CN114388172B - Borosilicate glass slurry, selective emitter, preparation method and application - Google Patents
Borosilicate glass slurry, selective emitter, preparation method and application Download PDFInfo
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- CN114388172B CN114388172B CN202111669049.2A CN202111669049A CN114388172B CN 114388172 B CN114388172 B CN 114388172B CN 202111669049 A CN202111669049 A CN 202111669049A CN 114388172 B CN114388172 B CN 114388172B
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- 239000005388 borosilicate glass Substances 0.000 title claims abstract description 57
- 239000002002 slurry Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000009792 diffusion process Methods 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910021419 crystalline silicon Inorganic materials 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 41
- 229910052796 boron Inorganic materials 0.000 claims description 41
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 29
- 229910052710 silicon Inorganic materials 0.000 claims description 29
- 239000010703 silicon Substances 0.000 claims description 29
- 239000002994 raw material Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- -1 alcohol ester Chemical class 0.000 claims description 6
- 239000004065 semiconductor Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 4
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001856 Ethyl cellulose Substances 0.000 claims description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 2
- 229960001826 dimethylphthalate Drugs 0.000 claims description 2
- 229920001249 ethyl cellulose Polymers 0.000 claims description 2
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229940116411 terpineol Drugs 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims 1
- 229920002451 polyvinyl alcohol Polymers 0.000 claims 1
- 239000012808 vapor phase Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000007650 screen-printing Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000003723 Smelting Methods 0.000 description 9
- 238000000498 ball milling Methods 0.000 description 9
- 238000010791 quenching Methods 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 238000009837 dry grinding Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- 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
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Power Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Sustainable Energy (AREA)
- Sustainable Development (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention relates to borosilicate glass slurry, a selective emitter, a preparation method and application thereof, wherein the preparation method comprises the following steps: the invention provides borosilicate glass powder for a selective emitter and a preparation method thereof, wherein a borosilicate glass source with high purity is used for carrying out local high-temperature diffusion or laser diffusion to form a local heavily doped layer with good performance, shallow junction diffusion of other areas is kept, and the process is simple and practical. The p+ layer contact prepared by the borosilicate glass paste disclosed by the invention is combined with the processes of laser doping, single diffusion, screen printing and the like, so that the preparation process of the crystalline silicon heavily doped p+ layer can be effectively simplified, the high yield and low energy consumption of a crystalline silicon solar cell are met, and the production cost is reduced. The borosilicate glass paste provided by the invention can be used for forming a Selective Emitter (SE) of a TOPCO battery, so that the open-circuit voltage of the solar battery is improved, and the photoelectric conversion efficiency of the TOPCO battery is effectively improved.
Description
Technical Field
The invention relates to the field of semiconductor or crystalline silicon solar cells, and can be used for preparing high-quality heavily doped layers of semiconductor and crystalline silicon solar cells. The method is applied to the high-efficiency n-type TOPCon crystalline silicon solar cell/high-efficiency p-type TOPCon crystalline silicon solar cell structure, the p+ layer surface can rapidly realize the preparation of a local selective emitter p++ layer through high Wen Juyu diffusion or laser doping, the silver electrode contacts with the local heavily doped layer, the Schottky barrier is reduced, and good ohmic contact between the electrode and the silicon substrate can be realized.
Background
In the TOPCO battery as an important development direction of a photovoltaic battery, a doped layer coated with boron is generally used as a p+ layer structure of the TOPCO battery on a substrate layer, but the p+ layer structure is limited by the influence of a boron diffusion coefficient, the surface concentration is low, when aluminum-containing powder is added on high-conductivity silver powder to improve ohmic contact, the p+ doped layer is also dissolved by sputtering aluminum powder, the problem of high-temperature diffusion coefficient of boron is limited, the boron diffusion time is 2-3 times of that of phosphorus diffusion, the surface doping concentration is generally only reduced to about 1E 19-3E 19, the p+ layer diffusion sheet resistance is generally 80-120 omega/≡, and the probability of burning through p-n junction by sputtering aluminum powder is also increased. Even burn through the p-n junction, resulting in reduced cell open circuit voltage, fill factor, solar cell conversion efficiency.
Therefore, a heavily doped region is generally formed in the doped layer by local diffusion, boron is used as a lightly doped region to form different doping concentrations, for example, CN102709391B discloses a method for preparing a selective emitter solar cell, and a structural selective emitter SE is formed by alternately forming a highly doped and deeply diffused metal electrode region and a lightly doped and diffused non-metal electrode region.
