CN110112227A - A kind of preparation method of the double layer antireflection coating for silicon solar cell - Google Patents
A kind of preparation method of the double layer antireflection coating for silicon solar cell Download PDFInfo
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- CN110112227A CN110112227A CN201910297255.1A CN201910297255A CN110112227A CN 110112227 A CN110112227 A CN 110112227A CN 201910297255 A CN201910297255 A CN 201910297255A CN 110112227 A CN110112227 A CN 110112227A
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 32
- 239000010703 silicon Substances 0.000 title claims abstract description 32
- 239000011248 coating agent Substances 0.000 title claims abstract description 28
- 238000000576 coating method Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000006117 anti-reflective coating Substances 0.000 claims abstract description 43
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims abstract description 26
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052709 silver Inorganic materials 0.000 claims abstract description 21
- 239000004332 silver Substances 0.000 claims abstract description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000137 annealing Methods 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 52
- 238000012545 processing Methods 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000005530 etching Methods 0.000 claims description 19
- 239000011159 matrix material Substances 0.000 claims description 19
- 238000004528 spin coating Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 18
- 230000004048 modification Effects 0.000 claims description 17
- 238000012986 modification Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 239000004280 Sodium formate Substances 0.000 claims description 11
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 11
- 235000019254 sodium formate Nutrition 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 230000005070 ripening Effects 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000011265 semifinished product Substances 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 239000003643 water by type Substances 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 229920000058 polyacrylate Polymers 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 69
- 239000010410 layer Substances 0.000 description 63
- 210000004027 cell Anatomy 0.000 description 15
- 239000000203 mixture Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000011521 glass Substances 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- 230000003667 anti-reflective effect Effects 0.000 description 5
- 239000000523 sample Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000003980 solgel method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- -1 ester acrylate Chemical class 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NYNKCGWJPNZJMI-UHFFFAOYSA-N Clebopride malate Chemical compound [O-]C(=O)C(O)CC(O)=O.COC1=CC(N)=C(Cl)C=C1C(=O)NC1CC[NH+](CC=2C=CC=CC=2)CC1 NYNKCGWJPNZJMI-UHFFFAOYSA-N 0.000 description 1
- 235000009161 Espostoa lanata Nutrition 0.000 description 1
- 240000001624 Espostoa lanata Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000010307 cell transformation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- 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
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- 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
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
-
- 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
- H01L31/1876—Particular processes or apparatus for batch treatment of the devices
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Sustainable Development (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Life Sciences & Earth Sciences (AREA)
- Power Engineering (AREA)
- Sustainable Energy (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention relates to a kind of preparation methods of double layer antireflection coating for silicon solar cell, belong to novel energy resource material technology field.The present invention is using the modified SiO of urethane acrylate2Film, urethane acrylate has ammonia ester bond, its main feature is that the high-polymer molecule interchain can form a variety of hydrogen bonds, optical property and weatherability with high-wearing feature, adhesion strength, flexibility, high-peeling strength and excellent resistance to low temperature and polyacrylate brilliance, so that modified second layer antireflective coating has excellent mechanical endurance and flexibility, elongation at break is high；The present invention is using silver mirror reaction and annealing is combined to prepare Nano silver grain as first layer antireflective coating in substrate surface, formation in the silver nano-grain of random distribution is metal thermodynamics and the coefficient result of dynamics, when short annealing, silverskin system obtains enough kinetic energy, is intended to the lesser nanoparticle structure of surface area.
Description
Technical field
The present invention relates to a kind of preparation methods of double layer antireflection coating for silicon solar cell, belong to new energy materials
Technical field.
Background technique
Silicon solar cell transformation efficiency adequately effectively is improved using solar energy, is that current silicon solar cell urgently solves
Certainly the problem of.Solar energy is the inexhaustible renewable energy of the mankind and clean energy resource, and generation environment is not dirty
Dye, silicon solar cell are the devices for solar energy being converted into electric energy, and the refractive index of silicon is 3.42, are radiated on silicon substrate
A big chunk sunlight is reflected, and silion cell is not high to the utilization rate of sunlight, so that making the transformation efficiency of battery reduces,
People use new technology to surface texture and back side diffusion the emitter passivation of battery, so that the transformation efficiency of solar battery
It increases, and common method is to plate the good antireflective coating of one or more layers optical property in solar cell surface, it can
To eliminate or reduce the reflection of device surface light to increase the transmitance of light, and then in display, laser system and solar energy
The fields such as battery are widely used.
