CN100338784C - Continuous ion adsorbing preparation of multi-component sulfur photoelectric films - Google Patents
Continuous ion adsorbing preparation of multi-component sulfur photoelectric films Download PDFInfo
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- CN100338784C CN100338784C CNB2004100723223A CN200410072322A CN100338784C CN 100338784 C CN100338784 C CN 100338784C CN B2004100723223 A CNB2004100723223 A CN B2004100723223A CN 200410072322 A CN200410072322 A CN 200410072322A CN 100338784 C CN100338784 C CN 100338784C
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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 13
- 229910052717 sulfur Inorganic materials 0.000 title claims description 12
- 239000011593 sulfur Substances 0.000 title claims description 12
- 239000000243 solution Substances 0.000 claims abstract description 50
- 239000002243 precursor Substances 0.000 claims abstract description 35
- 150000001768 cations Chemical class 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 150000002500 ions Chemical class 0.000 claims abstract description 17
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims abstract description 13
- 229910021617 Indium monochloride Inorganic materials 0.000 claims abstract description 13
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 13
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 claims abstract description 13
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 claims abstract description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 150000001450 anions Chemical class 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 230000005693 optoelectronics Effects 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 150000001786 chalcogen compounds Chemical class 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000010409 thin film Substances 0.000 abstract description 15
- 238000001179 sorption measurement Methods 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 abstract 2
- 239000012683 anionic precursor Substances 0.000 abstract 1
- 239000012300 argon atmosphere Substances 0.000 abstract 1
- 239000012682 cationic precursor Substances 0.000 abstract 1
- 229910052798 chalcogen Inorganic materials 0.000 abstract 1
- 150000001787 chalcogens Chemical class 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 32
- 238000000034 method Methods 0.000 description 19
- 239000000463 material Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052733 gallium Inorganic materials 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- -1 CdS Chemical class 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
本发明是多元硫属光电薄膜的连续离子吸附反应制备方法；首次采用不同比例的混合阳离子前驱体溶液，制备组成可控的CuInS2、CuInSe2、Cu(ln，Ga)Se2等太阳能光电薄膜，用来组装低成本、高光电转换效率的薄膜太阳能电池。本发明的阳离子前驱体溶液的组分和含量为CuCl2∶GaCl3∶InCl3为0.5∶0∶1～2∶1∶1；pH值为1～3；硫离子源可采用pH值为10～13，浓度为0.1～1mol/l的Na2S水溶液或Na2SeSO3水溶液或硫脲水溶液。在所述阳离子前驱体溶液、阴离子前驱体溶液中通过连续吸附反应进行镀膜，并经氩气氛下400～550℃热处理后制得所需的光电薄膜。The invention is a continuous ion adsorption reaction preparation method for multi-element chalcogen photoelectric thin films; for the first time, mixed cation precursor solutions with different proportions are used to prepare solar photoelectric thin films with controllable composition such as CuInS 2 , CuInSe 2 , Cu(ln, Ga)Se 2 , etc. , used to assemble thin-film solar cells with low cost and high photoelectric conversion efficiency. The composition and content of the cation precursor solution of the present invention are CuCl 2 : GaCl 3 : InCl 3 is 0.5: 0: 1～2: 1: 1; the pH value is 1～3; ～13, Na 2 S aqueous solution or Na 2 SeSO 3 aqueous solution or thiourea aqueous solution with a concentration of 0.1～1 mol/l. Coating is carried out in the cationic precursor solution and the anionic precursor solution through continuous adsorption reaction, and the required photoelectric thin film is prepared after heat treatment at 400-550 DEG C under an argon atmosphere.
Description
Technical field
The invention belongs to the continuous ion adsorbing preparation of multi-component sulfur photoelectric films.
Background technology
Along with developing rapidly of modern economy, people constantly enlarge the demand of the energy.Conventional energy resources such as present widely used traditional energy coal, oil and natural gas will face the situation of critical shortage because it is non-renewable.In addition, these energy in use cause very big pollution to environment easily.And characteristics such as solar power generation is renewable owing to having, cleanliness without any pollution might become the following topmost energy.In recent years, with CuInSe
2, Cu (In, Ga) Se
2Deng chalcogen compound is the representative thin-film solar cells because have the conversion ratio height, consumptive material is few, substrate is cheap, be convenient to characteristics such as large-scale production, be subjected to people's generally attention and obtain developing rapidly.
