CN102268702A - Photoelectrochemical deposition method for preparing copper-indium-gallium-selenium (CIGS) film - Google Patents
Photoelectrochemical deposition method for preparing copper-indium-gallium-selenium (CIGS) film Download PDFInfo
- Publication number
- CN102268702A CN102268702A CN2011101891635A CN201110189163A CN102268702A CN 102268702 A CN102268702 A CN 102268702A CN 2011101891635 A CN2011101891635 A CN 2011101891635A CN 201110189163 A CN201110189163 A CN 201110189163A CN 102268702 A CN102268702 A CN 102268702A
- Authority
- CN
- China
- Prior art keywords
- film
- photoelectrochemistry
- cigs thin
- deposition
- indium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention relates to a photoelectrochemical deposition method for a CIGS film. According to the invention, the photoelectrochemical deposition method is employed to deposit a CIGS film on a substrate immersed in an electrolyte; the electrolyte is selected from the group consisting of an aqueous solution, an organic solution, ionic liquid and a mixed solution thereof, and contains at least one selected from the group consisting of copper ions, indium ions, gallium ions and selenium ions; technological parameters for the photoelectrochemical deposition are that the working electrode potential is -6.0 to 1.5 V (vs SCE), at least a monochromatic light is selected as incident light, and the included angle between the incident direction of the incident light and the working electrode is in a range of 0 degree to 90 degrees. At last, heat treatment can be carried out on the obtained film. The invention enables the difficulties of poor morphology of obtained films, difficult deposition of indium and gallium, slow growth speed of films and the like in conventional electrodeposition methods for CIGS films to be overcome; the CIGS film obtained in the invention has the advantages of good quality, fast growth speed, controllable components, good morphology, etc.; the deposition method provided in the invention enables low cost and easiness in realizing large-scale deposition of CIGS films, which is favorable for large scale industrial popularization and application of the deposition method.
Description
Technical field
The present invention relates to a kind of CIGS thin-film solar cell absorption layer preparation methods, be meant the photoelectrochemistry deposition preparation method of CIGS thin-film especially, belong to the solar cell preparing technical field.
Background technology
Present CuInSe
2(CIS) thin film solar cell has become one of solar cell of most important and tool development prospect.CuInSe
2Film is the direct gap semiconductor material, and energy gap is 1.05eV, and can form copper-indium-galliun-selenium Cu (In, Ga) Se by doping Ga
2(CIGS) enable the gap length degree and in 1.05～1.67eV, adjust continuously, be suitable for the opto-electronic conversion requirement of sunlight; Copper-indium-galliun-selenium (CIGS) film has the high light uptake factor and (reaches 10
5Cm
-1), and stable performance, there is not the light decay effect, therefore be subjected to photovoltaic circle extensive concern.
The method that research at present prepares copper-indium-galliun-selenium (CIGS) thin-film material has vacuum and antivacuum preparation method.Vacuum method can more accurately be controlled the component of rete, obtain high-quality CIGS film, but because vacuum method prepares that thin-film material must carry out under high vacuum, vacuum apparatus, the highly purified raw material of needs costliness, exist also simultaneously that raw material availability is not high, problems such as complex process, the big area that is difficult to realize rete and successive sedimentation.These drawbacks limit the CIGS battery is large-scale produces and use.In the antivacuum method, modal is electrodip process, this method can be carried out big area, multicomponent mixture, lasting thin film deposition under low temperature and non-vacuum condition, have that equipment and technology are simple, with low cost, interface junction gets togather, material use efficiency height advantages such as (surpassing 95%).Therefore being equipped with solar cell with this legal system becomes one of main direction of studying that reduces cost, obtains the large-area high-quality film with the CIGS film.
But traditional electrical sedimentation quality of forming film shows aspects such as overlong time, the thin film composition of the certain thickness thin-film material needs of preparation is wayward (indium and gallium deposition difficulty etc.), pattern is relatively poor not as vacuum method.
Summary of the invention
The difficult problem of slow, indium of film growth rates and gallium deposition difficulty, pattern difference when the objective of the invention is to overcome traditional prepared by electrodeposition CIGS thin-film, existing and provide that a kind of processing method is simple, easy to operate, the photoelectrochemistry deposition preparation method of CIGS thin-film that CIGS thin-film fast growth, controllable component, film morphology are good.
The photoelectrochemistry deposition preparation method of CIGS thin-film of the present invention is to adopt the sedimentary method of photoelectrochemistry to deposit CIGS thin-film in the substrate that places electrolytic solution; At least a in the described electrolytic solution in cupric, indium, gallium, the plasma selenium; Described photoelectrochemistry deposition process parameters is: the working electrode current potential is-6.0～1.5V (vs SCE); Select at least a monochromatic ray as incident light, the incident direction of described incident light and the angle of working electrode are 0～90 °.
