U.S. patent application number 13/057000 was filed with the patent office on 2011-06-09 for formation of a transparent conductive oxide film for use in a photovoltaic structure.
This patent application is currently assigned to ELECTRICITE DE FRANCE. Invention is credited to Daniel Lincot, Jean Rousset.
Application Number | 20110132764 13/057000 |
Document ID | / |
Family ID | 40418853 |
Filed Date | 2011-06-09 |
United States Patent
Application |
20110132764 |
Kind Code |
A1 |
Lincot; Daniel ; et
al. |
June 9, 2011 |
FORMATION OF A TRANSPARENT CONDUCTIVE OXIDE FILM FOR USE IN A
PHOTOVOLTAIC STRUCTURE
Abstract
A process for producing a photovoltaic structure that includes a
thin coating film, generally made of a transparent conductive
oxide, deposited on top of a sublayer having photovoltaic
properties. The coating film is deposited electrochemically in an
electrolysis bath and at least partly assisted by illumination
coming from a light source.
Inventors: |
Lincot; Daniel; (Antony,
FR) ; Rousset; Jean; (Paris, FR) |
Assignee: |
ELECTRICITE DE FRANCE
Paris
FR
CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE- CNRS
Paris
FR
|
Family ID: |
40418853 |
Appl. No.: |
13/057000 |
Filed: |
July 28, 2009 |
PCT Filed: |
July 28, 2009 |
PCT NO: |
PCT/FR2009/051518 |
371 Date: |
February 1, 2011 |
Current U.S.
Class: |
205/91 ;
204/242 |
Current CPC
Class: |
Y02E 10/541 20130101;
C25D 7/08 20130101; H01L 31/0749 20130101; H01L 31/1884 20130101;
C25D 9/04 20130101; H01L 31/1836 20130101 |
Class at
Publication: |
205/91 ;
204/242 |
International
Class: |
C25D 9/04 20060101
C25D009/04; C25D 7/12 20060101 C25D007/12; C25D 19/00 20060101
C25D019/00 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 1, 2008 |
FR |
08 55344 |
Claims
1. A process for producing a photovoltaic structure, said structure
comprising a thin coating film deposited on top of a sublayer
having photovoltaic properties, wherein the coating film is
deposited electrochemically, the deposition being at least partly
assisted by illumination coming from a light source.
2. The process as claimed in claim 1, wherein the illumination of
the photovoltaic sublayer causes an electrical effect conducive to
uniform and homogeneous deposition of the coating film, at least at
the start of growth of the coating film.
3. The process as claimed in claim 1, wherein the coating film is
based on a transparent oxide and the coating film is intended to
act as at least one of transparent and conductive window of a
photovoltaic cell.
4. The process as claimed in claim 3, wherein the coating film is
based on zinc oxide.
5. The process as claimed in claim 4, wherein the film is deposited
by electrolysis with zinc ions dissolved in an electrolysis bath,
by a cathodic reaction.
6. The process as claimed in claim 5, wherein the cathodic reaction
is performed with addition of an oxygen donor element taken from at
least one of oxygen, hydrogen peroxide and nitrates.
7. The process as claimed in claim 1, wherein the coating film is
made conductive by doping with at least one element introduced in
solution, taken from chlorine, fluorine, iodine, bromine, gallium,
indium, boron and aluminum.
8. The process as claimed in claim 1, wherein the illumination is
within the spectral range between 100 and 1500 nm and with an
incident power between 0.1 mW/cm.sup.2 and 1 W/cm.sup.2.
9. The process as claimed in claim 1, wherein the photovoltaic
sublayer consists of a I-III-VI.sub.2 alloy of the
Cu(In,Ga,Al)(S,Se).sub.2 type.
10. The process as claimed in claim 1, wherein the coating film is
deposited directly on the photovoltaic sublayer.
11. The process as claimed in claim 1, wherein the coating film is
deposited on at least one interface film located above the
photovoltaic sublayer.
12. The process as claimed in claim 11, wherein the interface film
is a film based on cadmium sulfide.
13. The process as claimed in claim 11, wherein the interface film
is a film based on zinc sulfide.
