CN117438499A - Silicon-based coating, preparation method thereof and photovoltaic material - Google Patents
Silicon-based coating, preparation method thereof and photovoltaic material Download PDFInfo
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- CN117438499A CN117438499A CN202311380293.6A CN202311380293A CN117438499A CN 117438499 A CN117438499 A CN 117438499A CN 202311380293 A CN202311380293 A CN 202311380293A CN 117438499 A CN117438499 A CN 117438499A
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- based coating
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 134
- 239000010703 silicon Substances 0.000 title claims abstract description 134
- 238000000576 coating method Methods 0.000 title claims abstract description 104
- 239000011248 coating agent Substances 0.000 title claims abstract description 102
- 239000000463 material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 56
- 239000003921 oil Substances 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 229920002545 silicone oil Polymers 0.000 claims description 53
- 238000000034 method Methods 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- -1 methyl hydrogen Chemical class 0.000 claims description 23
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 21
- 238000000137 annealing Methods 0.000 claims description 16
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000012159 carrier gas Substances 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000012495 reaction gas Substances 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- HNQXCHVZYRDHJN-UHFFFAOYSA-N cyanosilicon Chemical compound [Si]C#N HNQXCHVZYRDHJN-UHFFFAOYSA-N 0.000 claims description 3
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052754 neon Inorganic materials 0.000 claims description 3
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 3
- 229920003216 poly(methylphenylsiloxane) Polymers 0.000 claims description 3
- 229910052704 radon Inorganic materials 0.000 claims description 3
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000307 polymer substrate Polymers 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 2
- 238000012549 training Methods 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 description 24
- 230000008021 deposition Effects 0.000 description 18
- 239000010453 quartz Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 230000008569 process Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000001505 atmospheric-pressure chemical vapour deposition Methods 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-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
- 230000002411 adverse Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000005303 weighing Methods 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/24—Deposition of silicon only
-
- 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
- H01L31/04—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 adapted as photovoltaic [PV] conversion devices
-
- 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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1864—Annealing
-
- 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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
- H01L31/1868—Passivation
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The invention provides a silicon-based coating, a preparation method thereof and a photovoltaic material, wherein the preparation method comprises the following steps: introducing silicon oil serving as raw material gas into a chamber provided with a to-be-deposited object, wherein the silicon oil is thermally decomposed and deposited on the surface of the to-be-deposited object to form a silicon-based coating; the silicon-based coating is SiO x C y A compound. Compared with other raw gases, the invention solves the cost expenditure problems of the equipment in the prior art, such as special gas station matching, dangerous gas leakage detection alarm, professional personnel training configuration and the like.
Description
Technical Field
The invention relates to the technical field of solar cells, in particular to a silicon-based coating, a preparation method thereof and a photovoltaic material.
Background
The semiconductor or photovoltaic materials are widely applied to industries such as electronics, new energy sources and the like, the semiconductor and the photovoltaic materials are usually subjected to chemical treatment to be applied to products, the CVD technology is one treatment mode, CVD is chemical vapor deposition, the CVD technology is widely applied to the processing of the semiconductor or the photovoltaic materials, common processing equipment comprises PECVD, LPCVD, APCVD and the like, diffusion processes such as phosphorus diffusion and boron diffusion and the like besides CVD can be adopted to process raw materials in a gas diffusion mode, the related equipment in the industry can be selected according to specific processing requirements to process the semiconductor or the photovoltaic materials, the processing of the semiconductor or the photovoltaic materials is usually realized by feeding sheet materials into a furnace to react under certain temperature and pressure, and in the process of processing the semiconductor or the photovoltaic materials, a plurality of devices are generally adopted to thermally decompose reactants to deposit a required coating film.
In conventional equipment, the silicon-based coating is usually deposited in PECVD, APCVD, LPCVD, or ALD (atomic layer deposition), thermal oxygen oxidation, wet chemical oxidation, etc., using SiH as the gas 4 、Si 2 Cl 2 The toxic, inflammable, explosive and corrosive dangerous silicon source gases such as TEOS and the like cause the expensive and complex matched special gas devices and facilities, occupy a large amount of occupied area and resources, and are difficult to use conveniently and safely in general occasions.
