CN112410872A - Polycrystalline silicon material and preparation method thereof - Google Patents
Polycrystalline silicon material and preparation method thereof Download PDFInfo
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- CN112410872A CN112410872A CN202011293081.0A CN202011293081A CN112410872A CN 112410872 A CN112410872 A CN 112410872A CN 202011293081 A CN202011293081 A CN 202011293081A CN 112410872 A CN112410872 A CN 112410872A
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B28/00—Production of homogeneous polycrystalline material with defined structure
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/06—Silicon
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B31/00—Diffusion or doping processes for single crystals or homogeneous polycrystalline material with defined structure; Apparatus therefor
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Abstract
The invention provides a polycrystalline silicon material and a preparation method thereof. The technical scheme is based on the metal ion doping principle to compound the components of the polycrystalline silicon, and introduces a trace amount of CoCl2、Ag2CrO4、BaCl2O8And the components are equal, the crystal structure is protected by TiC and GaAs, and the formula proportion is optimized. On the basis, the preparation method of the polysilicon material is provided, and the method is based on the improved Siemens method and is used for preparing SiHCl3In the process of (2), germanium tetrachloride and Bi (NO) are added3)3、BaCl2O8Obtaining doped trichlorosilane; then condensing to remove impurities and further doping CoCl2、Ag2CrO4Magnesium trisilicate; in the reduction process, TiC, GaAs and trichlorosilane are vaporized together and then are sent to be reducedAnd the furnace is used for embedding metal ions in crystal lattices along with the growth of crystals so as to obtain the polycrystalline silicon material. The photoelectric conversion efficiency of the polysilicon material can reach about 28%, and meanwhile, the service life of the polysilicon material is obviously prolonged, and the polysilicon material has outstanding technical advantages.
Description
Technical Field
The invention relates to the technical field of photovoltaic materials, in particular to a polycrystalline silicon material and a preparation method thereof.
Background
Polycrystalline silicon is a form of elemental silicon. When molten elemental silicon is solidified under undercooling conditions, silicon atoms are arranged in the form of a diamond lattice into a plurality of crystal nuclei, and if the crystal nuclei grow into crystal grains with different crystal plane orientations, the crystal grains are combined and crystallized into polycrystalline silicon.
Polycrystalline silicon is the most important and basic functional material in the semiconductor industry, the electronic information industry and the solar photovoltaic cell industry. The silicon-based single crystal silicon is mainly used as a raw material of a semiconductor, is a main raw material for preparing single crystal silicon, and can be used as various transistors, rectifier diodes, silicon controlled rectifiers, solar cells, integrated circuits, electronic computer chips, infrared detectors and the like.
The polysilicon material used in the solar cell at present is mostly an aggregate containing a large amount of single crystal particles, or is formed by melting and casting waste single crystal silicon materials and metallurgical grade silicon materials. The process comprises the steps of selecting polycrystalline lump materials or monocrystalline silicon head and tail materials with the resistivity of 100-300 ohm centimeters, crushing, properly corroding with mixed solution of hydrofluoric acid and nitric acid in a ratio of 1:5, washing with deionized water to be neutral, and drying. The polycrystalline silicon material is filled in a quartz crucible, a proper amount of borosilicate is added, the mixture is placed in a casting furnace, and the mixture is heated and melted in a vacuum state. And (3) after melting, keeping the temperature for about 20 minutes, then injecting into a graphite casting mold, slowly solidifying and cooling to obtain a polycrystalline silicon ingot, and slicing to obtain the square solar cell.
Compared with monocrystalline silicon, the polycrystalline silicon material has relatively low raw material cost and manufacturing cost, low requirement on a cutting process and high yield. However, the electrical properties are poor, the photoelectric conversion efficiency is about 15%, and the photoelectric conversion efficiency of monocrystalline silicon is about 17% -24%. Furthermore, the service life of polycrystalline silicon solar cells is also shorter than that of single crystalline silicon solar cells.