14. The process as claimed in claim 11, wherein the interface film
is a film based on indium sulfide or gallium sulfide.
15. The process as claimed in claim 12, wherein the interface film
is covered with a film of undoped zinc oxide or an undoped zinc
oxide alloy.
16. The process as claimed in claim 1, wherein the coating film is
deposited electrochemically at a temperature in the 50.degree. C.
to 150.degree. C. range.
17. A facility for implementing the process as claimed in claim 1,
comprising an electrolysis bath and a light source illuminating the
photovoltaic film.
Description
[0001] The present invention relates to the formation of a thin
coating film that can be used within a photovoltaic device such as
for example a solar cell.
[0002] This coating film may typically be a transparent conductive
film serving as "front" electrode in the photovoltaic structure.
The required properties for this film are that it be: [0003]
transparent in the visible and [0004] conductive in the solar
cell.
[0005] This coating film is often made of a material comprising
predominantly an oxide such as zinc oxide (ZnO).
[0006] FIG. 1 shows schematically a photovoltaic structure that may
have such a coating film.
[0007] A metal film MET (for example based on molybdenum) is
deposited on a substrate SUB (for example by vacuum evaporation or
by sputtering). The substrate may be made of conventional glass.
This metal film MET has a thickness that may be between 0.5 and 1
micron.
[0008] Next, a photovoltaic film PHO is deposited on the metal film
MET. The material of the film PHO may be silicon, CdTe or an
I-III-VI.sub.2 alloy typically comprising: [0009] copper, [0010]
indium, gallium and/or aluminum and [0011] selenium and/or
sulfur.
[0012] The film PHO typically has a thickness of about 2 microns.
It is generally deposited by vacuum evaporation, by cathode
sputtering, by chemical vapor deposition, by screen printing or
electrochemically.
[0013] Usually deposited on this photovoltaic film PHO is an
interface film INT, called a "buffer layer", often based on cadmium
sulfide, zinc sulfide or indium sulfide. It may be deposited
chemically in solution (the chemical bath deposition (CBD)
technique), under vacuum or in the vapor phase. Its thickness is
generally between 5 and 100 nm.
[0014] The next two films, referenced ELE and TRA respectively,
which are deposited on the buffer layer INT in the example
illustrated in FIG. 1, form in particular the subject matter of the
present invention. The film TRA itself is optional, but the surface
film ELE acts as electrode in the photovoltaic structure.
[0015] The film TRA must be transparent so as to allow the light to
reach the photovoltaic film PHO. It may be based on an oxide (for
example based on lightly doped ZnO) and may have a thickness of
about 50 to 100 nm. It is generally deposited by cathode sputtering
or by chemical vapor deposition (CVD).
[0016] The film ELE may vary from 0.5 to 1 micron in thickness. It
may be based on an oxide (for example zinc oxide) like the film
TRA. The film ELE is itself doped for the purpose of making this
film ELE conductive so as to serve as "front" electrode. The doping
may be n-type doping, for example doped with aluminum. The film ELE
must be transparent in the visible so that the photovoltaic film
PHO can be illuminated. It must also be conductive in the solar
cell.
[0017] Solar cells based on CuInSe.sub.2-type alloys using the
addition of sulfur, gallium or aluminum form the basis of a new
photovoltaic system the industrial exploitation of which is
starting to grow. The performance of such cells ranges up to 19.9%
in the laboratory, with in general standard values in the
laboratory of 15-17%. Modules have efficiencies of: [0018] 11-14%
for the system using gallium added to the I-III-VI.sub.2
photovoltaic alloy; and [0019] around 6-9% for the system using
sulfur.
[0020] All these photovoltaic devices have, without exception, the
structure illustrated in FIG. 1.
[0021] Usually, the surface film ELE is deposited by vacuum
sputtering. In certain cases, it may be deposited by chemical vapor
deposition and doped with boron.
[0022] However, for implementation on an industrial scale, it is
preferable to use an atmospheric deposition method, such as
electrochemical bath deposition. This technique is simple--it is
unnecessary to apply a vacuum--and has a definite advantage in
terms of production cost, investment cost and capability of
treating large areas (as in the electroplating field in
particular).