Antireflective coating is a kind of optical coating being of wide application, and is widely used in daily life, industry, astronomy
The fields such as, military science, electronics, such as: applying a thin layer of film in lens surface prevents the light of the reflective of glasses and raising glasses
Learn performance；Counterfeit money in order to prevent, using the clast of some films play the role of antireflective reach distinguish true from false, electrofax is set
Standby, precision instrument probe camera lens etc. can all use antireflective coating；It is various each as microelectronics industry and computer quickly develop
The film of the different performance of sample is studied, and the anti-dazzle electrostatic prevention film of display and eye protective screen of computer become the new application neck of antireflective coating
Domain has a vast market foreground.Antireflective coating for solar battery will not only have low antireflective rate, but also have
There is good physical and chemical performance.Improve common two approach of solar battery efficiency: (1) coated with antireflection film；(2) make the sun
Energy battery surface has uneven structure.The transmitance for increasing light by plated film improves the efficiency of battery, such as: porous two
Silicon oxide film makes the transformation efficiency of battery improve 5-6%, and wherein porous structure can also improve the breaking resistance of matrix；Nitridation
Silicon fiml makes the transformation efficiency of battery be increased to 16.7%, and film compactness is good and can be passivated the defect of silicon chip surface；Titanium dioxide
With zirconium oxide film can improve glass matrix alkali resistance and waterproof and dampproof performance；Secondly at can also be to battery surface
Reason, makes it have certain concave/convex-shaped structure, makes the sunlight of all directions incidence that can enter sun electricity after multiple reflections
In pond, to increase incident sunlight, so that cell conversion efficiency greatly improves.
Antireflection film generallys use the alternate multilayer alternating of single layer anti reflective coating, double layer antireflection coating, high low-refraction
The methods of anti-reflection film system and gradually changed refractive index film obtain.Aciding, magnetron sputtering method, gas can be divided into according to the method for plated film
Phase sedimentation and sol-gel method etc..Aciding makes glass surface corrosion obtain refractive index using analysis alkali, except modes such as silicon
Much lower hole surface film, the refractive index of film are then adjusted by voidage.Magnetron sputtering method refers to be splashed under vacuum conditions
The alternate material of high low-refraction is penetrated to glass surface, double-deck, three layers, four layers or more of antireflection film system may be selected, lead to
It crosses the refractive index for controlling film layer and thickness and achievees the purpose that destructive interference.Gas phase deposition technology is to utilize the object occurred in gas phase
Reason and chemical reaction process generate decorative or functional metal, nonmetallic or compound film technology in glass surface, are
One of the method for commonly preparing double-layer reflection reducing coating film can obtain the film of different stacking densities by changing the angle of deposition
Layer, the refractive index of film layer is gradual change, but the resistance to delineation ability of film layer is weaker.Sol-gel method is prepared in wet chemical method
One of common method of thin-film material, metallic compound through solution, colloidal sol, gel and solidify, it is thermally treated at a lower temperature
Generate nanoparticle.
Under the conditions of current technology, it is difficult to increase battery by the processing of silicon wafer and the improvement of encapsulation technology merely
Power, and the transmitance by improving photovoltaic glass can increase the energy of photoelectric conversion, promote generating efficiency, be that current industry is closed
The hot spot of note and important developing direction.Develop the anti-reflection ultrawhite pressure with high transmission in solar battery response spectral range
Figured plate glass, can equal extent raising solar cell power generation efficiency, have extraordinary economic prospect.Photovoltaic is with subtracting
The popularization and application for reflecting film glass promote solar cell power generation for the reduction of the raising of the efficiency of solar battery, cost
Competitiveness, have the function of for the period of cost recovery that generates electricity by way of merging two or more grid systems of shortening positive.
