U.S. patent application number 12/734821 was filed with the patent office on 2011-01-20 for method for electrochemically depositing a metal electrode of a solar cell.
This patent application is currently assigned to WUXI SUNTECH POWER CO., LTD.. Invention is credited to Liping Chen, Jingjia Ji, Zhengrong Shi, Stuart Wenham.
Application Number | 20110011745 12/734821 |
Document ID | / |
Family ID | 39891659 |
Filed Date | 2011-01-20 |
United States Patent
Application |
20110011745 |
Kind Code |
A1 |
Ji; Jingjia ; et
al. |
January 20, 2011 |
METHOD FOR ELECTROCHEMICALLY DEPOSITING A METAL ELECTRODE OF A
SOLAR CELL
Abstract
A method for electrochemically depositing a metal electrode of a
solar cell, comprising the steps of: making the surface of the
solar cell having a cathode contact with an electrolyte solution,
connecting an anode of the solar cell and a solid metal,
illuminating the main light-receiving surface of the solar cell,
wherein metal ions in the electrolyte solution accept electrons
formed on the cathode surface of the solar cell so that a metal is
formed and deposited on the cathode surface of the solar cell,
meanwhile, the solid metal provides electrons to the anode of the
solar cell so that the metal ions are formed and dissolved in the
electrolyte solution. By using this method, a problem of a
decreased cell efficiency due to a short circuit caused by the
deposition of metal on the anode will be solved, meanwhile, a
possibility of damaging the solar cell and depositing metal
unevenly as a result of using any kind of plating fixtures is
avoided, the electrochemical reaction rate is effectively
controlled, an evenness of the deposition of metal is guaranteed,
and the manufacture of a solar cell having a selective diffusion
structure is promoted.
Inventors: |
Ji; Jingjia; (Wuxi, CN)
; Wenham; Stuart; (Sydney, AU) ; Chen; Liping;
(Wuxi, CN) ; Shi; Zhengrong; (Wuxi, CN) |
Correspondence
Address: |
NIXON & VANDERHYE, PC
901 NORTH GLEBE ROAD, 11TH FLOOR
ARLINGTON
VA
22203
US
|
Assignee: |
WUXI SUNTECH POWER CO.,
LTD.
WUXI, JIANGSU
CN
|
Family ID: |
39891659 |
Appl. No.: |
12/734821 |
Filed: |
January 29, 2008 |
PCT Filed: |
January 29, 2008 |
PCT NO: |
PCT/CN2008/000220 |
371 Date: |
September 30, 2010 |
Current U.S.
Class: |
205/91 |
Current CPC
Class: |
H01L 31/022425 20130101;
Y02E 10/50 20130101; C25D 7/126 20130101; C25D 5/006 20130101 |
Class at
Publication: |
205/91 |
International
Class: |
C25D 5/00 20060101
C25D005/00 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 30, 2007 |
CN |
200710188267.8 |
Claims
1. A method for electrochemically depositing a metal electrode of a
solar cell, characterized by comprising the steps of: making the
surface of the solar cell (30) having a cathode contact with an
electrolyte solution (20), connecting an anode of the solar cell
(30) and a solid metal (50), illuminating the main light-receiving
surface of the solar cell (30) by a light source (60), wherein
metal ions in the electrolyte solution (20) accept electrons formed
on the cathode surface of the solar cell (30) so that a metal is
formed and deposited on the cathode surface of the solar cell (30),
meanwhile, the solid metal (50) provides electrons to the anode of
the solar cell so that the metal ions are formed and dissolved in
the electrolyte solution (20).
2. The method according to claim 1, characterized in that the solar
cell (30) does not contact the electrolyte solution (20) except for
its surface having the cathode.
3. The method according to claim 1, characterized in that the
surface contacting the electrolyte solution (20) of the solar cell
(30) only comprises the cathode.
4. The method according to claim 1, characterized in that the
surface contacting the electrolyte solution (20) of the solar cell
(30) comprise both the cathode and the anode.
5. The method according to claim 1, characterized in that the
electrolyte solution (20) includes metal ions, acid radicals, water
and additives.
6. The method according to claim 5, characterized in that the
electrolyte solution (20) comprises at least one metal ion.
7. The method according to claim 5, characterized in that the
electrolyte solution (20) comprises at least one acid radical.
8. The method according to claim 5, characterized in that the
electrolyte solution (20) comprises at least one additive.
9. The method according to claim 1, characterized in that the main
light-receiving surface is the surface contacting the electrolyte
solution (20) of the solar cell (30).
10. The method according to claim 1, characterized in that the main
light-receiving surface is the surface of the solar cell (30) which
does not contact the electrolyte solution (20).
11. The method according to claim 1, characterized in that within
the step of illuminating, the light source (60) for illuminating is
the natural light or the light emitted by an illuminator.
12. The method according to claim 1, characterized in that within
the step of illuminating, the surface of the solar cell (30) is
directly illuminated by light.
13. The method according to claim 1, characterized in that within
the step of illuminating, the surface of the solar cell (30) is
illuminated by light passing through the electrolyte or other
mediums.