[0023] Moreover, as this deposition technique would continue on
from the chemical deposition of the subjacent film TRA (for example
based on CdS or ZnS), or even from the photovoltaic film PHO
deposited electrochemically, the consistency of the production
sequence is maintained, with a "front side" approach involving
entirely wet processing. The advantage in terms of production cost
is substantial.
[0024] The electrochemical synthesis of a material widely used for
the production of the surface film ELE or the film TRA, in
particular zinc oxide ZnO, has been described in the document WO
96/31638. In that document, the supply of oxygen comes from the
molecular oxygen dissolved in the electrolysis bath. In another
document (M. Izaki, T. Omi and T. A. Pattinson, Appl. Phys. Lett,
68, 2439, 1996), the oxygen comes from nitrate ions.
[0025] The document by D. Lincot, B. Cavana, S. Quenet, S. Peulon
and H. W. Schock, Proceedings 14.sup.th EC Photovoltaic Solar
Energy Conference, Stephen and Ass. Ed., 2168, 1997, furthermore
shows that it is possible to deposit zinc oxide surface films
directly on a molybdenum/I-III-VI.sub.2 alloy stack with an
efficiency close to 10%. Electrodeposition may therefore be used in
the synthesis of ZnO conductive films as window films in
photovoltaic cells based on an alloy of the CIS type (CIS standing
for Cu(In,Ga)(Se,S).sub.2).
[0026] The document by D. Gal, G. Hodes, D. Lincot and H. W. Hodes,
Thin Solid Films, 361-362, 79, 2000, deals with the direct
deposition of transparent ZnO oxide films INT on CIS using a medium
comprising dimethylsulfoxide (DMSO) heated to 130.degree. C. and in
the presence of dissolved oxygen. The stack is then completed with
an aluminum-doped ZnO film ELE. This film is therefore conductive
and it is deposited by sputtering. Thus, in the above document, it
is not a question of replacing the technique (sputtering) for
depositing the conductive surface film ELE but of applying the
electrodeposition technique to the synthesis of the subjacent
(ZnO-based) film TRA and to possible other buffer layers.
[0027] Thus, the deposition of conductive transparent oxide films
on top of the photovoltaic film, electrochemically, is a
particularly advantageous technique. It has already been
implemented in the field of photovoltaic cells. However, the
results obtained can still be improved. In particular the adhesion
of the films thus deposited, their homogeneity and their
morphological quality merit further improvements.
[0028] The present invention aims to improve the situation.
[0029] The invention provides for this purpose a process for
producing a photovoltaic structure comprising a thin coating film
deposited on top of a sublayer having photovoltaic properties.
According to the invention, the coating film is deposited
electrochemically, the deposition being partly or completely
assisted by illumination coming from a light source.
[0030] It has been observed that the illumination of the
photovoltaic film induces an electrical effect that promotes
uniform and homogeneous deposition of the coating film, at least at
the start of growth of the coating film (called the "nucleation"
step). In particular, it has been observed that the material
deposited, right from nucleation, is laterally uniform and dense,
this being unexpected, in particular for depositing a film of an
oxide such as zinc oxide. The effect of the illumination may be
explained by a charge density generated by the photovoltaic film
which is uniformly distributed over the surface on which the
coating film is deposited, a situation that favors good homogeneous
morphology of the coating film. This satisfactory effect is also
due to the suitable choice of deposition temperature, preferably in
the 50.degree. C.-150.degree. C. range (in an aqueous, nonaqueous
or hybrid medium, depending on the temperature chosen). In this
temperature range specifically, zinc oxide formation is favored. In
particular, it has been observed that at lower temperatures (room
temperature for example), what are predominantly present are
hydroxides (for example Zn(OH).sub.2), whereas at higher
temperatures (for example around 70 to 80.degree. C.), oxides (ZnO
for example) are predominantly present. Thus, by combining
illumination with a suitable deposition temperature it is possible
to achieve satisfactory results. Moreover, it has been found that
the illumination also increases the coating film growth rate. The
coating film may then have a thickness ranging up to a few microns,
but it nevertheless exhibits good mechanical stability.
