CN106549081A - A kind of method for making electrode of solar battery - Google Patents
A kind of method for making electrode of solar battery Download PDFInfo
- Publication number
- CN106549081A CN106549081A CN201510590830.9A CN201510590830A CN106549081A CN 106549081 A CN106549081 A CN 106549081A CN 201510590830 A CN201510590830 A CN 201510590830A CN 106549081 A CN106549081 A CN 106549081A
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- China
- Prior art keywords
- photocuring
- solar cell
- silicon chip
- metal paste
- electrode
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- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 42
- 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
- 238000000016 photochemical curing Methods 0.000 claims abstract description 44
- 239000007788 liquid Substances 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
- 238000005245 sintering Methods 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 16
- 150000003624 transition metals Chemical class 0.000 claims abstract description 16
- 238000006263 metalation reaction Methods 0.000 claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 46
- 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 30
- 229910052759 nickel Inorganic materials 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 19
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 16
- 230000005540 biological transmission Effects 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 150000001298 alcohols Chemical group 0.000 claims description 10
- 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
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- 238000001723 curing Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011133 lead Substances 0.000 claims description 3
- 239000000203 mixture 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
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 238000001465 metallisation Methods 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 230000005611 electricity Effects 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 210000004027 cell Anatomy 0.000 description 59
- 239000010410 layer Substances 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 229910052709 silver Inorganic materials 0.000 description 10
- 239000004332 silver Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000012190 activator Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 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
- 239000002390 adhesive tape Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 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
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 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
- 238000007639 printing Methods 0.000 description 3
- 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 3
- 230000009466 transformation Effects 0.000 description 3
- 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
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 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
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-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
- 239000011149 active material Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 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
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 150000004816 dichlorobenzenes Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue 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
- 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
- 150000001455 metallic ions 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000002360 preparation method 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
- 238000009738 saturating Methods 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
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention relates to area of solar cell, discloses a kind of method for making electrode of solar battery, the method is comprised the following steps：(1) toward the metal paste of the surface coating containing transition metal complex of silicon chip of solar cell；(2) surface for being coated with the silicon chip of solar cell of the metal paste needs the region to form electrode to carry out photocuring so that the metal paste in the region carries out photocuring reaction；(3) silicon chip of solar cell of Jing photocurings 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 that step (3) is obtained is carried out into high temperature sintering, then carries out surface active and surface metalation on the electrode pattern successively.The method that the present invention is provided significantly reduces cost, improves production efficiency, and the electricity conversion of the corresponding solar cell of electrode of solar battery for obtaining is higher.
Description
Technical field
The present invention relates to area of solar cell, in particular it relates to a kind of electrode of solar battery that makes
Method.
Background technology
As fossil energy is petered out, novel energy such as solar energy, wind energy gradually rises.Solar-electricity
Pond is used as a kind of device for directly luminous energy being changed into electric energy by photoelectric effect or Photochemical effects, tool
There is various installation form, safety non-pollution, inexhaustible, nexhaustible, therefore obtained big
Power develops.Contain PN junction in silicon chip of solar cell, electric current can be produced under light illumination, in order to by electricity
Conductance goes out, and needs 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 is typically by printing or inkjet printing difference
Silver paste is printed on into the both sides of silicon chip of solar cell, to form the lead of positive and negative electrode, then is passed through
Low-temperature bake and high temperature sintering, ultimately form electrode of solar battery.However, the method is needed with silver paste
As raw material, silver powder, glass dust and organic carrier in the silver paste, are usually contained, wherein, the cost of silver powder
It is high, so as to the cost that result in the technique also accordingly can be improved.Additionally, serigraphy other cheap gold
Category there is also some problems, and for example, serigraphy copper has a defect oxidizable during high temperature sintering, and silk
There is the low defect of electric conductivity in wire mark brush nickel.
