CN114388172A - 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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- CN114388172A CN114388172A CN202111669049.2A CN202111669049A CN114388172A CN 114388172 A CN114388172 A CN 114388172A CN 202111669049 A CN202111669049 A CN 202111669049A CN 114388172 A CN114388172 A CN 114388172A
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- borosilicate glass
- doped region
- slurry
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- boron source
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- 239000005388 borosilicate glass Substances 0.000 title claims abstract description 64
- 239000002002 slurry Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000009792 diffusion process Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910021419 crystalline silicon Inorganic materials 0.000 claims abstract description 13
- 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 27
- 229910052710 silicon Inorganic materials 0.000 claims description 27
- 239000010703 silicon Substances 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 239000004065 semiconductor Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- -1 dodecyl alcohol ester Chemical class 0.000 claims description 5
- 239000003960 organic solvent Substances 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
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 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
- 239000002245 particle Substances 0.000 claims description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 2
- 239000004925 Acrylic resin Substances 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
- 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
- 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
- LQZZUXJYWNFBMV-UHFFFAOYSA-N ethyl butylhexanol Natural products CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000007650 screen-printing Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 11
- 238000000498 ball milling Methods 0.000 description 9
- 238000003723 Smelting Methods 0.000 description 8
- 238000010791 quenching Methods 0.000 description 6
- 230000000171 quenching effect Effects 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009837 dry grinding Methods 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
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000003801 milling Methods 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
- IFPMZBBHBZQTOV-UHFFFAOYSA-N 1,3,5-trinitro-2-(2,4,6-trinitrophenyl)-4-[2,4,6-trinitro-3-(2,4,6-trinitrophenyl)phenyl]benzene Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C(C=2C(=C(C=3C(=CC(=CC=3[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)C(=CC=2[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O)=C1[N+]([O-])=O IFPMZBBHBZQTOV-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010296 bead milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 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
- 150000002148 esters Chemical class 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052733 gallium 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
- 238000010902 jet-milling Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 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
- 239000005368 silicate glass Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 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
- 239000012808 vapor phase Substances 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 C03C, in particular to borosilicate glass slurry, a selective emitter, a preparation method and application, wherein the borosilicate glass slurry comprises the following components: the invention provides borosilicate glass powder, and a borosilicate glass slurry for a selective emitter and a preparation method thereof. (2) The p + layer prepared by the borosilicate glass paste is contacted, and the processes of laser doping, single diffusion, screen printing and the like are combined, so that the preparation process of the crystalline silicon heavily doped p + layer can be effectively simplified, the high productivity and low energy consumption of the crystalline silicon solar cell are met, and the production cost is reduced. The borosilicate glass slurry provided by the invention can be used for forming a TOPCon battery Selective Emitter (SE), so that the open-circuit voltage of a solar battery is improved, and the photoelectric conversion efficiency of the TOPCon battery is effectively improved.
Description
Technical Field
The invention relates to C03C, in particular to a preparation method of a high-quality heavily doped layer for a semiconductor or crystalline silicon solar cell, which belongs to the field of semiconductor or crystalline silicon solar cells. The method is applied to a high-efficiency n-type TOPCon crystalline silicon solar cell/high-efficiency p-type TOPCon crystalline silicon solar cell structure, the preparation of a p + + layer of a local selective emitter can be quickly realized on the surface of a p + layer through high-temperature local diffusion or laser doping, a silver electrode of the p + + layer is in contact with a local heavily doped layer, a Schottky barrier is reduced, and good ohmic contact between the electrode and a silicon substrate can be realized.
Background
The TOPCon battery is taken as an important direction of photovoltaic battery development, a boron doped layer is generally coated on a substrate layer to be used as a p + layer structure of the TOPCon battery, but the TOPCon battery is limited by the influence of boron diffusion coefficient, the surface concentration of the TOPCon battery 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 aluminum powder sputtering, the TOPCon battery is limited by the problem of boron high-temperature diffusion coefficient, the boron diffusion time is 2-3 times of phosphorus diffusion, the surface doping concentration is generally only reduced by about 1E 19-3E 19, the p + layer diffusion sheet resistance is generally 80-120 omega/□, and the probability that the aluminum powder burns through a p-n junction in a sputtering mode is also increased. Even burning through the p-n junction, reduces the cell open circuit voltage, fill factor, and solar cell conversion efficiency.
