CN104372313A - Preparation method of back electrode of thin film solar cell and thin film solar cell - Google Patents
Preparation method of back electrode of thin film solar cell and thin film solar cell Download PDFInfo
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- CN104372313A CN104372313A CN201410513715.7A CN201410513715A CN104372313A CN 104372313 A CN104372313 A CN 104372313A CN 201410513715 A CN201410513715 A CN 201410513715A CN 104372313 A CN104372313 A CN 104372313A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 239000010409 thin film Substances 0.000 title claims abstract description 41
- 239000000758 substrate Substances 0.000 claims abstract description 121
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229920002101 Chitin Polymers 0.000 claims abstract description 64
- 238000007747 plating Methods 0.000 claims abstract description 32
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 31
- 239000000126 substance Substances 0.000 claims abstract description 29
- 230000003197 catalytic effect Effects 0.000 claims abstract description 19
- 230000004913 activation Effects 0.000 claims abstract description 18
- 238000004140 cleaning Methods 0.000 claims abstract description 15
- YPTUAQWMBNZZRN-UHFFFAOYSA-N dimethylaminoboron Chemical compound [B]N(C)C YPTUAQWMBNZZRN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 27
- 229910021641 deionized water Inorganic materials 0.000 claims description 27
- 150000002815 nickel Chemical class 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 10
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 9
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- -1 polyethylene terephthalate Polymers 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 239000001488 sodium phosphate Substances 0.000 claims description 5
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 5
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 5
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 42
- 239000011248 coating agent Substances 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 239000011259 mixed solution Substances 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract 2
- 239000012459 cleaning agent Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 239000002932 luster Substances 0.000 abstract 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 abstract 1
- 229920002799 BoPET Polymers 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- 230000008569 process Effects 0.000 description 9
- 229910052763 palladium Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 241000412565 Argentina sphyraena Species 0.000 description 2
- AILDTIZEPVHXBF-UHFFFAOYSA-N Argentine Natural products C1C(C2)C3=CC=CC(=O)N3CC1CN2C(=O)N1CC(C=2N(C(=O)C=CC=2)C2)CC2C1 AILDTIZEPVHXBF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000016594 Potentilla anserina Nutrition 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 229910021617 Indium monochloride Inorganic materials 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
-
- 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
Abstract
The invention provides a preparation method of a back electrode of a thin film solar cell, and the thin film solar cell. The preparation method comprises the following steps of substrate cleaning: cleaning a substrate by a cleaning agent and drying the cleaned substrate, substrate surface modification: dipping the cleaned substrate in a chitin-nickel sulfate mixed solution for surface modification, after surface modification, taking out the substrate and carrying out drying, substrate surface catalytic activation: putting the modified substrate into a dimethylaminoborane solution for reduction until the substrate surface produces metallic luster, and nickel chemical plating: dipping the substrate subjected to catalytic activation into a nickel chemical plating liquid for nickel plating so that the back electrode of the thin film solar cell is obtained. The preparation method utilizes a palladium-free catalysis technology to deposit the back electrode, utilizes chitin as a medium, avoids substrate surface chemical coarsening, produces a coating with high flatness, greatly reduces a production cost and is conducive to large-scale popularization.
Description
Technical field
The present invention relates to technical field of solar batteries, particularly relate to a kind of preparation method and the thin-film solar cells of use prepared by the method for back electrode of thin film solar cell.
Background technology
Solar cell is the device directly light energy conversion being become electric energy by photovoltaic effect or Photochemical effects.In solar cells, copper-indium-galliun-selenium (CIGS) thin-film solar cells has excellent photoelectric properties, there is not light decay and causes advantages such as subtracting effect, be acknowledged as the solar cell of following most prospect.
At present, flexible CIGS thin-film solar cells is the focus of technical field of solar batteries research, its typical structure comprises flexible base board, back electrode, light absorbing zone (CIGS), n-type semiconductor buffer layer (CdS), and the Window layer of electrically conducting transparent (i-ZnO and ZnO:Al film).Wherein, the deposition of back electrode often adopts chemical plating technology.But, need in traditional plating process to carry out surface coarsening to the mode of substrate surface chemical corrosion, to improve the bonding force of coating and substrate surface, affect the planeness of back electrode.As: when adopting polyethylene terephthalate (PET) to make flexible substrate, often need to carry out chemical roughen to pet sheet face in advance at pet sheet surface chemistry nickel plating technology, not only easily cause environmental pollution, also affect the planeness of coating surface.In addition, often need to adopt precious metal palladium catalysis at Ni-Speed, process costs is high, is unfavorable for large-scale promotion.