Therefore, there is a need to develop new preparation processes for silicon-based coatings to overcome the above technical difficulties.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a silicon-based coating, a preparation method thereof and a photovoltaic material, and silicon oil is used as a liquid silicon source for thermal decomposition deposition of a silicon-based coating film, so that the silicon-based coating is safe, nontoxic and convenient to use, and is not limited by adverse conditions such as special gas, toxic gas, flammable and explosive gas, corrosive gas and the like.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a silicon-based coating, comprising the steps of:
introducing silicone oil as raw material gasThe silicon oil is thermally decomposed and deposited on the surface of the to-be-deposited object to form a silicon-based coating in the cavity provided with the to-be-deposited object; the silicon-based coating is SiO x C y A compound.
According to the invention, silicone oil is selected as a raw material gas for thermal decomposition deposition coating, and is used as a safe silicon source gas, so that a large amount of land area, professional facility equipment, personnel, management, approval, design, construction and the like are not required, the cost of depositing the silicon-based coating film is greatly reduced, and the use convenience is improved.
The silicone oil of the present invention refers to a linear polysiloxane product which is kept in a liquid state at room temperature, and is generally classified into two types, namely, methyl silicone oil and modified silicone oil.
Silicone oils are generally colorless (or pale yellow), odorless, nontoxic, and nonvolatile liquids. It has a low vapor pressure, a high flash and fire point, and a low freezing point. As the number of segments n increases, the viscosity increases and thus the silicone oils can have a variety of viscosities ranging from 0.65 centistokes up to millions of centistokes. The silicone oil has heat resistance, electrical insulation, weather resistance, hydrophobicity, physiological inertia, small surface tension, low viscosity-temperature coefficient, high compression resistance and radiation resistance.
The most commonly used silicone oils have all of the organic groups methyl, known as methyl silicone oil. The organic groups may also be substituted with other organic groups to improve certain properties of the silicone oil and to suit various applications. Common other groups are any one or a combination of at least two of hydrogen, ethyl, phenyl, chlorophenyl or trifluoropropyl.
The silicone oil is divided into methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, methyl chlorophenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoro propyl silicone oil, methyl vinyl silicone oil, methyl hydroxyl silicone oil, ethyl hydrogen silicone oil, hydroxyl hydrogen silicone oil or cyano silicone oil and the like according to chemical structures.
The invention adopts silicone oil as the raw material gas for deposition and simultaneously needs to ensure the quality of the deposited coating, namely, the surface of the deposited coating has higher density and crystallinity so as to meet the use requirement of subsequent products.
Preferably, the value of x is in the range of 0 to 2, for example, 0, 0.2, 0.5, 0.8 or 1, and the value of y is in the range of 0 to 1, for example, 0, 0.1, 0.2, 0.5, 0.8 or 1, and the like.
Preferably, the to-be-deposited substance comprises a crystalline silicon wafer, a metal, glass or a polymer substrate, preferably a crystalline silicon wafer.
The thermal decomposition temperature is preferably 200 to 1200 ℃, and may be 200 ℃, 312 ℃, 423 ℃, 534 ℃, 645 ℃, 756 ℃, 867 ℃, 978 ℃, 1089 ℃, 1200 ℃ or the like, for example, but is not limited to the values recited, and other values not recited in the range are applicable as well, and preferably 800 to 1200 ℃. The pressure is 0.01 to 1000mbar, for example 0.01mbar, 110mbar, 200mbar, 330mbar, 450mbar, 500mbar, 600mbar, 700mbar, 800mbar or 1000mbar, etc., but is not limited to the recited values, and other values not recited in this range are equally applicable.
In order to improve the surface quality of the silicon-based coating obtained by silicone oil deposition, the invention preferably controls the thermal decomposition temperature in the above range so as to improve the compactness and crystallinity of the silicon-based coating.
Preferably, the thermally decomposed carrier gas comprises a shielding gas and/or a reaction gas.