The preparation method of used for solar batteries optoelectronic film has a lot, as vacuum vapour deposition or sputtering method, molecular beam epitaxy and sheath gas-phase reaction method etc.These methods need environment dustless, vacuum usually, and will produce in hypertoxic sulphur or hydrogen sulfide atmosphere.And continuous ion adsorbing method (SILAR) preparation sulfide solar energy photoelectric thin-film has characteristics such as cost is low, pollution-free, preparation technology is simple, and technical merit advanced person is expected to realize cheap large-scale production.Adopting copper sulphate and thiocarbamide as " material physical chemistry " (Materials Chemistry and Physicis) report in one piece of article " continuous ion adsorbing method growth CuS film " [Growth of copper sulphide thin films by successive ionic layer adsorption andreaction (SILAR) method] in January, 2000 is raw material, at the sheet glass that is of a size of 26mm * 76mm * 1mm after the cleaning be of a size of on the monocrystalline silicon piece of 20mm * 20mm * 0.5mm and be equipped with the CuS optoelectronic film with the SILAR legal system. the cation precursor solution is the copper-bath of 0.1M, and the adding excessive ammonia is adjusted to pH value 10; The anion precursor solution is the thiourea solution (PH=6) of 0.1M.The solution for preparing is joined respectively in the beaker of 50mL, and the deionized water of preparation capacity is used for cleaning.Reaction is at room temperature carried out: the first step was immersed in backing material in the copper-bath of 0.1M 20 seconds, and at this moment bivalent cupric ion is adsorbed onto substrate surface, cleans 30 seconds to remove unnecessary ion with redistilled water then; Second step was immersed in backing material in the 0.1M thiourea solution about 20 seconds S
2-Ion is adsorbed also and the Cu of substrate surface
2+Reacting generates CuxS, still cleans with redistilled water then and removes unnecessary responseless ion in 30 seconds.Repeat 25 multi-component sulfur semiconductive thin films of this technological process, can make the CuxS film of about 4000 of thickness.
The problem that exists in the multi-component sulfur photoelectric films preparation at present is: (1) preparation multi-component sulfur film than maturation method as evaporation or sputtering method etc., need under vacuum, react, not only equipment manufacturing cost costliness, easy pollution, large-area preparation difficulty also can cause a large amount of wastage of material and be difficult to and reclaim.(2) continuous ionic absorption is adopted the ion presoma that separates with reaction method (SILAR), by heterogeneous growth mechanism film formation at low temp, is applicable to multiple substrate, and equipment is simple, and is pollution-free, and reactant liquor also can fully be recycled.But its research only is confined to binary compounds such as CdS, PbS, ZnS abroad, does not see the report that has the SILAR legal system to be equipped with multi-component sulfur photoelectric films such as ternary, quaternary.
Summary of the invention
The present invention adopts the mixed-cation precursor solution of different proportion first, by adjusting process parameter and composite mixed, at glass, silicon chip, electro-conductive glass, porous TiO
2Produce stable performance on the substrates such as film, porous ZnO film, form controlled CuInS
2, CuInSe
2, Cu (In, Ga) Se
2Etc. solar energy photoelectric thin-film, be used for the thin-film solar cells of assembling low-cost, high-photoelectric transformation efficiency.
Concrete grammar of the present invention and step are as follows:
Adopting the metal halide and the sulfide of AG is raw material, at room temperature is prepared.
1. cation precursor solution preparation: the component of cation precursor solution and content are CuCl
2: GaCl
3: InCl
3Be 0.5: 0: 1～2: 1: 1, pH value is 1～3.
If the pH value of solution not in the scope that requires, can be adjusted to 1～3 with its pH value by dripping HCl.
2. anion precursor solution preparation: it is 10～13 that the pH value can be adopted in the sulphion source, and concentration is the Na of 0.1～1mol/l
2The S aqueous solution or Na
2SeSO
3The aqueous solution or thiourea solution;
If the pH value of solution not in the scope that requires, can be adjusted to 10～13 with its pH value by dropping ammonia.
The above-mentioned solution for preparing is positioned over different vessels respectively, filters before the use.
3. plated film: in the primary first-order equation circulation, after at first substrate being immersed the cation precursor solution and adsorbs, with deionized water wash to remove the not firm cation of absorption; Then substrate is immersed in the anion precursor solution, the Cu that adsorb on the substrate this moment
2+, In
3+Deng cation and S
2-, Se
2-Generate chalcogen compound Deng anionic reactive, and then remove unnecessary responseless ion with deionised water, the time of above-mentioned adsorption reaction and washing all was controlled between 20～50 seconds; By repeating this reaction cycle 30～50 times, make the chalcongen semiconductor multi-element film.Preferred 100～the 500nm of the thickness of film.