Summary of the invention
The technical problems to be solved by the invention: it for the problem that existing antireflective coating hardness is low, crocking resistance is poor, mentions
A kind of preparation method of double layer antireflection coating for silicon solar cell is supplied.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
(1) it is that 2% sodium formate solution and silver ammino solution mix and be placed in matrix surface by mass fraction, heats to get metal
Film handles metal film short annealing to get first layer antireflective coating；
(2) taking ethyl orthosilicate, dehydrated alcohol, mass fraction is 3% hydrochloric acid, deionized water, urethane acrylate, by positive silicon
Acetoacetic ester, dehydrated alcohol, mass fraction are that 3% hydrochloric acid and deionized water mix, and stir and ripening is to get colloidal sol, in colloidal sol
Middle addition urethane acrylate, is stirred processing, is cooled to room temperature to get modification sol；
(3) substrate preheating with first layer antireflective coating is handled, modification sol is dripped on the surface of first layer antireflective coating
On, spin-coat process is to get semi-finished product film；Double of finished film performs etching processing to get second layer antireflective coating, is as used for silicon
The double layer antireflection coating of solar battery.
The preparation step of silver ammino solution described in step (1) are as follows: in mass ratio 1: 1: 1 is molten for 2% silver nitrate by mass fraction
Liquid, mass fraction are 1% sodium hydroxide solution and mass fraction is that 10% ammonium hydroxide is uniformly mixed to get silver ammino solution.
Heat treatment step described in step (1) are as follows: mass fraction is 2% sodium formate solution and silver-colored ammonia by 1: 1 by volume
Solution mixing is placed in matrix surface, heats 1~2min at being 50~70 DEG C in bath temperature.
Short annealing processing step described in step (1) are as follows: by metal film in temperature be 300~350 DEG C, nitrogen flow is
Short annealing handles 1~2h under 2L/min.
Ethyl orthosilicate described in step (2), dehydrated alcohol, mass fraction are 3% hydrochloric acid, deionized water, polyurethane propylene
Ratio between acid esters is respectively as follows: according to parts by weight, weighs 30~40 parts of ethyl orthosilicates, 50~60 parts of anhydrous second respectively
Alcohol, 1~10 part of mass fraction are 3% hydrochloric acid, 20~30 parts of deionized waters, 10~20 parts of urethane acrylates.
Stirring described in step (2) and ripening step are as follows: by ethyl orthosilicate, dehydrated alcohol, mass fraction 3%
Hydrochloric acid and deionized water mixing, low whipping speed are after stirring 1~2h under 400~500r/min at room temperature still aging 1~2
It.
Step is stirred processing step described in (2) are as follows: urethane acrylate is added in colloidal sol, is in temperature
110~120 DEG C, mixing speed is to be stirred 20~30min under 300~400r/min.
The pre-heat treatment step described in step (3) are as follows: by with first layer antireflective coating matrix temperature be 180~
3~5min is preheated at 190 DEG C.
Spin-coat process step described in step (3) are as follows: by modification sol drop on the surface of first layer antireflective coating, turning
Speed is that 3~5 layers of spin coating are repeated under 3000~3100r/min, and the time of each spin coating is 30~40s, in temperature after each spin coating
It is to retract 20~40min of processing at 400~600 DEG C, is cooled to room temperature.
Etch processing steps described in step (3) are as follows: using SF6 as etching gas, in the condition of 200~250W of power
Lower double of finished film performs etching processing.