In the photoelectrochemistry of the CIGS thin-film of the present invention deposition preparation method, described electrolytic solution is selected from least a in the aqueous solution, organic solution, the ionic liquid; Copper, indium, gallium, plasma selenium volumetric molar concentration are respectively 0～0.15mol/L, 0～0.30mol/L, 0～0.50mol/L and 0～0.3mol/L in the described electrolytic solution, and described copper, indium, gallium, plasma selenium mole total concn are 0.001～1.25mol/L; The temperature of described electrolytic solution is 20～150 ℃, and pH is 0.3～14.
In the photoelectrochemistry deposition preparation method of CIGS thin-film of the present invention, contain complexing agent in the described electrolytic solution, described complexing agent is selected from least a in Trisodium Citrate, potassium thiocyanate, tetra-sodium acid potassium, citric acid, ethylenediamine tetraacetic acid (EDTA) (EDTA), nitrilotriacetic acid(NTA) (NTA), hydroxy ethylene diphosphonic acid (HEDP), tartrate, thionamic acid, potassium cyanide, ammonium fluoride and the quadrol, and the total mol concentration of described complexing agent is in 0.01～1mol/L scope.
In the photoelectrochemistry deposition preparation method of CIGS thin-film of the present invention, contain in the described electrolytic solution to be useful on and improve electroconductibility and eliminate the electromigratory supporting electrolyte of reactive ion; Described supporting electrolyte is selected from least a in sodium-chlor, sodium sulfate, SODIUMNITRATE, Repone K, vitriolate of tartar, saltpetre, ammonium chloride, lithium chloride, Lithium Sulphate, the lithium nitrate, and the total mol concentration of described supporting electrolyte is in 0.01～1mol/L scope.
In the photoelectrochemistry of the CIGS thin-film of the present invention deposition preparation method, described substrate is selected from plating Mo soda-lime glass, ZAO glass, ATO glass, ito glass, FTO glass, stainless steel foil, Mo paper tinsel, Al paper tinsel, Cu paper tinsel, Au paper tinsel, Ti paper tinsel, be coated with a kind of in the PI film of conductive layer.
In the photoelectrochemistry of the CIGS thin-film of the present invention deposition preparation method, it is at least a monochromatic ray among 250～2500nm that described incident light is selected from wavelength, and the light intensity of described incident light is 0.1mW/cm
2～10000mW/cm
2
In the photoelectrochemistry deposition preparation method of CIGS thin-film of the present invention, described photoelectrochemistry depositing time is 10～150 minutes, and described CIGS thin-film thickness is 0.01～5 μ m.
In the photoelectrochemistry deposition preparation method of CIGS thin-film of the present invention, described CIGS thin-film can place vacuum, argon gas or the nitrogen that contains Se or contain S, in 250～550 ℃ of thermal treatments 0.1～5.5 hour, with the crystalline quality that improves film and adjust the film band gap.
In the photoelectrochemistry of the CIGS thin-film of the present invention deposition preparation method, the chemistry of described CIGS thin-film is to be CuIn
aGa
bSe
c, wherein: a=0～2, b=0～2, c=0～5: described CuIn
aGa
bSe
cContain In in the film
1-2Se
1～3, CuSe
1～3, CuIn
1～2Se
1～4, CuIn
0.01～2Ga
0.01～2Se
0.01～5In at least a.
A kind of method for preparing copper-indium-gallium-selenium semiconductor sun hull cell based on the photoelectrochemistry deposition of photoelectrochemistry principle that the present invention proposes, can not only avoid adopting technology that PVD method or CVD method exist and equipment complexity, with high costs, be difficult to deficiency such as scale operation, the film growth rates that also can effectively overcome the preparation of traditional electrical sedimentation is slow, the problem of indium and gallium deposition difficulty, film morphology difference.The CIGS thin-film of photoelectrochemistry deposition preparation has that film morphology is good, controllable component, film adhesion are strong, fast growth, low cost, high-level efficiency, high quality and be easy to realize advantage such as big area deposition, is to promote the effective means of large-scale industrial production high quality solar cell with copper-indium-gallium-selenium semiconductor film.Its mechanism is sketched in following:
In the electrodeposition process, because copper-indium-galliun-selenium is a semi-conductor, so continuous increase along with film thickness, electroconductibility reduces thereupon, and electric transmission is affected, and causes sedimentation velocity to reduce rapidly, and employing photoelectrochemistry sedimentation, promptly, the conductivity of galvanic deposit copper-indium-gallium-selenium semiconductor film can be strengthened, the purpose that promotes thin film deposition speed and do not destroy the thin film deposition quality can be reached by in electrodeposition process, introducing illumination.Simultaneously, based on the photoelectrochemistry principle, semi-conductor is when being subjected to frequency greater than the illumination of its characteristic absorbance limit, will cause taking place near the semi-conductor of electron-hole pair electrolyte interface to distribute again, this distribution more not only can influence the speed of electrochemical reaction, and can change the electrode electro Chemical reaction properties, particularly can promote to relate to the carrying out of the deposition reaction of difficult deposition of elements indium and gallium, thereby better realize the regulation and control of composition.Improvement for pattern is mainly reflected in two aspects, and on the one hand, the photoelectrochemistry deposition can promote the migration of reactive ion, thereby reduces concentration polarization, effectively avoids the growth of dendrite.On the other hand, because the photoelectrochemistry deposition can promote the deposition of difficult deposition of elements indium and gallium, so just can effectively suppress the generation of sheet of copper selenium two second phases.The light wave combination of the present invention by incident light and intensity adjustments are controlled the indium in the film and the content of gallium simultaneously; The pattern of controlling film by the light wave combination and the angle between light and the working electrode of incident light; CIGS thin-film can be placed vacuum, argon gas or the nitrogen that contains Se or contain S, by thermal treatment under 250～550 ℃ temperature range 0.1～5.5 hour, with the crystalline quality that improves film and adjust the film band gap.