The content of the invention
The invention aims to overcome the sun be prepared by printing or inkjet printing using existing method
The drawbacks described above existed during energy battery positive and negative electrode, and a kind of new making electrode of solar battery is provided
Method.
Specifically, the method for the making electrode of solar battery that the present invention is provided is comprised the following steps：
(1) toward the metal paste of the surface coating containing transition metal complex of silicon chip of solar cell；
(2) surface for being coated with the silicon chip of solar cell of the metal paste needs to form electrode
Region carries out photocuring so that the metal paste in the region carries out photocuring reaction；
(3) silicon chip of solar cell of Jing photocurings is soaked with development liquid medicine so that do not carry out
Metal paste on the region of photocuring is dissolved in the development liquid medicine, to form electrode pattern；
(4) product that step (3) is obtained is carried out into high temperature sintering, then in the table of the electrode pattern
Carry out surface active and surface metalation on face successively.
In the method for the making electrode of solar battery that the present invention is provided, the transition in the metal paste
Photocuring reaction, inorganic-organic key therein are carried out after metal complex Jing ultraviolet lights or laser irradiation
Fracture and decompose, catabolite is easy to be retained in silicon chip of solar cell surface, and the metal at unexposed place
Then easily developed liquid medicine is removed slurry from silicon chip of solar cell surface, after Jing high fevers sintering, exposure
The electrode pattern of place's residual is combined closely with silicon chip of solar cell, and active material is in surface activation process rank
Duan Rongyi is embedded in the electrode pattern, and is difficult to be embedded in non-electrode area of the pattern, so as in electrode pattern
Realize follow-up surface metalation in region.The method of the making electrode of solar battery that the present invention is provided is adopted
The mode of chemical deposition or plating instead of typography, significantly reduce cost, improve production effect
Rate, and the electricity conversion of the corresponding solar cell of electrode of solar battery for obtaining is higher, base
Originally solar cell corresponding with the electrode of solar battery obtained using silver paste typography can be reached
Suitable level.
Additionally, a preferred embodiment of the invention, the mode of the surface metalation is for successively
Nickel coating, copper plate and plating protection oxidant layer are carried out, so, on the one hand, need not after copper plate
High temperature sintering process is carried out, and layers of copper surface is additionally provided with protection oxidant layer, therefore, overcome and adopt silk
Oxidizable defect during the high temperature sintering that wire mark brush layers of copper is present；On the other hand, the presence of nickel dam can be by
Silicon chip of solar cell is separated with layers of copper, it is to avoid due to contacting and band between layers of copper and silicon chip of solar cell
The problem that the cell photoelectric transformation efficiency for coming is reduced, and the presence of layers of copper efficiently solves metal nickel dam and leads
The low problem of electrical efficiency.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The method of the making electrode of solar battery that the present invention is provided is comprised the following steps：
(1) toward the metal paste of the surface coating containing transition metal complex of silicon chip of solar cell；
(2) surface for being coated with the silicon chip of solar cell of the metal paste needs to form electrode
Region carries out photocuring so that the metal paste in the region carries out photocuring reaction；
(3) silicon chip of solar cell of Jing photocurings is soaked with development liquid medicine so that do not carry out
Metal paste on the region of photocuring is dissolved in the development liquid medicine, to form electrode pattern；
(4) product that step (3) is obtained is carried out into high temperature sintering, then on the electrode pattern according to
It is secondary to carry out surface active and surface metalation.