Summary of the invention
The object of the embodiment of the present invention is the preparation method providing a kind of back electrode of thin film solar cell, adopts without palladium chtalyst technique, and the poor flatness, the cost that are intended to solution back electrode coating surface be high, the problem that is unfavorable for large-scale promotion.
Goal of the invention of the present invention is achieved through the following technical solutions:
A preparation method for back electrode of thin film solar cell, comprising: clean substrate: cleaned by substrate clean-out system, and is dried by the substrate after cleaning; Surface modified substrate: be immersed in the chitin of configuration and the mixing solutions of single nickel salt by the substrate after clean, takes out and dries after surface modified substrate; Substrate surface catalytic activation: modified substrate is put into dimethylamino Borane solution and reduces, until substrate surface takes out after there is metalluster; Chemical nickel plating: the substrate after catalytic activation is immersed in nickel chemical plating fluid and carries out nickel plating, obtained back electrode of thin film solar cell.
Above-mentioned preparation method, wherein: described clean-out system is deionized water, dehydrated alcohol, described substrate clean-out system to be carried out cleaning be cleaned under ultrasound condition with deionized water, dehydrated alcohol successively by substrate.
Above-mentioned preparation method, wherein: also comprise after described clean substrate: UV-irradiation: irradiate under the substrate after cleaning, drying is placed on ultra-violet lamp, carries out secondary and cleans; Wherein, the irradiation time of ultra-violet lamp is 10 ~ 20min, exposure intensity 1 ~ 5mw/cm
2.
Above-mentioned preparation method, wherein: also comprise before described surface modified substrate: the prefabricated chitin of substrate surface: the substrate after clean is immersed in 5 ~ 10min in chitin solution, taking-up is placed in 50 ~ 60 DEG C of baking ovens and dries 10 ~ 20min, until substrate surface is dry.
Above-mentioned preparation method, wherein: the compound method of described chitin solution is for pour in deionized water by chitin, get acetic acid again and add this deionized water, stir, obtain described chitin solution, wherein, the volume ratio of described deionized water and acetic acid is 100:1, and the mass concentration of the chitin solution configured is 0.1 ~ 0.3g/L.
Above-mentioned preparation method, wherein: the preparation of the mixing solutions of described chitin and single nickel salt comprises: chitin is poured in deionized water, get acetic acid again and add this deionized water, stir, obtain the chitin solution that mass concentration is 0.1 ~ 0.3g/L, wherein, the volume ratio of described deionized water and acetic acid is 100:1; Single nickel salt is poured in described chitin solution, stir, obtain the mixing solutions of chitin and single nickel salt; Wherein, single nickel salt volumetric molar concentration is 1 ~ 2mol/L.
Above-mentioned preparation method, wherein: the dimethylamino Borane solution concentration that described substrate surface catalytic activation uses is 0.2 ~ 0.5mol/L, temperature is 30 ~ 40 DEG C, and reduce modified substrate is put into dimethylamino Borane solution, its recovery time is 5 ~ 10min.
Above-mentioned preparation method, wherein: the configuration of described nickel chemical plating fluid is is the single nickel salt of 0.15mol/L by volumetric molar concentration, the sodium borohydride of the trisodium phosphate of 0.1mol/L and 0.05mol/L is added to the water and mixes.
Above-mentioned preparation method, wherein: described substrate is polyethylene terephthalate.
In addition, the present invention also provides a kind of production cost low, being conducive to the thin-film solar cells of large-scale promotion, by preparing the high back electrode of coating surface planeness without the mode of palladium chtalyst process deposits back electrode, being conducive to the electricity conversion improving thin-film solar cells.
A kind of thin-film solar cells, comprises substrate, deposits back electrode on the substrate, light absorbing zone, buffer layer and Window layer successively, and wherein, described back electrode is prepared by the preparation method of back electrode of thin film solar cell described above.