The present invention can be used for the preparation of all kinds of copper-indium-galliun-selenium batteries, as researchs such as ground and space copper-indium-galliun-selenium solar cell, flexible substrates copper-indium-galliun-selenium solar cell and the hydrogen manufacturing of copper-indium-galliun-selenium photoelectrochemistry.The present invention compares with the preparation method of similar CIGS thin-film, and the most outstanding advantage is aspects such as fast growth, controllable component, film morphology be good.
In sum, processing method of the present invention is simple, easy to operate, a difficult problem such as solved that the film growth rates that traditional electrical deposition CIGS thin-film runs into is slow, indium and gallium deposition difficulty, rete pattern are relatively poor, have fast growth, controllable component, film morphology is good, cost is low, be easy to realize the big area deposition of CIGS thin-film, help large-scale industry and promote and characteristics such as application.
Description of drawings
Accompanying drawing 1 is existing traditional electrical deposition CIGS thin-film SEM pattern.
Accompanying drawing 2 is the CIGS thin-film SEM pattern of the embodiment of the invention 2 preparations.
SEM pattern by accompanying drawing 1,2 can be observed, smooth, the compact structure of photoelectrochemistry deposit film smooth surface, and pattern obviously improves, and has solved the problem of existing traditional prepared by electrodeposition copper, indium and selenium film rete pattern difference.
Specific embodiments
Below in conjunction with embodiment, the present invention is described in further detail, but these embodiment must not be interpreted as limiting the scope of the invention.
Embodiment 1
Earlier consist of 0.30mol/L H at solute
2SeO
3, in the 500ml aqueous solution of 1mol/L Repone K, pH is adjusted to 0.3 with dilute hydrochloric acid or sodium hydroxide; Adopt the photoelectrolysis groove, with the stainless steel-based end be working electrode, big area Pt net is a counter electrode, saturated calomel electrode (SCE) is a reference electrode; Adopt following photoelectrochemistry deposition parameter: incident light is that (light intensity is 0.1mWcm for the monochromatic source of 250nm
-2), working electrode current potential 0.5V (vsSCE), electrolyte temperature are 80 ℃, depositing time is 10 minutes.The film that contains selenium of pre-deposition 1～1.5 micron thickness on cathode substrate.And then consist of 0.15mol/L Cu (NO at solute
3)
2, 0.30mol/L InCl
3, 0.5mol/L GaCl
3, in the 500ml aqueous solution of 1mol/L trisodium citrate, pH is adjusted to 0.9 with dilute hydrochloric acid or sodium hydroxide; With containing the identical experiment condition of selenium film with pre-deposition, at pre-deposition contain the film that deposits cupric, indium and gallium in the substrate of selenium film.The film CuIn of the copper-indium-galliun-selenium of 3～5 micron thickness that will make at last
aGa
bSe
c(a=0～2, b=0～2, c=0～5) place the argon gas that contains Se, and thermal treatment is 5.5 hours under 250 ℃ of temperature.After testing, gained CuIn
aGa
bSe
cFilm energy gap E
g=1.3eV, uptake factor are 10
5Cm
-1, resistivity is 5.3 Ω cm, carrier concentration is 9.3 * 10
18c
M-3
Embodiment 2
Consist of 0.003mol/L CuCl at solute
2, 0.01mol/L InCl
3, 0.001mol/L SeO
2, the 0.1mol/L lithium chloride in the 500ml aqueous solution of 0.2mol/L trisodium citrate, is adjusted to 1.8 with dilute hydrochloric acid or sodium hydroxide with pH; Adopting the photoelectrolysis groove, is working electrode with the FTO substrate of glass, and the big area graphite flake is a counter electrode, and saturated calomel electrode (SCE) is a reference electrode; Adopt following photoelectrochemistry deposition parameter: incident light is that (light intensity is 10000mWcm to the 500W xenon source
-2) xenon source, working electrode current potential-0.6V (vs SCE); On cathode substrate, deposit the CuIn of cupric, indium and the selenium of 0.1～2 micron thickness
1～2Se
1～4Film; Electrolyte temperature is 20 ℃, and depositing time is 40 minutes.After testing, gained CuIn
1～2Se
1～4Film energy gap E
g=1.0eV, uptake factor are 10
5Cm
-1, resistivity is 8.3 Ω cm, carrier concentration is 1.0 * 10
19Cm
-3
In this example, under the identical situation of other conditions, traditional electrical deposition and photoelectrochemistry deposition CuIn have been contrasted
1～2Se
1～4The composition of film, thickness and pattern have following discovery:
Table 1 traditional electrical deposition and photoelectrochemistry deposition CuIn
1～2Se
1～4Thin film composition
As can be seen from Table 1, In content obviously increases in the sedimentary film of photoelectrochemistry, and Se content obviously reduces, and illustrates that the sedimentary method of photoelectrochemistry has solved the difficult sedimentary problem of indium in traditional prepared by electrodeposition copper, indium and selenium film process.
