CN106549081B - A kind of method for making electrode of solar battery - Google Patents
A kind of method for making electrode of solar battery Download PDFInfo
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- CN106549081B CN106549081B CN201510590830.9A CN201510590830A CN106549081B CN 106549081 B CN106549081 B CN 106549081B CN 201510590830 A CN201510590830 A CN 201510590830A CN 106549081 B CN106549081 B CN 106549081B
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- Prior art keywords
- solar cell
- photocuring
- silicon chip
- metal paste
- electrode
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- 238000000034 method Methods 0.000 title claims abstract description 43
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000010703 silicon Substances 0.000 claims abstract description 60
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 60
- 239000007788 liquid Substances 0.000 claims abstract description 41
- 238000000016 photochemical curing Methods 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 39
- 239000002184 metal Substances 0.000 claims abstract description 39
- 239000003814 drug Substances 0.000 claims abstract description 30
- 238000011161 development Methods 0.000 claims abstract description 27
- 238000005245 sintering Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 18
- 150000003624 transition metals Chemical class 0.000 claims abstract description 18
- 238000006263 metalation reaction Methods 0.000 claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 45
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 31
- 229910052802 copper Inorganic materials 0.000 claims description 31
- 239000010949 copper Substances 0.000 claims description 31
- 238000007747 plating Methods 0.000 claims description 28
- 229910052759 nickel Inorganic materials 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 18
- 230000005540 biological transmission Effects 0.000 claims description 14
- 150000001298 alcohols Chemical group 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- -1 tetramethyl hydroxide Chemical compound 0.000 claims description 7
- 238000007654 immersion Methods 0.000 claims description 6
- 238000007639 printing Methods 0.000 claims description 5
- 238000007711 solidification Methods 0.000 claims description 5
- 230000008023 solidification Effects 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000001723 curing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 239000000908 ammonium hydroxide Substances 0.000 claims 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 230000005611 electricity Effects 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 210000004027 cell Anatomy 0.000 description 62
- 239000010410 layer Substances 0.000 description 28
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 10
- 239000004332 silver Substances 0.000 description 10
- 239000012190 activator Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 239000002390 adhesive tape Substances 0.000 description 5
- 238000007650 screen-printing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005234 chemical deposition Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- GYUPBLLGIHQRGT-UHFFFAOYSA-N pentane-2,4-dione;titanium Chemical compound [Ti].CC(=O)CC(C)=O GYUPBLLGIHQRGT-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000001455 metallic ions Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000001994 activation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000004816 dichlorobenzenes Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 208000021760 high fever Diseases 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The present invention relates to area of solar cell, discloses a kind of method for making electrode of solar battery, and this method comprises the following steps：(1) toward metal paste of the surface coating containing transition metal complex of silicon chip of solar cell；(2) being coated with the surface of the silicon chip of solar cell of the metal paste needs to form the region of electrode progress photocuring so that the metal paste in the region carries out photocuring reaction；(3) silicon chip of solar cell through photocuring is soaked with development liquid medicine so that do not carry out the metal paste on the region of photocuring and be dissolved in the development liquid medicine, to form electrode pattern；(4) product for obtaining step (3) carries out high temperature sintering, then carries out surface active and surface metalation successively on the electrode pattern.Method provided by the invention significantly reduces cost, improves production efficiency, and the electricity conversion of solar cell corresponding to obtained electrode of solar battery is higher.
Description
Technical field
The present invention relates to area of solar cell, in particular it relates to a kind of method for making electrode of solar battery.
Background technology
Because fossil energy is petered out, novel energy such as solar energy, wind energy gradually rises.Solar cell is as a kind of
Directly luminous energy is changed into by photoelectric effect or photochemical effect the device of electric energy, have that installation form is various, safe nothing
The advantages of polluting, be inexhaustible, nexhaustible, therefore greatly developed.Contain PN junction in silicon chip of solar cell, can be with
Electric current is produced under light illumination, in order to which electric current is exported, it is necessary to make positive and negative two electrodes on silicon chip of solar cell surface.