The preparation method of back electrode of thin film solar cell of the present invention, whole preparation process adopts without palladium chtalyst process deposits back electrode, by chitin as medium, improve the bonding force of coating and substrate surface, avoid substrate surface chemical roughen, the coating that planeness is high can be prepared, reduce production cost widely, be conducive to large-scale promotion.And prepare the high back electrode of coating surface planeness by this preparation method, be applied in thin-film solar cells, be conducive to the electricity conversion improving thin-film solar cells, reduce the production cost of thin-film solar cells.
Accompanying drawing explanation
Fig. 1 is preparation method's schematic diagram of the back electrode of thin film solar cell that the embodiment of the present invention provides.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Figure 1 shows that the preparation method of back electrode of thin film solar cell provided by the invention, comprising:
Step S101, clean substrate: substrate clean-out system is cleaned, and the substrate after cleaning is dried.
In the embodiment of the present invention, polyethylene terephthalate (PET) is selected to be substrate, as the flexible substrate making thin-film solar cells, effectively can improve the light transmission of solar film battery, expand its use range, reduce costs simultaneously, solve metal and polyimide flex substrate cost high, the problem of light transmission difference.
The clean-out system adopted includes but not limited to deionized water, dehydrated alcohol; Substrate clean-out system being carried out cleaning is cleaned under ultrasound condition with deionized water, dehydrated alcohol successively by substrate.
In other embodiment of the present invention, substrate clean-out system being carried out cleaning can also be substrate deionized water or dehydrated alcohol are cleaned under ultrasound condition, certainly, also can omit ultrasound condition, directly substrate deionization or dehydrated alcohol be cleaned.
As preferred embodiment, in order to make substrate better be cleaned in the embodiment of the present invention, after clean substrate, usually also adopting the mode of UV-irradiation, secondary being carried out to substrate and cleans.Concrete operations be by cleaning, drying after substrate be placed on ultra-violet lamp under irradiate, carry out secondary clean; Wherein, the irradiation time of ultra-violet lamp is 10 ~ 20min, exposure intensity 1 ~ 5mw/cm
2.Mainly contain by the object of UV-irradiation: 1. by UV-irradiation, the surface and oil contaminant that substrate surface does not clean up can be removed herein; 2. increase the C-O key of substrate surface, for follow-up, the grafting of chitin group is prepared to substrate surface.
Step S102, surface modified substrate: be immersed in the chitin of configuration and the mixing solutions of single nickel salt by the substrate after clean, takes out and dries after surface modified substrate.
In the embodiment of the present invention, surface modified substrate normally substrate floods 5 ~ 10min in mixing solutions, takes out to be placed in 50 ~ 60 DEG C of baking ovens and dries 10 ~ 20min, until substrate surface is dry.Immerse mixed solution herein and the object of drying mainly contains: 1. chitin can be hydrolyzed, alkylation, acylations, carboxymethylation, sulfonation, nitrated, halogenation, oxidation, reduction, the chemical reaction such as condensation and complexing, chitin can be made by chemical action grafting to substrate surface by this step, become " bridge " that substrate is connected with nickel (Ni); 2. chitin can effective chelated metal ions, by this step, and Ni
2+ion has arrived substrate surface by chemical bond grafting.
Wherein, the preparation of the mixing solutions of chitin and single nickel salt comprises: poured in deionized water by chitin, then gets acetic acid and add this deionized water, stir, obtain the chitin solution that mass concentration is 0.1 ~ 0.3g/L, wherein, the volume ratio of deionized water and acetic acid is 100:1; Single nickel salt is poured in this chitin solution, stir, obtain the mixing solutions of chitin and single nickel salt; Wherein, single nickel salt volumetric molar concentration is 1 ~ 2mol/L.
Step S103, substrate surface catalytic activation: modified substrate is put into dimethylamino Borane solution and reduces, until substrate surface takes out after there is metalluster.
In the embodiment of the present invention, the dimethylamino Borane solution concentration that substrate surface catalytic activation uses is 0.2 ~ 0.5mol/L, and temperature is 30 ~ 40 DEG C, and reduce modified substrate is put into dimethylamino Borane solution, its recovery time is 5 ~ 10min.Herein, the object after activation: the W metal atom or the cluster that are attached with dispersion by this step substrate surface, this atom or cluster have katalysis, can the carrying out of catalysis subsequent chemistry nickel plating step.If do not have activation step, then follow-up electroless plating reaction is difficult to carry out.Be attached with W metal atom or the cluster of dispersion by catalytic activation substrate surface, this atom or cluster have katalysis.
