the latter is not shown in Fig. 2) ensures the
ohmic back contact of the multilayer heterostructure.
The diagram corresponds to the case of relatively high-
resistant CdTe (charge carrier concentration n =
313cm10 ). The diffusion potential Ud ≈ 0.87 eV. It is
evident that increase of the concentration of majority
charge carriers leads to increase of Ud and, consequently,
improves the SC diode characteristics.
Forward recombination-tunnel currents (that are
typical for the р-Cu1.8S/n-IIVI junctions [11-13]) are
predominant in the structures under investigation. The
observed minimal densities of dark diode currents are
28A/cm103...2 .
Fig. 3 presents dependences of the quantum
efficiency Н and charge carrier collection coefficient Q on
the wavelength of radiation incident on p-Cu1.8S/n-CdТе
SC. To analyze photocarrier losses, let us present the
photocurrent Iph in the structures under investigation as
Iph = eTQ = eTQsQL.
Here, Т is the intensity of light that is part of the
photosensitive component (in the limiting case this is
transmission of the Cu1.8S layer); the coefficients Qs and
QL characterize photocarrier losses on the illuminated
surface at the р-Cu1.8S/n-CdTe junction interface and in
the CdTe bulk, respectively.
Fig. 2. Energy band diagram of the p-Cu1.8S/n-CdTe/n-
CdSe/Мо solar converter: F is the Fermi level, W – space-
charge region width, GGL – graded-gap layer.
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2015. V. 18, N 1. P. 101-105.
doi: 10.15407/ spqeo18.01.101
© 2015, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
104
Fig. 3. Spectral dependences of quantum efficiency Н and
charge carrier collection coefficient Q of solar converters.
One can see from Fig. 3 that there is a peak in the
curve, and Q values are close to unity. The latter fact is
supported by the results of investigations of field
dependences (photocurrent vs negative bias voltage). As
the voltage U increases, the photoactive region becomes
broader, the width of space-charge region W grows and
the sweeping field at the illuminated SC surface
becomes stronger. These factors have to promote
increase of efficiency in the long-wave and short-wave
spectral regions, if Q < 1.
Shown in Fig. 3 (inset) are the dependences Iph(U).
One can see (inset, curve 1) that, if SC is illuminated
with light with the wavelength is λ = 0.45 m, then Iph
does not depend on U. The most probable reason for the
above effect is absence of photocurrent losses in the
given spectral region and, consequently, Q = 1. At λ =
0.4 m, photocurrent flattens out as U increases (inset,
curve 2). In this case, the value of Q is determined as the
ratio between the short-circuit current (U = 0) and the
photocurrent Iph value at saturation; then the quantum
efficiency is Q = 0.87.
The obtained results testify that photocurrent losses
in the long-wave spectral region (λ > 0.45 m) is
determined only by recombination of charge carriers in
the quasi-neutral region of CdTe, and growth of Iph
(inset, curve 3) is because of increase in the space-
charge region width W. Then, the photocurrent can be
written as
Iph = eTQL = eT{1 – [exp (– W)]/(1 + Lp)},
where is the coefficient of light absorption in CdTe,
and Lp is the hole diffusion length. For those SC
specimens, in which the above situation is realized, Lp
values were determined using the method proposed
in [15].
At W >> 1, the photocurrent Iph = eTQL =
eT (Lp + W)/(1 + Lp) is a linear function of the space-
charge region width W. Extrapolation of the linear
dependence Iph(W) from the region of high U values to
zero photocurrent determines the diffusion length Lp of
minority charge carriers. When determining Lp, the
specimens were illuminated with light of the wavelength
λ = 0.84 m. The dependences Iph(W) are well presented
by straight lines. The hole diffusion length Lp lies within
0.6…0.8 m for different SC specimens under
investigation.
The main operating parameters of SC were
measured under natural solar illumination. The
emittance of incident radiation was measured with a
pyranometer М-80М and was 0.74 mW/cm
2
. The best
parameters were those measured for Cu1.8S-CdTe SC, in
which CdTe was doped with indium. At the above
emittance of incident radiation, this SC demonstrated the
peak open-circuit emf Uoc = 0.71 V, fill factor (FF) of
load characteristic FF = 0.7, short-circuit current density
Isc = 15.8 mA/cm
2
, efficiency η = 10.7%. The SC area
(with allowance made for ~10% shadowing with the
upper current-collecting electrode) was s = 0.25 cm
2
.
4. Conclusion
Strongly degenerate digenite Cu1.8S is the optimal р-
component for fabrication of p-Cu1.8S-n-IIVI surface-
barrier structures that can serve as the basis for making
efficient photoconverters of UV and visible radiation.
Our investigations performed in this work have shown
that the above surface-barrier structure is promising for
application in solar power engineering. The potentialities
for achievement of good parameters in n-CdТе-based SC
are close to those known for р-СdТе-based SC.
We propose the method of growing n-CdТе that
makes easier a number of technological operations
inherent to manufacturing technology for р-СdТе.
Cadmium telluride is grown on the Мо/СdSe substrates
through a graded-gap x1xTeCdSe interlayer. The
structure of p-Cu1.8S/n-CdTe/n-CdSe/Мо SC enables one
to increase the degree of structural perfection of n-CdTe
photosensitive layers without additional high-temperature
treatments as well as to obtain back ohmic contacts
without additional doping of CdTe. The sufficiently high
quantum efficiency obtained for n-CdТе is close to the
limiting one for the Cu1.8S/n-CdTe structure. The feasible
way for increasing SC efficiency with the above structure
is related with improvement of the diode characteristics of
the surface-barrier structure and, consequently, increase of
Uос and the fill factor of load characteristics FF.
The above improvements require maximal doping
of CdTe with a donor impurity. So, a search for a
method of doping polycrystalline CdTe layers that could
minimize the probability of separating barrier shorting is
urgent. It is necessary to increase both reproducibility of
manufacturing technology and stability of properties
inherent to polycrystalline SC.
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105
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