14. The method according to claim 1, characterized in that the
anode of the solar cell (30) is connected electrically with the
solid metal (50) by a conductive wire (40).
15. The method according to claim 1, characterized in that the
solid metal (50) is composed of at least one metal.
16. The method according to claim 1, characterized in that the
solid metal (50) has at least one surface contacting the
electrolyte solution (20).
17. The method according to claim 1, characterized in that further
comprising the step of connecting an external power supply between
the anode of the solar cell (30) and the solid metal (50).
18. The method according to claim 17, characterized in that the
external power supply is a direct current power supply whose
cathode is connected with the anode of the solar cell (30) and
whose anode is connected with the solid metal (50).
19. The method according to claim 18, characterized in that the
output power of the direct current power supply is not less than
zero.
20. The method according to claim 1, characterized in that the
composition of the solid metal (50) is the same as the composition
of the metal deposited on the cathode surface of the solar cell
(30).
21. The method according to claim 1, characterized in that the
solar cell (30) is fixed above the electrolyte solution (20).
22. The method according to claim 1, characterized in that the
solar cell (30) is moved along a horizontal direction.
Description
TECHNICAL FIELD
[0001] The invention generally relates to a method for
electrochemically depositing metal, and especially relates to a
method for electrochemically depositing a metal electrode on a
cathode surface of a solar cell.
BACKGROUND TECHNIQUE
[0002] Currently, most methods for forming conductive electrodes of
a commercial solar cell comprise the steps of: screen-printing a
cathode surface of a solar cell with a silver paste and an anode
surface of the solar cell with an aluminum paste, and
simultaneously forming a conductive cathode and a conductive anode
on the cathode and anode of the solar cell, respectively, by
co-firing at high temperature. The advantage of this method for
forming conductive electrodes of a solar cell is that, the process
is simple and dependable, and is prone to be applied to a
large-scale production.
[0003] However, a simple process of forming conductive electrodes
of a solar cell by screen printing and co-firing limits the
increase of the photoelectric conversion efficiency of the solar
cell. For ensuring a preferable Ohmic contact between the paste for
screen-printing and the surface of the solar cell after being
co-fired, and for ensuring the reduction in a series resistance of
the solar cell, not only a metal fingers should be designed to be
wider (generally wider than 100 microns), but also an emitter
square resistance should be designed to be lower (generally 50 ohm
per square). The design of the wide metal fingers reduces a valid
work area of the solar cell, and the design of the lower emitter
square resistance reduces a short-circuit current of the solar
cell. These are main reasons why the photoelectric conversion
efficiency of a current commercial solar cell is low.
[0004] Obviously, one of main measures of enhancing the
photoelectric conversion efficiency of a solar cell is increasing
its emitter square resistance. However, after the emitter square
resistance of the solar cell is increased, if the processes of
screen-printing a paste and co-firing are still adopted, the
contact resistance of the solar cell will be increased, and thus
the photoelectric conversion efficiency of the solar cell will be
reduced. Therefore, one of problems which must be solved after the
emitter square resistance of a solar cell increased is to reduce
the contact resistance between a conductive metal electrode and the
solar cell.
[0005] One of methods for resolving the above-mentioned problem is
adopting a selective diffusion process. The so-called selective
diffusion process refers to making different areas of the emitter
of the solar cell with square resistances of two different values,
namely, the area where the conductive metal electrode is formed
with a lower square resistance, and the other light-receiving
surface with a higher square resistance. This technological design
enhances a short-circuit current of the solar cell, as well as
decreases a contact resistance between conductive metal electrodes
and the solar cell. Therefore, the selective diffusion process is
one of main measures of enhancing the photoelectric conversion
efficiency of the solar cell.
[0006] Nevertheless, it's difficult to apply the above-mentioned
processes of screen-printing and co-firing to a solar cell being
selectively diffused. The main reason is that, in the process of
screen-printing, it is hard to align a metal paste to the area with
a lower square resistance on the emitter of the solar cell.
[0007] Usually, to solve the alignment problem, the method of
chemically depositing a conductive metal electrode on the surface
of a solar cell is used instead of the method of screen printing.
In a buried contact solar cell, a conductive metal electrode is
formed on the emitter of the solar cell by chemically depositing a
metal, such as copper. The method concretely comprises the steps
of: covering the emitter surface having a higher square resistance
of a solar cell with a passive film or an antireflective film,
laser-etching grooves on the passive film, carrying out deep
diffusion for reducing the square resistance of the groove area on
the emitter surface, and chemically depositing metal to form a
conductive metal electrode of the solar cell on its emitter area
having a lower square resistance.
[0008] The process of chemically depositing copper is an extremely
slow-moving chemistry process. Generally, it takes about ten hours
to obtain a conductive metal electrode with a required thickness.
For avoiding the problems of stress and adsorption due to a high
speed of the deposition, the rate of chemically depositing a
conductive metal electrode is generally controlled to be slower
than 2 microns per hour.