The metal paste can for it is existing it is various containing transition metal complex and Jing ultraviolet lights or swash
Enough there is fracture and decompose in the organic and inorganic bond energy after light irradiation in transition metal complex contained therein
And formation is not dissolved in the liquid of the photocuring reaction product of development liquid medicine, for example, which can be dense
Spend for 0.5-20 weight %, be preferably solution of the concentration for the transition metal complex of 2-15 weight %.Its
In, the metal in the transition metal complex is preferably at least one in tin, titanium, aluminium and lead.Institute
The complex ligand body stated in transition metal complex is preferably acetylacetonate compound, carboxylate radical chemical combination
At least one in thing, carbonyls and alkoxide compound.Specifically, the transition metal complex
Thing is preferably stannous octoate, titanium acetylacetone, aluminium (trihydroxy butanone)3In at least one.The transition
Solvent in the solution of metal complex can be the conventional selection of this area, for example, can be water, alcohol
At least one in class solvent, esters solvent, alkane solvents and benzene kind solvent etc., wherein, the alcohol
The example of class solvent include but is not limited to methyl alcohol, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol,
At least one in amylalcohol, enanthol etc., the example of the esters solvent include but is not limited to methyl acetate,
At least one in ethyl acetate, propyl acetate etc., the example of the alkane solvents are included but is not limited to
At least one in pentane, hexane, octane, hexamethylene, cyclohexanone etc., the example of the benzene kind solvent
At least one including but not limited in benzene,toluene,xylene, chlorobenzene, dichloro-benzenes etc..Additionally, institute
State the consumption typically 0.5-20mg/cm of the metal paste containing transition metal complex2, preferably
1-10mg/cm2。
The present invention is to the metal paste containing transition metal complex is coated to solar cell silicon
Mode on piece surface is not particularly limited, it is for instance possible to use spin coating, showering, erasing, spraying
Carry out etc. mode, it is preferred to use the mode of spin coating or spraying is carried out.
The present invention is not particularly limited to the mode of the photocuring, can adopt ultraviolet light polymerization,
Laser curing can be adopted.
When the photocuring is ultraviolet light polymerization, the mode of the photocuring is preferably：Toward coating
Cover mask on the surface of the silicon chip of solar cell for stating metal paste, the mask include transmission region and
The pattern of light tight region and the transmission region is electrode pattern, then carries out ultraviolet light polymerization so that
The metal paste of the transmission region carries out photocuring reaction.Wherein, the position that the mask is covered can be with
The position for forming electrode as needed is adjusted, and as a rule, the mask can cover in solar energy
The whole surface of cell silicon chip, it is also possible to cover in its part surface.Further, since solar cell
Positive and negative electrode is generally separately positioned on two surfaces up and down of silicon chip of solar cell, therefore, above-mentioned shape
Should distinguish on two surfaces up and down of silicon chip of solar cell into the step of electrode of solar battery
Operation is once.Now, the condition of the photocuring generally includes UV energy for 500-3000mj/cm2。
The time of the photocuring is so that metal paste carries out photocuring reaction and formed insoluble in development liquid medicine
Material be defined, as well known to those skilled in the art to this, therefore not to repeat here.
When the photocuring is laser curing, the mode of the photocuring is preferably：It is described toward being coated with
The surface of the silicon chip of solar cell of metal paste needs the region to form electrode to be irradiated using laser,
So that the metal paste on Jing laser-irradiated domains carries out photocuring reaction.Now, the bar of the photocuring
Part generally includes laser energy for 500-3000mj/cm2.Equally, the time of the photocuring is so that gold
The material that category slurry carries out photocuring reaction and formed insoluble in development liquid medicine is defined, to this art technology
Known in personnel, therefore not to repeat here.