But the current SE structure can be realized by a mask back etching mode and a laser local in-situ doping mode. The mask back etching process is complex, the diffusion time is long, and the cost is high. The laser local in-situ doping is to carry out local high-temperature diffusion on the original borosilicate glass layer with the well-diffused p+ layer by using a laser source again to form the p++ layer, the process is simple and quick, but limited by the boron content of the original borosilicate glass layer, the doping effect is poor, the high-efficiency doping requirement cannot be met, and the series resistance is increased due to the large surface sheet resistance, so that the conversion efficiency of the battery is influenced.
Disclosure of Invention
In order to solve the problems, the first aspect of the invention provides borosilicate glass slurry, which comprises the following preparation raw materials in percentage by weight:
10.0 to 80.0wt%, preferably 30.0 to 60.0 wt%, more preferably 45.0 to 55.0 wt% of borosilicate glass powder;
20.0 to 90.0wt% of an organic solvent or deionized water, preferably 30.0 to 60.0 wt%, more preferably 40.0 to 50.0wt%;
the resin is 0.1 to 20.0wt%, preferably 1.0 to 10.0 wt%, more preferably 3.0 to 7.0 wt%.
As a preferable technical scheme of the invention, the raw materials for preparing the borosilicate glass powder comprise a boron source, a silicon source and a third main group metal source.
The boron source is boron or boron oxide. In a doped layer in generalThe lightly doped region p+ layer is boron, and a boron source such as boron oxide (B) 2 O 3 ) The boron source is dissolved in a glass system, is taken as a trivalent boron source to be diffused to a silicon substrate at high temperature to form a p++ layer structure, and acts together with a lightly doped region to reduce electrode coverage, and is beneficial to reducing the softening temperature of slurry glass and improving wetting and leveling of the substrate, but the same main components of the two doped regions also cause the problems of limited boron content and the like during preparation, so that the reduction of contact resistance and the reduction of the p-n junction burning-through probability are influenced. The proportion of the boron source in the glass powder is 5.0-50.0wt%, preferably 10-35 wt%, more preferably 20-30 wt%.
The silicon source is silicon or silicon oxide. By adding a silicon source as a skeleton, and a silicon source such as acidic silicon oxide (SiO 2 ) The method is favorable for improving chemical stability and high-temperature fluidity and promoting boron diffusion, but the boron source and the silicon source have poor dispersion and compatibility, so that a uniform p++ structure is difficult to form. The proportion of the silicon source in the glass powder is 40-95.0wt%, preferably 50-80 wt%, more preferably 60.0-70.0wt%.
The third main group metal source is a third main group metal or an oxide of the third main group metal, and examples thereof include aluminum, indium, gallium, and oxides thereof, such as aluminum oxide (Al 2 O 3 ) Indium oxide (In) 2 O 3 ) Gallium oxide (Ga) 2 O 3 ). In order to improve the dispersion compatibility of the boron source and the silicon source, other third main group metal sources can be added, wherein the inventor also finds that the addition of the third main group metal source is favorable for improving the doping characteristic, and the dispersion capability in molecules of the third main group metal source is favorable for promoting the compatibility of the boron source and the silicon source, but the larger dosage can influence the effect of the silicon substrate, and the proportion of the third main group metal source in the glass powder is 0-5.0wt%, preferably 0.5-3.0wt%, and more preferably 1.0-2.0wt% calculated according to the weight ratio.
The preparation method of borosilicate glass powder of the present invention includes, but is not limited to, a smelting ball milling method, a sol-gel sintering ball milling method, and a smelting dry milling method, wherein the smelting ball milling method is to weigh raw materials, mix, smelt at 800-1500 ℃, quench the raw materials by water quenching or dry quenching, dry-bake the raw materials, and ball mill the raw materials by water milling, solvent milling, and then dry the raw materials. The sol-gel sintering ball milling method is to prepare the raw materials into gel, and obtain the gel through high-temperature sintering ball milling. The smelting dry grinding method is obtained by weighing raw materials, mixing, smelting, quenching, drying, zirconium bead grinding or air flow grinding and the like.
As a preferable technical scheme of the invention, the organic solvent comprises at least one of diethylene glycol butyl ether acetate, alcohol ester twelve, terpineol, diethylene glycol butyl ether acetate, dimethyl adipate, N-methyl pyrrolidone, dimethyl phthalate and dimethyl terephthalate.