[0009] The method for forming the solar cell electrode by
chemically depositing metal also has another problem, namely, the
service life of a solution for chemically depositing metal is
short. Generally, the solution can only be used for several
batches. So when the method of chemically depositing metal is used
on a large-scale production, a great deal of waste liquid will be
produced. Since there are some organic substances which are
difficult to be disposed in the discharged waste liquid, the use of
the process of chemically depositing metal increases the production
cost of the solar cell.
[0010] More than that, the solution for chemically depositing metal
is quite unsteady and the phenomenon of metal self-separation
occurs easily, which may affect a normal production. Moreover, the
process condition of chemically depositing metal must be controlled
sternly. For example, the temperature of the solution for
chemically depositing copper must be controlled strictly. For
reducing the possibility of copper self-separation, when chemically
depositing copper, both air bubbling and filtration are required.
For keeping the stability of the solution density, it is also
required to constantly add a complement liquid. The adding of the
complement liquid must be controlled very strictly, since too much
complement liquid will result in copper self-separation and too
little will reduce the rate of depositing copper.
[0011] Moreover, most operations of chemically depositing copper
are implemented at a temperature higher than room temperature, for
example, higher than 50 .quadrature.. Such a process needs a great
deal of energy supply, which further increases the cost. Since the
reaction time is long, the amount of the energy consumed during the
production is considerable.
[0012] The above problem is solved by a plating process, instead of
the process of chemically depositing metal. Compared with the
process of chemically depositing metal, the advantage of the
plating process is that its speed of depositing metal is fast. When
the plating process is adopted, the time during which a conductive
electrode of the solar cell is formed is shortened to within one
hour from about ten hours when using the process of chemically
depositing metal. Generally, if the plating process is adopted, the
process of forming the conductive electrode of the solar cell can
be completed between 10 to 20 minutes.
[0013] Another advantage of the use of the plating process instead
of the process of chemically depositing metal is that, it has a
larger operation range and is especially suitable for industrial
production because the process of electrochemically depositing
metal is simpler than the process of chemically depositing metal.
For example, the requirement for temperature is not strict and this
process can be carried out at room temperature. This is
advantageous for the production control, and economizes the cost
needed for heating. The composition of the electrolyte solution
used in the plating process is also very simple, so the electrolyte
solution generally can be repeatedly used for a long time.
[0014] Furthermore, the conductive electrode of the solar cell
formed by a general chemistry deposition process is in amorphous
state, while the conductive electrode of the solar cell deposited
electrochemically is in micro-crystal state. Therefore, the
conductive metal electrode deposited electrochemically has better
conductivity performance. As a result, the plated metal electrode
can reduce the loss of current produced by the solar cell on the
conductive metal electrode, thereby improving the photoelectric
conversion efficiency of the solar cell.
[0015] The plating process is highly suitable for industrial
production because the chemistry of depositing metal by the plating
process is very simple, for example, the variety in the pH value of
the electrolyte solution and the composition of the solution has a
little influence on the plating process, and the management to the
solution is also quite simple. More importantly, the production
cost of the conductive metal electrode of the solar cell/formed by
the plating process is very low, and the processing of the waste
liquid in the plating process is also simpler than that in the
process of chemically depositing metal.
[0016] However, there is still certain difficulty in practically
applying the traditional plating process to the large-scale
production of the solar cell. A main problem is the contact between
a plating fixture and the solar cell, and the evenness of the metal
plated on the solar cell. The above-mentioned plating fixture is an
important tool during a traditional plating operation. One of the
functions of the plating fixture during the plating operation is to
fix the object to be plated in a certain position or in a certain
range; another function of the plating fixture is to conduct the
current of an external power supply to the object to be plated.
[0017] In fact, the resistance of the surface of a solar cell is
very large before metallization. Generally, a contact resistance
between the plating fixture and the surface of the solar cell is
very large, which finally results in poor evenness of the metal
plated on the surface of the solar cell. Moreover, since the
semi-conductor material for forming the solar cell is fragile, a
crack of the solar cell often occurs during loading/unloading the
solar cell on/from the plating fixture.
[0018] Usually, the method for resolving the above-mentioned
problem caused by the mechanical and electrical contact of the
solar cell and the plating fixture is that, immersing the solar
cell in an electrolyte, and then depositing a conductive metal
electrode on the solar cell by using the electric energy generated
by the solar cell subjected to illumination. Since the conductive
metal electrode is formed on the surface of the solar cell by way
of the electric energy generated by the solar cell after being
illuminated, in this method traditional plating fixtures are not
needed to conduct the current of an external power supply to the
surface to be plated of the solar cell, so that various problems
caused by using the plating fixtures are solved.
[0019] Nevertheless, this method which actualizes the deposition of
metal on the surface of a solar cell by using the electric energy
generated by the solar cell itself also has many defects. First,
for protecting metal on the anode surface of the solar cell, a
direct current power supply should be provided in addition. The
anode of the direct current power supply is connected to a metal
located in an electrolyte solution, and the cathode of the direct
current power supply is connected to the anode metal of the solar
cell located in the electrolyte solution. Only such a connection
can ensure that the metal on the anode of the solar cell will not
be damaged while metal is deposited on the cathode of the solar
cell. In fact, such a connection used for depositing metal may make
metal to be deposited on the cathode and the anode of the solar
cell at the same time, which results in an unnecessary increase of
the production cost.