The present invention to it is described development liquid medicine species be not particularly limited, can for it is existing it is various can
Dissolving transition metal complex and can not dissolve by being formed after transition metal complex Jing photocurings
Electrode pattern liquid, it is preferable that the development liquid medicine is alcohols solvent and/or tetramethyl hydrogen-oxygen
Change aqueous ammonium, more preferably alcohols solvent or alcohols solvent and tetramethylammonium hydroxide aqueous solution is mixed
Compound.When the mixture for being alcohols solvent and tetramethylammonium hydroxide aqueous solution by the development liquid medicine,
The weight of the alcohols solvent and tetramethylammonium hydroxide aqueous solution is than preferably 0.1-1000：1, it is more excellent
Elect 0.1-500 as：1.The example of the alcohols solvent is included but is not limited to：Methyl alcohol, ethanol, butanol,
At least one in isopropanol etc., from the ready availability angle of raw material, the alcohols solvent is particularly preferred
For ethanol and/or methyl alcohol.Additionally, 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 photocuring area can not will be carried out
Metal paste on domain dissolves and retains electrode pattern.As a rule, the condition of the immersion includes：
The temperature of development liquid medicine 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 for being formed is tight with silicon chip of solar cell
Close combination, improves both adhesions.Wherein, the condition of the high temperature sintering generally includes sintering temperature
It can be 300-900 DEG C, sintering time can be 0.5-2 hours；Preferably, the bar of the high temperature sintering
Part includes sintering temperature for 400-800 DEG C, and sintering time is 0.5-1 hours.
The surface active is the committed step that non-metallic substrate realizes chemical plating or plating, surface active
Purpose is activated centre a certain amount of in non-metallic substrate surface attachment, is catalyzed subsequent plating process.Institute
The mode for stating surface active is known to the skilled person, and generally includes non-metallic substrate surface (this
Non-metallic substrate in invention is the silicon chip of solar cell with electrode pattern) with containing active metal from
The activating solution of son and reducing agent is contacted, and hereafter active metallic ion is reduced agent and is reduced to active metal particulate
And tightly adsorb on non-metallic substrate surface.Wherein, preferred 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 be with nickel coating, it is also possible to
Copper plate, can be with chromium coating.A preferred embodiment of the invention, the surface metalation
Mode for carry out successively nickel coating, copper plate and plating protection oxidant layer, can not only so overcome and adopt silk
Oxidizable defect during the high temperature sintering that wire mark brush layers of copper is present, but also can avoid due to layers of copper with too
The problem that the cell photoelectric transformation efficiency for contacting and bringing between positive energy cell silicon chip is reduced, and layers of copper
There is a problem of efficiently solving metal nickel dam electrical efficiency low.
The present invention is not particularly limited to the mode of the nickel coating, copper plate and plating protection oxidant layer, can
To be carried out using chemical deposition or galvanoplastic independently of one another, wherein, concrete operations mode and condition
Can be to be carried out using existing mode, in this regard, those skilled in the art can know that here is not gone to live in the household of one's in-laws on getting married
State.Additionally, in order that the solar cell for arriving has higher electricity conversion, it is preferable that institute
The thickness for stating nickel dam is 0.1-4 microns, more preferably 1-4 microns；The thickness of the layers of copper is that 1-20 is micro-
Rice, more preferably 2-15 microns；The thickness of the protective layer agent be 1-10 microns, more preferably 2-8
Micron.
The layers of copper affects the photoelectricity of solar cell being oxidized easily at high temperature or in air
Transformation efficiency, therefore, in order to prevent layers of copper to be oxidized, needs plate protection oxidant layer on layers of copper surface.
It is described protection oxidant layer can for it is existing it is various be difficult oxidized metal level, for example, can for nickel dam,
At least one in layers of chrome, tin layers, silver layer etc., preferably nickel dam and/or layers of chrome.
The method of the making electrode of solar battery that the present invention is provided is preferably also included in toward the solar energy
After the surface metallization slurry of cell silicon chip, before photocuring, the silicon chip of solar cell is existed
Temperature is that 0.1-60min, preferred process 1-30min are processed at 60-150 DEG C, preferably at 80-120 DEG C,
The efficiency and accuracy to pattern selectively development can so be improved.
Mainly the theing improvement is that for method of the making electrode of solar battery that the present invention is provided employs
The mode of chemical deposition or plating instead of typography and form electrode, and the concrete distribution mode of electrode is
This those skilled in the art can be known that therefore not to repeat here by the conventional selection of this area.
Hereinafter will be described the present invention by embodiment.