In addition, the inventor finds that by selecting proper resin, even mixing of borosilicate glass powder and high-concentration boron diffusion can be further promoted in the processes of subsequent high-temperature diffusion, local laser doping and the like, and efficient doping is promoted. As a preferred embodiment of the present invention, the resin includes at least one of ethylcellulose, hydroxyethylcellulose, PVB, polyvinylpyrrolidone, polyvinyl acetal Ding Quanzhi, and acrylic resin.
As a preferable technical scheme of the invention, the preparation raw materials of the slurry comprise 0.1-5.0 wt% of organic auxiliary agent according to weight percentage; the organic auxiliary agent comprises any one of an organic dispersing agent, a thixotropic agent, a slipping agent and a leveling agent, and the preferable proportion is 0.3-2.0 wt%, and more preferable proportion is 0.5-1.0 wt%.
As a preferable technical scheme of the invention, the granularity D50 (measured by a laser granularity distribution instrument) of the borosilicate glass powder is 0.1-5.0 mu m, preferably 0.5-3.0 mu m, and more preferably 1.0-2.0 mu m; the borosilicate glass powder has a specific surface area (BET specific surface area test method) of 0.5-3.0 m 2 Preferably 0.8 to 2.0 m 2 Preferably 1.0 to 1.5 m 2 /g; the Tg (differential thermal analysis test) of the borosilicate glass powder is 400-900 ℃, preferably 500-700 ℃, and more preferably 550-600 ℃.
The second aspect of the invention provides a selective emitter comprising a lightly doped region and a heavily doped region on a silicon substrate; the raw material of the lightly doped region is a gas-phase boron source, and the raw material of the heavily doped region is borosilicate glass slurry as described above.
The third aspect of the present invention provides a method for preparing a selective emitter, comprising:
and (3) forming a lightly doped region: high-temperature diffusion of a gas-phase boron source;
and (3) forming a heavily doped region: and (3) coating and drying the borosilicate glass slurry, and diffusing the gas-phase boron source at high temperature or after diffusing the gas-phase boron source.
In the formation of the heavily doped region, borosilicate glass slurry is coated, dried and locally doped by laser, and then vapor boron source is diffused at high temperature.
The preparation method of the doped layer provided by the invention can be selected from the three methods, wherein (1) before high-temperature diffusion of a conventional gas-phase boron source, borosilicate glass slurry with local patterns is screen-printed on the surface of a silicon wafer, then the silicon wafer is locally doped by laser after being dried, and after relevant slurry on the surface of the silicon wafer is cleaned, the silicon wafer and the conventional gas-phase boron source are simultaneously diffused to obtain an SE structure; (2) After the borosilicate glass slurry with the local pattern printed on the surface of the silicon wafer is dried, the borosilicate glass slurry is directly diffused with a conventional gas-phase boron source at the same time, and the borosilicate glass layer has high boron content, so that the local obviously high boron diffusion concentration can be obtained on the surface of the silicon wafer; (3) After the conventional gas-phase boron source is diffused at high temperature, borosilicate glass slurry with local patterns is screen printed on the surface of the silicon wafer, the local diffusion is carried out in a laser doping mode, and then the related cleaning is carried out.
The borosilicate glass slurry is coated on the surface of the silicon wafer, wherein the coating mode comprises any one of screen printing, ink-jet printing, spin coating and spray coating; and drying borosilicate glass slurry coated on the silicon surface, and adopting any one of laser doping and high-temperature diffusion to prepare the high-quality heavily-doped p++ layer selective emitter. And preparing silver-aluminum paste above the p++ layer of the TOPCO battery by a screen printing technology, and forming an electrode with good ohmic contact after high-temperature sintering at 720-820 ℃.
In a fourth aspect, the invention provides the use of borosilicate glass paste in semiconductor, crystalline silicon solar cells.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides borosilicate glass slurry for a selective emitter and a preparation method thereof, wherein a borosilicate glass source with high purity is used for carrying out local high-temperature diffusion or laser diffusion to form a local heavily doped layer with good performance, shallow junction diffusion of other areas is kept, and the process is simple and practical.
(2) The p+ layer contact prepared by the borosilicate glass paste disclosed by the invention is combined with the processes of laser doping, single diffusion, screen printing and the like, so that the preparation process of the crystalline silicon heavily doped p+ layer can be effectively simplified, the high yield and low energy consumption of a crystalline silicon solar cell are met, and the production cost is reduced.