Disclosure of Invention
The invention aims to provide a polycrystalline silicon material and a preparation method thereof aiming at overcoming the technical defects of the prior art, and aims to solve the technical problem that the photoelectric conversion efficiency of the conventional polycrystalline silicon material is low.
Another technical problem to be solved by the present invention is that the conventional polysilicon material has a short lifetime.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the polycrystalline silicon material comprises the following components in parts by weight: 97-97.5 parts of polycrystalline silicon and CoCl20.02-0.04 part of Ag2CrO4 0.04 to 0.08 parts of BaCl2O80.03-0.05 part of TiC 0.01-0.05 part of Pb (NO)3)20.02-0.04 part, 0.02-0.04 part of germanium tetrachloride, 0.08-0.1 part of GaAs, and Sb2O30.01 to 0.05 part, 0.05 to 0.07 part of magnesium trisilicate, and Bi (NO)3)30.08-0.1 part.
Preferably, the ammonium metavanadate also comprises 0.03-0.05 weight part.
Preferably, the paint also comprises 0.01-0.07 weight part of nickel acetylacetonate.
Preferably, the material also comprises 0.02-0.04 weight part of Na2S2O3。
Preferably, the paint also comprises 0.04-0.08 weight part of ammonium heptamolybdate.
Preferably, the polysilicon material consists of the following components in parts by weight: 97.2 parts of polycrystalline silicon, CoCl20.03 part of Ag2CrO40.06 part of BaCl2O80.04 part, TiC 0.03 part, Pb (NO)3)20.03 part, 0.03 part of germanium tetrachloride, 0.09 part of GaAs and Sb2O30.03 portion, 0.06 portion of magnesium trisilicate, Bi (NO)3)30.09 part.
Preferably, the polysilicon material consists of the following components in parts by weight: 97.2 parts of polycrystalline silicon, CoCl20.03 part of Ag2CrO40.06 part of BaCl2O80.04 part, TiC 0.03 part, Pb (NO)3)20.03 part, 0.03 part of germanium tetrachloride, 0.09 part of GaAs and Sb2O30.03 portion, 0.06 portion of magnesium trisilicate, Bi (NO)3)30.09 part of ammonium metavanadate, 0.04 part of nickel acetylacetonate and Na2S2O30.03 part and 0.06 part of ammonium heptamolybdate.
On the basis of the technical scheme, the invention further provides a preparation method of the polycrystalline silicon material, which comprises the following steps: pulverizing industrial silicon with purity not less than 99%, mixing with anhydrous HCl, reacting in fluidized bed reactor at 400 deg.C for 20min, and adding germanium tetrachloride and Bi (NO) in formula amount3)3、BaCl2O8Continuously reacting for 70min to obtain doped SiHCl3(ii) a Then the doped SiHCl is added at 6 DEG C3Maintaining for 20min, collecting liquid phase, adding CoCl in formula amount2、Ag2CrO4Heating to 170 ℃ and keeping for 30min to obtain doped purified SiHCl3(ii) a Subjecting the doped purified SiHCl3Sending the silicon rod and TiC and GaAs with the formula amount into a vaporizer, mixing the mixture with hydrogen, sending the mixture into a reduction furnace, electrifying and heating the silicon rod in the reduction furnace to 1150-1200 ℃, growing for 70min, and then sending Pb (NO) with the formula amount into the silicon rod3)2Continuing to grow for 80 min; then cooling, and feeding Sb into the furnace when the temperature is reduced to 900 DEG C2O3And continuously cooling to normal temperature.