At present, the preparation method of solar cell positive and negative electrode respectively prints silver paste typically by printing or inkjet printing
Brush is in the both sides of silicon chip of solar cell, to form the lead of positive and negative electrode, then by low-temperature bake and high temperature sintering, most
End form is into electrode of solar battery.However, this method is needed using silver paste as raw material, silver powder, glass are usually contained in the silver paste
Powder and organic carrier, wherein, the cost of silver powder is high, also can accordingly be improved so as to result in the cost of the technique.In addition, silk screen
Other cheap metals are printed there is also some problems, for example, the defects of oxidizable during high temperature sintering be present in silk-screen printing copper, and silk
The defects of electric conductivity is low be present in wire mark brush nickel.
The content of the invention
The invention aims to overcome to use existing method preparing solar cell just by printing or inkjet printing
Existing drawbacks described above during negative electrode, and a kind of method of new making electrode of solar battery is provided.
Specifically, the method provided by the invention for making electrode of solar battery comprises the following steps：
(1) toward metal paste of the surface coating containing transition metal complex of silicon chip of solar cell；
(2) being coated with the surface of the silicon chip of solar cell of the metal paste needs to form the region of electrode progress light
Solidification so that the metal paste in the region carries out photocuring reaction；
(3) silicon chip of solar cell through photocuring is soaked with development liquid medicine so that do not carry out the area of photocuring
Metal paste on domain is dissolved in the development liquid medicine, to form electrode pattern；
(4) product for obtaining step (3) carries out high temperature sintering, is then carried out successively on the surface of the electrode pattern
Surface active and surface metalation.
In the method for making electrode of solar battery provided by the invention, the transition metal complex in the metal paste
Thing carries out photocuring reaction after ultraviolet light or laser irradiation, and inorganic-organic key therein is broken and decomposed, and catabolite is easy
In being retained in silicon chip of solar cell surface, and the metal paste at unexposed place then easily developed liquid medicine from solar cell silicon
Piece surface is removed, and after being sintered through high fever, the electrode pattern remained at exposure is combined closely with silicon chip of solar cell, active matter
Matter is easily embedded in the electrode pattern in the surface activation process stage, and is not easy to be embedded in non-electrode area of the pattern, so as in electricity
Pole area of the pattern realizes follow-up surface metalation.The method provided by the invention for making electrode of solar battery is heavy using chemistry
Product or the mode of plating instead of typography, significantly reduce cost, improve production efficiency, and obtained solar energy
The electricity conversion of solar cell corresponding to battery electrode is higher, can reach substantially with being obtained using silver paste typography
Electrode of solar battery corresponding to the suitable level of solar cell.
In addition, a preferred embodiment of the invention, the mode of the surface metalation is to carry out nickel plating successively
Layer, copper plate and plating protection oxidant layer, so, on the one hand, need not carry out high temperature sintering processing, and copper after copper plate
Layer surface is additionally provided with protection oxidant layer, therefore, overcomes and is lacked using oxidizable during high temperature sintering existing for silk-screen printing layers of copper
Fall into；On the other hand, the presence of nickel dam can separate silicon chip of solar cell and layers of copper, avoid due to layers of copper and solar cell
The problem of cell photoelectric transformation efficiency for contacting and bringing between silicon chip reduces, and the presence of layers of copper efficiently solves metallic nickel
The problem of layer electrical efficiency is low.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The method provided by the invention for making electrode of solar battery comprises the following steps：
(1) toward metal paste of the surface coating containing transition metal complex of silicon chip of solar cell；
(2) being coated with the surface of the silicon chip of solar cell of the metal paste needs to form the region of electrode progress light
Solidification so that the metal paste in the region carries out photocuring reaction；
(3) silicon chip of solar cell through photocuring is soaked with development liquid medicine so that do not carry out the area of photocuring
Metal paste on domain is dissolved in the development liquid medicine, to form electrode pattern；
(4) product for obtaining step (3) carries out high temperature sintering, then carries out surface work successively on the electrode pattern
Change and surface metalation.