The present invention is compared with other methods, and advantageous effects are:
(1) present invention using silver mirror reaction and combines annealing to prepare Nano silver grain as first layer anti-reflection in substrate surface
Film is penetrated, prepares silicon dioxide gel under acidic catalysis conditions with ethyl orthosilicate and ethyl alcohol, with the polyurethane third of high refractive index
The silicon dioxide gel of the ester modified preparation of olefin(e) acid lifts plated film, reacted ion etch process, in substrate surface by spin-coating method
One layer of nano moth-eye antireflection structure is formed as second layer antireflective coating, two layers of antireflective coating is compound, and preparing has well
The double layer antireflection coating of mechanical strength and crocking resistance；
(2) present invention uses ion etch process, one layer of nano moth-eye antireflection structure is formed in substrate surface, with etch period
Increase, etching depth increases, while nanostructure is changed from column to cone cell, and the width of nano moth-eye structure increases, the upper half
Sidewall, then gradually smooth at bottom, this pattern has continuous refractive index gradient, is advantageously implemented anti-reflection effect, with
Etching depth further increases, and average reflectance reduces, this is beneficial to the absorption efficiency for improving silica-based solar cell；Due to
Random structure is advantageously implemented more smooth gradually changed refractive index in the randomness of pattern and arrangement, thus will also obtain more
Superior anti-reflection anti-reflection effect；Nano moth-eye structure, by forming characteristic size 200nm nano junction below in body surface
Structure is equivalent to one layer of graded index interface, can be effectively reduced surface reflection；
(3) silica dioxide antireflection film is prepared using sol-gel method in the present invention, sol-gel method operates simple, environment temperature
Performance low, that doping and the film of being prepared can be controlled well is spent, and all size can be prepared on various substrates
With film of various shapes, SiO2Density of film is low, refractive index is adjustable, thermal stability is high, acoustic propagation velocity is low and easily prepared
The features such as；
(3) present invention is using the modified SiO of urethane acrylate2Film, urethane acrylate have ammonia ester bond, its main feature is that
The high-polymer molecule interchain can form a variety of hydrogen bonds, have high-wearing feature, adhesion strength, flexibility, high-peeling strength and excellent
The optical property and weatherability of resistance to low temperature and polyacrylate brilliance, so that modified second layer antireflective coating has
Excellent mechanical endurance and flexibility, elongation at break are high；
(4) present invention using silver mirror reaction and combines annealing to prepare Nano silver grain as first layer anti-reflection in substrate surface
Film is penetrated, the formation in the silver nano-grain of random distribution is that metal thermodynamics and dynamics are coefficient as a result, ought quickly move back
When fiery, silverskin system obtains enough kinetic energy, is intended to the lesser nanoparticle structure of surface area.
Specific embodiment
Mass fraction is 2% silver nitrate solution by mass ratio 1: 1: 1, mass fraction is 1% sodium hydroxide solution and quality
Score is that 10% ammonium hydroxide is uniformly mixed to get silver ammino solution, and mass fraction is 2% sodium formate solution and silver-colored ammonia by 1: 1 by volume
Solution mixing is placed in matrix surface, heats 1~2min at being 50~70 DEG C in bath temperature to get metal film, metal film is existed
Temperature is 300~350 DEG C, and nitrogen flow is that short annealing handles 1~2h to get first layer antireflective coating under 2L/min；By weight
Measure number meter, weigh respectively 30~40 parts of ethyl orthosilicates, 50~60 parts of dehydrated alcohols, 1~10 part of mass fraction be 3% hydrochloric acid,
Ethyl orthosilicate, dehydrated alcohol, mass fraction are 3% salt by 20~30 parts of deionized waters, 10~20 parts of urethane acrylates
Acid and deionized water mixing, low whipping speed are still aging 1~2 day at room temperature after stirring 1~2h under 400~500r/min,
Up to colloidal sol, urethane acrylate is added in colloidal sol, is 110~120 DEG C in temperature, mixing speed is 300~400r/
It is stirred 20~30min under min, is cooled to room temperature to get modification sol；By the matrix with first layer antireflective coating in temperature
Degree is that 3~5min is preheated at 180~190 DEG C, is 3000 in revolving speed by modification sol drop on the surface of first layer antireflective coating
3~5 layers of spin coating are repeated under~3100r/min, time of each spin coating is 30~40s, after each spin coating temperature be 400~
20~40min of processing is retracted at 600 DEG C, is cooled to room temperature to get semi-finished product film；Using SF6 as etching gas, in power
Double of finished film performs etching processing to get second layer antireflective coating, as silicon solar electricity under conditions of 200~250W
The double layer antireflection coating in pond.
