CN111074217A - Amorphous silicon-doped target material and solar cell preparation method - Google Patents

Amorphous silicon-doped target material and solar cell preparation method Download PDF

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CN111074217A
CN111074217A CN201911346159.8A CN201911346159A CN111074217A CN 111074217 A CN111074217 A CN 111074217A CN 201911346159 A CN201911346159 A CN 201911346159A CN 111074217 A CN111074217 A CN 111074217A
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target material
amorphous silicon
doped
silicon
powder
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上官泉元
刘宁杰
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Jiangsu Jietai Photoelectric Technology Co Ltd
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Jiangsu Jietai Photoelectric Technology Co Ltd
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    • 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
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • 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
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/131—Wire arc spraying
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/14—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying for coating elongate material
    • C23C4/16—Wires; Tubes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02524—Group 14 semiconducting materials
    • H01L21/02532—Silicon, silicon germanium, germanium
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/0257—Doping during depositing
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    • H01L21/02587—Structure
    • H01L21/0259—Microstructure
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    • H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
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    • 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
    • H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
    • H01L31/202—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials including only elements of Group IV of the Periodic Table
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Abstract

The invention prepares a silicon target mixed with doping elements in advance, completes the amorphous silicon doping film coating by using a PVD method, and can directly form in-situ doped amorphous silicon on the surface of a silicon wafer in the PVD film coating process; and according to the requirement of doping concentration, phosphorus element or boron element with corresponding concentration is doped into the silicon target for doping the amorphous silicon layer film by TOPCon, and the doping can be realized by one PVD coating process. Compared with the method of adding doping elements by using gas silane through LPCVD coating and then using an ion implantation method, the method has the advantages of simple process, low cost and high use safety.