Preferably, the shielding gas comprises any one or a combination of at least two of nitrogen, argon, helium, neon, krypton, xenon or radon, wherein typical but non-limiting combinations are combinations of nitrogen and argon, combinations of helium and argon, combinations of nitrogen and helium, combinations of neon and radon, combinations of xenon and argon.
Preferably, the reaction gas comprises oxygen and/or carbon dioxide.
Preferably, the thermally decomposed gas stream comprises a first gas stream comprising a shielding gas and a feed gas and a second gas stream comprising a shielding gas and a reaction gas.
Preferably, the flow rate of the reaction gas in the second gas flow is adjusted gradually from 0 to more than 1.0 times of the stoichiometric ratio of the target product theoretically required reaction gas, for example, 1.0, 1.01, 1.02, 1.05, 1.06, 1.08 or more than 1.1, etc.
After the silicon oil is used as the raw material gas for deposition, the content proportion of elements in the silicon oil is relatively fixed, so that different target coatings can be obtained for the same raw material gas.
Preferably, the silicone oil comprises any one or a combination of at least two of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, methyl chlorophenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoropropyl silicone oil, methyl vinyl silicone oil, methyl hydroxyl silicone oil, ethyl hydrogen silicone oil, hydroxyl hydrogen silicone oil or cyano silicone oil, and preferably is methyl silicone oil.
The invention preferably adopts methyl silicone oil, the molecular weight of the methyl silicone oil is smaller, and the surface quality of the silicon-based coating obtained by deposition is higher.
Preferably, the viscosity of the silicone oil is 10 to 3000cps, for example, 10cps, 340cps, 670cps, 1000cps, 1300cps, 1670cps, 2000cps, 2330cps, 2660cps or 3000cps, etc., but not limited to the recited values, other non-recited values within the range are equally applicable.
Preferably, the preparation method further comprises: annealing the deposited silicon-based coating.
The invention further increases the annealing step, and better improves the density of the surface of the silicon-based coating.
The annealing temperature is preferably 800 to 1200 ℃, and may be 800 ℃, 845 ℃, 889 ℃, 934 ℃, 978 ℃, 1023 ℃, 1067 ℃, 1112 ℃, 1156 ℃, 1200 ℃, or the like, for example, but is not limited to the recited values, and other values not recited in the range are equally applicable.
Preferably, the annealing time is 30 to 300min, for example, 30min, 60min, 90min, 120min, 150min, 180min, 210min, 240min, 270min or 300min, etc., but not limited to the recited values, and other non-recited values within the range are equally applicable.
The invention preferably controls the annealing temperature and time within the above ranges, which is more beneficial to improving the quality of the silicon-based coating surface.
Under the requirements of special application occasions, the invention can still prepare SiO with high porosity through high-temperature rapid thermal decomposition x C y . For example, in the process of preparing Poly-Si by LPCVD, in order to protect the service life of a quartz furnace tube, a layer of SiO with high porosity can be deposited on the inner wall of the quartz furnace tube by chemical vapor deposition of the silicon oil by high-temperature rapid thermal decomposition (generally at 900-1200 ℃) x C y Coating and then parasitic depositing Poly-Si in the subsequent production from outside to inside on the SiO with high porosity x C y On the coating, thereby forming a coating from Si to SiO 2 Gradual change buffer coating of quartz effectively eliminates direct from high thermal expansion coefficient Si to low thermal expansion coefficient SiO without the protective coating 2 The huge surface stress is caused, so that the service life of the quartz furnace tube is prolonged.
In a second aspect, the present invention provides a silicon-based coating prepared by the method for preparing a silicon-based coating according to the first aspect.
The silicon-based coating provided by the second aspect of the invention is prepared by adopting the preparation method containing the silicon-based coating, has high surface density, high crystallinity of a product and excellent surface quality, and can be well compounded with a sediment to be deposited by carrying out component connection transition on different interfaces of a substrate and the coating.