The metal paste can be existing various to irradiate it containing transition metal complex and through ultraviolet light or laser
The organic and inorganic bond energy in transition metal complex contained therein enough occurs fracture decomposition and is formed and be not dissolved in developer afterwards
The liquid of the photocuring reaction product of water, for example, its can be concentration be 0.5-20 weight %, being preferably that concentration is 2-15
The solution of weight % transition metal complex.Wherein, the metal in the transition metal complex be preferably tin, titanium, aluminium and
At least one of lead.Complex ligand body in the transition metal complex is preferably acetylacetonate compound, carboxylate radical
At least one of compound, carbonyls and alkoxide compound.Specifically, the transition metal complex is preferably pungent
Sour stannous, titanium acetylacetone, aluminium (trihydroxy butanone)3At least one of.It is molten in the solution of the transition metal complex
Agent can be the conventional selection of this area, for example, can be water, alcohols solvent, esters solvent, alkane solvents and benzene kind solvent
At least one of Deng, wherein, the example of the alcohols solvent includes but is not limited to methanol, ethanol, normal propyl alcohol, isopropanol, just
At least one of butanol, isobutanol, amylalcohol, enanthol etc., the example of the esters solvent include but is not limited to methyl acetate, vinegar
At least one of acetoacetic ester, propyl acetate etc., the examples of the alkane solvents include but is not limited to pentane, hexane, octane,
At least one of hexamethylene, cyclohexanone etc., the example of the benzene kind solvent include but is not limited to benzene,toluene,xylene, chlorine
At least one of benzene, dichloro-benzenes etc..In addition, the dosage of the metal paste containing transition metal complex is typically
0.5-20mg/cm2, preferably 1-10mg/cm2。
The present invention is to the metal paste containing transition metal complex is coated to silicon chip of solar cell surface
Mode be not particularly limited, it is for instance possible to use the mode such as spin coating, showering, erasing, spraying is carried out, it is preferred to use spin coating
Or the mode of spraying is carried out.
The present invention is not particularly limited to the mode of the photocuring, ultraviolet light can be used to solidify, can also used
Laser curing.
When the photocuring is that ultraviolet light solidifies, the mode of the photocuring is preferably：It is past to be coated with the metal pulp
Mask is covered on the surface of the silicon chip of solar cell of material, the mask includes transmission region and light tight region and the printing opacity
The pattern in region is electrode pattern, then carries out ultraviolet light solidification so that the metal paste of the transmission region carries out photocuring
Reaction.Wherein, the position that the position that the mask covers can form electrode as needed is adjusted, as a rule, described
Mask can cover in the whole surface of silicon chip of solar cell, can also cover in its part surface.Further, since solar energy
The positive and negative electrode of battery is generally separately positioned on up and down on two surfaces of silicon chip of solar cell, therefore, the above-mentioned formation sun
The step of energy battery electrode, should operating once in silicon chip of solar cell respectively on two surfaces up and down.Now, it is described
It is 500-3000mj/cm that the condition of photocuring, which generally includes UV energy,2.The time of the photocuring is to cause metal paste
The material for carrying out photocuring reaction and being formed insoluble in development liquid medicine is defined, as well known to those skilled in the art to this, does not make herein
Repeat.
When the photocuring is laser curing, the mode of the photocuring is preferably：It is past to be coated with the metal paste
The surface of silicon chip of solar cell need the region to form electrode to be irradiated using laser so that through on laser-irradiated domain
Metal paste carry out photocuring reaction.Now, it is 500-3000mj/ that the condition of the photocuring, which generally includes laser energy,
cm2.Equally, the time of the photocuring forms the thing insoluble in development liquid medicine to cause metal paste to carry out photocuring reaction
Matter is defined, as well known to those skilled in the art to this, and therefore not to repeat here.
The present invention is not particularly limited to the species of the development liquid medicine, can be that existing various can dissolve transition
Metal complex and the liquid object that the electrode pattern formed afterwards through photocuring by the transition metal complex can not be dissolved
Matter, it is preferable that the development liquid medicine is alcohols solvent and/or tetramethylammonium hydroxide aqueous solution, more preferably alcohols solvent or
The mixture of person's alcohols solvent and tetramethylammonium hydroxide aqueous solution.When by it is described development liquid medicine be alcohols solvent and tetramethyl hydrogen
When aoxidizing the mixture of aqueous ammonium, the weight of the alcohols solvent and tetramethylammonium hydroxide aqueous solution is than preferably 0.1-
1000：1, more preferably 0.1-500：1.The example of the alcohols solvent includes but is not limited to：Methanol, ethanol, butanol, isopropanol
At least one of Deng, the angle ready availability from raw material, the alcohols solvent is particularly preferably ethanol and/or methanol.This
Outside, the concentration of the tetramethylammonium hydroxide aqueous solution can be 0.005-2 weight %, preferably 0.01-1 weight %.