Embodiment 1
The method that the embodiment is used for the making electrode of solar battery for illustrating present invention offer.
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 in 80 DEG C of baking oven dry
Roasting 30min.Cover mask afterwards toward on the surface of silicon chip of solar cell, the mask includes transparent area
The pattern of domain and light tight region and the transmission region is electrode pattern, then carries out UV exposures, is exposed
Light energy is 2000mj/cm2, wherein, as the pattern of the transmission region of mask is electrode pattern, therefore,
UV exposed portions are electrode pattern.Remove mask afterwards, and by the solar-electricity of Jing UV exposure-processeds
Pond silicon chip temperature is that (the development liquid medicine is methyl alcohol and tetramethylammonium hydroxide aqueous solution to 15 DEG C of development liquid medicine
Mixture, wherein, the weight ratio of methyl alcohol and tetramethylammonium hydroxide aqueous solution is 500:1, tetramethyl
The concentration of ammonium hydroxide aqueous solution is 0.01 weight %) immersion 120s so that in mask light tight region
Stannous octoate aqueous dissolution is formed during transmission region is not dissolved in the development liquid medicine in development liquid medicine
Electrode pattern.High temperature sintering 1 hour at 650 DEG C is placed in afterwards.
By the above-mentioned silicon chip of solar cell Jing after high temperature sintering in the activator (Atotech that temperature is 28 DEG C
(Atotech) the Noviganth Activator PL activators of company, similarly hereinafter) middle placement 3min, obtain
To the silicon chip of solar cell Jing after surface active.
Silicon chip of solar cell Jing after surface active is put into chemical nickel-plating liquid, and (chemical nickel-plating liquid is peace
The Noviganth Ni KV nickel-plating liquids of Mei Te (Atotech) company, similarly hereinafter) in, the water-bath at 40 DEG C
Constant temperature is taken out after electroplating 7 minutes, obtains nickel dam.
Silicon chip of solar cell after nickel coating is put into copper plating bath, and (copper plating bath is Atotech
(Atotech) the 210 Acid Copper acid copper plating baths of Cupracid of company, similarly hereinafter) in, 25
Take out after constant temperature water bath is electroplated 30 minutes at DEG C, obtain layers of copper.
Then (nickel-plating liquid is Atotech the silicon chip of solar cell after copper plate to be put into nickel-plating liquid
(Atotech) the Unibright HDN Bright Nickel bright nickel plating baths of company, similarly hereinafter) in,
Take out after constant temperature water bath is electroplated 15 minutes at 60 DEG C, obtain nickel dam.
The electrode of solar battery of acquisition is designated as into A1.
Embodiment 2
The method that the embodiment is used for the making electrode of solar battery for illustrating present invention offer.
The titanium acetylacetone aqueous solution that concentration is 8 weight % is sprayed into into the surface of silicon chip of solar cell
On, then 10min is toasted in 140 DEG C of baking oven.Hide toward on the surface of silicon chip of solar cell afterwards
Lid mask, the mask include that 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 1500mj/cm2, wherein, due to the printing opacity of mask
The pattern in region is electrode pattern, therefore, UV exposed portions are electrode pattern.Mask is removed afterwards,
And by the silicon chip of solar cell temperature of Jing UV exposure-processeds be 30 DEG C development liquid medicine (development liquid medicine
It is 1 by weight for ethanol and methyl alcohol:1 mixed liquor) immersion 60s so that in mask light tight region
Titanium acetylacetone aqueous dissolution development liquid medicine in, during transmission region is not dissolved in the development liquid medicine
Form electrode pattern.High temperature sintering 0.5 hour at 800 DEG C is placed in afterwards.
The above-mentioned silicon chip of solar cell Jing after high temperature sintering is placed in the activator that temperature is 25 DEG C
5min, obtains the silicon chip of solar cell Jing after surface active.