Therefore, a heavily doped region is generally formed in the doped layer by local diffusion, and boron is used as a lightly doped region to form different doping concentrations, for example, CN102709391B discloses a method for manufacturing a selective emitter solar cell, which forms a selective emitter SE with a structure of alternating highly doped and deeply diffused metal electrode regions and lowly doped and lightly diffused non-metal electrode regions.
But the current SE structure can be realized by a mask reverse etching and laser local in-situ doping mode. The mask reverse 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 a well diffused p + layer by using a laser source again to form a p + + layer, the process is simple and rapid, but is limited by the limit of boron content of the original borosilicate glass layer, the doping effect is poor, the high-efficiency doping requirement cannot be met, and due to the fact that the surface sheet resistance of the borosilicate glass layer is large, the series resistance can be increased, and the improvement of the conversion efficiency of the battery is influenced.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides a borosilicate glass slurry, which is prepared from the following raw materials in percentage by weight:
10.0-80.0 wt%, preferably 30.0-60.0 wt%, more preferably 45.0-55.0 wt%;
20.0-90.0 wt% of organic solvent or deionized water, preferably 30.0-60.0%, more preferably 40.0-50.0%;
0.1 to 20.0 wt% of resin, preferably 1.0 to 10.0 wt%, more preferably 3.0 to 7.0 wt%.
As a preferred technical scheme of the invention, the preparation raw materials of the borosilicate glass powder comprise a boron source, a silicon source and a third main group metal source.
The boron source is boron or an oxide of boron. Typically, the p + layer of the lightly doped region in the doped layer is boron, and for better compatibility with the lightly doped region, a boron source, such as boron oxide (B)2O3) The boron source is dissolved in a glass system and is used as a trivalent boron source to diffuse to a silicon substrate at high temperature to form a p + + layer structure to act with a lightly doped region, so that electrode covering is reduced, the softening temperature of the slurry glass is reduced, and wetting and leveling with the substrate are improved. The proportion of the boron source in the glass powder is 5.0-50.0 wt%, preferably 10-35 wt%, and more preferably 20-30 wt% calculated by weight ratio.
The silicon source is silicon or silicon oxide. By adding a silicon source as a skeleton, and a silicon source, e.g. acidic silicon oxide (SiO)2) The method is beneficial to improving the chemical stability and high-temperature fluidity and promoting the diffusion of boron, but the dispersion and compatibility between the boron source and the silicon source are poor, and a uniform p + + structure is difficult to form. The weight ratio of the silicon source in the glass powder is 40-95.0 wt%, preferably 50-80 wt%, and more preferably 60.0-70.0 wt%.
The source of the third main group metal is a thirdOxides of metals of main group or of metals of group III, there being mentioned, for example, aluminium, indium, gallium and oxides thereof, such as aluminium oxide (Al)2O3) Indium oxide (In)2O3) Gallium oxide (Ga2O 3). In order to improve the dispersion compatibility of the boron source and the silicon source, other group III metal sources can be added, wherein the inventor also finds that the addition of the group III metal source is also beneficial to improving the doping characteristics, the dispersion capability in the molecule is beneficial to promoting the compatibility of the boron source and the silicon source, but the effect of the silicon substrate can be influenced by more usage amount, and the proportion of the group III metal source in the glass powder is 0-5.0 wt%, preferably 0.5-3.0 wt%, and more preferably 1.0-2.0 wt%.
The preparation method of the borosilicate glass powder can be exemplified by a smelting ball milling method, a sol-gel sintering ball milling method and a smelting dry milling method, which are not particularly limited, wherein the smelting ball milling method comprises the steps of weighing and mixing raw materials, smelting at 800-1500 ℃, quenching by water quenching or dry quenching and the like, drying, ball milling by water milling, solvent milling and the like, and drying. The sol-gel sintering ball milling method is to prepare the raw materials into gel, and to obtain the sol-gel sintering ball milling material after high-temperature sintering ball milling. The smelting dry-milling method is obtained by dry-milling raw materials such as weighing, mixing, smelting, quenching, drying, zirconium bead milling or jet milling and the like.
