CN112011790A - Stainless steel foil blackening liquid for photovoltaic and blackening treatment method of stainless steel foil - Google Patents
Stainless steel foil blackening liquid for photovoltaic and blackening treatment method of stainless steel foil Download PDFInfo
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- CN112011790A CN112011790A CN201910459029.9A CN201910459029A CN112011790A CN 112011790 A CN112011790 A CN 112011790A CN 201910459029 A CN201910459029 A CN 201910459029A CN 112011790 A CN112011790 A CN 112011790A
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- stainless steel
- blackening
- steel foil
- liquid
- blackening liquid
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- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 87
- 239000010935 stainless steel Substances 0.000 title claims abstract description 87
- 239000011888 foil Substances 0.000 title claims abstract description 68
- 239000007788 liquid Substances 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 22
- -1 rare earth salt Chemical class 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 14
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 14
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 13
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 13
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 13
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 13
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 239000008139 complexing agent Substances 0.000 claims abstract description 11
- 239000006172 buffering agent Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 7
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 7
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 7
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 7
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 7
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 7
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 7
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 7
- 229940039790 sodium oxalate Drugs 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000872 buffer Substances 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 3
- 239000001433 sodium tartrate Substances 0.000 claims description 3
- 229960002167 sodium tartrate Drugs 0.000 claims description 3
- 235000011004 sodium tartrates Nutrition 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 abstract description 17
- 229910052751 metal Inorganic materials 0.000 abstract description 17
- 238000009792 diffusion process Methods 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 13
- 231100000252 nontoxic Toxicity 0.000 abstract description 4
- 230000003000 nontoxic effect Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 43
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 11
- 239000000758 substrate Substances 0.000 description 10
- 239000012535 impurity Substances 0.000 description 9
- 230000000903 blocking effect Effects 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 230000005516 deep trap Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The application relates to a stainless steel foil blackening liquid for photovoltaic and a stainless steel foil blackening treatment method. The blackening liquid takes water as a solvent and contains the following components: 2-5g/L of copper sulfate, 10-20g/L of sodium sulfate, 2-3g/L of sodium molybdate, 2-4g/L of potassium permanganate, 0.1-0.3g/L of rare earth salt, 0.2-0.8g/L of complexing agent, 10-13g/L of catalyst, 0.01-0.5g/L of surfactant and 2-4g/L of buffering agent. The application provides a stainless steel foil blackening liquid for photovoltaic is nontoxic, environmental protection, pollution-free, uses this blackening liquid to blacken the stainless steel foil surface, can make the stainless steel foil surface can not produce any corruption and the surface is very smooth level and smooth, and then makes the blackening film thickness of stainless steel surface growth out even, and strong with the base member associativity. The resulting blackened film forms a diffusion barrier for the metal element.
Description
Technical Field
The invention relates to the technical field of stainless steel surfaces, in particular to a photovoltaic stainless steel foil blackening liquid and a stainless steel foil blackening treatment method.
Background
The stainless steel foil becomes the preferred material of the substrate of the flexible Copper Indium Gallium Selenide (CIGS) thin-film solar cell at present due to the advantages of excellent high-temperature performance, good flexibility, light weight, low price, suitability for a roll-to-roll process of large-scale production and the like.
However, when the stainless steel foil is used as a substrate, Fe, Cu, and other elements in the stainless steel foil diffuse into the CIGS absorber through the molybdenum (Mo) electrode under high-temperature preparation conditions of the absorber, forming deep-level defects in the CIGS, affecting the crystal quality of the CIGS, and thus affecting the photoelectric properties of the cell.
In order to solve the problem of diffusion of impurities in the substrate, it is common practice to prepare a suitable barrier layer system between the substrate and the Mo electrode. For example, the document discloses that the flexible CIGS barrier layer is of a three-layer structure, the barrier layer is made of titanium, chromium, titanium nitride or tantalum nitride near the base layer, the middle layer is made of any one of titanium nitride, tantalum nitride, tungsten nitride or zirconium nitride, the barrier layer is made of titanium, chromium or titanium nitride near the electrode layer, and the diffusion barrier layer obtained by screening the structure of the diffusion barrier layer and the composition of each structure can effectively prevent impurity elements of the stainless steel foil from entering the absorption layer, so that the cell performance is improved. There are other documents disclosing diffusion barriers of different structures.