Preferably, the silicon-based coating comprises SiO x C y A compound wherein x ranges from 0 to 2 and y ranges from 0 to 1. The range of x may be, for example, 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, or the like. The range of y may be, for example, 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, or the like.
The silicon-based coating can be flexibly regulated and controlled in the chemical formula, and the process controllability is strong.
The thickness of the silicon-based coating layer is preferably 50 to 3000nm, and may be, for example, 50nm, 378nm, 706nm, 1034nm, 1362nm, 1689nm, 2017nm, 2345nm, 2673nm, 3000nm, or the like, but is not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the compactness of the silicon-based coating is 0.2-3.22 g/cm 3 For example, it may be 0.2g/cm 3 、0.3g/cm 3 、0.5g/cm 3 、0.8g/cm 3 、1.0g/cm 3 、1.2g/cm 3 、1.5g/cm 3 、2.0g/cm 3 、2.5g/cm 3 、3.0g/cm 3 Or 3.22g/cm 3 And the like, but are not limited to the recited values, and other non-recited values within this range are equally applicable.
The roughness of the silicon-based coating is preferably 2 to 10nm, and may be, for example, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm, or 10nm, etc., but is not limited to the recited values, and other values not recited in the range are equally applicable.
Preferably, siO in the silicon-based coating x C y The crystallization rate of the compound is 30 to 80%, and may be, for example, 30%, 36%, 42%, 47%, 53%, 58%, 64%, 69%, 75% or 80%, etc., but is not limited to the values recited, and other values not recited in the range are applicable as well.
The surface quality of the preferable silicon-based coating reaches the above level, and the quality of the silicon-based coating is obviously improved.
In a third aspect, the present invention provides a photovoltaic material comprising a silicon-based coating according to the second aspect.
The photovoltaic material provided by the invention has the advantages that the performance of the photovoltaic material is obviously improved due to the silicon-based coating in the second aspect.
Preferably, the photovoltaic material comprises a solar wafer.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The preparation method of the silicon-based coating solves the problems of the prior art in the aspects of convenient and fast selection and safe process gas, and solves the cost expenditure problems of special gas stations, dangerous gas leakage detection alarm, professional training configuration and the like required by equipment;
(2) The silicon-based coating provided by the invention has the advantages of high surface density, low roughness and high crystallinity, and the density is more than or equal to 2.32g/cm 3 The roughness is less than or equal to 10nm, the crystallinity is more than or equal to 63 percent, preferably more than or equal to 83 percent, the thickness can reach the micron level, the silicon-based coating has excellent quality, and the application prospect in photovoltaic materials and semiconductor materials is wide, and the application fields such as mask coating of solar cells with IBC (inter-digital back contact) structure, lateral passivation coating of the rear half of slicing of HJT (heterojunction) solar cells, passivation layer of Topcon (tunneling oxidation passivation) solar cells and the like are wide.
Drawings
FIG. 1 is a surface view of example 1 of the present invention before and after deposition of a silicon-based coating.
FIG. 2 is a surface view of example 3 of the present invention before and after deposition of a silicon-based coating.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings.
The present invention will be described in further detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
For the convenience of test, the following deposition processes all adopt chemical vapor deposition methods, and the devices all adopt quartz furnace tubes with the inner diameter of 420mm and the length of 3500 mm. However, the solution of the present invention is not limited to the above-mentioned apparatus, and other sizes or apparatuses for chemical vapor deposition are possible, and will not be described herein.
Example 1
The embodiment provides a preparation method of a silicon-based coating, which comprises the following steps:
placing a silicon wafer (monocrystalline silicon wafer) in a quartz furnace tube, heating the silicon wafer in the quartz furnace tube to 860 ℃ by adopting an infrared thermal field on the outer wall of the quartz tube, keeping the temperature in a liquid silicon oil tank at room temperature, and simultaneously introducing nitrogen and silicon oil (methyl silicone oil, the viscosity is 0.65CS, the molecular weight is 3800) as first air flows, wherein the nitrogen is simultaneously used as carrier gas and pushing gas, the flow rate of the carrier gas is 4000sccm, the flow rate of the pushing gas is 1000sccm, and the flow rate of the silicon oil is 3000sccm; the methyl silicone oil is used as raw material gas to carry out thermal decomposition at 860 ℃ and 200mbar, a silicon-based coating is deposited on the silicon wafer, and the deposition time is 180 minutes, so that the silicon wafer containing the silicon-based coating is obtained; the silicon-based coated wafer is annealed at 1000 ℃ for 250 minutes.