(3) The borosilicate glass slurry provided by the invention can be used for forming a Selective Emitter (SE) of a TOPCO battery, a silicon wafer with higher sheet resistance except a heavily doped region is prepared, the metal-semiconductor contact performance of the silver aluminum slurry and a p+ layer of a crystalline silicon solar battery is optimized, the metal-induced recombination is reduced, the open-circuit voltage of the solar battery is improved, and the photoelectric conversion efficiency of the TOPCO battery is effectively improved.
Detailed Description
Examples
IV test of borosilicate glass powder, borosilicate glass paste and TOPCO cell provided in examples 1 to 4 and reference examples 1 to 4
Parameters (parameters)
Borosilicate glass powders provided in examples 1 to 4 and reference examples 1 to 4 were designed according to the following weight percentages as shown in table 1. The borosilicate glass slurry is prepared by adopting a smelting ball milling method, namely raw materials required by preparation are weighed, mixed and then smelted, wherein the smelting temperature is 1300 ℃ and the time is 1h, and the borosilicate glass powder with the granularity of about 1.0-1.5 mu m is obtained after ball milling in a solvent and drying after dry quenching. Borosilicate glass slurries prepared in examples 1-4 were used in laser SE structure preparation, and the related raw material formulations were designed as follows, with the glass frit contents in examples 1-4 being 50.0wt%,5wt% hydroxyethyl cellulose, 45wt% deionized water, calculated as weight ratio.
TABLE 1
Reference example 1 used a borosilicate-free glass paste doping process, i.e., a conventional gas phase boron source high temperature diffusion process. And (5) mixing and homogenizing the raw materials by adopting a three-roller mill after weighing to obtain a target product. Before high-temperature diffusion of a conventional gas-phase boron source, a target product is subjected to local laser doping after borosilicate glass slurry with local patterns is screen-printed on the surface of a silicon wafer is dried, and after relevant slurry on the surface of the silicon wafer is cleaned, the target product and the conventional gas-phase boron source are simultaneously diffused to obtain a SE structure. According to the preparation process of the TOPCO battery, the subsequent battery preparation process is completed, and finally the IV test parameters of the TOPCO battery are tested, as shown in Table 2.
TABLE 2
As can be seen from tables 1 and 2, reference example 1 has a good open circuit voltage, and series resistance and contact resistivity are high. The series resistance and FF are improved by the preparation of borosilicate glass SE structure, and the electrical property is improved by 0.11% at most.
IV test of borosilicate glass powder, borosilicate glass paste and TOPCO cell provided in examples 5 to 8 and reference examples 2 to 5
Parameters (parameters)
The conventional sheet resistance based on reference example 1 is only 110Ω/≡and there is room for improvement. The borosilicate glass slurries provided in examples 5-8 and reference examples 2-5 are designed according to the following weight percentage, the borosilicate glass slurries prepared in examples 5-8 and reference examples 2-5 are calculated according to the weight ratio, the borosilicate glass slurries comprise 50.0wt% of glass powder in examples 5-8 and reference examples 2-5, 5wt% of hydroxyethyl cellulose and 45wt% of deionized water, and are prepared by adopting a smelting ball milling method, namely raw materials required by preparation are weighed and mixed and smelted, the smelting temperature is 1300 ℃ for 1h, and the borosilicate glass powder with the granularity of about 1.0-1.5 mu m is obtained after ball milling in a solvent and drying. The sheet resistance of the p+ layer lightly doped region and the sheet resistance of the p++ layer of the locally doped heavily doped region are shown in Table 4.
TABLE 3 Table 3
TABLE 4 Table 4
The experimental designs of examples 5-8 and reference examples 2-5 were completed by adopting an N-TOPCO battery structure, using the same industrialized front silver-aluminum paste to print on the p+ layer of the N-TOPCO crystalline silicon substrate, drying to obtain a film thickness of 15 microns, and performing a current-voltage performance test on the obtained battery piece by sintering at 750-760 ℃, wherein the data comprise open circuit voltage (Voc), series resistance (Rs), fill Factor (FF) and conversion efficiency (Eta), as shown in a graph 4. The battery pieces of examples 2 to 5 and reference examples 5 to 8 were laser cut into specific patterns, and the contact resistivity of TOPCon solar cell electrodes was tested using TLM equipment, and the results are shown in table 5.