4. heat treatment: made sample is heat-treated under the argon atmospher of certain flow rate and is made required optoelectronic film, and heat treatment temperature is 400～550 ℃, heat treatment time 1～2 hour.
Utilize the continuous ion adsorbing legal system to be equipped with solar energy photoelectric thin-film, have that consumptive material is few, equipment and preparation technology is simple, the film life-span is long, preparation is pollution-free, reactant reclaims easily, be applicable to characteristics such as multiple backing material.This method and technology level advanced person realizes cheap large-scale production easily.
2000 annual productions of global solar battery have reached 200MW, estimate that photovoltaic battery cost in 2010 can be reduced to the level of competing with conventional energy resource.Domestic in recent years solar cell market is about 2-3MW at present with the 15-20% speed increment, and good market prospects.With the SILAR method is the thin-film solar cells of basis preparation; cost is about 5-6 unit/WP, and the sales figure of Shanghai solar energy Science and Technology Co., Ltd. is compared with calendar year 2001, only is 1/5 of monocrystalline silicon battery; after accomplishing scale production, expectation can be received huge economic benefit.
Embodiment
CuInS
23 embodiment of solar energy photoelectric thin-film:
| Raw material | CuCl 2·2H 2O | InCl 3·4H 2O | Na 3S·9H 2O |
| 1# | 3.4g | 8.1g | 5.75g |
| 2# | 4.95g | 6.85g | 6.25g |
| 3# | 5.1g | 5.85g | 6g |
The concrete technology of SILAR method is as follows:
1) preparation of precursor solution:
A, weighing:, take by weighing the CuCl of different material amount respectively by different quality requirement in the last table
2, InCl
3, Na
2S.
B, the preparation of mixed-cation precursor solution: with load weighted CuCl
2And InCl
3Be dissolved in the deionized water preparation 500mL cation precursor solution, adding 5～10 HCl, to be adjusted to suitable pH value be 1.5, and stirring is dissolved it fully;
C, the preparation of anion precursor solution: with load weighted Na
2S9H
2O
3Be dissolved in dried up in preparation 500mL anion precursor solution, adding 5～10 ammoniacal liquor, to be adjusted to the pH value be 13, and stirring is dissolved it fully.
D, the solution for preparing is placed beaker respectively, leave standstill, be used for step plated film down after the filtration.
2) plated film
After the precursor solution preparation was finished, the technical process of plated film was divided into following circulation step:
● substrate is immersed CuCl
2And InCl
3The mixed-cation precursor solution in carry out surface adsorption, adsorption time is 20 seconds
● substrate immersed in the deionized water wash, washing time is 40 seconds;
● substrate is immersed anion precursor solution Na
2Carry out surface adsorption among the S, and react, the time is 50 seconds
● substrate immersed in the deionized water wash; Washing time is 40 seconds;
This circulation is carried out 50 times repeatedly, obtained the film of the about 400nm of thickness.
3) heat treatment
In tube furnace, carry out the heat treatment of film, adopt the Ar atmosphere protection,
Ar gas velocity 200～300ml/min.
400 ℃ of heat treatment temperatures
Heat treatment time 2 hours.
Gained material photoelectric properties are as follows:
| Form | Absorption coefficient | Energy gap Eg | Resistance Ω-cm | Carrier concentration * 10 16cm -3 | Hall mobility cm 2/V-s |
| 1# | 10 5 | 1.2 | 250 | 0.5 | 10 |
| 2# | 10 5 | 1.4 | 10 | 10 | 70 |
| 3# | 10 5 | 1.3 | 100 | 5.2 | 40 |
CuInSe
23 embodiment of solar energy photoelectric thin-film:
| Form | CuCl 2·2H 2O | InCl 3·4H 2O | Na 2SeSO 3 |
| 4# | 3g | 7.5g | 4g |
| 5# | 5g | 7g | 5g |
| 6# | 4.5g | 5g | 5g |
Technical process is as follows:
1, batching
A, take by weighing the CuCl of different quality according to last table
22H
2O, InCl
34H
2O is dissolved in preparation cation precursor solution in the 500mL deionized water, add 5～10 HCl and be adjusted to pH value=2, and stirring is dissolved it fully
B, with load weighted Na
2SeSO
3Be dissolved in dried up middle preparation 500mL anion precursor solution, add 5～10 ammoniacal liquor and be adjusted to pH value=12, and stirring dissolved it fully.