The present invention is not particularly limited to the condition of the immersion, as long as the gold that will can not carried out on photocuring region
Category slurry dissolves and retains electrode pattern.As a rule, the condition of the immersion includes：Development liquid medicine temperature can be
10-80 DEG C, preferably 15-60 DEG C；Soak time can be 10-240s, preferably 20-120s.
The purpose of the high temperature sintering is in order that the electrode pattern that must be formed is combined closely with silicon chip of solar cell, is carried
Both high adhesions.Wherein, it can be 300-900 DEG C, during sintering that the condition of the high temperature sintering, which generally includes sintering temperature,
Between can be 0.5-2 hours；Preferably, it is 400-800 DEG C that the condition of the high temperature sintering, which includes sintering temperature, and sintering time is
0.5-1 hours.
The surface active is that non-metallic substrate realizes chemical plating or the committed step of plating, the purpose of surface active be
A certain amount of activated centre of non-metallic substrate surface attachment, it is catalyzed subsequent plating process.The mode of the surface active is this
Known in art personnel, generally include by non-metallic substrate surface (present invention in non-metallic substrate be with electrode pattern
Silicon chip of solar cell) contacted with the activating solution containing active metallic ion and reducing agent, hereafter active metallic ion is gone back
Former agent is reduced to active metal particulate and tightly adsorbed on non-metallic substrate surface.Wherein, preferable activator is Atotech
(Atotech) the Noviganth Activator PLhh activators of company's production.
The present invention is not particularly limited to the mode of the surface metalation, can with nickel coating, can also copper plate, also
Can be with chromium coating.A preferred embodiment of the invention, the mode of the surface metalation for carry out successively nickel coating,
Copper plate and plating protection oxidant layer, it can not only so overcome and be lacked using oxidizable during high temperature sintering existing for silk-screen printing layers of copper
Fall into, but also can avoid because the cell photoelectric transformation efficiency for contacting and bringing between layers of copper and silicon chip of solar cell reduces
The problem of, and the presence of layers of copper solve thes problems, such as that metal nickel dam electrical efficiency is low.
The present invention protects the mode of oxidant layer to be not particularly limited the nickel coating, copper plate and plating, can be each only
On the spot carried out using chemical deposition or galvanoplastic, wherein, concrete operations mode and condition can use existing mode
Carry out, on the other hand, those skilled in the art can know that therefore not to repeat here.In addition, in order that obtained solar cell has
Higher electricity conversion, it is preferable that the thickness of the nickel dam is 0.1-4 microns, more preferably 1-4 microns；The layers of copper
Thickness be 1-20 microns, more preferably 2-15 microns；The thickness of the protective layer agent is 1-10 microns, and more preferably 2-8 is micro-
Rice.
The layers of copper influences the electricity conversion of solar cell being oxidized easily at high temperature or in air,
Therefore, in order to prevent layers of copper be oxidized, it is necessary to plate protection oxidant layer on layers of copper surface.The protection oxidant layer can be existing
It is various to be not easy oxidized metal level, for example, can be at least one of nickel dam, layers of chrome, tin layers, silver layer etc., preferably nickel
Layer and/or layers of chrome.
The method provided by the invention for making electrode of solar battery is preferably also included in toward the silicon chip of solar cell
Surface metallization slurry after, before photocuring, by the silicon chip of solar cell temperature be 60-150 DEG C at, preferably
0.1-60min, preferred process 1-30min are handled at 80-120 DEG C, can so improve the efficiency selectively developed to pattern
And accuracy.
Main the improvement is that of the method provided by the invention for making electrode of solar battery employs chemical deposition
Or the mode of plating instead of typography and form electrode, and the specific distribution mode of electrode is the conventional selection of this area, right
This those skilled in the art can know that therefore not to repeat here.
The present invention will be described in detail by way of examples below.
Embodiment 1
The embodiment is used for the method for illustrating making electrode of solar battery provided by the invention.