Description

Amorphous silicon-doped target material and solar cell preparation method
Technical Field
The invention relates to the technical field of solar cell preparation, in particular to a method for preparing a target material for in-situ doping of amorphous silicon in a solar cell and a method for preparing the solar cell by in-situ doping of amorphous silicon based on the prepared target material.
Background
A solar cell is a semiconductor device that can convert solar energy into electric energy, and a high efficiency solar cell is an effective way to reduce the cost of generating electricity using solar energy.
The crystalline silicon solar cell utilizes a crystalline silicon substrate, surface treatment is carried out by a similar semiconductor technology to form the solar cell, the solar cell taking N-type silicon as the substrate has the advantages of high power generation efficiency, small attenuation and the like, but the surface needs to be effectively passivated, and generally, a passivation film is an insulator and cannot allow carriers to pass through.
The TOPCon battery uses an ultra-thin silicon oxide film to grow on the surface of a clean silicon wafer, then grows a doped amorphous silicon layer on the silicon oxide film, correspondingly collects electrons or holes according to the type of collected carriers, and is phosphorus or boron for the distribution of doped elements. And when the thickness of the silicon oxide is about 1nm, the majority carriers can penetrate through the silicon oxide layer and enter the doped amorphous silicon layer in a tunnel effect mode, so that the collection effect of the majority carriers is realized. The higher the doping concentration, the better the passivation effect and at the same time the better the conductivity to the majority carriers. This passivation + selective penetration effect is considered to be an effective way to improve solar energy conversion efficiency.
The conventional method for realizing doped amorphous silicon is to place a silicon wafer at a proper temperature to form an amorphous silicon Layer (LPCVD) on the surface through decomposition of silane, then inject phosphorus or boron atoms into the amorphous silicon layer through another ion injection device, perform high-temperature annealing to convert the amorphous silicon into polycrystalline silicon, and simultaneously re-diffuse the original doped elements which are not uniformly distributed and are subjected to ion injection at a high temperature to realize uniform distribution.
In the LPCVD coating process, the other side of the silicon wafer needs to be protected to avoid coating, the only method is to put two silicon wafers together back to back during coating, although the method is simple, the method cannot avoid that the other side has certain permeation to coat a layer of film, and a cleaning process needs to be added before high-temperature annealing to remove the film. Therefore, the method of growing amorphous silicon by LPCVD and then preparing doped polysilicon by ion implantation has the defects of 4 working procedures and 4 independent devices, and has the defects of high investment cost, complex process, high energy consumption of high-temperature coating, low silane utilization rate and the like.
The formation of amorphous silicon by PVD vacuum sputtering of a silicon target is a common method, and if the silicon target is doped with phosphorus in advance, doped amorphous silicon can be produced by PVD vacuum sputtering. However, the silicon targets currently available on the market as cylindrical targets are formed by the crystal pulling method, which is not only costly, but also has limited doping concentrations.
Disclosure of Invention
In order to solve the technical problem, the invention provides a preparation method of a target material doped with amorphous silicon, which comprises the following steps:
1) mixing high-purity silicon powder and doping elements in required proportion in advance;
2) transferring the mixture material obtained based on the step 1) into a vacuum high-temperature sealing furnace to generate silicon and doped element alloy, cooling and taking out the alloy, crushing the cooled alloy, cleaning and screening powder with a certain particle size;
3) and (3) spraying the powder obtained in the step 2) onto a steel pipe serving as a substrate through a high-temperature arc spray gun by using inert gas such as argon and the like as carrier gas, so as to obtain the alloy target material uniformly distributed on the steel pipe.
Wherein, in the step 1), the purity of the high-purity silicon powder is more than or equal to 99.99 percent, and the doping element is phosphorus element or boron element.
Wherein, in the step 2), the particle size of the obtained powder is 50-200 um.
In the step 3), the steel pipe repeatedly rotates and translates for many times in the spraying process, and the thickness of the alloy target material is 3-10 mm; wherein the diameter of the steel pipe is 50-300 mm, and the length of the steel pipe is 1000-4000 mm; the mass percentage content of the doping elements in the obtained target material is 0.1-1.5%, the oxygen content in the target material is less than or equal to 2000ppm, and the nitrogen content in the target material is less than or equal to 300 ppm.
The invention also provides another preparation method of the amorphous silicon-doped target material, which comprises the following steps:
1) mixing high-purity silicon powder and doping elements in required proportion in advance;
2) spraying the mixed material onto the surface of the target core by a spraying method to form the alloy target material.
Wherein, in the step 1), the size of the high-purity silicon powder is as follows: 50-200 meshes, and the purity is more than or equal to 99.99%; the doping elements are phosphorus elements or boron elements: the size is 50-200 meshes, and the purity is more than or equal to 99.9%; and the high-purity silicon powder and the doping elements are uniformly ground after being mixed.
In the step 2), the target core is a steel pipe or a titanium steel pipe, the diameter of the target core is 50-300 mm, and the length of the target core is 1000-4000 mm; the spraying thickness is 3-10 mm; the mass percentage content of the doping elements in the obtained target material is 0.1-1.5%, the oxygen content in the target material is less than or equal to 2000ppm, and the nitrogen content in the target material is less than or equal to 300 ppm.
In the step 2), during spraying, high-temperature and high-pressure argon is mixed with the mixed powder, molten liquid powder is sprayed out through a nozzle, and an alloy target is formed on the surface of the target core.
The invention also provides a preparation method of the solar cell doped with amorphous silicon, which is based on the target material obtained by any one of the methods and adopts a PVD method to complete amorphous silicon-doped coating so as to form in-situ doped amorphous silicon on the surface of a silicon wafer.
According to the technical scheme, the silicon target mixed with the doping elements in advance is prepared, the doping amorphous silicon coating is completed by utilizing a PVD method, and in-situ doping amorphous silicon can be directly formed on the surface of a silicon wafer in the PVD coating process; and according to the requirement of doping concentration, phosphorus element or boron element with corresponding concentration is doped into the silicon target for doping the amorphous silicon layer film by TOPCon, and the doping can be realized by one PVD coating process. Compared with the method of adding doping elements by using gas silane through LPCVD coating and then using an ion implantation method, the method has the advantages of simple process, low cost and high use safety.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below.
Example 1:
the invention provides a preparation method of a target material doped with amorphous silicon, which comprises the following steps:
1) mixing high-purity silicon powder and doping elements in required proportion in advance; wherein, the purity of the high-purity silicon powder is more than or equal to 99.99 percent, and the doping element is phosphorus element or boron element;
2) transferring the mixture material obtained based on the step 1) into a vacuum high-temperature sealing furnace to generate silicon and doped element alloy, cooling and taking out the alloy, crushing the cooled alloy, cleaning and screening powder with a certain particle size; wherein the particle size of the obtained powder is 50-200 um;
3) spraying the powder obtained in the step 2) onto a steel pipe serving as a substrate through a high-temperature arc spray gun by using inert gas such as argon and the like as carrier gas, so as to obtain alloy target materials uniformly distributed on the steel pipe; the steel pipe repeatedly rotates and translates for many times in the spraying process, and the thickness of the alloy target material is 3-10 mm; the diameter of the steel pipe is preferably 135mm, the length of the steel pipe is determined according to the width of PVD (physical vapor deposition) coating equipment, a longer target can cover more silicon wafers at one time, the productivity of the silicon wafers generated by coating is improved, and the length range is 1000-4000 mm; the mass percentage content of the doping elements in the obtained target material is 0.1-1.5%, the oxygen content in the target material is less than or equal to 2000ppm, and the nitrogen content in the target material is less than or equal to 300 ppm.
Example 2:
the invention provides a preparation method of a target material doped with amorphous silicon, which comprises the following steps:
1) mixing high-purity silicon powder and doping elements in required proportion in advance; wherein, the size of the high-purity silicon powder is as follows: 50-200 meshes, and the purity is more than or equal to 99.99%; the doping elements are phosphorus elements or boron elements: the size is 50-200 meshes, and the purity is more than or equal to 99.9%; and the high-purity silicon powder and the doping elements are mixed and then are uniformly ground;
2) spraying the mixed material onto the surface of a target core by a spraying method to form an alloy target material; the target core is a steel pipe or a titanium steel pipe, the diameter of the target core is 50-300 mm, the length of the target core is determined according to the width of PVD (physical vapor deposition) coating equipment, a longer target can cover more silicon wafers at one time, the productivity of the silicon wafers generated by coating is improved, and the length range is 1000-4000 mm; the spraying thickness is 3-10 mm; the mass percentage content of the doping elements in the obtained target material is 0.1-1.5%, the oxygen content in the target material is less than or equal to 2000ppm, and the nitrogen content in the target material is less than or equal to 300 ppm; during spraying, high-temperature high-pressure argon gas and mixed powder are mixed, molten liquid powder is sprayed out through a nozzle, and an alloy target material is formed on the surface of a target core.
Example 3:
the invention provides a preparation method of a doped amorphous silicon solar cell, which is based on the target material obtained in the embodiment 1 or 2, and adopts a PVD method to complete the doped amorphous silicon coating so as to form in-situ doped amorphous silicon on the surface of a silicon wafer.
The invention prepares a silicon target mixed with doping elements in advance, completes the amorphous silicon doping film coating by using a PVD method, and can directly form in-situ doped amorphous silicon on the surface of a silicon wafer in the PVD film coating process; and according to the requirement of doping concentration, phosphorus element or boron element with corresponding concentration is doped into the silicon target for doping the amorphous silicon layer film by TOPCon, and the doping can be realized by one PVD coating process. Compared with the method that doping elements are added by using an ion implantation process for film coating by using a gas silane LPCVD process, the method has the advantages of simple process, low cost and high use safety.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to the above-described embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (9)