C, the solution for preparing is placed beaker respectively, leave standstill, be used for step plated film down after the filtration.
2) plated film
After the precursor solution preparation was finished, the technical process of plated film was divided into following circulation step:
● substrate is immersed CuCl
22H
2O, InCl
34H
2Carry out surface adsorption in the mixed-cation precursor solution of O, adsorption time is 50 seconds
● substrate immersed in the deionized water wash; Washing time is 50 seconds
● substrate is immersed anion precursor solution solution Na
2SeSO
3In carry out surface adsorption, and react, the time is 20 seconds
● substrate immersed in the deionized water wash; Washing time is 20 seconds
This circulation is carried out 50 times repeatedly, obtained the film of the about 400nm of thickness.
3) heat treatment
In tube furnace, carry out the heat treatment of film, adopt the Ar atmosphere protection, Ar gas velocity 200～300ml/min.400 ℃ of heat treatment temperatures, heat treatment time 2 hours
Gained material photoelectric properties are as follows:
| Form | Absorption coefficient | Energy gap Eg | Resistance Ω-cm | Carrier concentration * 10 16cm -3 | Hall mobility cm 2/V-s |
| 4# | 10 5 | 0.9 | 300 | 3.5 | 5 |
| 5# | 10 5 | 1 | 20 | 20 | 60 |
| 6# | 10 5 | 0.95 | 80 | 7.2 | 20 |
Cu (In, Ga) Se
23 embodiment of solar energy photoelectric thin-film:
| Form | CuCl 2·2H 2O | InCl 3·4H 2O | GaCl 3 | Na 2SeSO 3 |
| 7# | 3g | 6.5g | 0.7g | 4g |
| 8# | 5g | 4.5g | 1.1g | 4g |
| 9# | 5g | 5g | 0.95g | 5g |
Technical process is as follows:
1, batching
A, take by weighing the CuCl of different quality according to last table
22H
2O, InCl
34H
2O, GaCl
3, be dissolved in preparation cation precursor solution in the 500mL deionized water, add 5～10 HCl and be adjusted to suitable pH value=3, and stirring is dissolved it fully
B, with load weighted Na
2S9H
2O is dissolved in dried up middle preparation 500mL anion precursor solution, add 5～10 ammoniacal liquor and be adjusted to suitable pH value=11, and stirring is dissolved it fully.
C, the solution for preparing is placed beaker respectively, leave standstill, be used for step plated film down after the filtration.
2) plated film
After the precursor solution preparation was finished, the technical process of plated film was divided into following circulation step:
● substrate is immersed CuCl
22H
2O, InCl
34H
2O, GaCl
3Carry out surface adsorption in the mixed-cation precursor solution, adsorption time is 40 seconds
● substrate immersed in the deionized water wash, washing time is 20 seconds;
● substrate is immersed anion precursor solution solution Na
2SeSO
3In carry out surface adsorption, and react, the time is 40 seconds
● substrate immersed in the deionized water wash, washing time is 50 seconds;
This circulation is carried out 50 times repeatedly, obtained the film of the about 400nm of thickness.
3) heat treatment
In tube furnace, carry out the heat treatment of film, adopt the Ar atmosphere protection, Ar gas velocity 200～300ml/min.400 ℃ of heat treatment temperatures, 2 hours gained materials of heat treatment time photoelectric properties are as follows:
Gained material photoelectric properties are as follows:
| Form | Absorption coefficient | Energy gap Eg | Resistance Ω-cm | Carrier concentration * 10 16cm -3 | Hall mobility cm 2/V-s |
| 7# | 10 5 | 1.0 | 240 | 2.5 | 20 |
| 8# | 10 5 | 1.2 | 30 | 20 | 60 |
| 9# | 10 5 | 1.1 | 80 | 4.2 | 30 |
The present invention all material combination and method open and that disclose can be by using for reference this paper disclosure, although combination of the present invention and method are described by preferred embodiment, but those skilled in the art obviously can change method as herein described and raw material etc. in not breaking away from content of the present invention, spirit and scope, or increase and decrease some step etc., more particularly, the replacement that all are similar and change apparent to those skilled in the artly, these all are regarded as being included in spirit of the present invention, scope and the content.