The barrier layers disclosed above are all metal or nonmetal layers deposited by physical vapor deposition or chemical vapor deposition on the surface of a smooth stainless steel foil, and generally have a sufficient thickness to ensure a good barrier effect, and the consumption of raw materials such as the metal or nonmetal is large, so that the cost is not negligible.
Disclosure of Invention
In order to solve the technical problems, the invention provides a blackening solution for a stainless steel foil for photovoltaic and a blackening treatment method for the stainless steel foil.
The specific technical scheme provided by one embodiment of the application is as follows:
a stainless steel foil blackening liquid for photovoltaic use, which takes water as a solvent and contains the following components: 2-5g/L of copper sulfate, 10-20g/L of sodium sulfate, 2-3g/L of sodium molybdate, 2-4g/L of potassium permanganate, 0.1-0.3g/L of rare earth salt, 0.2-0.8g/L of complexing agent, 10-13g/L of catalyst, 0.01-0.5g/L of surfactant and 2-4g/L of buffering agent.
Optionally, the contents of the components in the blackening liquid are as follows: 3-4g/L of copper sulfate, 12-16g/L of sodium sulfate, 2.2-2.7g/L of sodium molybdate, 2.5-3.5g/L of potassium permanganate, 0.15-0.25g/L of rare earth salt, 0.4-0.6g/L of complexing agent, 11-12g/L of catalyst, 0.1-0.3g/L of surfactant and 2.5-3.5g/L of buffering agent.
Optionally, the rare earth salt is at least one of rare earth sulfate and rare earth nitrate.
Optionally, the complexing agent is at least one of disodium ethylenediaminetetraacetate and sodium tartrate.
Optionally, the catalyst is at least one of sodium dihydrogen phosphate and glacial acetic acid.
Optionally, the surfactant is at least one of sodium dodecylbenzene sulfonate, sodium dodecyl sulfonate and triton.
Optionally, the buffer is at least one of ammonium nitrate and sodium oxalate.
Optionally, the stainless steel foil has a thickness of 10 μm to 100 μm.
The specific technical scheme provided by another embodiment of the application is as follows:
a blackening treatment method of a stainless steel foil comprises the following steps: and placing the stainless steel foil in blackening liquid for oxidation blackening, wherein the blackening liquid is the stainless steel foil blackening liquid for the photovoltaic.
Optionally, the temperature for oxidative blackening is 45-55 deg.C, and the time is 5-10 min.
The photovoltaic stainless steel foil blackening liquid provided by the embodiment of the application is non-toxic, environment-friendly and pollution-free, the blackening liquid is used for blackening the surface of the stainless steel foil, the surface of the stainless steel foil cannot be corroded, the surface is very smooth and flat, the thickness of a blackening film grown on the surface of the stainless steel foil is uniform, and the bonding property of the blackening film and a substrate is strong. The generated blackening film forms a diffusion barrier of metal elements, so that the diffusion of elements such as Fe, Cu and the like in stainless steel to a Mo electrode and a CIGS absorption layer is better blocked in the subsequent CIGS high-temperature selenization process.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention are clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
In one aspect, the invention provides a blackening solution for a photovoltaic stainless steel foil, which takes water as a solvent and comprises the following components: 2-5g/L of copper sulfate, 10-20g/L of sodium sulfate, 2-3g/L of sodium molybdate, 2-4g/L of potassium permanganate, 0.1-0.3g/L of rare earth salt, 0.2-0.8g/L of complexing agent, 10-13g/L of catalyst, 0.01-0.5g/L of surfactant and 2-4g/L of buffering agent. Preferably, the contents of the components in the blackening liquid are as follows: 3-4g/L of copper sulfate, 12-16g/L of sodium sulfate, 2.2-2.7g/L of sodium molybdate, 2.5-3.5g/L of potassium permanganate, 0.15-0.25g/L of rare earth salt, 0.4-0.6g/L of complexing agent, 11-12g/L of catalyst, 0.1-0.3g/L of surfactant and 2.5-3.5g/L of buffering agent. Further preferably, the contents of the components in the blackening liquid are as follows: 3.6g/L of copper sulfate, 13g/L of sodium sulfate, 2.5g/L of sodium molybdate, 3g/L of potassium permanganate, 0.2g/L of rare earth salt, 0.5g/L of complexing agent, 12g/L of catalyst, 0.2g/L of surfactant and 3g/L of buffering agent.