[0031] It has also been found that the coating film nucleation step
carried out under given temperature and illumination conditions is
generally improved in the presence of an interface film (INT) or
INT and TRA films, compared with the use of a bare PHO film. This
result leads to a spectacular increase in the photovoltaic
performance, never observed hitherto. This has been achieved
despite the brittleness of the INT and TRA films.
[0032] As indicated above, the coating film may be based on a
transparent oxide, for example based on zinc oxide (ZnO). However,
other alternative materials that can be deposited on a photovoltaic
film, or on a photovoltaic film coated with a conductive film, are
possible. Already, the coating film may be another form of oxide,
but also sulfides or selenides. If the coating film is such an
oxide film, it may be designed to act as transparent and/or
conductive window in a photovoltaic cell. However, it is not
necessary for the material of the coating film to be transparent in
order to implement the invention since only the nucleation of the
coating film requires to be assisted via illumination.
[0033] For example, the transparent conductive ZnO film may be
deposited electrolytically in an aqueous medium or in a nonaqueous
medium, for example dimethylsulfoxide, or in a mixture thereof,
using dissolved zinc ions and an oxygen donor element such as
dissolved oxygen, or another precursor (hydrogen peroxide, nitrate
ions or any other soluble oxygen precursor), by a cathodic
reaction.
[0034] The illumination may be in the visible, as monochromatic or
polychromatic light. A spectral range between 100 and 1500 nm, for
example between 200 and 1300 nm (solar illumination), has given
good results with an incident power of between 0.1 mW/cm.sup.2 and
1 mW/cm.sup.2 (preferably between 1 mW/cm.sup.2 and 300 mW/cm.sup.2
in one embodiment).
[0035] The coating film may or may not be doped, for example with
at least one element introduced in solution, taken from chlorine,
fluorine, iodine, bromine, gallium, indium, boron and aluminum,
and, in a standard embodiment, it may be doped in particular with
chlorine.
[0036] As indicated above, the photovoltaic sublayer may be based
on a I-III-VI.sub.2 alloy of the Cu(In,Ga,Al)(S,Se).sub.2 type
deposited electrochemically or by any other technique, such as
evaporation, sputtering, screen printing, chemical vapor deposition
or inkjet deposition, whether partly or completely.
[0037] For example, I-III elements may be deposited by
electrolysis, or by sputtering, and then a selenization and/or
sulfurization operation may be carried out subsequently. A
preferred embodiment is that described in document WO 03/094246 in
which the I-III-VI.sub.2 alloy is entirely deposited
electrochemically and then annealed by rapid thermal processing.
However, other photovoltaic materials are conceivable (for example
thin-film or bulk silicon, or the like).
[0038] The coating film may be deposited directly on the
photovoltaic sublayer or, as a variant, it may be deposited on one
or more interface films located above the photovoltaic
sublayer.
[0039] Moreover, these other interface films may be deposited
electrochemically or using other techniques. The materials
constituting these films may for example be based on cadmium
sulfide (CdS) and/or zinc sulfide (ZnS) and/or indium or gallium
sulfide (In.sub.2S.sub.3 or Ga.sub.2S.sub.3 respectively). These
films can be deposited by chemical vapor deposition or in solution,
especially CBD, or by physical deposition, evaporation, cathode
sputtering, or the like. However, it is particularly advantageous
to deposit these films again by electrolysis, so that: [0040] the
photovoltaic sublayer, [0041] the interface film(s), and [0042] the
coating film (ZnO for example) are all deposited electrolytically,
and therefore using a single treatment of the same type and without
recourse to other techniques (sputtering or the like).
[0043] Here again, the ability to deposit a dense homogeneous
coating film (in particular made of ZnO) on an interface film of
the aforementioned type was unexpected since, without illumination,
it was found that the coating film being formed was deposited
inhomogeneously, in islands. Owing to the illumination during
deposition, the coating film is adherent and exhibits both good
lateral uniformity and good homogeneity, in particular in the
presence of the interface film.