Claims (5)
1. the continuous ion adsorbing preparation of a multi-component sulfur photoelectric films,
Concrete grammar of the present invention comprises the steps:
1). the preparation of cation precursor solution: the component of cation precursor solution and content are CuCl
2: GaCl
3: InCl
3Be 0.6～1.7: 0～0.3: 1; The pH value is 1.5～3;
2). the preparation of cation precursor solution: it is 11～13 that negative ion source can adopt the pH value, and concentration is the Na of 0.02～0.052mol/l
2The S aqueous solution or Na
2SeSO
3The aqueous solution or thiourea solution;
3). plated film: after at first cleaned substrate being immersed the cation precursor solution and adsorbs, with deionized water wash to remove the not firm cation of absorption; Then substrate is immersed in the anion precursor solution, the Cu that adsorb on the substrate this moment
2+, In
3+Cation and S
2-, Se
2-Anionic reactive generates chalcogen compound, and then removes unnecessary responseless ion with deionised water, and above-mentioned absorption, washing and reaction time are 20～50 seconds; Repeat this reaction cycle 40～50 times, make the chalcongen semiconductor multi-element film;
4). heat treatment: institute's made membrane is heat-treated under the argon atmospher of gas velocity 200～300ml/min and is made required optoelectronic film, and heat treatment temperature is 400～450 ℃, heat treatment time 2 hours.
2. the continuous ion adsorbing preparation of a kind of multi-component sulfur photoelectric films as claimed in claim 1 is characterized in that described cation precursor solution is adjusted to 1.5～3 by dripping HCl with its pH value.
3. the continuous ion adsorbing preparation of a kind of multi-component sulfur photoelectric films as claimed in claim 1 is characterized in that described cation precursor solution is adjusted to 11～13 by dropping ammonia with its pH value.
4. the continuous ion adsorbing preparation of a kind of multi-component sulfur photoelectric films as claimed in claim 1 is characterized in that described substrate is glass, silicon chip, electro-conductive glass, porous TiO
2Film or porous ZnO film.
5. the continuous ion adsorbing preparation of a kind of multi-component sulfur photoelectric films as claimed in claim 1 is characterized in that the described chalcongen semiconductor multi-element film thickness that makes is 300～400nm.
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|---|---|---|---|
| CNB2004100723223A CN100338784C (en) | 2004-10-12 | 2004-10-12 | Continuous ion adsorbing preparation of multi-component sulfur photoelectric films |
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|---|---|---|---|
| CNB2004100723223A CN100338784C (en) | 2004-10-12 | 2004-10-12 | Continuous ion adsorbing preparation of multi-component sulfur photoelectric films |
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| Publication Number | Publication Date |
|---|---|
| CN1614790A CN1614790A (en) | 2005-05-11 |
| CN100338784C true CN100338784C (en) | 2007-09-19 |
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|---|---|---|---|---|
| CN101546791B (en) * | 2009-04-29 | 2011-07-27 | 华东理工大学 | A kind of preparation method of CuInS2 ultrathin film and prepared CuInS2 ultrathin film |
| CN103560009B (en) * | 2013-09-24 | 2017-02-08 | 石家庄铁道大学 | Hierarchical porous TiO2/quantum dot/dye stacked thin film solar cell photoanode and preparation method thereof |
| CN103881709B (en) * | 2014-04-10 | 2016-06-08 | 石家庄铁道大学 | A kind of multi-stage porous TiO2The preparation method of/quantum dot composite material |
| CN104638064A (en) * | 2015-01-26 | 2015-05-20 | 西南交通大学 | A preparation method of ZnO-CuInS2 heterogeneous core-shell structure nanorod array |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1137330A (en) * | 1993-12-14 | 1996-12-04 | 时至准钟表股份有限公司 | solar cell device |
| US5956571A (en) * | 1997-05-02 | 1999-09-21 | Yang; Mei-Hua | Solar battery with thin film type of single crystal silicon |
| CN1418379A (en) * | 2000-03-09 | 2003-05-14 | 伊索沃尔塔奥地利绝缘材料厂股份公司 | Method for producing photovoltaic thin film module |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1137330A (en) * | 1993-12-14 | 1996-12-04 | 时至准钟表股份有限公司 | solar cell device |
| US5956571A (en) * | 1997-05-02 | 1999-09-21 | Yang; Mei-Hua | Solar battery with thin film type of single crystal silicon |
| CN1418379A (en) * | 2000-03-09 | 2003-05-14 | 伊索沃尔塔奥地利绝缘材料厂股份公司 | Method for producing photovoltaic thin film module |
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