In a preferred embodiment of the present invention, the organic solvent includes at least one of diethylene glycol butyl ether acetate, alcohol ester dodeca, terpineol, diethylene glycol butyl ether acetate, dimethyl adipate, N-methylpyrrolidone, dimethyl phthalate, and dimethyl terephthalate.
In addition, the inventor finds that by selecting proper resin, the uniform mixing of borosilicate glass powder and the high-concentration diffusion of boron can be further promoted in the subsequent processes of high-temperature diffusion, local laser doping and the like, and the realization of high-efficiency doping is promoted. In a preferred embodiment of the present invention, the resin includes at least one of ethyl cellulose, hydroxyethyl cellulose, PVB, polyvinylpyrrolidone, polyvinyl butyral, and acrylic resin.
As a preferable technical scheme, the slurry also comprises 0.1-5.0 wt% of organic auxiliary agent according to the weight percentage; the organic auxiliary agent includes, but is not limited to, any one of an organic dispersant, a thixotropic agent, a slipping agent and a leveling agent, and the preferable proportion is 0.3 to 2.0 wt%, and more preferably 0.5 to 1.0 wt%.
As a preferred technical scheme of the invention, the particle size D50 (measured by a laser particle size distribution instrument) of the borosilicate glass powder is 0.1-5.0 μm, preferably 0.5-3.0 μm, and more preferably 1.0-2.0 μm; the borosilicate glass powder has a specific surface area (BET specific surface area test method) of 0.5-3.0 m2A ratio of 0.8 to 2.0 m/g is preferred2A more preferable range is 1.0 to 1.5 m/g2(ii)/g; the borosilicate glass powder has a Tg (differential thermal analysis test) of 400-900 ℃, preferably 500-700 ℃, and more preferably 550-600 ℃.
The invention provides a selective emitter in a second aspect, which comprises a lightly doped region and a heavily doped region located in 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 slurry.
The third aspect of the present invention provides a method for preparing a selective emitter, including:
and (3) forming a lightly doped region: diffusing the gas-phase boron source at high temperature;
and (3) forming a heavily doped region: after coating and drying the borosilicate glass slurry, the borosilicate glass slurry and the gas-phase boron source are simultaneously diffused at high temperature or diffused after the gas-phase boron source is diffused.
As a preferred technical scheme of the invention, in the formation of the heavy doping region, borosilicate glass slurry is coated, dried and locally laser-doped, and then is diffused at high temperature with a gas-phase boron source.
The preparation method of the doping layer provided by the invention can select the three methods, (1) before the high-temperature diffusion of the conventional gas-phase boron source, local laser doping is carried out after borosilicate glass slurry with local patterns printed on the surface of the silicon wafer by screen printing is dried, and after relevant slurry on the surface of the silicon wafer is cleaned, the borosilicate glass slurry and the conventional gas-phase boron source are diffused simultaneously to obtain an SE structure; (2) after being dried, borosilicate glass slurry for screen printing local patterns on the surface of a silicon wafer is directly diffused with a conventional gas phase boron source at the same time, and a borosilicate glass layer has very high boron content, so that locally obviously high boron diffusion concentration can be obtained on the silicon surface; (3) after the high-temperature diffusion of a conventional gas-phase boron source, the borosilicate glass slurry with local patterns is subjected to screen printing on the surface of a silicon wafer, the local diffusion is carried out in a laser doping mode, and then the related cleaning is carried out.
Coating borosilicate glass slurry on the surface of a silicon wafer in any one of a screen printing mode, an ink-jet printing mode, a spin coating mode and a spraying mode; after the borosilicate glass slurry coated on the silicon surface is dried, the selective emitter preparation of the high-quality heavily doped p + + layer is realized by adopting any one of laser doping and high-temperature diffusion. The method comprises the steps of preparing silver-aluminum paste above a p + + layer of the TOPCon battery by a screen printing technology, and sintering at the high temperature of 720-820 ℃ to form an electrode with good ohmic contact.