Silicon chip of solar cell Jing after surface active is put in chemical nickel-plating liquid, at 35 DEG C, water-bath is permanent
Temperature plating was taken out after 10 minutes, obtained nickel dam.
Silicon chip of solar cell after nickel coating is put in copper plating bath, the constant temperature water bath plating at 20 DEG C
Take out after 40 minutes, obtain layers of copper.
Then the silicon chip of solar cell after copper plate is put in nickel-plating liquid, the constant temperature water bath at 55 DEG C
Plating was taken out after 15 minutes, obtained nickel dam.
The electrode of solar battery of acquisition is designated as into A2.
Embodiment 3
The method that the embodiment is used for the making electrode of solar battery for illustrating present invention offer.
By the aluminium (trihydroxy butanone) that concentration is 15 weight %3The aqueous solution is sprayed into silicon chip of solar cell
On surface, then 30min is toasted in 80 DEG C of baking oven.Afterwards toward on the surface of silicon chip of solar cell
Mask is covered, the mask includes that the pattern of transmission region and light tight region and the transmission region is electricity
Pole figure case, then carries out UV exposures, and exposure energy is 700mj/cm2, wherein, it is saturating due to mask
The pattern in light region is electrode pattern, therefore, UV exposed portions are electrode pattern.Mask is removed afterwards,
And by the silicon chip of solar cell temperature of Jing UV exposure-processeds be 60 DEG C development liquid medicine (development liquid medicine
Tetramethylammonium hydroxide aqueous solution for concentration is 1 weight %) immersion 60s so that the light tight area of mask
Aluminium (trihydroxy butanone) on domain3In development liquid medicine, transmission region is not dissolved in the development to aqueous dissolution
Electrode pattern is formed in liquid medicine.High temperature sintering 1 hour at 500 DEG C is placed in afterwards.
The above-mentioned silicon chip of solar cell Jing after high temperature sintering is placed in the activator that temperature is 30 DEG C
2min, obtains the silicon chip of solar cell Jing after surface active.
Silicon chip of solar cell Jing after surface active is put in chemical nickel-plating liquid, at 45 DEG C, water-bath is permanent
Temperature plating was taken out after 6 minutes, obtained nickel dam.
Silicon chip of solar cell after nickel coating is put in copper plating bath, the constant temperature water bath plating at 30 DEG C
Take out after 25 minutes, obtain layers of copper.
Then the silicon chip of solar cell after copper plate is put in nickel-plating liquid, the constant temperature water bath at 60 DEG C
Plating was taken out after 10 minutes, obtained nickel dam.
The electrode of solar battery of acquisition is designated as A3.
Comparative example 1
The method that the comparative example is used for the making electrode of solar battery for illustrating reference.
The comparative example makes electrode of solar battery using serigraphy silver paste technique, and concrete grammar is as follows：
Using serigraphy back side silver paste antenna, back side aluminium paste antenna, 500 DEG C of continuous tunnel furnaces process 2min；
Then front side silver paste antenna is printed, 900 DEG C of continuous tunnel furnaces process 1min.
The electrode of solar battery of acquisition is designated as into D.
Test case
Test case is used for the test for illustrating electrode of solar battery performance.
(1) adhesive force test：
The adhesive force of coating is tested according to the cross cut test of GB/T 9286-1998 paint films, specifically：
Sample surfaces draw the grid of 5 × 5 1mm × 1mm, cover grid with special 3M adhesive tapes, wipe adhesive tape
With the complete good contact of grid, 90 seconds are stood afterwards, it is monolateral with the rapid pull-up glue in 60 degree of directions from adhesive tape
Band, and repeat it is viscous take off three times, whether observation coating is sticked up by adhesive tape.Adhesion performance is required：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.Acquired results are such 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 test：
The thickness of each coating is measured using coating film thickness measuring instrument XRF2000L, acquired results are such as
Shown in table 2.