The stannous octoate aqueous solution that concentration is 2 weight % is sprayed into silicon chip of solar cell, and (specification is：156cm2×
156cm2, thickness be 180 μm, similarly hereinafter) surface on, then toast 30min in 80 DEG C of baking oven.Afterwards toward solar cell
Mask is covered on the surface of silicon chip, the mask includes transmission region and the pattern of light tight region and the transmission region for electricity
Pole figure case, then carry out UV exposures, exposure energy 2000mj/cm2, wherein, because the pattern of the transmission region of mask is electricity
Pole figure case, therefore, UV exposed portions are electrode pattern.Remove mask afterwards, and by the solar cell silicon through UV exposure-processeds
Piece temperature be 15 DEG C development liquid medicine (the development liquid medicine is the mixture of methanol and tetramethylammonium hydroxide aqueous solution, wherein, first
The weight of alcohol and tetramethylammonium hydroxide aqueous solution ratio is 500:1, the concentration of tetramethylammonium hydroxide aqueous solution is 0.01 weight
Measure %) immersion 120s so that the stannous octoate aqueous dissolution in mask light tight region is in the liquid medicine that develops, and transmission region is not
It is dissolved in the development liquid medicine and forms electrode pattern.High temperature sintering 1 hour at 650 DEG C is placed in afterwards.
By the above-mentioned silicon chip of solar cell after high temperature sintering in the activator (Atotech that temperature is 28 DEG C
(Atotech) 3min is placed in the Noviganth Activator PL activators of company, similarly hereinafter), is obtained after surface active
Silicon chip of solar cell.
Silicon chip of solar cell after surface active is put into chemical nickel-plating liquid, and (chemical nickel-plating liquid is Atotech
(Atotech) the Noviganth Ni KV nickel-plating liquids of company, similarly hereinafter) in, constant temperature water bath takes out after electroplating 7 minutes at 40 DEG C,
Obtain nickel dam.
Silicon chip of solar cell after nickel coating is put into copper plating bath, and (copper plating bath is Atotech (Atotech) company
The Acid Copper acid copper plating baths of Cupracid 210, similarly hereinafter) in, at 25 DEG C constant temperature water bath electroplate 30 minutes after take
Go out, obtain layers of copper.
Then the silicon chip of solar cell after copper plate being put into nickel-plating liquid, (nickel-plating liquid is Atotech (Atotech)
The Unibright HDN Bright Nickel bright nickel plating baths of company, similarly hereinafter) in, constant temperature water bath electroplates 15 points at 60 DEG C
Taken out after clock, obtain nickel dam.
The electrode of solar battery of acquisition is designated as A1.
Embodiment 2
The embodiment is used for the method for illustrating making electrode of solar battery provided by the invention.
The titanium acetylacetone aqueous solution that concentration is 8 weight % is sprayed on the surface of silicon chip of solar cell, Ran Hou
10min is toasted in 140 DEG C of baking oven.Afterwards toward mask is covered on the surface of silicon chip of solar cell, the mask includes printing opacity
The pattern of region and light tight region and the transmission region is electrode pattern, then carries out UV exposures, and exposure energy is
1500mj/cm2, wherein, because the pattern of the transmission region of mask is electrode pattern, therefore, UV exposed portions are electrode pattern.
Mask is removed afterwards, and is 30 DEG C of development liquid medicine (development liquid medicine by the silicon chip of solar cell temperature through UV exposure-processeds
It is 1 by weight for ethanol and methanol:1 mixed liquor) immersion 60s so that the titanium acetylacetone water in mask light tight region
Solution is dissolved in development liquid medicine, and transmission region is not dissolved in the development liquid medicine and forms electrode pattern.800 DEG C are placed in afterwards
Lower high temperature sintering 0.5 hour.
The above-mentioned silicon chip of solar cell after high temperature sintering is placed into 5min in the activator that temperature is 25 DEG C, obtained
Silicon chip of solar cell after surface active.
Silicon chip of solar cell after surface active is put into chemical nickel-plating liquid, the constant temperature water bath plating 10 at 35 DEG C
Taken out after minute, obtain nickel dam.
Silicon chip of solar cell after nickel coating is put into copper plating bath, after constant temperature water bath is electroplated 40 minutes at 20 DEG C
Take out, obtain layers of copper.
Then the silicon chip of solar cell after copper plate is put into nickel-plating liquid, constant temperature water bath electroplates 15 points at 55 DEG C
Taken out after clock, obtain nickel dam.
The electrode of solar battery of acquisition is designated as A2.
Embodiment 3
The embodiment is used for the method for illustrating making electrode of solar battery provided by the invention.