Step S104, chemical nickel plating: the substrate after catalytic activation is immersed in nickel chemical plating fluid and carries out nickel plating, obtained back electrode of thin film solar cell.
In the embodiment of the present invention, the configuration of nickel chemical plating fluid is is the single nickel salt of 0.15mol/L by volumetric molar concentration, the sodium borohydride of the trisodium phosphate of 0.1mol/L and 0.05mol/L is added to the water and mixes.This step is at room temperature carried out usually; There are Ni atom or the cluster of catalytic activity, the carrying out of catalytic chemistry nickel plating step, thus form complete Ni layer at substrate surface.
Therefore, the preparation method of back electrode of thin film solar cell of the present invention, whole preparation process adopts without palladium chtalyst process deposits back electrode, and technique is simple, reduces production cost widely, is conducive to large-scale promotion.Adopt the chitin of pure natural reagent as surface modification reagent used, any pollution can not be caused to environment, play the effect improving adhesivity and integrity degree simultaneously; In addition, use nickel catalyzator, do not introduce impurity, have enough catalytic activitys can catalysis nickel plating simultaneously; And chemical nickel plating on surface does not use chemical roughen, do not reduce the intensity of flexible base board, the planeness of prepared coating surface is high.
As preferred embodiment, the present invention also comprised before surface modified substrate: the prefabricated chitin of substrate surface, its concrete operations are: the substrate after clean is immersed in 5 ~ 10min in chitin solution, take out to be placed in 50 ~ 60 DEG C of baking ovens and dry 10 ~ 20min, until substrate surface is dry.Wherein, the compound method of chitin solution for pour in deionized water by chitin, then is got acetic acid and is added this deionized water, stir, obtain chitin solution, wherein, the volume ratio of deionized water and acetic acid is 100:1, and the mass concentration of the chitin solution configured is 0.1 ~ 0.3g/L.Herein, the object that immersion chitin solution is also dried is: chitin can pass through chemical action grafting to substrate surface under 50 ~ 60 DEG C of temperature regulate, and becomes " bridge " that substrate is connected with Ni.By this step first at the prefabricated one deck chitin of substrate surface, can make through step S104, back electrode and the substrate surface nickel dam of acquisition after chemical nickel plating operation are more evenly complete.
Below enforcement of the present invention is described in further detail.
Embodiment one
Clean substrate: PET film is cleaned under ultrasound condition with deionized water, dehydrated alcohol successively, cleaning post-drying.
UV-irradiation: irradiate 10min under cleaned PET film is placed on ultra-violet lamp, ultra-violet lamp exposure intensity 1mw/cm
2.
The prefabricated chitin of substrate surface: the PET film after UV-irradiation is immersed in 5min in chitin solution, takes out to be placed in 50 DEG C of baking ovens and dries 10min, until pet sheet face is dry.Wherein, chitin concentration of polymer solution is 0.1g/L.
Surface modified substrate: the PET plate after the prefabricated chitin of substrate surface is immersed in 5min in the mixing solutions of chitin and single nickel salt, takes out to be placed in 55 DEG C of baking ovens and dries 10min, until pet sheet face is dry.Wherein, chitin concentration is 0.1g/L, and single nickel salt volumetric molar concentration is 1mol/L.
Substrate surface catalytic activation: modified PET film is put into dimethylamino Borane solution and reduce 5min, until argentine gloss appears in PET film surface, dimethylamino Borane solution concentration is 0.2mol/L, and temperature is 40 DEG C.
Chemical nickel plating: the PET film after catalytic activation is at room temperature immersed nickel plating 20min in chemical plating fluid, obtained back electrode of thin film solar cell.Wherein the configuration of chemical plating fluid be volumetric molar concentration be the single nickel salt of 0.15mol/L, the sodium borohydride of the trisodium phosphate of 0.1mol/L and 0.05mol/L is added to the water and mixes,
Back electrode of thin film solar cell prepared by the present embodiment, pet sheet face nickel dam is complete, and stripping strength is greater than 40N/cm, and resistivity is 6 μ Ω cm, and average shear strength can reach 45MPa.