[0044] It should be pointed out in particular that the performance
of the photovoltaic device based on CuInSe.sub.2-type photovoltaic
films obtained by implementing the invention has already, with the
illumination for assisting the deposition of the ZnO film on the
photovoltaic sublayer, certainly increased the photovoltaic
efficiency. However, this efficiency has also be increased owing to
the presence of an interface film (CdS, ZnS, In.sub.2S.sub.3 or
Ga.sub.2S.sub.3) on which the coating film (ZnO) can be deposited
electrolytically with illumination assistance. To the knowledge of
the inventors, the results achieved by implementing the invention
are currently the best for devices based on transparent conductive
films deposited electrolytically, with levels of efficiency
comparable to those in the prior art using conventional
processes.
[0045] The interface films may themselves be coated with an
intermediate zinc oxide film or with a film of an alloy of zinc
oxide with in particular magnesium (ZnMgO) deposited by sputtering,
by CVD or in solution. The aim of the invention is in fact to form
a coating film on a photovoltaic material whether or not coated
with other films beforehand. For example, the following types of
heterostructures may be envisaged: CIS/CdS, CIS/ZnS, CIS/CdS/ZnO,
CIS/ZnS/ZnO, CIS/ZnO, CIS/In.sub.2S.sub.3, CIS/In.sub.2S.sub.3/ZnO
or the like, in which the ZnO film may or may not be doped, or else
divided into a doped film and an undoped complementary film. The
ZnO-based interface film may, as indicated above, be based on
(Zn,Mg)O.
[0046] Referring to FIG. 2, the present invention also relates to a
facility for implementing the above process and comprising, in
particular, an electrolysis bath 1 and a light source 2
illuminating this bath. For ease of representation, the
illumination rail 2 is shown in FIG. 2 above the bath. However, in
a preferred embodiment, the illumination comes from the side,
substantially perpendicular to the substrate, and not from above.
The film may be deposited in aqueous medium, in organic medium or
in a mixture thereof. The oxygen may be supplied by bubbling (at 3)
air or molecular oxygen O.sub.2 into the bath, which dissolves
therein.
[0047] The invention also relates to the photovoltaic structure
comprising a thin coating film deposited on top of a sublayer
having photovoltaic properties, and in which in particular the
coating film is a transparent oxide film deposited directly on the
photovoltaic sublayer and has a uniform homogeneous morphology at
least at the interface with the photovoltaic sublayer.
[0048] The coating film may be characterized by a controlled
surface roughness, in the form of crystalline facets, columnar
grains and/or needles, so as to be able to increase the
photocurrent generated by the photovoltaic cell.
[0049] It will thus be understood that implementing the invention
offers one possible way of synthesizing, in solution, the
conductive and/or transparent oxide film (especially a zinc oxide
film) under atmospheric conditions and not requiring the use of
gaseous reactants. The invention makes it possible, as will be seen
in the embodiment examples described below, to obtain transparent
conductive zinc oxide films resulting in devices having an
efficiency similar to that obtained with the conventional
sputtering deposition technique. The invention therefore opens the
way for replacing vacuum techniques, to produce the transparent
conductive film, with a very simple, inexpensive and low-cost
electrochemical method.
[0050] The invention provides the following advantages: [0051] the
coating film may be deposited at low temperature (below 100.degree.
C.), requiring no expensive vacuum deposition or vapor deposition
equipment; [0052] it is possible to deposit coatings on large areas
using an industrially reproducible coating technique, of great
interest for producing low-cost large-scale photovoltaic panels;
[0053] it is possible, as will be seen, to dispense with the TRA
film in FIG. 1 (denoted hereafter by "i-ZnO", i.e. the "intrinsic"
(undoped) transparent interface film on which the doped conductive
film ELE is usually deposited), thereby making it possible to
dispense with one step in the solar cell production process; and
[0054] it is also possible, as will be seen below, to avoid the
toxic element cadmium for producing the interface film INT.