Aspect film growth rates, traditional electrical deposition and photoelectrochemistry deposition CuIn
1～2Se
1～4The thickness of film is respectively 0.3 micron and 1.9 microns, and this explanation photoelectrochemistry deposition has promoted CuIn greatly
1～2Se
1～4Growth for Thin Film has shown that it is in the great potential that promotes on the film growth rates.
Accompanying drawing 1,2 has provided traditional electrical deposition and photoelectrochemistry deposition CuIn
1～2Se
1～4The pattern of film.Can observe by the SEM pattern, smooth, the compact structure of photoelectrochemistry deposit film smooth surface, pattern obviously improves, and has solved the problem of traditional prepared by electrodeposition copper, indium and selenium film rete pattern difference.
Embodiment 3
Trisodium citrate among the embodiment 2 replaces with potassium cyanide or tetra-sodium acid potassium or nitrilotriacetic acid(NTA), and sedimentation potential transfers to 1.5V (vs SCE), and other conditions are constant, finally can obtain the better CuIn of pattern
1～2Se
1～4Semiconductor film material.After testing, gained CuIn
1～2Se
1～4Film energy gap E
g=1.1eV, uptake factor are 10
5Cm
-1, resistivity is 7.0 Ω cm, carrier concentration is 7.9 * 10
18Cm
-3
Embodiment 4
Consist of 0.02mol/L CuSO at solute
4, 0.04mol/L In
2(SO
4)
3, 0.1mol/L Ga
2(SO
4)
3, 0.04mol/L SeO
2, in the 500ml dimethyl sulfoxide (DMSO) (DMSO) of 0.5mol/L sodium sulfate and the water mixed solution (mol ratio is 1: 1～50: 1), its pH is adjusted to 3 with dilute hydrochloric acid or sodium hydroxide; Adopting the photoelectrolysis groove, is working electrode with the ITO substrate, and big area Pt net is a counter electrode, and saturated calomel electrode (SCE) is a reference electrode; Adopt following photoelectrochemistry deposition parameter: incident light is that (light intensity is 1000mWcm for the monochromatic source of 2500nm
-2), working electrode current potential-2.5V (vs SCE); On cathode substrate, deposit the CIGS thin-film CuIn of 0.01～1 micron thickness
aGa
bSe
c(a=0～2, b=0～1, c=0～4); The photoelectrochemistry deposition process is carried out (water content is below the 1ppm) in the glove box of argon gas or nitrogen atmosphere, electrolyte temperature is 50 ℃, and depositing time is 90 minutes.At last the CIGS thin-film that makes is placed the vacuum that contains S, thermal treatment is 3 hours under 400 ℃ of temperature.After testing, gained CuIn
aGa
bSe
cFilm energy gap E
g=1.6eV, uptake factor are 10
5Cm
-1, resistivity is 5.8 Ω cm, carrier concentration is 9.5 * 10
18Cm
-3
Embodiment 5
With dimethyl sulfoxide (DMSO) (DMSO) and water among dimethyl formamide (DMF) the replacement embodiment 4, other conditions are identical with embodiment 4, finally can prepare the copper-indium-gallium-selenium semiconductor film material.After testing, gained CuIn
aGa
bSe
cFilm energy gap E
g=1.3eV, uptake factor are 10
5Cm
-1, resistivity is 10.8 Ω cm, carrier concentration is 8.5 * 10
17Cm
-3
Embodiment 6
In the 500ml mol ratio 1: 1.5～1: 3.0 choline chloride 60 (C
5H
14ONCl) and urea ((NH
2)
2CO) dissolving 0.04mol CuCl in the composite ionic liquid
2, 0.04mol InCl
3, 0.02molGaCl
3, 0.06M SeCl
4(being anhydrous chloride), and, its pH is adjusted to 14 with sodium hydroxide as photoelectrolysis; Adopting the photoelectrolysis groove, is working electrode with the Mo paper tinsel, and big area Pt net is a counter electrode, and saturated calomel electrode (SCE) is a reference electrode; Adopt following photoelectrochemistry deposition parameter: incident light is that (light intensity is 80mWcm for the monochromatic source of 850nm
-2), working electrode current potential-4.2V (vs SCE); In substrate, deposit the CIGS thin-film CuIn of 0.3～3 micron thickness
aGa
bSe
c(a=0～2, b=0～2, c=0～5); Electrodeposition process carries out (water content is below the 1ppm) in the glove box of argon gas or nitrogen atmosphere, electrolyte temperature is 150 ℃, and depositing time is 10 minutes.After testing, gained CuIn