The invention provides the application of the borosilicate glass slurry in semiconductor and 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.
(2) The p + layer prepared by the borosilicate glass paste is contacted, and the processes of laser doping, single diffusion, screen printing and the like are combined, so that the preparation process of the crystalline silicon heavily doped p + layer can be effectively simplified, the high productivity and low energy consumption of the 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 TOPCon battery Selective Emitter (SE), a silicon wafer with higher sheet resistance except for a heavily doped region is prepared, the metal-semiconductor contact performance of the silver-aluminum slurry and a crystalline silicon solar battery p + layer 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 TOPCon battery is effectively improved.
Detailed Description
Examples
Examples 1 to 4 andIV measurements of borosilicate glass powder, borosilicate glass paste and TOPCon cell provided in reference examples 1 to 4
Test parameters
The borosilicate glass powders provided in examples 1 to 4 and reference examples 1 to 4 were designed in 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 for preparation are weighed, mixed and smelted, the smelting temperature is 1300 ℃, the time is 1h, and after dry quenching, the borosilicate glass slurry is ball-milled in a solvent and then dried to obtain the borosilicate glass powder with the granularity of about 1.0-1.5 mu m. The borosilicate glass slurry prepared in the examples 1 to 4 is applied to the preparation of a laser SE structure, and the formula of the relevant raw materials is designed as follows, wherein the glass powder content of the examples 1 to 4 is 50.0 wt%, 5 wt% of hydroxyethyl cellulose and 45 wt% of deionized water according to the weight ratio.
TABLE 1
Reference example 1 adopts a boron-free silicate glass slurry doping process, i.e., a conventional vapor phase boron source high temperature diffusion process. The raw materials are weighed and mixed and homogenized by a three-roll mill to obtain a target product. Before the high-temperature diffusion of a conventional gas-phase boron source, the target product is subjected to local laser doping after borosilicate glass slurry with local patterns 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 diffused simultaneously to obtain an SE structure. According to the preparation process of the TOPCon battery, the subsequent battery preparation process is completed, and finally the IV test parameters of the TOPCon 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 a high series resistance and contact resistivity. Through the preparation of a borosilicate glass SE structure, both the series resistance and FF are improved, and the highest electric property has 0.11 percent of gain.
IV measurements of borosilicate glass powder, borosilicate glass paste and TOPCon cell provided in examples 5 to 8 and reference examples 2 to 5
Test parameters
The conventional sheet resistance based on reference example 1 was only 110 Ω/□, and there was still room for improvement. The borosilicate glass slurry provided in the embodiments 5 to 8 and 2 to 5 is designed according to the following weight percentage, and the borosilicate glass slurry prepared in the embodiments 5 to 8 and 2 to 5 comprises, by weight, 50.0 wt% of glass powder, 5 wt% of hydroxyethyl cellulose and 45 wt% of deionized water, as shown in table 3, and is prepared by a melting ball-milling method, that is, the required raw materials for preparation are weighed, mixed and then melted, wherein the melting temperature is 1300 ℃ and the time is 1h, and after dry quenching, the mixture is ball-milled in a solvent and then dried, so that the borosilicate glass powder with the particle size of about 1.0 to 1.5 μm is obtained. The sheet resistance of the p + layer lightly doped region and the sheet resistance of the p + + layer of the local doped heavily doped region are shown in table 4.
TABLE 3
TABLE 4
The experimental design of the embodiments 5-8 and the reference examples 2-5 is completed by adopting an N-TOPCon battery structure, the same industrialized front silver-aluminum paste is printed on a p + layer of an N-type TOPCon crystalline silicon substrate, the film thickness is 15 microns after drying, and the battery piece obtained is subjected to current-voltage performance test by sintering at 750 ℃ and 760 ℃, wherein the data comprises open-circuit voltage (Voc), series resistance (Rs), Filling Factor (FF) and conversion efficiency (Eta), as shown in a graph 4. The cell sheets of examples 2 to 5 and reference examples 5 to 8 were laser cut into a special pattern, and the contact resistivity of the TOPCon solar cell electrode was measured using a TLM apparatus, and the results are shown in table 5.