It is that 2% sodium formate solution and silver ammino solution mix and be placed in matrix surface by mass fraction, heats to get metal
Film handles metal film short annealing to get first layer antireflective coating；Take ethyl orthosilicate, dehydrated alcohol, mass fraction 3%
Ethyl orthosilicate, dehydrated alcohol, mass fraction are 3% hydrochloric acid and deionized water by hydrochloric acid, deionized water, urethane acrylate
Mixing, is stirred and ripening is to get colloidal sol, and urethane acrylate is added in colloidal sol, is stirred processing, is cooled to room
Temperature is to get modification sol；Substrate preheating with first layer antireflective coating is handled, modification sol is dripped in first layer antireflective
On the surface of film, spin-coat process is to get semi-finished product film；To get second layer antireflective coating, i.e., double of finished film performs etching processing
For the double layer antireflection coating for silicon solar cell.The preparation step of silver ammino solution are as follows: in mass ratio 1: 1: 1 by mass fraction
For 2% silver nitrate solution, mass fraction be 1% sodium hydroxide solution and mass fraction is that 10% ammonium hydroxide is uniformly mixed molten to get silver-colored ammonia
Liquid.Heat treatment step are as follows: mass fraction is that 2% sodium formate solution and silver ammino solution mix and be placed in matrix table by 1: 1 by volume
1min is heated at being 50 DEG C in bath temperature in face.Short annealing processing step are as follows: by metal film temperature be 300 DEG C, nitrogen stream
Amount is that short annealing handles 1h under 2L/min.Ethyl orthosilicate, dehydrated alcohol, mass fraction are 3% hydrochloric acid, deionized water, poly- ammonia
Ratio between ester acrylate is respectively as follows: according to parts by weight, weighs 30 parts of ethyl orthosilicates, 50 parts of dehydrated alcohols, 1 respectively
Part mass fraction is 3% hydrochloric acid, 20 parts of deionized waters, 10 parts of urethane acrylates.Stir simultaneously ripening step are as follows: will just
Silester, dehydrated alcohol, mass fraction are that 3% hydrochloric acid and deionized water mix, and low whipping speed is to stir 1h under 400r/min
Afterwards, at room temperature still aging 1 day.It is stirred processing step are as follows: urethane acrylate is added in colloidal sol, is in temperature
110 DEG C, mixing speed is to be stirred 20min under 300r/min.The pre-heat treatment step are as follows: first layer antireflective coating will be had
Matrix preheats 3min at being 180 DEG C in temperature.Spin-coat process step are as follows: drip modification sol on the surface of first layer antireflective coating
On, 3 layers of spin coating are repeated in the case where revolving speed is 3000r/min, time of each spin coating is 30s, in temperature is 400 DEG C after each spin coating
Under retract processing 20min, be cooled to room temperature.Etch processing steps are as follows: using SF6 as etching gas, in the item of power 200W
Double of finished film performs etching processing under part.