[0055] Other features and advantages of the invention will become
apparent on examining the following detailed description, together
with the appended drawings in which, apart from FIGS. 1 and 2
described earlier:
[0056] FIG. 3A is a scanning electron micrograph in lateral cross
section of a molybdenum/I-III-VI.sub.2 alloy/CdS
interface/intrinsic ZnO window/ZnO stack electrodeposited according
to the invention on glass;
[0057] FIG. 3B is an enlargement of the micrograph of FIG. 3A;
[0058] FIG. 3C is a top view of the stack of FIGS. 3A and 3B;
[0059] FIG. 3D is an enlargement of the micrograph of FIG. 3C;
[0060] FIG. 3E shows the J-V characteristic of the stack shown in
FIGS. 3A to 3D;
[0061] FIG. 4A is a scanning electron micrograph in lateral cross
section of a molybdenum/I-III-VI.sub.2 alloy/ZnS interface/ZnO
stack electrodeposited directly on glass according to the
invention;
[0062] FIG. 4B is a top view of the stack shown in FIG. 4A;
[0063] FIG. 4C is an enlargement of the micrograph shown in FIG.
4B;
[0064] FIG. 4D shows the J-V characteristic of the stack shown in
FIGS. 4A to 4C;
[0065] FIG. 5A is a scanning electron micrograph in lateral cross
section of a molybdenum/I-III-VI.sub.2 alloy/ZnO stack on glass,
directly electrodeposited according to the invention on the
photovoltaic alloy;
[0066] FIG. 5B is an enlargement of the micrograph shown in FIG.
5A;
[0067] FIG. 5C is a top view of the stack shown in FIGS. 5A and
5B;
[0068] FIG. 5D is an enlargement of the micrograph shown in FIG.
5C;
[0069] FIG. 5E shows the J-V characteristic of a
molybdenum/I-III-VI.sub.2 alloy/ZnO stack on glass directly
electrodeposited according to the invention on the photovoltaic
alloy;
[0070] FIG. 6 shows the J-V characteristic of a
molybdenum/I-III-VI.sub.2 alloy/CdS interface/ZnO stack on glass
electrodeposited according to the invention; and
[0071] FIG. 7 shows the J-V characteristic of a
molybdenum/I-III-VI.sub.2 alloy/intrinsic ZnO window/ZnO stack on
glass electrodeposited according to the invention, over a large
area (17.5 cm.sup.2), whereas the other J-V characteristics were
recorded on small areas (0.1 cm.sup.2).
[0072] In the embodiment examples described below, the coating film
is based on zinc oxide deposited electrochemically, using a zinc
salt dissolved in an aqueous solvent, in the presence of an oxygen
donor species, which may very advantageously be dissolved gaseous
oxygen. The electrolyte also contains a support salt so as to make
it conductive. The deposition is carried out by applying a cathodic
potential to the electrode according to the following
electrochemical reaction:
Zn(II)+1/2O.sub.2+2e.sup.-.fwdarw.ZnO
in which it will be understood that the electrons, denoted by
2e.sup.-, are favorably supplied by the photocurrent that the
photovoltaic film PHO, or the film covered with its interface film,
produces during the illumination thereof.
[0073] The ZnO oxide is deposited on the electrode in thin-film
form, the thickness of which is controlled by the amount of
electricity exchanged during the reaction. Again referring to FIG.
1, the electrode receiving the deposit may be formed from the
following stack, on the glass substrate SUB: [0074] the molybdenum
(Mo) film MET; [0075] the film PHO of I-III-VI.sub.2 alloy such as
Cu(In,Ga,Al)(S,Se).sub.2 (called CIS hereafter); [0076] the front
film INT (based on CdS or ZnS); and [0077] the front film TRA
(i-ZnO), which advantageously may be dispensed with. It should also
be recalled that the ZnO may be deposited electrolytically directly
on the film of photovoltaic material based on the I-III-VI.sub.2
alloy.
[0078] The deposition is typically carried out in water at a
temperature of about 70.degree. C. It lasts about 1 hour or less,
and leads to the formation of a dense film with a thickness between
500 and 800 nm.
[0079] Deposition Conditions are Described by Way of Example
Below.
[0080] The electrolyte used (called a "chloride bath") contains
Zn.sup.2+ ions of 5 mM concentration introduced into demineralized
water (18 M.cm.sup.-3) in the form of ZnCl.sub.2 salt and Cl.sup.-
ions of 0.1 M concentration introduced in the form of KCl salt. The
bath is saturated with oxygen by bubbling gaseous oxygen thereinto.