In this embodiment, siO is formed on a wafer of a solar cell x C y The compound can be used as a mask layer when LPCVD deposits poly-si, solves the problem of electric leakage of a battery piece formed by plating around, or is used as a mask when producing an IBC (inter-digital back contact) battery structure.
The graph before depositing the silicon-based coating in this embodiment is shown on the left side in fig. 1, and the graph on the right side is a surface graph after depositing the silicon-based coating, so that it can be seen that the surface deposition is uniform and the adhesion is good.
Example 2
The embodiment provides a preparation method of a silicon-based coating, which comprises the following steps:
placing a ceramic wafer (aluminum oxide) in a quartz furnace tube, heating a silicon wafer in the quartz furnace tube to 880 ℃ by adopting an infrared thermal field on the outer wall of the quartz tube, keeping the temperature in a liquid silicon oil tank at room temperature, and simultaneously introducing nitrogen and silicon oil (methyl silicone oil, the viscosity is 20cst, the molecular weight is 2000) as first air flows, wherein the nitrogen is simultaneously used as carrier gas and pushing gas, the flow rate of the carrier gas is 5000sccm, the flow rate of the pushing gas is 2000sccm, and the flow rate of the silicon oil is 4000sccm; methyl silicone oil is used as raw material gas to be thermally decomposed at 880 ℃ and 300mabr, a silicon-based coating is deposited on the ceramic plate, and the deposition time is 200min, so that the ceramic plate with the silicon-based coating is obtained; the ceramic wafer with the silicon-based coating is annealed at 800 ℃ for 300min.
Example 3
The embodiment provides a preparation method of a silicon-based coating, which comprises the following steps:
placing a silicon wafer (polysilicon) in a quartz furnace tube, heating the silicon wafer in the quartz furnace tube to 920 ℃ by adopting an infrared thermal field on the outer wall of the quartz tube, keeping the temperature in a liquid silicon oil tank at room temperature, and simultaneously introducing nitrogen and silicon oil (methyl silicone oil, the viscosity is 100cst, the molecular weight is 6000) as first air flows, wherein the nitrogen is simultaneously used as carrier gas and pushing gas, the flow rate of the carrier gas is 5000sccm, the flow rate of the pushing gas is 2000sccm, and the flow rate of the silicon oil is 4500sccm; then oxygen is fed as a second air flow, the flow rate of the oxygen is gradually increased to 1000sccm from 0 and then gradually decreased to 0, the total time of oxygen feeding is 120min, methyl silicone oil is used as raw material gas to carry out thermal decomposition at 920 ℃ and 250mbar, a silicon-based coating is deposited on a silicon wafer, and the deposition time is 150min, so that the silicon wafer with the silicon-based coating is obtained; and annealing the silicon-based coated silicon wafer at 1200 ℃ for 30min.
The graph before depositing the silicon-based coating in this embodiment is shown on the left side in fig. 2, and the graph on the right side is a surface graph after depositing the silicon-based coating, so that it can be seen that the surface deposition is uniform and the adhesion is good.