aGa
bSe
cFilm energy gap E
g=1.2eV, uptake factor are 10
5Cm
-1, resistivity is 5.9 Ω cm, carrier concentration is 1.5 * 10
18Cm
-3
Under the identical situation of other conditions, traditional electrical deposition and photoelectrochemistry deposition CuIn have been contrasted
aGa
bSe
cThe composition of film, pattern and thickness have following discovery:
Table 2 traditional electrical deposition and photoelectrochemistry deposition CuIn
aGa
bSe
cThin film composition is analyzed
Table 2 as can be seen, the sedimentary CuIn of photoelectrochemistry
aGa
bSe
cThe content of indium and gallium obviously increases in the film, and Se content obviously reduces, and illustrates that the sedimentary method of photoelectrochemistry has solved indium and the difficult sedimentary problem of gallium in traditional prepared by electrodeposition CIGS thin-film process.In addition from the pattern also sedimentary CuIn of photoelectrochemistry as can be seen
aGa
bSe
cFilm rete pattern is better.
Aspect film growth rates, traditional electrical deposition and photoelectrochemistry deposition CuIn
aGa
bSe
cThe thickness of film is respectively 0.5 micron and 2.5 microns, and this explanation photoelectrochemistry deposition has promoted CuIn greatly
aGa
bSe
cGrowth for Thin Film speed.
Embodiment 7
At 500ml ionic liquid [BMP] Tf
2Dissolving 0.03mol CuCl among the N (1-butyl-1-methylpyrrolidinium bis (trifluoromethylsulfonyl) amide, water content is less than 2ppm)
2, 0.03mol InCl
3, 0.04mol GaCl
3, 0.008M SeCl
4(being anhydrous chloride), and, its pH is adjusted to 10 with sodium hydroxide as electrolytic solution; Adopt the photoelectrolysis groove, with the stainless steel-based end be working electrode, big area Pt net is a counter electrode, saturated calomel electrode (SCE) is a reference electrode; Adopt following photoelectrochemistry deposition parameter: incident light is that (light intensity is 10mWcm for the monochromatic source of 1800nm
-2), working electrode current potential-6V (vs SCE); In substrate, deposit the CIGS thin-film CuIn of 4～5 micron thickness
aGa
bSe
c(a=0～2, b=0～2, c=0～5); Electrodeposition process carries out (water content is below the 1ppm) in the glove box of argon gas or nitrogen atmosphere, electrolyte temperature is 150 ℃, and depositing time is 150 minutes.At last the CIGS thin-film that makes is placed the nitrogen that contains Se, thermal treatment is 0.1 hour under 550 ℃ of temperature.
After testing, gained CuIn
aGa
bSe
cFilm energy gap E
g=1.5eV, uptake factor are 10
5Cm
-1, resistivity is 7.8 Ω cm, carrier concentration is 9.1 * 10
18Cm
-3
Claims (9)
1. the photoelectrochemistry of CIGS thin-film deposition preparation method is to adopt the sedimentary method of photoelectrochemistry to deposit CIGS thin-film in the substrate that places electrolytic solution; At least a in the described electrolytic solution in cupric, indium, gallium, the plasma selenium; Described photoelectrochemistry deposition process parameters is: the working electrode current potential is-6.0～1.5V (vsSCE); Select at least a monochromatic ray as incident light, the incident direction of incident light and the angle of working electrode are 0～90 °.
2. the photoelectrochemistry of CIGS thin-film according to claim 1 deposition preparation method is characterized in that: described electrolytic solution is selected from least a in the aqueous solution, organic solution, the ionic liquid; Copper, indium, gallium, plasma selenium volumetric molar concentration are respectively 0～0.15mol/L, 0～0.30mol/L, 0～0.50mol/L and 0～0.3mol/L in the described electrolytic solution, and described copper, indium, gallium, plasma selenium mole total concn are 0.001～1.25mol/L; The temperature of described electrolytic solution is 20～150 ℃, and pH is 0.3～14.