It is that 2% sodium formate solution and silver ammino solution mix and be placed in matrix surface by mass fraction, heats to get metal
Film handles metal film short annealing to get first layer antireflective coating；Take ethyl orthosilicate, dehydrated alcohol, mass fraction 3%
Ethyl orthosilicate, dehydrated alcohol, mass fraction are 3% hydrochloric acid and deionized water by hydrochloric acid, deionized water, urethane acrylate
Mixing, is stirred and ripening is to get colloidal sol, and urethane acrylate is added in colloidal sol, is stirred processing, is cooled to room
Temperature is to get modification sol；Substrate preheating with first layer antireflective coating is handled, modification sol is dripped in first layer antireflective
On the surface of film, spin-coat process is to get semi-finished product film；To get second layer antireflective coating, i.e., double of finished film performs etching processing
For the double layer antireflection coating for silicon solar cell.The preparation step of silver ammino solution are as follows: in mass ratio 1: 1: 1 by mass fraction
For 2% silver nitrate solution, mass fraction be 1% sodium hydroxide solution and mass fraction is that 10% ammonium hydroxide is uniformly mixed molten to get silver-colored ammonia
Liquid.Heat treatment step are as follows: mass fraction is that 2% sodium formate solution and silver ammino solution mix and be placed in matrix table by 1: 1 by volume
1min is heated at being 60 DEG C in bath temperature in face.Short annealing processing step are as follows: by metal film temperature be 325 DEG C, nitrogen stream
Amount is that short annealing handles 1h under 2L/min.Ethyl orthosilicate, dehydrated alcohol, mass fraction are 3% hydrochloric acid, deionized water, poly- ammonia
Ratio between ester acrylate is respectively as follows: according to parts by weight, weighs 35 parts of ethyl orthosilicates, 55 parts of dehydrated alcohols, 5 respectively
Part mass fraction is 3% hydrochloric acid, 25 parts of deionized waters, 15 parts of urethane acrylates.Stir simultaneously ripening step are as follows: will just
Silester, dehydrated alcohol, mass fraction are that 3% hydrochloric acid and deionized water mix, and low whipping speed is to stir 1h under 450r/min
Afterwards, at room temperature still aging 1 day.It is stirred processing step are as follows: urethane acrylate is added in colloidal sol, is in temperature
115 DEG C, mixing speed is to be stirred 25min under 350r/min.The pre-heat treatment step are as follows: first layer antireflective coating will be had
Matrix preheats 4min at being 185 DEG C in temperature.Spin-coat process step are as follows: drip modification sol on the surface of first layer antireflective coating
On, 4 layers of spin coating are repeated in the case where revolving speed is 3050r/min, time of each spin coating is 35s, in temperature is 500 DEG C after each spin coating
Under retract processing 30min, be cooled to room temperature.Etch processing steps are as follows: using SF6 as etching gas, in the item of power 225W
Double of finished film performs etching processing under part.
It is that 2% sodium formate solution and silver ammino solution mix and be placed in matrix surface by mass fraction, heats to get metal
Film handles metal film short annealing to get first layer antireflective coating；Take ethyl orthosilicate, dehydrated alcohol, mass fraction 3%
Ethyl orthosilicate, dehydrated alcohol, mass fraction are 3% hydrochloric acid and deionized water by hydrochloric acid, deionized water, urethane acrylate
Mixing, is stirred and ripening is to get colloidal sol, and urethane acrylate is added in colloidal sol, is stirred processing, is cooled to room
Temperature is to get modification sol；Substrate preheating with first layer antireflective coating is handled, modification sol is dripped in first layer antireflective
On the surface of film, spin-coat process is to get semi-finished product film；To get second layer antireflective coating, i.e., double of finished film performs etching processing
For the double layer antireflection coating for silicon solar cell.The preparation step of silver ammino solution are as follows: in mass ratio 1: 1: 1 by mass fraction
For 2% silver nitrate solution, mass fraction be 1% sodium hydroxide solution and mass fraction is that 10% ammonium hydroxide is uniformly mixed molten to get silver-colored ammonia
Liquid.Heat treatment step are as follows: mass fraction is that 2% sodium formate solution and silver ammino solution mix and be placed in matrix table by 1: 1 by volume
2min is heated at being 70 DEG C in bath temperature in face.Short annealing processing step are as follows: by metal film temperature be 350 DEG C, nitrogen stream
Amount is that short annealing handles 2h under 2L/min.Ethyl orthosilicate, dehydrated alcohol, mass fraction are 3% hydrochloric acid, deionized water, poly- ammonia
Ratio between ester acrylate is respectively as follows: according to parts by weight, weigh respectively 40 parts of ethyl orthosilicates, 60 parts of dehydrated alcohols,
10 parts of mass fractions are 3% hydrochloric acid, 30 parts of deionized waters, 20 parts of urethane acrylates.Stir simultaneously ripening step are as follows: will
Ethyl orthosilicate, dehydrated alcohol, mass fraction are that 3% hydrochloric acid and deionized water mix, and low whipping speed is to stir under 500r/min
After 2h, still aging 2 days at room temperature.It is stirred processing step are as follows: urethane acrylate is added in colloidal sol, is in temperature
120 DEG C, mixing speed is to be stirred 30min under 400r/min.The pre-heat treatment step are as follows: first layer antireflective coating will be had
Matrix preheats 5min at being 190 DEG C in temperature.Spin-coat process step are as follows: drip modification sol on the surface of first layer antireflective coating
On, 5 layers of spin coating are repeated in the case where revolving speed is 3100r/min, time of each spin coating is 40s, in temperature is 600 DEG C after each spin coating
Under retract processing 40min, be cooled to room temperature.Etch processing steps are as follows: using SF6 as etching gas, in the item of power 250W
Double of finished film performs etching processing under part.