TABLE 5
The test result shows that the borosilicate glass slurry provided by the invention can be used for forming a Selective Emitter (SE) of a TOPCO battery, a silicon wafer with higher sheet resistance except a heavily doped region is prepared, the metal-semiconductor contact performance of the silver aluminum slurry and a p+ layer of a crystalline silicon solar battery is optimized, the metal-induced recombination is reduced, the open-circuit voltage of the solar battery is improved, the photoelectric conversion efficiency of the TOPCO battery is effectively improved, and the absolute value of the conversion efficiency can be improved by more than 0.4%.
Claims (5)
1. The borosilicate glass slurry is characterized by comprising the following preparation raw materials in percentage by weight:
10.0-80.0wt% of borosilicate glass powder; the borosilicate glass powder is prepared from a boron source, a silicon source and a third main group metal source;
20.0-90.0wt% of organic solvent or deionized water;
0.1-20.0wt% of resin;
0.1 to 5.0 weight percent of organic auxiliary agent;
the proportion of the boron source in the glass powder is 5.0-50.0wt% calculated according to the weight ratio; the proportion of the silicon source in the glass powder is 40-95.0wt% calculated according to the weight ratio; the proportion of the third main group metal source in the glass powder is 0-5.0wt% calculated according to the weight ratio;
the organic solvent comprises at least one of diethylene glycol butyl ether acetate, alcohol ester twelve, terpineol, diethylene glycol butyl ether acetate, dimethyl adipate, N-methylpyrrolidone, dimethyl phthalate and dimethyl terephthalate;
the resin comprises at least one of ethyl cellulose, hydroxyethyl cellulose, PVB, polyvinylpyrrolidone, polyvinyl alcohol Ding Quanzhi and acrylic resin;
the granularity D50 of the borosilicate glass powder is 0.1-5.0 mu m; the borosilicate glass powder has a specific surface area of 0.5-3.0 m 2 /g; the Tg of the borosilicate glass powder is 400-900 ℃.
2. A selective emitter comprising a lightly doped region and a heavily doped region on a silicon substrate; the raw material of the lightly doped region is a gas-phase boron source, and the raw material of the heavily doped region is the borosilicate glass paste of claim 1.
3. A method of preparing a selective emitter according to claim 2, comprising:
and (3) forming a lightly doped region: high-temperature diffusion of a gas-phase boron source;
and (3) forming a heavily doped region: and (3) coating and drying the borosilicate glass slurry, and diffusing the gas-phase boron source at high temperature or after diffusing the gas-phase boron source.
4. A method of fabricating a selective emitter according to claim 3, characterized in that in said heavily doped region formation, borosilicate glass paste is applied and baked, locally laser doped, and then vapor phase boron source is simultaneously diffused at high temperature.
5. Use of the borosilicate glass paste according to claim 1 in semiconductor, crystalline silicon solar cells.
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| CN105679400A (en) * | 2016-01-22 | 2016-06-15 | 四川银河星源科技有限公司 | Conductive paste for solar cell and preparation method of conductive paste |
| CN111106188A (en) * | 2019-12-17 | 2020-05-05 | 晶澳（扬州）太阳能科技有限公司 | N-type battery, preparation method of selective emitter of N-type battery and N-type battery |
| WO2020096478A1 (en) * | 2018-11-08 | 2020-05-14 | Общество с ограниченной ответственностью "Научное Предприятие Монокристалл Пасты" | Aluminum paste for producing a rear contact of silicon solar cells |
| CN113643841A (en) * | 2021-08-05 | 2021-11-12 | 江苏正能电子科技有限公司 | Acetate-resistant back silver, preparation method thereof and PERC battery comprising acetate-resistant back silver |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105679400A (en) * | 2016-01-22 | 2016-06-15 | 四川银河星源科技有限公司 | Conductive paste for solar cell and preparation method of conductive paste |
| WO2020096478A1 (en) * | 2018-11-08 | 2020-05-14 | Общество с ограниченной ответственностью "Научное Предприятие Монокристалл Пасты" | Aluminum paste for producing a rear contact of silicon solar cells |
| CN111106188A (en) * | 2019-12-17 | 2020-05-05 | 晶澳（扬州）太阳能科技有限公司 | N-type battery, preparation method of selective emitter of N-type battery and N-type battery |
| CN113643841A (en) * | 2021-08-05 | 2021-11-12 | 江苏正能电子科技有限公司 | Acetate-resistant back silver, preparation method thereof and PERC battery comprising acetate-resistant back silver |
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