[0020] This method has another disadvantage. Since the electric
potential on the cathode surface of the solar cell is a summation
of the electric potential generated by the solar cell and the
electric potential of the external power supply, this is, the
electric potential on the cathode surface of the solar cell depends
on not only the electric potential generated by the solar cell, but
also the electric potential applied to the solar cell by the
external power supply. Therefore, the evenness of the metal plated
on the surface of the solar cell depends on not only the evenness
of the illumination on the surface of the solar cell, but also the
evenness of the electric potential applied to the solar cell by the
external power supply. For example, only very fine contact of a
whole surface can achieve a well uniform electric potential on the
cathode surface of the solar cell. In fact, it is very difficult to
actualize such an even contact in industrial production.
SUMMARY OF THE INVENTION
[0021] Aiming at the above-mentioned defects in the prior art, one
object of the invention is to provide a process for actualizing the
electrochemical deposition of metal on the surface of a solar cell
which utilizes the characteristic that the solar cell will generate
an electric potential after accepting illumination.
[0022] Further, another object of the invention is to provide a
process of electrochemically depositing metal which can ensure that
a metal will only be deposited on the cathode surface of the solar
cell.
[0023] Furthermore, yet another object of the invention is to
provide a process of electrochemically depositing metal on the
cathode surface of the solar cell in which the rate of depositing
metal can be effectively controlled.
[0024] The last object of the invention is to provide a process of
electrochemically depositing metal on the cathode surface of the
solar cell which is suitable for a large-scale production.
[0025] For achieving the above mentioned objects, the invention
provides a method for electrochemically depositing a metal
electrode of a solar cell, the method comprising the steps of:
[0026] making the surface of the solar cell having a cathode
contact with an electrolyte solution,
[0027] connecting an anode of the solar cell and a solid metal,
[0028] illuminating the main light-receiving surface of the solar
cell by a light source,
[0029] wherein metal ions in the electrolyte solution accept the
electrons formed on the cathode surface of the solar cell so that a
metal is formed and deposited on the cathode surface of the solar
cell, meanwhile, the solid metal provides electrons to the anode of
the solar cell so that the metal ions are formed and dissolved in
the electrolyte solution.
[0030] Preferably, the solar cell does not contact the electrolyte
solution except for its surface having the cathode.
[0031] Preferably, the surface contacting the electrolyte solution
of the solar cell only comprises the cathode.
[0032] Preferably, the surface contacting the electrolyte solution
of the solar cell may comprise the cathode and the anode at the
same time.
[0033] Preferably, the electrolyte solution includes metal ions,
acid radicals, water and additives.
[0034] Preferably, the electrolyte solution comprises at least one
metal ion.
[0035] Preferably, the electrolyte solution comprises at least one
acid radical.
[0036] Preferably, the electrolyte solution comprises at least one
additive.
[0037] Preferably, the main light-receiving surface is the surface
contacting the electrolyte solution, or the surface of the solar
cell which does not contact the electrolyte solution.
[0038] Preferably, within the step of illuminating, the light
source for illuminating is the natural light or the light emitted
by an illuminator.
[0039] Preferably, within the step of illuminating, the surface of
the solar cell is illuminated by light directly or by light passing
through the electrolyte or other mediums.
[0040] Preferably, the anode of the solar cell is connected
electrically with the solid metal by a conductive wire.
[0041] Preferably, the solid metal is composed of as least one
metal or alloy.
[0042] Preferably, at least one surface of the solid metal contact
the electrolyte solution.
[0043] Preferably, the method further comprises the step of
connecting an external power supply between the anode of the solar
cell and the solid metal.
[0044] Preferably, the external power supply is a direct current
power supply whose cathode is connected with the anode of the solar
cell and whose anode is connected with the solid metal.
[0045] Preferably, the output power of the direct current power
supply is not less than zero.
[0046] Preferably, the composition of the solid metal is the same
as the composition of the metal deposited on the surface of the
cathode of the solar cell.
[0047] Preferably, the solar cell is fixed above the electrolyte
solution.
[0048] Preferably, the solar cell is moved along the horizontal
direction.
[0049] During the process of electrochemically depositing metal of
the invention, metal ions can only be deposited on the cathode of
the solar cell, so that a problem of the reduced cell efficiency
caused by a short-circuit due to the deposition of metal on the
anode is solved at root, while possibilities of damaging the solar
cell caused by any kind of electrical contact and the unevenness of
the deposition of metal are avoided.
[0050] Another advantage of the invention is that, an external
power supply is not needed to protect metal on the other surface of
the solar cell since the other surface of the solar cell does not
contact the electrolyte solution. Therefore, the electric potential
on the surface of the solar cell changes from zero, and can be
controlled effectively, so that the rate of an electrochemical
reaction on the cathode surface of the solar cell can be
controlled.