3. the photoelectrochemistry of CIGS thin-film according to claim 2 deposits preparation method, it is characterized in that: contain complexing agent in the described electrolytic solution, described complexing agent is selected from least a in Trisodium Citrate, potassium thiocyanate, tetra-sodium acid potassium, citric acid, ethylenediamine tetraacetic acid (EDTA) (EDTA), nitrilotriacetic acid(NTA) (NTA), hydroxy ethylene diphosphonic acid (HEDP), tartrate, thionamic acid, potassium cyanide, ammonium fluoride and the quadrol, and the total mol concentration of described complexing agent is in 0.01～1mol/L scope.
4. the photoelectrochemistry of CIGS thin-film according to claim 3 deposition preparation method is characterized in that: contain in the described electrolytic solution to be useful on and improve electroconductibility and eliminate the electromigratory supporting electrolyte of reactive ion; Described supporting electrolyte is selected from least a in sodium-chlor, sodium sulfate, SODIUMNITRATE, Repone K, vitriolate of tartar, saltpetre, ammonium chloride, lithium chloride, Lithium Sulphate, the lithium nitrate, and the total mol concentration of described supporting electrolyte is in 0.01～1mol/L scope.
5. the photoelectrochemistry of CIGS thin-film according to claim 4 deposition preparation method is characterized in that: described substrate is selected from plating Mo soda-lime glass, ZAO glass, ATO glass, ito glass, FTO glass, stainless steel foil, Mo paper tinsel, Al paper tinsel, Cu paper tinsel, Au paper tinsel, Ti paper tinsel, be coated with a kind of in the PI film of conductive layer.
6. the photoelectrochemistry of CIGS thin-film according to claim 5 deposits preparation method, and it is characterized in that: described incident light is selected from least a monochromatic ray of wavelength region in 250～2500nm, and the range of light intensity of described incident light is 0.1mW/cm
2～10000mW/cm
2
7. the photoelectrochemistry of CIGS thin-film according to claim 6 deposits preparation method, and it is characterized in that: described photoelectrochemistry depositing time is 10～150 minutes, and described CIGS thin-film thickness is 0.01～5 μ m.
8. the photoelectrochemistry of CIGS thin-film according to claim 7 deposits preparation method, and it is characterized in that: described CIGS thin-film can place vacuum, argon gas or the nitrogen that contains Se or contain S, in 250～550 ℃ of thermal treatments 0.1～5.5 hour.
9. according to the photoelectrochemistry deposition preparation method of any described CIGS thin-film of claim 1-8, it is characterized in that: the chemical formula of described CIGS thin-film is: CuIn
aGa
bSe
c, wherein: a=0～2, b=0～2, c=0～5; Described CuIn
aGa
bSe
cContain In in the film
1-2Se
1～3, CuSe
1～3, CuIn
1～2Se
1～4, CuIn
0.01～2Ga
0.01～2Se
0.01～5In at least a.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101891635A CN102268702A (en) | 2011-07-07 | 2011-07-07 | Photoelectrochemical deposition method for preparing copper-indium-gallium-selenium (CIGS) film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101891635A CN102268702A (en) | 2011-07-07 | 2011-07-07 | Photoelectrochemical deposition method for preparing copper-indium-gallium-selenium (CIGS) film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102268702A true CN102268702A (en) | 2011-12-07 |
Family
ID=45051149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101891635A Pending CN102268702A (en) | 2011-07-07 | 2011-07-07 | Photoelectrochemical deposition method for preparing copper-indium-gallium-selenium (CIGS) film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102268702A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102560186A (en) * | 2012-02-21 | 2012-07-11 | 苏州晶纯新材料有限公司 | Copper-indium-gallium alloy and preparation method thereof |
| CN103031571A (en) * | 2012-12-13 | 2013-04-10 | 彩虹集团公司 | Method for electrodepositing gallium at low temperature by using ionic liquid |
| CN103779433A (en) * | 2012-10-22 | 2014-05-07 | 中物院成都科学技术发展中心 | CIGS thin film prefabricated layer and fabrication method thereof |
| CN103779439A (en) * | 2012-10-22 | 2014-05-07 | 中物院成都科学技术发展中心 | CIGS thin film prefabricated layer and fabrication method thereof |
| CN103866360A (en) * | 2012-12-10 | 2014-06-18 | 中物院成都科学技术发展中心 | Method for coplating copper indium gallium selenium prefabricated layer by using ionic liquid through complex waveform pulse |