The invention provides a polycrystalline silicon material and a preparation method thereof. The technical scheme aims at the problem that the electrical property of the polysilicon material needs to be improved, and improves the components and the preparation process of the polysilicon material. Specifically, the invention compounds the components of the polysilicon based on the metal ion doping principle, and introduces a trace amount of CoCl2、Ag2CrO4、BaCl2O8And the components are equal, the crystal structure is protected by TiC and GaAs, and the formula proportion is optimized. On the basis, the invention provides a preparation method of the polycrystalline silicon material, which is based on an improved Siemens method and is used for preparing SiHCl3In the process of (2), germanium tetrachloride and Bi (NO) are added3)3、BaCl2O8Obtaining doped trichlorosilane; then condensing to remove impurities and further doping CoCl2、Ag2CrO4Magnesium trisilicate; in the reduction process, TiC, GaAs and trichlorosilane are vaporized together and then are sent into a reduction furnace, and metal ions are embedded in crystal lattices along with the growth of crystals, so that the polycrystalline silicon material is obtained. The polycrystalline silicon material provided by the invention basically does not influence the light transmittance of the material, and the photoelectric conversion efficiency is remarkably improved to about 28%; meanwhile, the crystal structure is more stable due to the supporting effect of the doping components, the service life of the material is obviously prolonged, and the method has outstanding technical advantages。
Detailed Description
Hereinafter, specific embodiments of the present invention will be described in detail. Well-known structures or functions may not be described in detail in the following embodiments in order to avoid unnecessarily obscuring the details. Approximating language, as used herein in the following examples, may be applied to identify quantitative representations that could permissibly vary in number without resulting in a change in the basic function. Unless defined otherwise, technical and scientific terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Example 1
The polycrystalline silicon material comprises the following components in parts by weight: 97 parts of polycrystalline silicon, CoCl20.02 part of Ag2CrO40.04 part of BaCl2O80.03 part, TiC 0.01 part, Pb (NO)3)20.02 part, 0.02 part of germanium tetrachloride, 0.08 part of GaAs0.08 part, Sb2O30.01 portion, 0.05 portion of magnesium trisilicate, Bi (NO)3)30.08 portion.
Example 2
The polycrystalline silicon material comprises the following components in parts by weight: 97.5 parts of polysilicon, CoCl20.04 part of Ag2CrO40.08 parts of BaCl2O80.05 part, TiC 0.05 part, Pb (NO)3)20.04 part, 0.04 part of germanium tetrachloride, 0.1 part of GaAs, and Sb2O30.05 part, 0.07 part of magnesium trisilicate, Bi (NO)3)30.1 part.
Example 3
The polycrystalline silicon material comprises the following components in parts by weight: 97.2 parts of polycrystalline silicon, CoCl20.03 part of Ag2CrO40.06 part of BaCl2O80.04 part, TiC 0.03 part, Pb (NO)3)20.03 part, 0.03 part of germanium tetrachloride, 0.09 part of GaAs and Sb2O30.03 portion, 0.06 portion of magnesium trisilicate, Bi (NO)3)30.09 part.
Example 4
A polysilicon material consisting of the following components in parts by weightThe composition is as follows: 97.2 parts of polycrystalline silicon, CoCl20.03 part of Ag2CrO40.06 part of BaCl2O80.04 part, TiC 0.03 part, Pb (NO)3)20.03 part, 0.03 part of germanium tetrachloride, 0.09 part of GaAs and Sb2O30.03 portion, 0.06 portion of magnesium trisilicate, Bi (NO)3)30.09 part of ammonium metavanadate, 0.04 part of nickel acetylacetonate and Na2S2O30.03 part and 0.06 part of ammonium heptamolybdate.
Example 5
A method for preparing the polysilicon material of the above embodiment 1, comprising the steps of: pulverizing industrial silicon with purity not less than 99%, mixing with anhydrous HCl, reacting in fluidized bed reactor at 400 deg.C for 20min, and adding germanium tetrachloride and Bi (NO) in formula amount3)3、BaCl2O8Continuously reacting for 70min to obtain doped SiHCl3(ii) a Then the doped SiHCl is added at 6 DEG C3Maintaining for 20min, collecting liquid phase, adding CoCl in formula amount2、Ag2CrO4Heating to 170 ℃ and keeping for 30min to obtain doped purified SiHCl3(ii) a Subjecting the doped purified SiHCl3Sending the silicon rod and TiC and GaAs with the formula amount into a vaporizer, mixing the mixture with hydrogen, sending the mixture into a reduction furnace, electrifying and heating the silicon rod in the reduction furnace to 1150-1200 ℃, growing for 70min, and then sending Pb (NO) with the formula amount into the silicon rod3)2Continuing to grow for 80 min; then cooling, and feeding Sb into the furnace when the temperature is reduced to 900 DEG C2O3And continuously cooling to normal temperature.