[0051] Another important advantage of the invention is that, since
an evenness of the illumination intensity is ensured, the electric
potential over the whole surface of the solar cell is quite even,
so that the metal is very evenly deposited over the whole cathode
surface of the solar cell.
[0052] Yet another advantage of the invention is that, an effect of
self-aligning can be achieved. This advantage is especially useful
for forming a solar cell having a selective diffusion
structure.
EXPLANATIONS OF THE DRAWINGS
[0053] FIG. 1 is a schematic view of carrying out an
electrochemical reaction on the cathode surface of a solar cell to
deposit metal by using the method of electrochemically depositing
metal of the invention.
DETAILED SPECIFICATION OF EMBODIMENTS
[0054] The concrete embodiments will be described below with
reference to the drawing.
[0055] FIG. 1 is a schematic view of carrying out an
electrochemical reaction on the cathode surface of a solar cell to
deposit metal by using the method of electrochemically depositing
metal of the invention.
[0056] As shown in FIG. 1, the devices used in the method of
electrochemically depositing metal of the invention are mainly
comprise an electrolytic tank 10, an electrolyte solution 20, a
solar cell 30, a conductive metal wire 40, a metal block 50 and an
illuminator 60.
[0057] A main function of the electrolytic tank 10 is containing
the electrolyte solution 20. In the case where the main
light-receiving surface of the solar cell 30 is its cathode
surface, another function of the electrolytic tank 10 of the
invention is permitting the light emitted by the illuminator 60 to
pass through and irradiate on the main light-receiving surface of
the solar cell 30. Thus, the electrolytic tank 10 of the invention
may be made of a transparent and corrosion-resisting material, such
as quartz, glass, a transparent organic material and so on.
[0058] In the case where the main light-receiving surface of the
solar cell does not comprise its cathode, namely, its
light-receiving surface and cathode surface are two surfaces of the
solar cell respectively, the illuminator should be located above
the solar cell, so that the light emitted by the illuminator can
directly irradiate the upper surface of the solar cell.
[0059] The electrolyte solution 20 in the electrolytic tank 10 of
the invention is composed mainly of metal ions and acid radicals,
such as copper sulphate, nickel chloride, and so on. According to
different requirements for the deposited metal, the electrolyte
solution 20 may comprise only one metal ion or more.
[0060] Similarly, According to different requirements for the
deposited metal, the electrolyte solution 20 may comprise only one
acid radical or more, such as sulfate radical and nitrate
radical.
[0061] For reducing the stress of the deposited metal and enhancing
the flatness of the deposited metal, an appropriate additive may be
added in the electrolyte solution 20 according to different
electrolyte solutions and the process of electrochemically
depositing metal.
[0062] One important technical feature of the invention is that,
only the surface having the cathode of the solar cell 30 contacts
the electrolyte solution 20 and the other surface does not contact
the electrolyte solution 20.
[0063] For the simplicity of industrial production, two surfaces of
more than 90% commercial solar cells are the cathode and anode,
respectively. Therefore, the method of the invention is especially
adapted for depositing metal on the commercial solar cell. When the
method of the invention is used for the above commercial solar
cell, an external power supply is not necessary for protecting
metal on the anode of the solar cell, since the anode is located on
the reverse side of the cathode and does not contact the
electrolyte solution.
[0064] As shown in FIG. 1, the conductive wire 40 is electrically
connected between the solid metal 50 and the solar cell 30.
Generally, the main composition of the solid metal 50 is the same
as the composition of the metal to be deposited on the cathode
surface of the solar cell 30.
[0065] The solid metal 50 may be a metal with a single composition,
or be an alloy composed of more than one metal. The solid metal 50
can be placed at any position in the electrolytic tank 10 while it
has a good contact with the electrolyte solution 20. When the
cathode surface of the solar cell 30 is the main light-receiving
surface, the position of the solid metal 50 must not influence the
irradiation of the light emitted by the illuminator 60 on the
surface of the solar cell 30.
[0066] FIG. 1 shows a complete reaction process of
electrochemically depositing a metal electrode on the cathode
surface of the solar cell by the method of the invention.
[0067] Different from the traditional plating process, the
electrochemical reaction of the invention does not need electric
energy provided from external, but is realized using electric
energy generated by the solar cell itself.
[0068] In FIG. 1, the illuminator 60 is located below the
electrolytic tank 10. The position of the illuminator 60 depends on
the structure of the solar cell 30. In the case where the cathode
of the solar cell 30 is its main light-receiving surface, the lower
surface, i.e. the cathode surface, of the solar cell 30 is
irradiated by the light emitted by the illuminator 60 passing
through the transparent electrolytic tank 10 and the electrolyte
solution 20.
[0069] A solar cell is a device converting a light energy to an
electric energy. After the solar cell is irradiated by the light, a
negative potential is generated on the surface of the emitter, i.e.
the cathode. Thus, the illumination allows the solar cell 30 to
release electrons after generating the negative potential. Metal
ions in the electrolyte solution 20 driven by the negative
potential move toward the cathode, and then a metal atom is formed
and deposited on the cathode surface of the solar cell 30 after the
metal ions accept electrons on the cathode surface of the solar
cell 30. At the same time, under the function of a positive
potential of the anode of the solar cell 30, the solid metal 50 in
the electrolyte solution 20 constantly losses electrons through the
conductive wire 40 to form metal ions to be dissolved in the
electrolyte solution 20, so that the density of the metal ions in
the electrolyte solution 20 is kept constant. At last, an
electrochemical reaction process is realized without an external
power supply.