Reference examples: the double layer antireflection coating of Dongguan company production.
The double layer antireflection coating that embodiment and reference examples are prepared is detected, specific detection is as follows:
With the transmitance of ultraviolet-visible spectrometer testing film.
The crocking resistance of film is tested: being tested crocking resistance with wipe method, is used the cotton ball for being moistened with ethyl alcohol in experiment
The surface of film is wiped, film surface appearance and test light transmission rate are observed, determines that the crocking resistance of film is strong and weak.
It is tested with hardness of the pencil hardometer to film and (sample surfaces is delineated with the power of 1kg), will be installed first
Pencil hardometer put down gently on determinand surface, then pushed ahead with certain speed, whether to visually observe sample surfaces
It scratches, pencil is from firmly to soft test, finally until pen tip will not scratch film surface completely.
Specific test result such as table 1.
1 performance characterization contrast table of table
| Detection project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Reference examples |
| Transmitance/% | 88.9 | 88.8 | 86.2 | 50.1 |
| Crocking resistance | It is not damaged | It is not damaged | It is not damaged | It has damage |
| Hardness/H | 4 | 4 | 4 | 3 |
As shown in Table 1, double layer antireflection coating prepared by the present invention has good hardness and crocking resistance.
Claims (10)
1. a kind of preparation method of the double layer antireflection coating for silicon solar cell, it is characterised in that specific preparation step are as follows:
(1) it is that 2% sodium formate solution and silver ammino solution mix and be placed in matrix surface by mass fraction, heats to get metal
Film handles metal film short annealing to get first layer antireflective coating；
(2) taking ethyl orthosilicate, dehydrated alcohol, mass fraction is 3% hydrochloric acid, deionized water, urethane acrylate, by positive silicon
Acetoacetic ester, dehydrated alcohol, mass fraction are that 3% hydrochloric acid and deionized water mix, and stir and ripening is to get colloidal sol, in colloidal sol
Middle addition urethane acrylate, is stirred processing, is cooled to room temperature to get modification sol；
(3) substrate preheating with first layer antireflective coating is handled, modification sol is dripped on the surface of first layer antireflective coating
On, spin-coat process is to get semi-finished product film；Double of finished film performs etching processing to get second layer antireflective coating, is as used for silicon
The double layer antireflection coating of solar battery.
2. a kind of preparation method of double layer antireflection coating for silicon solar cell according to claim 1, feature
Be: the preparation step of silver ammino solution described in step (1) are as follows: in mass ratio 1: 1: 1 by mass fraction be 2% silver nitrate solution,
Mass fraction is 1% sodium hydroxide solution and mass fraction is that 10% ammonium hydroxide is uniformly mixed to get silver ammino solution.
3. a kind of preparation method of double layer antireflection coating for silicon solar cell according to claim 1, feature
It is: heat treatment step described in step (1) are as follows: mass fraction is that 2% sodium formate solution and silver-colored ammonia are molten by 1: 1 by volume
Liquid mixing is placed in matrix surface, heats 1~2min at being 50~70 DEG C in bath temperature.
4. a kind of preparation method of double layer antireflection coating for silicon solar cell according to claim 1, feature
Be: short annealing processing step described in step (1) are as follows: by metal film temperature be 300~350 DEG C, nitrogen flow 2L/
Short annealing handles 1~2h under min.