In the blackening liquid, copper sulfate is used as a main blackening film forming component and is used for oxidizing iron in the stainless steel foil. The sodium sulfate and the sodium molybdate are used as auxiliary film forming agents, so that black iron sulfide can be generated on the surface of steel, and meanwhile, under the condition of containing a catalyst, a copper element can generate a black cuprous oxide deposition layer with a special tissue form. The addition of potassium permanganate increases the rate of oxide film formation.
In the blackening solution, the rare earth salt mainly plays a role in providing rare earth elements, the rare earth elements have an inner-4 f electronic layer which is not filled, due to the existence of the unsaturated electronic layer, electrons of a sublayer have tight closure on atomic nuclei, the atoms have larger nuclear charge number, the adsorption capacity is stronger, the atoms can be adsorbed on active points of crystal growth to form nuclei on the surface of a metal matrix, the growth of an adjacent matrix can be inhibited, and the crystallization of a film layer is refined. In addition, the rare earth elements have a catalytic action, so that the reaction of the blackening film becomes more complex, various rich salts are formed, the blackening film becomes compact and uniform, and the corrosion resistance and the adhesive force of the blackening film are enhanced. Therefore, rare earth salt is used as an additive to be added into the blackening liquid to make up for the defects of poor normal-temperature blackening adhesion and corrosion resistance.
In an embodiment of the invention, the rare earth salt is at least one of rare earth sulfate and rare earth nitrate. For example, it may be one or more of cerium sulfate, cerium nitrate, lanthanum sulfate, lanthanum nitrate, and the like.
In the blackening liquid, the complexing agent is mainly used for complexing copper and controlling the replacement speed of the copper so as to ensure the binding force. In the embodiment of the invention, at least one of disodium ethylene diamine tetraacetate and sodium tartrate is adopted.
In the blackening liquid, the catalyst plays a role in catalyzing blackening and oxidation and can improve the reaction film forming speed. By adding the catalyst, the time required for oxidation blackening can be shortened. In the embodiment of the invention, the catalyst is at least one of sodium dihydrogen phosphate and glacial acetic acid.
In the blackening liquid, the surfactant can wet all parts of the surface of the stainless steel foil and fully contact the blackening liquid, so that a uniform and fine oxide layer is obtained, and the phenomena of blooming and ash floating are eliminated. In the embodiment of the invention, the surfactant is at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate and triton.
In the blackening liquid, the buffering agent is used for maintaining the pH value of the blackening liquid to be stable, so that the blackening operation is normal and stable. In an embodiment of the present invention, the buffer is at least one of ammonium nitrate and sodium oxalate. When the buffer contains ammonium nitrate, the NH produced by its hydrolysis4+The reaction progress of the blackening film can be well controlled, the blackening agent is prevented from aging, and the quality of the generated blackening film is improved.
The blackening liquid provided by the embodiment of the invention can be used for blackening stainless steel, particularly stainless steel foil for photovoltaic. The photovoltaic stainless steel foil is a stainless steel foil used as a substrate in a thin-film solar cell, and has a thickness of generally 5 μm to 500. mu.m, preferably 10 μm to 100. mu.m, and more preferably 30 μm. Aiming at the stainless steel with a small thickness, the blackening liquid provided by the embodiment of the invention has low content of copper sulfate which plays a main role, but a certain oxidation speed is ensured through the synergistic effect of other components such as a catalyst and the like. The blackening liquid is non-toxic, environment-friendly and pollution-free, so that the flatness and flexibility of the stainless steel foil after blackening are not affected, and meanwhile, the thickness of an oxide layer can be well controlled.