Example 4
The embodiment provides a preparation method of a silicon-based coating, which comprises the following steps:
placing a silicon wafer (monocrystalline silicon) in a quartz furnace tube, heating the silicon wafer in the quartz furnace tube to 1120 ℃ by adopting an infrared thermal field on the outer wall of the quartz tube, keeping the temperature in a liquid silicon oil tank at room temperature, and simultaneously introducing nitrogen and silicon oil (methyl silicone oil, the viscosity is 200cst, the molecular weight is 9400) as first air flows, wherein the nitrogen is simultaneously used as carrier gas and pushing gas, the flow rate of the carrier gas is 3000sccm, the flow rate of the pushing gas is 1000sccm, and the flow rate of the silicon oil is 3500sccm; then carbon dioxide is fed as a second air flow, the flow rate of oxygen is gradually increased to 500sccm from 0 and then gradually decreased to 0, the total time of carbon dioxide feeding is 30min, methyl silicone oil is used as raw material gas to carry out thermal decomposition at 920 ℃ and 350mbar, a silicon-based coating is deposited on a silicon wafer, and the deposition time is 120min, so that the silicon wafer with the silicon-based coating is obtained; and annealing the silicon-based coated silicon wafer at 1000 ℃ for 100min.
Example 5
This example provides a method for preparing a silicon-based coating by replacing methyl silicone oil with phenyl silicone oil (CAS number63148-58-3, formula C 11 H 16 OSi, molecular weight 192.33) the remainder were the same as in example 1.
Example 6
This example provides a method for preparing a silicon-based coating by replacing methyl silicone oil with methyl hydroxyl silicone oil (CAS number 70131-67-8, molecular formula HO-Si (CH) 3 ) 2 O-] n H) Except for this, the procedure was the same as in example 1.
Example 7
This example provides a method of preparing a silicon-based coating, which is the same as example 1, except that annealing is not performed.
Example 8
This example provides a method for preparing a silicon-based coating, which is the same as example 1 except that the annealing temperature is 600 ℃.
Example 9
This example provides a method for preparing a silicon-based coating, which is the same as example 1 except that the annealing temperature is 1300 ℃.
Example 10
This example provides a method for preparing a silicon-based coating, which is the same as example 1 except that the silicon wafer is replaced with a metallic iron sheet.
Example 11
This example provides a method of preparing a silicon-based coating, which is the same as example 2 except that the second gas flow is not introduced.
Example 12
This example provides a method for preparing a silicon-based coating, which is the same as example 1 except that methylsilicone oil is thermally decomposed at 400 ℃ as a raw material gas.
Comparative example 1
This comparative example provides a method for preparing a silicon-based coating, which is the same as example 1 except that the silicone oil is replaced with TEOS.
Comparative example 2
This comparative example provides a method for preparing a silicon-based coating by replacing silicone oil with SiH 4 Except for this, the procedure was the same as in example 1.
And (3) compactness test of the silicon-based coating: weighing and calculating the film density of the film thickness; the crystallinity was measured and calculated using XRD. The film thickness measurement is carried out by adopting SEM; the surface roughness was measured using an atomic force microscope.
The test results of the above examples and comparative examples are shown in table 1.
TABLE 1
From table 1, the following points can be seen:
(1) As can be seen from comprehensive examples 1-12, the preparation method of the silicon-based coating provided by the invention can prepare the coating with high density, high crystallinity and low surface roughness, wherein the density is more than or equal to 2.32g/cm 3 The roughness is less than or equal to 10nm, and the crystallinity is more than or equal to 63 percent, preferably more than or equal to 83 percent;
(2) It can be seen from the combination of examples 1 and examples 5 to 6 and comparative examples 1 to 2 that the selection of different deposition substances has a great influence on the crystallinity, the density and the roughness of the finally obtained coating, and the invention can prepare a coating with higher crystallinity and better density by preferably adopting methyl silicone oil;
(3) According to the invention, by selecting an annealing process and controlling the annealing temperature within a specific range, a coating with high crystallinity, high density and low surface roughness can be obtained, and the performance is better;
(4) As can be seen from the combination of the embodiment 1 and the embodiment 10, the substrate adopted in the embodiment 1 is a silicon wafer, and compared with the substrate adopted in the embodiment 10 is a metal iron sheet, the performance of the coating is not obviously changed, so that the preparation method of the silicon-based coating provided by the invention can be suitable for different substrates, but the bonding degree of the silicon wafer and the silicon-based coating in the embodiment 1 is firmer, namely, the silicon-based coating provided by the invention is more suitable for the surface of the silicon wafer, has stronger bonding strength, and has better thermal shock resistance compared with the embodiment 10;
(5) As can be seen from a combination of example 1 and example 11, the reactant gas was introduced as the second gas stream in example 1, and the silicon-based coating obtained in example 1 had higher density and crystallinity than that obtained in example 11 without introducing the second gas stream, whereas the density obtained in example 11 was only 2.96g/cm 3 The crystallinity is also reduced to 80%, so that the invention can further improve the compactness and crystallinity of the surface coating by arranging the second air flow;
(6) It can be seen from a combination of examples 1 and 12 that the thermal decomposition temperature of example 1 is 860 c, and the thermal decomposition temperature of example 12 is only 400 c, and the density of example 1 is much higher than that of example 12, because the thermal decomposition temperature is slow in example 12, the deposition rate is slow, the deposition rate should be originally slow, but the crystallinity is low during the deposition due to the lower overall temperature, and even if the annealing process is subsequently performed, it is difficult to further increase the density and crystallinity, thus indicating that the invention can further increase the density, crystallinity and reduce the surface roughness of the silicon-based coating by controlling the thermal decomposition temperature in a preferred range.