Embodiment two
Clean substrate: PET film is cleaned under ultrasound condition with deionized water, dehydrated alcohol successively, cleaning post-drying.
UV-irradiation: irradiate 20min under cleaned PET film is placed on ultra-violet lamp, ultra-violet lamp exposure intensity 5mw/cm
2.
The prefabricated chitin of substrate surface: the PET film after UV-irradiation is immersed in 10min in chitin solution, takes out to be placed in 60 DEG C of baking ovens and dries 10min, until pet sheet face is dry.Wherein, chitin mass concentration is 0.3g/L.
Surface modified substrate: the PET plate after prefabricated for substrate surface chitin is immersed in 5min in the mixing solutions of chitin and single nickel salt, takes out to be placed in 55 DEG C of baking ovens and dries 10min, until pet sheet face is dry.Wherein, chitin mass concentration is 0.3g/L, and single nickel salt volumetric molar concentration is 2mol/L.
Substrate surface catalytic activation: modified PET film is put into dimethylamino Borane solution and reduce 10min, until argentine gloss appears in PET film surface, dimethylamino Borane solution concentration is 0.5mol/L, and temperature is 30 DEG C.
Chemical nickel plating: the PET film after catalytic activation is immersed plating 20min, at room temperature nickel plating in chemical plating fluid, obtained back electrode of thin film solar cell.Wherein chemical plating fluid preparation be volumetric molar concentration be the single nickel salt of 0.15mol/L, the sodium borohydride of the trisodium phosphate of 0.1mol/L and 0.05mol/L is added to the water and mixes.
Back electrode of thin film solar cell prepared by the present embodiment, pet sheet face nickel dam is complete, and stripping strength is greater than 45N/cm, and resistivity is 4.5 μ Ω cm, and average shear strength can reach 50MPa.
Embodiment three
The present embodiment is substantially identical with the preparation method of above-described embodiment two, and difference is only: the irradiation time of ultra-violet lamp is 15min, exposure intensity 3mw/cm
2.
Embodiment four
The present embodiment is substantially identical with the preparation method of above-described embodiment two, and difference is only: omit UV-irradiation.Directly cleaned PET film is immersed in 8min in chitin solution, takes out to be placed in 55 DEG C of baking ovens and dry 15min, until pet sheet face is dry.Wherein, chitin strength of solution is 0.2g/L.
Embodiment five
The present embodiment is substantially identical with the preparation method of above-described embodiment two, difference is only: omit the prefabricated chitin of substrate surface, directly the PET after UV-irradiation is immersed in 7min in the mixing solutions of chitin and single nickel salt, taking-up is placed in 55 DEG C of baking ovens and dries 15min, until pet sheet face is dry.Wherein, chitin mass concentration is 0.2g/L, and single nickel salt volumetric molar concentration is 1.5mol/L.
Embodiment six
The present embodiment is substantially identical with the preparation method of above-described embodiment two, and difference is only: reduce 8min in dimethylamino Borane solution, and concentration is 0.3mol/L.
Therefore, the preparation method of back electrode of thin film solar cell of the present invention, whole preparation process adopts without palladium chtalyst process deposits back electrode, by chitin as medium, improve the bonding force of coating and substrate surface, avoid substrate surface chemical roughen, the coating that planeness is high can be prepared, reduce production cost widely, be conducive to large-scale promotion.
Embodiment seven
A kind of thin-film solar cells, comprise substrate, deposit back electrode on the substrate, light absorbing zone, buffer layer and Window layer successively, wherein, this back electrode is the back electrode prepared by any one preparation method of above-described embodiment.Light absorbing zone is copper-indium-galliun-selenium (CIGS) film light absorbing zone, and it adopts electrodip process at back electrode surface deposition CIGS film, and the PET film after surface deposition CIGS is the light absorbing zone of CIGS flexible thin-film solar cell.
The concrete operations preparing CIGS film light absorbing zone at the back electrode surface enforcement electrodip process prepared by any one preparation method of above-described embodiment are: the PET film that will deposit back electrode film immerses in electrolytic solution, 50min is deposited under the constant potential condition of voltage 0.5v, then, put into 300 DEG C of resistance furnace thermal treatment 30min after cleaning to be prepared from, wherein, use nitrogen protection in this resistance furnace, PET film face uses water-cooled protection; Concentration is the CuCl of 2mmol/L by this electrolytic solution
2, 20mmol/L InCl
3, 15mmol/L CaCL
3, the Seignette salt of 20mmol/L and the HCl of 4mmol/L be added to the water to mix and form.