The bath is maintained at a temperature of 70.degree. C. throughout
the duration of the electrodeposition. Stirring is provided by
using a bar magnet. The reference potential is a
K.sub.2SO.sub.4-saturated mercurous sulfate electrode or MSE
(K.sub.2SO.sub.4-saturated Hg/Hg.sub.2SO.sub.4 electrode). It is
placed in a compartment separated from the electrolysis solution by
an alumina frit of low porosity filled with a saturated potassium
sulfate solution. An electrolytic bridge is used to maintain it at
room temperature so as to avoid any fluctuation in potential that
may appear due to the effect of the temperature when the bath is
heated. The deposition potential is set at -1.4 V/MSE. A zinc plate
is used as counterelectrode and makes it possible both to pass the
current into the external circuit and to regenerate the electrolyte
with Zn.sup.2+ ions, thus preventing it from being exhausted by
consumption at the working electrode.
[0081] Film conductivity is obtained by adding doping impurities to
the solution, for example, and as described above, chloride ions
incorporated into the film, which then has a high conductivity
stable over time, this constituting an advantageous property for
the operation of solar devices.
[0082] According to the invention, a light source is used to assist
the deposition, at least during the nucleation phase.
[0083] The light flux is delivered by a solar simulator, the
homogeneous light flux of which is about 100 mW/cm.sup.2 at 15 cm
distance. This flux may be adjusted by modifying the distance
between the lamp and the film, up to 5 m in the configuration used,
thereby making it possible to reduce the flux arriving at the
surface of the specimen down to a few mW/cm.sup.2. Under the
conditions of this example, the current densities used during the
deposition are between 0.1 and 0.4 mA/cm.sup.2. To promote light
transmission through the electrochemical reactor and increase
illumination homogeneity, a parallelepipedal glass cell is used,
the specimen being placed vertically in this configuration and the
illumination being horizontal. The deposition of a ZnO film
generally lasts between half an hour and one hour.
[0084] Once the deposition has been carried out, the cells are
complete and are characterized conventionally.
[0085] The deposition of ZnO films by electrolysis according to the
process of the invention has made it possible to achieve
photovoltaic conversion efficiencies of more than 12%, reaching in
certain cases a record value of 16.3%. These efficiencies are
comparable to those obtained using the sputtering technique for
depositing ZnO.
[0086] FIGS. 3A to 3D show the morphology of a stack of the Mo/CIS
(or CIGS, for a slight incorporation of gallium)/CdS/i-ZnO and ZnO
type by electrodeposition according to the invention. Thus, here
the ZnO conductive film conventionally formed by sputtering is
replaced with a ZnO film deposited by electrolysis according to the
invention.
[0087] The images are obtained by scanning electron microscopy.
These show good, compact and homogeneous, coverage of the
electrodeposited ZnO (FIG. 3A) on the subjacent, especially CIGS,
films. In particular, the electrodeposited ZnO film is highly
covering and of uniform thickness. Referring to FIG. 3D, the ZnO
film has, in the example shown, a surface with crystalline
facets.
[0088] The characteristic plot of current density per unit area
versus voltage (hereafter termed the "J-V characteristic") for this
type of stack is shown in FIG. 3E, which indicates an open-circuit
voltage Voc of 704 mV and a short-circuit photocurrent density Jsc
of -29 mA/cm.sup.2 for a form factor FF of 75.8% and an efficiency
.eta. of 15.8%. This efficiency is very comparable to that of 16.2%
for the same stack produced under the same conditions but with a
surface ZnO film obtained by sputtering according to the prior art.
It should be pointed out that the electrodeposition of ZnO
according to the invention may be carried out on CIGS/CdS/i-ZnO
structures produced conventionally, with no adaptation. Moreover, a
ZnO film was electrodeposited by the process according to the
invention on CIGS/CdS/i-ZnO specimens coming from another test
center, and the results are very similar: [0089] Voc=649 mV, [0090]
Jsc=-30.1 mA/cm.sup.2, [0091] FF=71.7%, [0092] .eta.=14.7%, which
clearly demonstrates the flexibility of the electrolysis deposition
technique.