| CN104362222A (en) * | 2014-11-28 | 2015-02-18 | 中南大学 | Method for preparing CIGS film based on photochemistry deposition |
| CN105088262A (en) * | 2014-05-19 | 2015-11-25 | 中南大学 | Method for extracting semiconductor elements through photoelectrochemistry metallurgy |
| CN105420779A (en) * | 2015-12-03 | 2016-03-23 | 西南石油大学 | Method for electrochemically preparing amorphous elemental selenium film |
| CN105633206A (en) * | 2014-11-06 | 2016-06-01 | 中物院成都科学技术发展中心 | Method for electrochemical modification of surface properties of copper indium gallium selenide thin film without water |
| CN108707920A (en) * | 2018-05-31 | 2018-10-26 | 中南大学 | Method for preparing manganese dioxide through photoelectrochemistry metallurgy |
| CN112144086A (en) * | 2020-09-24 | 2020-12-29 | 昆明理工大学 | Method for preparing selenide semiconductor by vacuum electrochemical deposition |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4436557A (en) * | 1982-02-19 | 1984-03-13 | The United States Of America As Represented By The United States Department Of Energy | Modified laser-annealing process for improving the quality of electrical P-N junctions and devices |
| EP0134669A1 (en) * | 1983-07-13 | 1985-03-20 | Semiconductor Energy Laboratory Co., Ltd. | Photoelectric conversion device and its manufacturing method |
| US4626613A (en) * | 1983-12-23 | 1986-12-02 | Unisearch Limited | Laser grooved solar cell |
| CN1204419A (en) * | 1995-12-12 | 1999-01-06 | 戴维斯,约瑟夫和尼格利 | Preparation of CuxInyGazSen (x=0-2,Y=0-2,z=0-2,n=0-3) precursor films by electrodeposition for fabricating high efficiency solar cell |
-
2011
- 2011-07-07 CN CN2011101891635A patent/CN102268702A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4436557A (en) * | 1982-02-19 | 1984-03-13 | The United States Of America As Represented By The United States Department Of Energy | Modified laser-annealing process for improving the quality of electrical P-N junctions and devices |
| EP0134669A1 (en) * | 1983-07-13 | 1985-03-20 | Semiconductor Energy Laboratory Co., Ltd. | Photoelectric conversion device and its manufacturing method |
| US4626613A (en) * | 1983-12-23 | 1986-12-02 | Unisearch Limited | Laser grooved solar cell |
| CN1204419A (en) * | 1995-12-12 | 1999-01-06 | 戴维斯,约瑟夫和尼格利 | Preparation of CuxInyGazSen (x=0-2,Y=0-2,z=0-2,n=0-3) precursor films by electrodeposition for fabricating high efficiency solar cell |
Non-Patent Citations (5)
| Title |
|---|
| ZHANG L ETC.: "Formation of CuInSe2 and Cu(In,Ga)Se2 films by electrodeposition and vacuumannealing treatment", 《SOLAR ENERGY MATER SOLAR CELLS》, vol. 80, no. 4, 31 December 2003 (2003-12-31) * |
| 刘芳洋等: "电化学沉积太阳电池用CuInSe2 和Cu ( In ,Ga) Se2 薄膜的研究进展", 《材料导报：综述篇》, 30 September 2009 (2009-09-30) * |
| 杨越等: "激光强化金属电沉积层性质研究", 《电镀与精饰》, vol. 13, no. 1, 31 January 1991 (1991-01-31) * |
| 袁加勇等: "激光电镀的机理和实验研究", 《激光与红外》, no. 12, 27 December 1986 (1986-12-27) * |
| 谢凤宽等: "激光辅助电沉积技术", 《材料工程》, no. 1, 30 December 2006 (2006-12-30) * |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102560186A (en) * | 2012-02-21 | 2012-07-11 | 苏州晶纯新材料有限公司 | Copper-indium-gallium alloy and preparation method thereof |
| CN102560186B (en) * | 2012-02-21 | 2013-04-17 | 苏州晶纯新材料有限公司 | Copper-indium-gallium alloy and preparation method thereof |
| CN103779433A (en) * | 2012-10-22 | 2014-05-07 | 中物院成都科学技术发展中心 | CIGS thin film prefabricated layer and fabrication method thereof |
| CN103779439A (en) * | 2012-10-22 | 2014-05-07 | 中物院成都科学技术发展中心 | CIGS thin film prefabricated layer and fabrication method thereof |
| CN103779433B (en) * | 2012-10-22 | 2016-09-21 | 中物院成都科学技术发展中心 | A kind of CIGS thin-film preformed layer and preparation method thereof |
| CN103779439B (en) * | 2012-10-22 | 2016-09-21 | 中物院成都科学技术发展中心 | A kind of CIGS thin-film preformed layer and preparation method thereof |
| CN103866360A (en) * | 2012-12-10 | 2014-06-18 | 中物院成都科学技术发展中心 | Method for coplating copper indium gallium selenium prefabricated layer by using ionic liquid through complex waveform pulse |
| CN103866360B (en) * | 2012-12-10 | 2016-10-05 | 中物院成都科学技术发展中心 | A kind of method that complicated wave form pulse ion liquid plates CIGS preformed layer altogether |
| CN103031571A (en) * | 2012-12-13 | 2013-04-10 | 彩虹集团公司 | Method for electrodepositing gallium at low temperature by using ionic liquid |
| CN105088262B (en) * | 2014-05-19 | 2019-02-01 | 中南大学 | A kind of method of optical electro-chemistry metallurgical extraction semiconductor element |