The detailed structural features of the present invention are described in the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
Claims (10)
1. A method for preparing a silicon-based coating, which is characterized by comprising the following steps:
introducing silicon oil serving as raw material gas into a chamber provided with a to-be-deposited object, wherein the silicon oil is thermally decomposed and deposited on the surface of the to-be-deposited object to form a silicon-based coating; the silicon-based coating is SiO x C y A compound.
2. The method according to claim 1, wherein the value range of x is 0 to 2 and the value range of y is 0 to 1;
preferably, the to-be-deposited matter comprises a crystal silicon wafer, metal, glass or polymer substrate.
3. The preparation method according to claim 1 or 2, wherein the thermal decomposition temperature is 200-1200 ℃ and the pressure is 0.01-1000 mbar.
4. The method of claim 1, wherein the thermally decomposed carrier gas comprises a shielding gas and/or a reaction gas;
preferably, the shielding gas comprises at least one of nitrogen, argon, helium, neon, krypton, xenon or radon;
preferably, the reaction gas comprises oxygen and/or carbon dioxide.
5. The method of claim 4, wherein the thermally decomposed gas stream comprises a first gas stream comprising a shielding gas and a feed gas and a second gas stream comprising a shielding gas and a reactant gas;
preferably, the flow rate of the reaction gas in the second gas stream is gradually adjusted from 0 to more than 1.0 times of the stoichiometric ratio of the target product theoretically required reaction gas.
6. The preparation method according to claim 1, wherein the silicone oil comprises any one or a combination of at least two of methyl silicone oil, ethyl silicone oil, phenyl silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, methyl chlorophenyl silicone oil, methyl ethoxy silicone oil, methyl trifluoropropyl silicone oil, methyl vinyl silicone oil, methyl hydroxyl silicone oil, ethyl hydrogen silicone oil, hydroxyl hydrogen silicone oil or cyano silicone oil, preferably methyl silicone oil;
preferably, the silicone oil has a viscosity of 10 to 3000cps.
7. The method of manufacturing according to claim 6, further comprising: annealing the to-be-deposited matter deposited with the silicon-based coating;
preferably, the annealing temperature is 800-1200 ℃;
preferably, the annealing time is 30-300 min.
8. A silicon-based coating, characterized in that it is produced by the method for producing a silicon-based coating according to any one of claims 1 to 7.
9. The silicon-based coating of claim 8, wherein the silicon-based coating comprises SiO x C y A compound wherein x has a value range of 0 to 2 and y has a value range of 0 to 1;
preferably, the thickness of the silicon-based coating is 50-3000 nm;
preferably, the compactness of the silicon-based coating is 0.2-3.22 g/cm 3 ；
Preferably, the roughness of the silicon-based coating is 2-10 nm;
preferably, siO in the silicon-based coating x C y The crystallization rate of the compound is 30-80%.
10. A photovoltaic material, characterized in that it comprises a silicon-based coating according to claim 8 or 9.
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