On the other hand, the invention also provides a method for blackening the stainless steel foil for the photovoltaic by utilizing the blackening liquid. Specifically, the blackening liquid is poured into a blackening tank, and the stainless steel foil is placed in the blackening liquid for oxidation blackening treatment. In the embodiment of the invention, the temperature for oxidation blackening is 45-55 ℃ and the time is 5-10 minutes. For example, in a roll-to-roll production process of thin film solar cells, stainless steel foil is generally put into use in the form of a coil of steel. And during the blackening treatment, heating the blackening liquid to 45-55 ℃, uncoiling the stainless steel band, and passing the stainless steel band through a blackening groove at the coiling speed of 1-2m/min to realize the blackening treatment in the blackening groove. The length of the stainless steel strip immersed in the blackening liquor is typically 10 m. And after blackening treatment, cleaning the stainless steel band conventionally.
The stainless steel foil is preferably pretreated before being subjected to the blackening treatment. The pretreatment may include, for example, degreasing, polishing, and activation.
In the process of rolling the stainless steel foil, part of oil liquid is remained on the surface of the stainless steel foil after rolling is finished. Incomplete oil removal can result in poor adhesion of the blackening film, peeling of the film layer of the workpiece, and mottling. The stainless steel foil may be degreased by prior art means such as chemical alkaline degreasing, ultrasonic degreasing, etc.
Polishing is to remove a thicker oxide layer on the surface of the stainless steel foil, so that the problems of poor binding force, poor uniformity and the like of a blackened film are avoided. The degreased stainless steel foil may be polished by means such as chemical polishing.
A thin oxide film is generated on the surface of the stainless steel foil after polishing, and the stainless steel foil can be removed in dilute phosphoric acid to activate the surface of the stainless steel foil, so that the binding force of the film is improved.
And generating a layer of compact oxide film on the surface of the stainless steel foil through blackening treatment. The thickness of the oxide film is 10nm-5 μm, and the oxide film forms a diffusion barrier of metal elements and blocks the diffusion of elements such as Fe, Cu and the like in stainless steel to a Mo electrode and a CIGS absorption layer. The oxide film layer can be used as a barrier layer alone or in combination with barrier layers of other structures. For example, after the blackening treatment is completed, an impurity blocking layer may be deposited on the stainless steel substrate, whereby a composite structure of an oxide film layer formed on the stainless steel foil and the impurity blocking layer functions as a blocking layer to prevent diffusion of a metal element.
The impurity blocking layer may be one or more of a metal layer, a metal oxide layer, and a metal nitride layer. For example, the impurity blocking layer may be a metal layer, and the metal may be molybdenum, chromium, titanium, aluminum, nickel, or the like. The impurity blocking layer may also be a metal oxide layer or a metal nitride layer, and may be, for example, molybdenum nitride, aluminum nitride, nickel nitride, molybdenum oxide, nickel oxide, or the like. The impurity barrier layer may also be a composite structure of a metal layer and a metal oxide layer, or a composite structure of a metal layer and a metal nitride layer, for example, composed of a layer of chromium and a layer of molybdenum nitride.
Wherein the thickness of the impurity blocking layer is set to 10nm to 2.5 μm, and for example, may be 100nm, 300nm, 500nm, 700 nm. The thickness of this barrier layer film sets for lessly, can be so that the toughness of film is better, the fragility is less, so, under the high temperature preparation environment of absorbed layer, the film is difficult for releasing the heat through the production and the extension of crackle under the too big condition of thermal stress, so avoided the film to take place fracture or demoulding phenomenon, just so can not provide convenient passageway for harmful element in the stainless steel substrate to the absorbed layer diffusion, consequently can further improve the effect of blockking to harmful element in the stainless steel substrate, improve thin-film solar cell's photoelectric conversion performance.