| CN105088262A (en) * | 2014-05-19 | 2015-11-25 | 中南大学 | Method for extracting semiconductor elements through photoelectrochemistry metallurgy |
| CN105633206A (en) * | 2014-11-06 | 2016-06-01 | 中物院成都科学技术发展中心 | Method for electrochemical modification of surface properties of copper indium gallium selenide thin film without water |
| CN105633206B (en) * | 2014-11-06 | 2017-06-09 | 中物院成都科学技术发展中心 | The method that non-aqueous electrochemical modifies CIGS thin-film surface characteristic |
| CN104362222B (en) * | 2014-11-28 | 2016-08-24 | 中南大学 | A kind of method preparing CIGS thin-film based on photochemical precipitation |
| CN104362222A (en) * | 2014-11-28 | 2015-02-18 | 中南大学 | Method for preparing CIGS film based on photochemistry deposition |
| CN105420779A (en) * | 2015-12-03 | 2016-03-23 | 西南石油大学 | Method for electrochemically preparing amorphous elemental selenium film |
| CN105420779B (en) * | 2015-12-03 | 2018-04-17 | 西南石油大学 | A kind of method that electrochemistry prepares amorphous elemental selenium film |
| CN108707920A (en) * | 2018-05-31 | 2018-10-26 | 中南大学 | Method for preparing manganese dioxide through photoelectrochemistry metallurgy |
| CN112144086A (en) * | 2020-09-24 | 2020-12-29 | 昆明理工大学 | Method for preparing selenide semiconductor by vacuum electrochemical deposition |
| CN112144086B (en) * | 2020-09-24 | 2021-12-14 | 昆明理工大学 | Method for preparing selenide semiconductor by vacuum electrochemical deposition |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102268702A (en) | Photoelectrochemical deposition method for preparing copper-indium-gallium-selenium (CIGS) film | |
| Chan et al. | Preparation of Cu2ZnSnS4 films by electrodeposition using ionic liquids | |
| CN100452446C (en) | A method for pulse electrodeposit CIGS semiconductor film material | |
| CN101824638B (en) | Method for electrochemically depositing copper-zinc-tin-selenium semiconductor thin film material | |
| US8187913B2 (en) | Process for producing photoelectric conversion devices | |
| CN104120467B (en) | Copper-zinc-tin film material with controllable components, copper-zinc-tin sulfenyl solar battery and preparation method of the two | |
| CN100552095C (en) | A kind of method of manufacturing cuprous thiocyanate membrane in liquid phase condition | |
| Pawar et al. | Effect of annealing atmosphere on the properties of electrochemically deposited Cu2ZnSnS4 (CZTS) thin films | |
| US20110132764A1 (en) | Formation of a transparent conductive oxide film for use in a photovoltaic structure | |
| Todorov et al. | Electro deposited In2S3 buffer layers for CuInS2 solar cells | |
| CN101570871B (en) | Method for electrodepositing copper indium diselenide or copper indium gallium selenide film by special pulsing power source | |
| CN105226117B (en) | A kind of method that copper indium gallium sulphur solar battery film material is prepared in bipotential step method electro-deposition after cure annealing | |
| CN101982567A (en) | Preparation method of copper indium selenium sulphur (CuInSe2-xSx) film for solar battery | |
| KR20150013997A (en) | Method for manufacturing Cu2ZnSnS4-xSex (0≤x≤4) thin film by one step electrodeposition using ionic liquids | |
| Ho et al. | Preparation of CuInSe2 thin films by using various methods (a short review) | |
| US9410259B2 (en) | Electrodeposition of gallium for photovoltaics | |
| CN105514192A (en) | Method of preparing solar cell buffer layer zinc sulfide thin film material through sulfide annealing after electrodeposition | |
| Lee et al. | Structural regulation of electrochemically deposited copper layers for fabrication of thin film solar cells with a CuInS2 photoabsorber | |
| CN105118888A (en) | Method for preparing cuprous-oxide photoelectric film through copper sulphate | |
| Abouabassi et al. | Investigation on electrochemical deposition of Sb2Se3 thin films in aqueous acidic medium | |
| CN105332026A (en) | Method for preparing Cu2FeSnS4 film through electrochemical deposition method | |
| CN105603449B (en) | A kind of Cu2ZnSnS4Semiconductive thin film and its electrochemical preparation method | |
| CN106480483A (en) | Copper-zinc-tin-sulfur film and preparation method thereof | |
| CN105633198A (en) | Electrochemical treatment method for surface etching of absorption layer of copper zinc tin sulfide thin film solar cell | |
| CN104362222B (en) | A kind of method preparing CIGS thin-film based on photochemical precipitation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20111207 |