[0070] Different from the plating process that requires an external
power supply, the above process of electrochemically depositing
metal of the invention does not need any external power supply, but
carries out the whole electrochemical reaction by way of the
electric potential generated by the solar cell 30 itself after
being illuminated. During the above process, the metal ions thus
can only be deposited on the cathode of the solar cell 30.
[0071] This characteristic has very important sense in industrial
production of the solar cell. If the electrochemical reaction is
carried out with an external power supply, the metal will be
deposited on the both cathode and anode unprotected on the surfaces
of solar cell, which results in a short-circuit of the solar cell
and decreases the photoelectric conversion efficiency of the solar
cell. And in the method of the invention, even if the anode surface
is exposed, it is impossible for the metal to be deposited on the
anode of the solar cell since the anode can only accept electrons
rather than release electrons after the solar cell is subjected to
illumination. Therefore, the problem of the decreased cell
efficiency caused by the short-circuit of the anode is solved at
root.
[0072] At the same time, since a solar cell slice is generally
about 200 .mu.m in thickness, any locally physical contact will
easily cause crack. And since the process of electrochemically
depositing metal of the invention needs no external power supply,
there is no electric contact during the electrochemistry process of
the invention, so that the possibility of damaging the solar cell
slice is avoided.
[0073] Further, since the resistance of the cathode surface of the
solar cell is generally large, an outside electric contact will
result in an unevenness of the electric potential on the cathode
surface of the solar cell, in turn an unevenness of the metal
deposited on the surface of the solar cell. And in the
electrochemical reaction of the invention, as long as the
illumination intensity on the surface of the solar cell is even,
the electric potential generated by the solar cell is even over its
whole surface, namely, the metal is evenly deposited on its
surface.
[0074] On the other hand, in the electrochemical reaction process
of the invention, the surface having the cathode of the solar cell
contacts the electrolyte solution and the other surface of the
solar cell does not contact the electrolyte solution, so that it is
not necessary to use an external power supply to protect metal on
the other surface of the solar cell. As a result, the electric
potential on the surface of the solar cell may change from zero,
the rate of the electrochemical reaction on the cathode surface of
the solar cell may be better controlled, and the rate of
electrochemically depositing metal may be changed arbitrarily by
varying the illuminating intensity.
[0075] The metal produced by the method of the invention is very
evenly deposited on the cathode surface of the solar cell. The
reason is that the electric potential generated by the solar cell
is directly proportional to the illuminating intensity accepted by
the solar cell. The potential over the whole surface of the solar
cell is very even on the condition of the even illuminating
intensity, and will not be influenced by the position, the shape
and the size of the anode metal block. An even electric potential
brings an even electrochemical reaction rate, in turn an even metal
deposition layer.
[0076] The method of the invention is especially useful for
producing the solar cell having a selective diffusion structure.
For reducing the reflective rate of the solar cell, an
antireflective film for reducing the reflective rate is generally
plated on the surface having a high square resistance of the solar
cell. The antireflective film acts as a mask during the process of
electrochemically depositing metal of the invention and prevents
the electrons generated by the cathode of the solar cell from
contacting the metal ions in the electrolyte solution. And the
electrons generated by the surface having a low square resistance,
which has been selectively diffused and is not protected by the
mask, of the solar cell contact the metal ions in the electrolyte
solution, that is, an electrochemical reaction occurs, and a
conductive metal electrode is formed on its surface.
[0077] The process of electrochemically depositing metal of the
invention may be carried out intermittently or continuously.
[0078] During a process of intermittently electrochemically
depositing metal, the solar cell 30 of the invention is fixed above
the electrolyte solution 20 with its surface having the cathode
contacting the electrolyte solution 20. When the solar cell 30
receives the light emitted by the illuminator 60, the metal ions in
the electrolyte solution 20 receive electrons from the cathode
surface of the solar cell, then a metal is formed and deposited on
the cathode surface of the solar cell.
[0079] During a process of continuously electrochemically
depositing metal, the solar cell 30 of the invention is moved along
a horizontal direction. The means for moving the solar cell 30 may
be a roller or a moveable carriage. For example, the solar cell 30
may be placed on a group of rollers with its surface having a
cathode contacting the electrolyte solution 20 below it. As this
group of rollers rotates toward a certain direction, the solar cell
30 is moved along a certain direction on this group of rollers to
realize the process of continuously electrochemically depositing
metal.
[0080] The followings are several detailed embodiments of using the
method of the invention.