The technical solution of the present invention will be further explained and illustrated with reference to the following specific examples.
Example 1
The contents of the components in the blackening liquid provided by the embodiment are as follows: 2g/L of copper sulfate, 10g/L of sodium sulfate, 2g/L of sodium molybdate, 2g/L of potassium permanganate, 0.1g/L of cerium sulfate, 0.2g/L of disodium ethylene diamine tetraacetate, 10g/L of sodium dihydrogen phosphate, 0.01g/L of sodium dodecyl benzene sulfonate and 2g/L of sodium oxalate.
Putting the blackening liquid into a blackening groove, heating to 45 ℃, and enabling the stainless steel belt with the length of 10 meters after oil removal to pass through the blackening groove at the winding speed of 2m/min to finish blackening treatment.
Example 2
The contents of the components in the blackening liquid provided by the embodiment are as follows: 5g/L of copper sulfate, 20g/L of sodium sulfate, 4g/L of sodium molybdate, 4g/L of potassium permanganate, 0.3g/L of cerium sulfate, 0.8g/L of disodium ethylene diamine tetraacetate, 13g/L of sodium dihydrogen phosphate, 0.5g/L of sodium dodecyl benzene sulfonate, 2g/L of ammonium nitrate and 2g/L of sodium oxalate.
Putting the blackening liquid into a blackening groove, heating to 45 ℃, and enabling the stainless steel belt with the length of 10 meters after oil removal to pass through the blackening groove at the winding speed of 2m/min to finish blackening treatment.
Example 3
The contents of the components in the blackening liquid provided by the embodiment are as follows: 3.6g/L of copper sulfate, 13g/L of sodium sulfate, 2.5g/L of sodium molybdate, 3g/L of potassium permanganate, 0.2g/L of cerium sulfate, 0.5g/L of disodium ethylene diamine tetraacetate, 12g/L of sodium dihydrogen phosphate, 0.2g/L of sodium dodecyl benzene sulfonate, 2g/L of ammonium nitrate and 1g/L of sodium oxalate.
Putting the blackening liquid into a blackening groove, heating to 50 ℃, and enabling the stainless steel belt with the length of 10 meters after oil removal to pass through the blackening groove at the winding speed of 1m/min to finish blackening treatment.
Example 4
The contents of the components in the blackening liquid provided by the embodiment are as follows: 4g/L of copper sulfate, 15g/L of sodium sulfate, 3g/L of sodium molybdate, 3.5g/L of potassium permanganate, 0.25g/L of cerium sulfate, 0.4g/L of disodium ethylene diamine tetraacetate, 11g/L of sodium dihydrogen phosphate, 0.4g/L of sodium dodecyl benzene sulfonate, 1g/L of ammonium nitrate and 2g/L of sodium oxalate.
Putting the blackening liquid into a blackening groove, heating to 55 ℃, and enabling the stainless steel belt with the length of 10 meters after oil removal to pass through the blackening groove at the winding speed of 1m/min to finish blackening treatment.
The stainless steel foils subjected to the blackening treatment in examples 1 to 4 were cut into 10cm × 10cm samples, designated as sample 1, sample 2, sample 3, and sample 4, respectively, and the oxide films of the samples 1 to 4 were measured for thickness uniformity and the film-based bonding force between the oxide films and the stainless steel foils were measured.
The oxide film thickness uniformity measurement procedure was as follows: the thickness of the oxide film was measured every 1cm interval using a film thickness measuring instrument (for example, a saki type, product model: CHY-CA). Recording the thickness values d of all the measurement points1、d2…dnThe average value d is taken as the average thickness of the oxide film. Then, the difference Δ d between the thickness value of each measurement point and the average thickness value is calculated1、d2…dnThen the percentage η of the absolute value of the difference to the average thickness is calculated1，η2…ηnThat is to say that,
get eta1，η2…ηnAs a percentage of the final thickness difference.