Table 2
(3) electricity conversion test：
Using the electricity conversion of solar battery cell separator SCT-A test silicon wafers.Wherein, survey
Strip part includes：The specification of monocrystalline silicon piece is 156cm2；Spectral region foundation IEC60904-9 requirements,
Irradiation intensity is 100mW/cm2.Acquired results are 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 employingization of the making electrode of solar battery that the present invention is provided
The typography that the mode for depositing or electroplating instead of silver paste is learned, cost is significantly reduced, is improve life
Produce efficiency, and the electricity conversion of the corresponding solar cell of electrode of solar battery for obtaining compared with
Height, can reach solar energy corresponding with the electrode of solar battery obtained using silver paste typography substantially
The suitable level of battery.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, the present invention are no longer separately illustrated to various possible combinations.
Additionally, can also be combined between a variety of embodiments of the present invention, as long as its
Without prejudice to the thought of the present invention, which should equally be considered as content disclosed in this invention.
Claims (11)
1. a kind of method for making electrode of solar battery, the method are comprised the following steps：
(1) toward the metal paste of the surface coating containing transition metal complex of silicon chip of solar cell；
(2) surface for being coated with the silicon chip of solar cell of the metal paste needs to form electrode
Region carries out photocuring so that the metal paste in the region carries out photocuring reaction；
(3) silicon chip of solar cell of Jing photocurings is soaked with development liquid medicine so that do not carry out
Metal paste on the region of photocuring is dissolved in the development liquid medicine, to form electrode pattern；
(4) product that step (3) is obtained is carried out into high temperature sintering, then on the electrode pattern according to
It is secondary to carry out surface active and surface metalation.
2. method according to claim 1, wherein, it is 0.5-20 that the metal paste is concentration
The solution of the transition metal complex of weight %；Preferably, the metal choosing in the transition metal complex
At least one from tin, titanium, aluminium and lead.
3. method according to claim 1 and 2, wherein, the photocuring is ultraviolet light polymerization
Or laser curing.
4. method according to claim 3, wherein, when the photocuring is ultraviolet light polymerization,
The mode of the photocuring is：Hide toward on the surface of the silicon chip of solar cell for being coated with the metal paste
Lid mask, the mask include that the pattern of transmission region and light tight region and the transmission region is electrode
Pattern, then carries out ultraviolet light polymerization so that the metal paste of the transmission region carries out photocuring reaction；
Preferably, the condition of the photocuring includes that UV energy is 500-3000mj/cm2。
5. method according to claim 3, wherein, when the photocuring is laser curing,
The mode of the photocuring is：Toward the surface needs of the silicon chip of solar cell for being coated with the metal paste
The region for forming electrode is irradiated using laser so that the metal paste on Jing laser-irradiated domains is carried out
Photocuring reaction；Preferably, the condition of the photocuring includes that laser energy is 500-3000mj/cm2。
6. method according to claim 1 and 2, wherein, the development liquid medicine is alcohols solvent
And/or tetramethylammonium hydroxide aqueous solution, preferably alcohols solvent or alcohols solvent and tetramethyl hydroxide
The mixture of aqueous ammonium.
7. method according to claim 1 and 2, wherein, the condition of the immersion includes：It is aobvious
The temperature of shadow liquid medicine is 10-80 DEG C, and soak time is 10-240s.
8. method according to claim 1 and 2, wherein, the condition of the high temperature sintering includes
Sintering temperature is 300-900 DEG C, and sintering time is 0.5-2 hours.
9. method according to claim 1 and 2, wherein, the mode of the surface metalation is
Nickel coating, copper plate and plating protection oxidant layer are carried out successively.
10. method according to claim 9, wherein, the protection oxidant layer is nickel dam and/or chromium
Layer.
11. methods according to claim 1 and 2, wherein, the method is additionally included in toward described in too
After the surface metallization slurry of positive energy cell silicon chip, before photocuring, by the solar cell silicon
Piece is to process 0.1-60min at 60-150 DEG C in temperature.
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