[0093] The J-V characteristic in FIG. 3E is labeled REF and the J-V
characteristics of the stacks described below will be compared with
this characteristic REF.
[0094] Referring now to FIGS. 4A to 4D, in the case of a stack of
the Mo/CIGS/ZnS and ZnO type by electrodeposition according to the
invention, again a very compact surface film of ZnO with
crystalline facets may be seen (FIG. 4C). The ZnS film is deposited
by CBD (chemical bath deposition).
[0095] The J-V characteristic of this type of stack is shown in
FIG. 4D, which indicates the following parameters:
Voc=656 mV and Jsc=-30.8 mA/cm.sup.2 for a form factor FF=73.1% and
an efficiency .eta. of 15.5%, notwithstanding the fact that the CdS
is replaced with ZnS and the undoped ZnO film is omitted.
[0096] Referring now to the case of a stack of the Mo/CIGS/CdS and
ZnO type by electrodeposition according to the invention, again a
homogeneous and compact surface film of ZnO is observed. The J-V
characteristic of this type of stack is shown in FIG. 6, which
indicates the following parameters:
Voc=652 mV and Jsc=-29.3 mA/cm.sup.2 for a form factor FF=63% and
an efficiency .eta. of 12.1%, notwithstanding the fact that the
undoped ZnO film has been omitted. However, it should be pointed
out here that replacement of cadmium by zinc in the interface film
INT gave better results in the previous example shown in FIGS. 4A
to 4D.
[0097] It may therefore be seen that the range of efficiencies
obtained is comparable to that in which a film of intrinsic ZnO is
sputtered before the ZnO electrodeposition. The process according
to the invention can therefore be applied directly after the
conventional step of CdS or ZnS deposition without requiring to
recreate a vacuum to deposit the i-ZnO film. Furthermore, the
results appear to be better when the interface film is based on ZnS
rather than CdS.
[0098] Referring now to FIGS. 5A to 5E in the case of a stack of
the Mo/CIGS and ZnO type deposited directly by electrodeposition
according to the invention, again a surface film of ZnO with
crystalline facets is seen (FIG. 5D) the homogeneity and
compactness of which are satisfactory (FIG. 5A). FIG. 5E shows the
J-V characteristic of a stack of the type in which ZnO is
electrodeposited directly on CIGS and indicates the following
results: [0099] Voc=580 mV, [0100] Jsc=-29.8 mA/cm.sup.2, [0101]
FF=67.5%, and [0102] efficiency .eta.=11.7%, which results
nevertheless remain satisfactory.
[0103] Admittedly the performance is substantially inferior to that
with CdS or ZnS buffer layers, but it remains, however, well above
10%, thereby validating this use of the invention in photovoltaic
applications.
[0104] The deposition technique according to the invention may be
applied homogeneously on large areas, with efficiency results
ranging up to 9.5% for the following stack:
glass/Mo/CIS(EVAP)/CdS(CBD)/i-ZnO(SPUT)/ZnO(ED) on plates of 17.5
cm.sup.2 area. FIG. 7 shows the J-V characteristic of such a
structure.
[0105] The use of light to assist the electrodeposition according
to the invention results in a spectacular improvement in the
lateral homogeneity of the deposition. This advantage is a key
point in the application of the process according to the invention
on large areas. Typically the deposition could be carried out on
areas ranging up to the order of 1 m.sup.2 or more, by virtue of an
appropriate electrolysis device.
[0106] Overall, the efficiencies obtained are high for CIS-based
cells with a CdS-based window film. The use of CIS substrates with
ZnS-based interface films is novel and very promising. Moreover,
the deposition of the ZnO surface film by electrolysis permanently
obviates the subjacent intrinsic ZnO (or ZnMgO) film usually
deposited by sputtering (reference TRA in FIG. 1).
[0107] Of course, the present invention is not limited to the
embodiment described above by way of example; rather it extends to
other variants.
[0108] For example, the transparent and/or conductive oxide coating
film may be electrodeposited by fixing the potential at the
electrode (deposition in what is called "potentiostatic" mode in a
preferred embodiment) or by fixing the current flowing through the
electrode (in what is called "galvanostatic" deposition mode).
* * * * *