By the aluminium (trihydroxy butanone) that concentration is 15 weight %3The aqueous solution is sprayed on the surface of silicon chip of solar cell,
Then 30min is toasted in 80 DEG C of baking oven.Afterwards toward mask is covered on the surface of silicon chip of solar cell, the mask includes
The pattern of transmission region and light tight region and the transmission region is electrode pattern, then carries out UV exposures, and exposure energy is
700mj/cm2, wherein, because the pattern of the transmission region of mask is electrode pattern, therefore, UV exposed portions are electrode pattern.
Mask is removed afterwards, and is 60 DEG C of development liquid medicine (development liquid medicine by the silicon chip of solar cell temperature through UV exposure-processeds
For the tetramethylammonium hydroxide aqueous solution that concentration is 1 weight %) immersion 60s so that the aluminium (trihydroxy in mask light tight region
Butanone)3In the liquid medicine that develops, transmission region is not dissolved in the development liquid medicine and forms electrode pattern aqueous dissolution.Afterwards
It is placed in high temperature sintering 1 hour at 500 DEG C.
The above-mentioned silicon chip of solar cell after high temperature sintering is placed into 2min in the activator that temperature is 30 DEG C, obtained
Silicon chip of solar cell after surface active.
Silicon chip of solar cell after surface active is put into chemical nickel-plating liquid, the constant temperature water bath plating 6 at 45 DEG C
Taken out after minute, obtain nickel dam.
Silicon chip of solar cell after nickel coating is put into copper plating bath, after constant temperature water bath is electroplated 25 minutes at 30 DEG C
Take out, obtain layers of copper.
Then the silicon chip of solar cell after copper plate is put into nickel-plating liquid, constant temperature water bath electroplates 10 points at 60 DEG C
Taken out after clock, obtain nickel dam.
The electrode of solar battery of acquisition is designated as A3.
Comparative example 1
The comparative example is used for the method for the making electrode of solar battery for illustrating reference.
The comparative example makes electrode of solar battery using silk-screen printing silver paste technique, and specific method is as follows：
Using silk-screen printing back side silver paste antenna, back side aluminium paste antenna, 500 DEG C of continuous tunnel furnaces handle 2min；Then print just
Face silver paste antenna, 900 DEG C of continuous tunnel furnaces handle 1min.
The electrode of solar battery of acquisition is designated as D.
Test case
Test case is used for the test for illustrating electrode of solar battery performance.
(1) adhesive force is tested：
The adhesive force of coating is tested according to the cross cut test of GB/T 9286-1998 paint films, specifically：5 are drawn in sample surfaces
× 5 1mm × 1mm grid, grid is covered with special 3M adhesive tapes, wipes adhesive tape and the complete good contact of grid, stands 90 seconds
Afterwards, it is unilateral with the rapid pull-up adhesive tape in 60 degree of directions from adhesive tape, and repeat to glue and take off three times, whether observation coating is sticked up by adhesive tape.
Adhesion performance requirement：0-1 levels, wherein, 0 grade of expression does not come off completely, and 1 grade represents less than 5% scope area and comes off.Gained
As a result it is as shown in table 1.
Table 1
| Project | A1 | A2 | A3 | D |
| Coating adhesion | 0 grade | 0 grade | 0 grade | 0 grade |
(2) thickness of coating is tested：
The thickness of each coating is measured using coating film thickness measuring instrument XRF2000L, acquired results are as shown in table 2.
Table 2
(3) electricity conversion is tested：
Using the electricity conversion of solar battery cell separator SCT-A test silicon wafers.Wherein, test condition bag
Include：The specification of monocrystalline silicon piece is 156cm2；Spectral region is according to IEC60904-9 requirements, irradiation intensity 100mW/cm2.Gained
As a result it is as shown in table 3.
Table 3
| Project | A1 | A2 | A3 | D |
| Electricity conversion | 16.6% | 16.7% | 16.5% | 16.8% |
As can be seen from the above results, the method provided by the invention for making electrode of solar battery using chemical deposition or
The mode of plating instead of the typography of silver paste, significantly reduce cost, improve production efficiency, and the obtained sun
The electricity conversion of solar cell is higher corresponding to energy battery electrode, can reach substantially with being obtained using silver paste typography
The suitable level of solar cell corresponding to the electrode of solar battery obtained.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (15)
1. a kind of method for making electrode of solar battery, this method comprise the following steps：
(1) toward metal paste of the surface coating containing transition metal complex of silicon chip of solar cell；
(2) it is coated with the surface of the silicon chip of solar cell of the metal paste and needs to be formed the region of electrode and carry out light to consolidate
Change so that the metal paste in the region carries out photocuring reaction；
(3) silicon chip of solar cell through photocuring is soaked with development liquid medicine so that on the region for not carrying out photocuring
Metal paste be dissolved in it is described development liquid medicine in, to form electrode pattern；
(4) product obtained step (3) carries out high temperature sintering, then carried out successively on the electrode pattern surface active and
Surface metalation.