Therefore, thin-film solar cells of the present invention, by preparing the high back electrode of coating surface planeness without the mode of palladium chtalyst process deposits back electrode, is conducive to the electricity conversion improving thin-film solar cells, reduce the production cost of thin-film solar cells, be conducive to large-scale promotion.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a preparation method for back electrode of thin film solar cell, is characterized in that, comprising:
Clean substrate: substrate clean-out system is cleaned, and the substrate after cleaning is dried;
Surface modified substrate: be immersed in the chitin of configuration and the mixing solutions of single nickel salt by the substrate after clean, takes out and dries after surface modified substrate;
Substrate surface catalytic activation: modified substrate is put into dimethylamino Borane solution and reduces, until substrate surface takes out after there is metalluster; And
Chemical nickel plating: the substrate after catalytic activation is immersed in nickel chemical plating fluid and carries out nickel plating, obtained back electrode of thin film solar cell.
2. preparation method as claimed in claim 1, it is characterized in that, described clean-out system is deionized water, dehydrated alcohol, and described substrate clean-out system to be carried out cleaning be cleaned under ultrasound condition with deionized water, dehydrated alcohol successively by substrate.
3. preparation method as claimed in claim 1, is characterized in that, also comprise after described clean substrate:
UV-irradiation: irradiate under the substrate after cleaning, drying is placed on ultra-violet lamp, carries out secondary and cleans; Wherein, the irradiation time of ultra-violet lamp is 10 ~ 20min, exposure intensity 1 ~ 5mw/cm
2.
4. preparation method as claimed in claim 1, is characterized in that, also comprise before described surface modified substrate:
The prefabricated chitin of substrate surface: the substrate after clean is immersed in 5 ~ 10min in chitin solution, takes out to be placed in 50 ~ 60 DEG C of baking ovens and dries 10 ~ 20min, until substrate surface is dry.
5. preparation method as claimed in claim 4, it is characterized in that, the compound method of described chitin solution is for pour in deionized water by chitin, get acetic acid again and add this deionized water, stir, obtain described chitin solution, wherein, the volume ratio of described deionized water and acetic acid is 100:1, and the mass concentration of the chitin solution configured is 0.1 ~ 0.3g/L.
6. preparation method as claimed in claim 1, it is characterized in that, the preparation of the mixing solutions of described chitin and single nickel salt comprises:
Poured in deionized water by chitin, then get acetic acid and add this deionized water, stir, obtain the chitin solution that mass concentration is 0.1 ~ 0.3g/L, wherein, the volume ratio of described deionized water and acetic acid is 100:1; And
Single nickel salt is poured in described chitin solution, stir, obtain the mixing solutions of chitin and single nickel salt; Wherein, single nickel salt volumetric molar concentration is 1 ~ 2mol/L.
7. preparation method as claimed in claim 1, it is characterized in that, the dimethylamino Borane solution concentration that described substrate surface catalytic activation uses is 0.2 ~ 0.5mol/L, temperature is 30 ~ 40 DEG C, reduce modified substrate is put into dimethylamino Borane solution, its recovery time is 5 ~ 10min.
8. preparation method as claimed in claim 1, is characterized in that, the configuration of described nickel chemical plating fluid is is the single nickel salt of 0.15mol/L by volumetric molar concentration, the sodium borohydride of the trisodium phosphate of 0.1mol/L and 0.05mol/L is added to the water and mixes.
9. the preparation method as described in claim 1-8 any one, is characterized in that, described substrate is polyethylene terephthalate.
10. a thin-film solar cells, comprise substrate, deposit back electrode on the substrate, light absorbing zone, buffer layer and Window layer successively, it is characterized in that, described back electrode is prepared by the preparation method of back electrode of thin film solar cell according to claim 1 to 9 any one.
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| CN109999865A (en) * | 2019-05-15 | 2019-07-12 | 台州学院 | A kind of preparation method of nickel phosphorus sulphur selenium elctro-catalyst |
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