1. The First Embodiment
[0081] The first step is fabricating a traditional solar cell as
follows:
[0082] A P-type silicon slice is processed by texturing, diffusing,
edge etching, coating a silicon-nitride film on an N-type surface,
screen-printing an aluminum paste on an P-type surface,
screen-printing a silver paste on the N-type surface and firing to
make a solar cell whose photoelectric conversion efficiency is
measured as 16.57%, and the open circuit voltage, the current
density, the series resistance, the parallel resistance and the
filling factor of the solar cell are 625 mV, 35.3 mA/cm2, 0.0075
.OMEGA., 13.11 .OMEGA. and 75.1%, respectively.
[0083] The second step is preparing electrolyte solutions:
[0084] Preparation of a copper electrolyte solution: evenly
dissolving 200 g of copper sulfate, 120 g of sulfuric acid and 4.5
ml of brightening agent VF100 in 1 L of water.
[0085] Preparation of a tin electrolyte solution: evenly dissolving
50 g of stannous sulfate, 60 g of sulfuric acid, 48 g of
thymosulfonic acid and 2.4 g of cresol in 1 L of water.
[0086] The third step is electrochemically depositing metal:
[0087] The cathode surface of the solar cell is contacted with the
above copper electrolyte solution, and the anode of the solar cell
is connected with a solid copper in the copper electrolyte
solution. An illuminator is placed below a transparent electrolytic
tank. After the solar cell is irradiated by light for 15 minutes,
it is measured that the thickness of the copper layer deposited on
the cathode conductive electrode of the solar cell is about 10
.mu.m.
[0088] Then the cathode of the solar cell after the above step is
contacted with the above mentioned tin electrolyte solution, and
the anode of the solar cell is connected with a solid tin in the
tin electrolyte solution. The illuminator is placed below the
transparent electrolytic tank. After the solar cell is irradiated
by light for 1 minute, it is measured that the thickness of the tin
layer deposited on the cathode conductive electrode of the solar
cell is about 0.01 .mu.m. At the same time, it is measured that the
photoelectric conversion efficiency of the solar cell has been
improved to 16.94%, and its open circuit voltage is 626 mV, the
current density is 35.2 mA/cm2, the series resistance is 0.004552,
the parallel resistance is 49.41 .OMEGA. and the filling factor is
76.9%.
2. The Second Embodiment
[0089] The first step is fabricating a buried contact solar cell as
follows:
[0090] A P-type silicon slice is processed by texturing, shallowly
diffusing, edge etching, oxidizing, laser-etching buried contact
grooves on an N-type surface, deeply diffusing inside the buried
contact grooves, sputtering aluminium on a P-type surface and
firing the aluminium, chemically plating nickel inside the buried
contact grooves, and forming a nickel-silicon alloy after firing
the nickel.
[0091] The second step is preparing electrolyte solutions:
[0092] Preparation of a nickel electrolyte solution: evenly
dissolving 150 g of nickel sulfate, 8 g of sodium chloride, 30 g of
boric acid and 40 g of anhydrous sodium sulfate in 1 L of
water.
[0093] Preparation of a copper electrolyte solution: evenly
dissolving 200 g of copper sulfate, 120 g of sulfuric acid and 4.5
ml of brightening agent VF 100 in 1 L of water.
[0094] Preparation of a copper-zinc alloy electrolyte solution:
evenly dissolving 75 g of cuprous cyanide, 9 g of zinc cyanide, 55
g of sodium cyanide, 10 g of sodium carbonate and 4 g of sodium
fluoride in 1 L of water.
[0095] The third step is electrochemically depositing the cathode
metal of the buried contact solar cell:
[0096] The cathode surface of the solar cell is contacted with the
above nickel electrolyte solution, and the anode of the solar cell
is connected with a solid nickel in the nickel electrolyte
solution. An illuminator is placed below the transparent
electrolytic tank. After the solar cell is irradiated by light for
5 minutes, it is measured that the thickness of the nickel layer
deposited inside the buried contact grooves of the solar cell is
about 0.1 .mu.m.
[0097] Then the cathode surface of the solar cell after the above
step is contacted with the above mentioned copper electrolyte
solution, and the anode of the solar cell is connected with a solid
copper in the copper electrolyte solution. The illuminator is
placed below the transparent electrolytic tank. After the solar
cell is irradiated by light for 20 minutes, it is measured that the
thickness of the copper layer deposited inside the buried contact
grooves of the solar cell is about 15 .mu.m.
[0098] Then the cathode surface of the solar cell after the above
steps is contacted with the above mentioned copper-zinc alloy
electrolyte solution, and the anode of the solar cell is connected
with a solid copper-zinc alloy in the copper-zinc alloy electrolyte
solution. The illuminator is placed below the transparent
electrolytic tank. After the solar cell is irradiated by light for
2 minutes, it is measured that the thickness of the copper-zinc
alloy layer deposited inside the buried contact grooves of the
solar cell is about 0.01 .mu.m. At the same time, it is measured
that the photoelectric conversion efficiency of the solar cell is
17.53%, the open circuit voltage is 620 mV, the current density is
35.7mA/cm2, the series resistance is 0.0040 .OMEGA., the parallel
resistance is larger than 100 .OMEGA. and the filling factor is
79.2%.