1. A preparation method of a target material doped with amorphous silicon is characterized by comprising the following steps:
1) mixing high-purity silicon powder and doping elements in required proportion in advance;
2) transferring the mixture material obtained based on the step 1) into a vacuum high-temperature sealing furnace to generate silicon and doped element alloy, cooling and taking out the alloy, crushing the cooled alloy, cleaning and screening powder with a certain particle size;
3) and (3) spraying the powder obtained in the step 2) onto a steel pipe serving as a substrate through a high-temperature arc spray gun by using inert gas such as argon and the like as carrier gas, so as to obtain the alloy target material uniformly distributed on the steel pipe.
2. The method for preparing the amorphous silicon-doped target material according to claim 1, wherein in the step 1), the purity of the high-purity silicon powder is not less than 99.99%, and the doping element is phosphorus or boron.
3. The method for preparing the amorphous silicon doped target material according to claim 1, wherein the grain size of the powder obtained in the step 2) is 50-200 um.
4. The method for preparing the amorphous silicon-doped target material according to claim 3, wherein in the step 3), the steel tube repeatedly rotates and translates for many times in the spraying process, and the thickness of the alloy target material is 3-10 mm; wherein the diameter of the steel pipe is 50-300 mm, and the length of the steel pipe is 1000-4000 mm; the mass percentage content of the doping elements in the obtained target material is 0.1-1.5%, the oxygen content in the target material is less than or equal to 2000ppm, and the nitrogen content in the target material is less than or equal to 300 ppm.
5. A preparation method of a target material doped with amorphous silicon is characterized by comprising the following steps:
1) mixing high-purity silicon powder and doping elements in required proportion in advance;
2) spraying the mixed material onto the surface of the target core by a spraying method to form the alloy target material.
6. The method for preparing the amorphous silicon-doped target material according to claim 5, wherein in the step 1), the high-purity silicon powder has the following size: 50-200 meshes, and the purity is more than or equal to 99.99%; the doping elements are phosphorus elements or boron elements: the size is 50-200 meshes, and the purity is more than or equal to 99.9%; and the high-purity silicon powder and the doping elements are uniformly ground after being mixed.
7. The method for preparing the amorphous silicon doped target material according to claim 5, wherein in the step 2), the target core is a steel tube or a titanium steel tube, the diameter of the target core is 50-300 mm, and the length of the target core is 1000-4000 mm; the spraying thickness is 3-10 mm; the mass percentage content of the doping elements in the obtained target material is 0.1-1.5%, the oxygen content in the target material is less than or equal to 2000ppm, and the nitrogen content in the target material is less than or equal to 300 ppm.
8. The method for preparing an amorphous silicon doped target material according to claim 5, wherein in the step 2), during sputtering, high temperature and high pressure argon gas is mixed with the mixed powder material, and molten liquid powder is sprayed through the nozzle to form an alloy target material on the surface of the target core.
9. A preparation method of a doped amorphous silicon solar cell is characterized in that based on the target material obtained in any one of claims 1-8, a PVD method is adopted to complete doped amorphous silicon coating so as to form in-situ doped amorphous silicon on the surface of a silicon wafer.
CN201911346159.8A 2019-12-24 2019-12-24 Amorphous silicon-doped target material and solar cell preparation method Pending CN111074217A (en)

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CN112359320A (en) * 2020-10-22 2021-02-12 江苏杰太光电技术有限公司 Gas source for preparing doped amorphous silicon film
WO2023285639A1 (en) * 2021-07-16 2023-01-19 Soleras Advanced Coatings Bv Conductive silicon sputtering targets

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