5. a kind of preparation method of double layer antireflection coating for silicon solar cell according to claim 1, feature
Be: ethyl orthosilicate described in step (2), dehydrated alcohol, mass fraction are 3% hydrochloric acid, deionized water, polyurethane acroleic acid
Ratio between ester is respectively as follows: according to parts by weight, weighs 30~40 parts of ethyl orthosilicates, 50~60 parts of dehydrated alcohols, 1 respectively
~10 parts of mass fractions are 3% hydrochloric acid, 20~30 parts of deionized waters, 10~20 parts of urethane acrylates.
6. a kind of preparation method of double layer antireflection coating for silicon solar cell according to claim 1, feature
It is: stirring described in step (2) and ripening step are as follows: by ethyl orthosilicate, dehydrated alcohol, mass fraction be 3% hydrochloric acid
It is mixed with deionized water, low whipping speed is still aging 1~2 day at room temperature after stirring 1~2h under 400~500r/min.
7. a kind of preparation method of double layer antireflection coating for silicon solar cell according to claim 1, feature
Be: step is stirred processing step described in (2) are as follows: urethane acrylate is added in colloidal sol, temperature be 110~
120 DEG C, mixing speed is to be stirred 20~30min under 300~400r/min.
8. a kind of preparation method of double layer antireflection coating for silicon solar cell according to claim 1, feature
Be: the pre-heat treatment step described in step (3) are as follows: by with first layer antireflective coating matrix temperature be 180~190 DEG C
3~5min of lower preheating.
9. a kind of preparation method of double layer antireflection coating for silicon solar cell according to claim 1, feature
It is: spin-coat process step described in step (3) are as follows: by modification sol drop on the surface of first layer antireflective coating, in revolving speed
To repeat 3~5 layers of spin coating under 3000~3100r/min, the time of each spin coating is 30~40s, is in temperature after each spin coating
20~40min of processing is retracted at 400~600 DEG C, is cooled to room temperature.
10. a kind of preparation method of double layer antireflection coating for silicon solar cell according to claim 1, feature
It is: etch processing steps described in step (3) are as follows: using SF6 as etching gas, under conditions of 200~250W of power
Double of finished film performs etching processing.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110673236A (en) * | 2019-10-14 | 2020-01-10 | 宁波盈瑞聚合科技有限公司 | Anti-glare optical film and production method thereof |
| CN111312797A (en) * | 2020-04-02 | 2020-06-19 | 武汉华星光电半导体显示技术有限公司 | Display panel and manufacturing method thereof |
| CN113102202A (en) * | 2021-04-06 | 2021-07-13 | 吉林大学 | Preparation method of butterfly compound eye imitation opal secondary structure high-transmittance antireflection film |
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2019
- 2019-04-15 CN CN201910297255.1A patent/CN110112227A/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110673236A (en) * | 2019-10-14 | 2020-01-10 | 宁波盈瑞聚合科技有限公司 | Anti-glare optical film and production method thereof |
| CN110673236B (en) * | 2019-10-14 | 2021-08-17 | 宁波盈瑞聚合科技有限公司 | Anti-glare optical film and production method thereof |
| CN111312797A (en) * | 2020-04-02 | 2020-06-19 | 武汉华星光电半导体显示技术有限公司 | Display panel and manufacturing method thereof |
| WO2021196400A1 (en) * | 2020-04-02 | 2021-10-07 | 武汉华星光电半导体显示技术有限公司 | Display panel and manufacturing method therefor |
| US11937482B2 (en) | 2020-04-02 | 2024-03-19 | Wuhan China Star Optoelectronics Semiconductor Display Technology Co., Ltd. | Display panel with color organic light-transmissive thin films and manufacturing method thereof |
| CN113102202A (en) * | 2021-04-06 | 2021-07-13 | 吉林大学 | Preparation method of butterfly compound eye imitation opal secondary structure high-transmittance antireflection film |
| CN113102202B (en) * | 2021-04-06 | 2022-05-24 | 吉林大学 | Preparation method of butterfly compound eye imitation opal secondary structure high-transmittance antireflection film |
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