3. The Third Embodiment
[0099] The first step is fabricating a solar cell with a whole-back
conductive electrode as follows:
[0100] An N-type silicon slice is processed by texturing, N-type
diffusing, oxidizing, opening the contact area for a P-type
electrode with a photoresist as a mask, P-type deeply diffusing,
opening the contact area for an N-type electrode with a photoresist
as a mask, chemically plating nickel on the electrode contact
areas, and forming a nickel-silicon alloy after firing the
nickel.
[0101] The second step is preparing electrolyte solutions:
[0102] Preparation of a nickel electrolyte solution: evenly
dissolving 150 g of nickel sulfate, 8 g of sodium chloride, 30 g of
boric acid and 40 g of anhydrous sodium sulfate in 1 L of
water.
[0103] Preparation of a copper electrolyte solution: evenly
dissolving 200 g of copper sulfate, 120 g of sulfuric acid and 4.5
ml of brightening agent VF100 in 1 L of water.
[0104] Preparation of a copper-tin electrolyte solution: evenly
dissolving 20 g of cuprous cyanide, 30 g of sodium stannate, 20 g
of sodium cyanide and 10 g of sodium hydroxide in 1 L of water.
[0105] The third step is electrochemically depositing an electrode
of the solar cell with a whole-back conductive electrode:
[0106] The conductive electrode surface of the solar cell is
contacted with the above nickel electrolyte solution, and the anode
of the solar cell is connected with a cathode of an external power
supply whose anode is connected with a solid nickel in the nickel
electrolyte solution. An illuminator is placed above the solar
cell. The current output of the external power supply is controlled
to be 1 A. After the solar cell is irradiated by light for 5
minutes, it is measured that the thickness of the nickel layer
deposited on the cathode surface and the anode surface of the solar
cell is about 0.1 .mu.m and 0.08 .mu.m, respectively.
[0107] Then the conductive electrode surface of the solar cell
after the above step is contacted with the above mentioned copper
electrolyte solution, and the anode of the solar cell is connected
with a cathode of an external power supply whose anode is connected
with a solid copper in the copper electrolyte solution. The
illuminator is placed above the solar cell. The current output of
the external power supply is controlled to be 1.5 A. After the
solar cell is irradiated by light for 20 minutes, it is measured
that the thickness of the copper layer deposited on the cathode
surface and the anode surface of the solar cell is about 15 .mu.m
and 12 .mu.m, respectively.
[0108] Then the conductive electrode surface of the solar cell
after the above steps is contacted with the above mentioned
copper-tin electrolyte solution, and the anode of the solar cell is
connected with a cathode of an external power supply whose anode is
connected with a solid copper and a solid tin in the copper-tin
electrolyte solution. The illuminator is placed above the solar
cell. The current output of the external power supply is controlled
to be 0.5 A. After the solar cell is irradiated by light for 2
minutes, it is measured that the thickness of the copper-tin layer
deposited on the cathode surface and the anode surface of the solar
cell is about 0.01 .mu.m and 0.008 .mu.m, respectively. At the same
time, it is measured that the photoelectric conversion efficiency
of the solar cell is 18.02%, its open circuit voltage is 620 mV,
the current density is 36.9 mA/cm2, the series resistance is 0.0051
.OMEGA., the parallel resistance is larger than 100 .OMEGA. and the
filling factor is 78.8%.
[0109] The invention is especially suitable for the solar cell
whose cathode and anode located on the different surfaces
respectively.
[0110] For example, the cathode and anode of most commercial solar
cells are provided on two different surfaces thereof, respectively.
The main light-receiving surface of the commercial solar cell is
its cathode surface. For decreasing the lightproof area of its
electrode, the cathode conductive metal electrode of this solar
cell is composed of many fingers. The anode of this commercial
solar cell is located on another surface. When the invention is
applied to the solar cell with this structure, its cathode surface
contacts the electrolyte solution while its anode surface contacts
a solid metal and does not contact the electrolyte solution. It is
easy to realize the continuous production with this process of
electrochemical reaction.
[0111] The invention is also suitable for the solar cell whose
cathode and anode are located on the same surface.
[0112] For eliminating the lightproof area of the conductive
electrode and enhancing the photoelectric conversion efficiency,
both the cathode and anode of a solar cell may be located on the
reverse side of the main light-receiving surface of the solar cell.
When the invention is applied to the solar cell with this kind of
structure, the surface having the cathode and anode of the solar
cell contacts the electrolyte solution. An external power supply is
connected between the anode of the solar cell and a solid metal,
while an illuminator is placed above the solar cell. When the
illuminator emits light and the external power supply outputs
electric energy, the reaction of electrochemically depositing metal
takes place synchronously on the cathode and anode of the solar
cell, namely, the conductive metal electrodes of the cathode and
anode are formed at the same time. The rate of depositing metal on
the cathode and anode can be adjusted by regulation of the luminous
intensity of the illuminator and the power supply strength of the
external power supply.
[0113] The invention is not limited to the above special
embodiments. A person skilled in the art may make various changes
and modifications without departing from the spirit and nature of
the invention, which should fall within the protection scope of the
claims attached to the invention.
* * * * *