The membrane-based binding force measurement process is as follows: firstly, the adhesive tape is pasted on the oxide film, then the adhesive tape is torn off, the steps of pasting and tearing off the adhesive tape are repeated, and the frequency of tearing off the adhesive tape is tested when the oxide film is separated from the stainless steel foil.
The specific results of each test of the oxide film are shown in table 1 below.
TABLE 1
As can be seen from Table 1, the oxide film has uniform blackness and good glossiness, and has good binding force with the substrate; and the thickness difference shows that the overall distribution of the thickness of the oxide film is even, which shows that the overall uniformity of the oxide film is better. It can be seen from the comparison of the experimental results of samples 1 to 4 that the performance of the oxide film can be adjusted by adjusting the composition of the blackening liquid, and the treatment effect of the blackening liquid on the stainless steel foil is the best in example 3.
In conclusion, the stainless steel foil blackening liquid for photovoltaic provided by the embodiment of the invention does not contain heavy metal cadmium, and is non-toxic, environment-friendly and pollution-free. The blackening liquid is used for blackening the surface of the stainless steel foil, a compact oxidation film is generated by utilizing the oxidation treatment of the metal elements of the stainless steel, a diffusion barrier of the metal elements is formed, the thickness of the oxidation film is uniform, the bonding force with the stainless steel foil is strong, and the diffusion of elements such as Fe, Cu and the like in the stainless steel to a Mo electrode and a CIGS absorption layer can be better blocked in the subsequent CIGS high-temperature selenizing process.
Although the embodiments of the present invention have been described above, the above description is only for the convenience of understanding the present invention, and is not intended to limit the present invention. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The stainless steel foil blackening liquid for the photovoltaic is characterized by taking water as a solvent and comprising the following components: 2-5g/L of copper sulfate, 10-20g/L of sodium sulfate, 2-3g/L of sodium molybdate, 2-4g/L of potassium permanganate, 0.1-0.3g/L of rare earth salt, 0.2-0.8g/L of complexing agent, 10-13g/L of catalyst, 0.01-0.5g/L of surfactant and 2-4g/L of buffering agent.
2. The stainless steel foil blackening liquid for photovoltaic use according to claim 1, wherein the blackening liquid is a black liquid,
the contents of the components in the blackening liquid are as follows: 3-4g/L of copper sulfate, 12-16g/L of sodium sulfate, 2.2-2.7g/L of sodium molybdate, 2.5-3.5g/L of potassium permanganate, 0.15-0.25g/L of rare earth salt, 0.4-0.6g/L of complexing agent, 11-12g/L of catalyst, 0.1-0.3g/L of surfactant and 2.5-3.5g/L of buffering agent.
3. The stainless steel foil blackening liquid for photovoltaic use according to claim 1 or 2, characterized in that,
the rare earth salt is at least one of rare earth sulfate and rare earth nitrate.
4. The stainless steel foil blackening liquid for photovoltaic use according to claim 1 or 2, characterized in that,
the complexing agent is at least one of disodium ethylene diamine tetraacetate and sodium tartrate.
5. The stainless steel foil blackening liquid for photovoltaic use according to claim 1 or 2, characterized in that,
the catalyst is at least one of sodium dihydrogen phosphate and glacial acetic acid.
6. The stainless steel foil blackening liquid for photovoltaic use according to claim 1 or 2, characterized in that,
the surfactant is at least one of sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate and triton.
7. The stainless steel foil blackening liquid for photovoltaic use according to claim 1 or 2, characterized in that,
the buffer is at least one of ammonium nitrate and sodium oxalate.
8. The stainless steel foil blackening liquid for photovoltaic use according to claim 1 or 2, characterized in that,
the thickness of the stainless steel foil is 5-500 μm.
9. A blackening treatment method of a stainless steel foil comprises the following steps: placing the stainless steel foil in blackening liquid for oxidation blackening, wherein the blackening liquid is the stainless steel foil blackening liquid for photovoltaic use of any one of claims 1-8.
10. The blackening treatment method of a stainless steel foil according to claim 9,
the temperature for oxidation blackening is 45-55 ℃ and the time is 5-10 minutes.
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