2. according to the method for claim 1, wherein, the metal paste is the transition metal that concentration is 0.5-20 weight %
The solution of complex compound.
3. according to the method for claim 2, wherein, the metal in the transition metal complex is selected from tin, titanium, aluminium and lead
At least one of.
4. method according to claim 1 or 2, wherein, the photocuring is ultraviolet light solidification or laser curing.
5. the method according to claim 11, wherein, when the photocuring is that ultraviolet light solidifies, the side of the photocuring
Formula is：Mask is covered on toward the surface of the silicon chip of solar cell coated with the metal paste, the mask includes transparent area
The pattern of domain and light tight region and the transmission region is electrode pattern, then carries out ultraviolet light solidification so that the printing opacity
The metal paste in region carries out photocuring reaction.
6. according to the method for claim 5, wherein, the condition of the photocuring is 500- including UV energy
3000mj/cm2。
7. the method according to claim 11, wherein, when the photocuring is laser curing, the mode of the photocuring
For：Need to form the region of electrode toward the surface of the silicon chip of solar cell coated with the metal paste and shone using laser
Penetrate so that carry out photocuring reaction through the metal paste on laser-irradiated domain.
8. according to the method for claim 7, wherein, the condition of the photocuring is 500-3000mj/ including laser energy
cm2。
9. method according to claim 1 or 2, wherein, the development liquid medicine is alcohols solvent and/or tetramethyl hydroxide
Aqueous ammonium.
10. according to the method for claim 9, wherein, the development liquid medicine is alcohols solvent or alcohols solvent and tetramethyl
The mixture of base ammonium hydroxide aqueous solution.
11. method according to claim 1 or 2, wherein, the condition of the immersion includes：The temperature of development liquid medicine is 10-
80 DEG C, soak time 10-240s.
12. method according to claim 1 or 2, wherein, the condition of the high temperature sintering is 300- including sintering temperature
900 DEG C, sintering time is 0.5-2 hours.
13. method according to claim 1 or 2, wherein, the mode of the surface metalation for carry out successively nickel coating,
Copper plate and plating protection oxidant layer.
14. according to the method for claim 13, wherein, the protection oxidant layer is nickel dam and/or layers of chrome.
15. method according to claim 1 or 2, wherein, this method is additionally included in the table toward the silicon chip of solar cell
After face coating metal paste, before photocuring, 0.1- is handled at being 60-150 DEG C in temperature by the silicon chip of solar cell
60min。
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| CN112614947B (en) * | 2020-12-15 | 2022-04-01 | 中国华能集团清洁能源技术研究院有限公司 | Tin-containing perovskite precursor liquid, photoactive layer, battery and preparation method |
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| CN102443288A (en) * | 2010-09-30 | 2012-05-09 | 三菱综合材料株式会社 | Transparent conductive film composition for solar cell and transparent conductive film thereof |
| CN102443287A (en) * | 2010-09-30 | 2012-05-09 | 三菱综合材料株式会社 | Transparent conductive film composition for solar cell and transparent conductive film thereof |
| CN103000253A (en) * | 2012-11-10 | 2013-03-27 | 江苏瑞德新能源科技有限公司 | Latent-curing conductive paste and method of forming electrode on substrate thereby |
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| JP2012094830A (en) * | 2010-09-30 | 2012-05-17 | Mitsubishi Materials Corp | Transparent conductive film composition for solar battery and transparent conductive film |
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| CN102443288A (en) * | 2010-09-30 | 2012-05-09 | 三菱综合材料株式会社 | Transparent conductive film composition for solar cell and transparent conductive film thereof |
| CN102443287A (en) * | 2010-09-30 | 2012-05-09 | 三菱综合材料株式会社 | Transparent conductive film composition for solar cell and transparent conductive film thereof |
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