TABLE 5
According to the test result, the borosilicate glass slurry provided by the invention can be used for forming a TOPCon battery Selective Emitter (SE), so that a silicon wafer with higher sheet resistance except for a heavily doped region is prepared, the metal-semiconductor contact performance of silver-aluminum slurry and a crystalline silicon solar battery p + layer is optimized, the metal-induced recombination is reduced, the open-circuit voltage of the solar battery is improved, the photoelectric conversion efficiency of the TOPCon battery is effectively improved, and the absolute value of the conversion efficiency can be improved by more than 0.4%.
Claims (10)
1. The borosilicate glass slurry is characterized in that the preparation raw materials of the slurry comprise the following components in percentage by weight:
10.0-80.0 wt% of borosilicate glass powder; the preparation raw materials of the borosilicate glass powder comprise a boron source, a silicon source and a third main group metal source;
20.0-90.0 wt% of organic solvent or deionized water;
0.1 to 20.0 wt% of resin.
2. The borosilicate glass paste according to claim 1, wherein the paste is prepared from the following raw materials in percentage by weight:
30.0-60.0% of borosilicate glass powder, more preferably 45.0-55.0%;
30.0-60.0% of organic solvent or deionized water, more preferably 40.0-50.0%;
0.1 to 20.0 wt% of the resin, more preferably 3.0 to 7.0 wt%.
3. The borosilicate glass paste according to claim 1, wherein the proportion of the boron source in the glass frit is 5.0 to 50.0 wt.%, preferably 10 to 35 wt.%, more preferably 20 to 30 wt.%; the weight ratio of the silicon source in the glass powder is 40-95.0 wt%, preferably 50-80 wt%, and more preferably 60.0-70.0 wt%; the proportion of the third main group metal source in the glass frit is 0 to 5.0 wt%, preferably 0.5 to 3.0 wt%, more preferably 1.0 to 2.0 wt%, calculated as a weight ratio.
4. The borosilicate glass paste according to claim 1, wherein said organic solvent comprises at least one of butyl carbitol acetate, dodecyl alcohol ester, terpineol, butyl carbitol acetate, dimethyl adipate, N-methyl pyrrolidone, dimethyl phthalate, and dimethyl terephthalate, and said resin comprises at least one of ethyl cellulose, hydroxyethyl cellulose, PVB, polyvinyl pyrrolidone, polyvinyl butyral, and acrylic resin.
5. The borosilicate glass paste according to claim 1, wherein the paste further comprises 0.1 to 5.0 wt% of an organic auxiliary agent.
6. The borosilicate glass paste according to any one of claims 1 to 5, wherein the particle size D50 of the borosilicate glass frit is 0.1 to 5.0 μm, preferably 0.5 to 3.0 μm, more preferably 1.0 to 2.0 μm; the specific surface area of the borosilicate glass powder is 0.5-3.0 m2A ratio of 0.8 to 2.0 m/g is preferred2A more preferable range is 1.0 to 1.5 m/g2(ii)/g; the Tg of the borosilicate glass powder is 400-900 ℃, preferably 500-700 ℃, and more preferably 550-600 ℃.
7. The selective emitter is characterized by comprising a lightly doped region and a heavily doped region which are positioned 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 slurry of any one of claims 1 to 6.
8. A method for preparing a selective emitter according to claim 7, comprising:
and (3) forming a lightly doped region: diffusing the gas-phase boron source at high temperature;
and (3) forming a heavily doped region: after coating and drying the borosilicate glass slurry, the borosilicate glass slurry and the gas-phase boron source are simultaneously diffused at high temperature or diffused after the gas-phase boron source is diffused.
9. The method of claim 8, wherein the heavily doped region is formed by coating, baking, local laser doping, and high temperature diffusion of a gas phase boron source.
10. Use of the borosilicate glass paste according to any of claims 1 to 6 in a semiconductor, crystalline silicon solar cell.
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| CN114944436A (en) * | 2022-05-11 | 2022-08-26 | 佛山科学技术学院 | Low-cost glass paste for preparing full back electrode crystalline silicon solar cell, cell structure and preparation method of cell structure |
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