The embodiments of the present invention have been described in detail, but the description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention. Any modification, equivalent replacement, and improvement made within the scope of the application of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The polycrystalline silicon material is characterized by comprising the following components in parts by weight: 97-97.5 parts of polycrystalline silicon and CoCl20.02 to 0.04 portion，Ag2CrO40.04 to 0.08 part of BaCl2O80.03-0.05 part of TiC 0.01-0.05 part of Pb (NO)3)20.02-0.04 part, 0.02-0.04 part of germanium tetrachloride, 0.08-0.1 part of GaAs, and Sb2O30.01 to 0.05 part, 0.05 to 0.07 part of magnesium trisilicate, and Bi (NO)3)30.08-0.1 part.
2. The polysilicon material of claim 1, further comprising 0.03 to 0.05 parts by weight of ammonium metavanadate.
3. The polysilicon material according to claim 1, further comprising 0.01 to 0.07 parts by weight of nickel acetylacetonate.
4. The polysilicon material according to claim 1, further comprising 0.02 to 0.04 parts by weight of Na2S2O3。
5. The polycrystalline silicon material of claim 1, further comprising 0.04 to 0.08 parts by weight of ammonium heptamolybdate.
6. The polysilicon material of claim 1, wherein the polysilicon material comprises the following components in parts by weight: 97.2 parts of polycrystalline silicon, CoCl20.03 part of Ag2CrO40.06 part of BaCl2O80.04 part, TiC 0.03 part, Pb (NO)3)20.03 part, 0.03 part of germanium tetrachloride, 0.09 part of GaAs and Sb2O30.03 portion, 0.06 portion of magnesium trisilicate, Bi (NO)3)30.09 part.
7. The polysilicon material of claim 1, wherein the polysilicon material comprises the following components in parts by weight: 97.2 parts of polycrystalline silicon, CoCl20.03 part of Ag2CrO40.06 part of BaCl2O80.04 part, TiC 0.03 part, Pb (NO)3)20.03 part, 0.03 part of germanium tetrachloride, 0.09 part of GaAs and Sb2O30.03 portion, 0.06 portion of magnesium trisilicate, Bi (NO)3)30.09 part of ammonium metavanadate, 0.04 part of nickel acetylacetonate and Na2S2O30.03 part and 0.06 part of ammonium heptamolybdate.
8. A method of forming a polysilicon material according to claim 1, comprising the steps of: pulverizing industrial silicon with purity not less than 99%, mixing with anhydrous HCl, reacting in fluidized bed reactor at 400 deg.C for 20min, and adding germanium tetrachloride and Bi (NO) in formula amount3)3、BaCl2O8Continuously reacting for 70min to obtain doped SiHCl3(ii) a Then the doped SiHCl is added at 6 DEG C3Maintaining for 20min, collecting liquid phase, adding CoCl in formula amount2、Ag2CrO4Heating to 170 ℃ and keeping for 30min to obtain doped purified SiHCl3(ii) a Subjecting the doped purified SiHCl3Sending the silicon rod and TiC and GaAs with the formula amount into a vaporizer, mixing the mixture with hydrogen, sending the mixture into a reduction furnace, electrifying and heating the silicon rod in the reduction furnace to 1150-1200 ℃, growing for 70min, and then sending Pb (NO) with the formula amount into the silicon rod3)2Continuing to grow for 80 min; then cooling, and feeding Sb into the furnace when the temperature is reduced to 900 DEG C2O3And continuously cooling to normal temperature.
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| CN202011293081.0A CN112410872A (en) | 2020-11-18 | 2020-11-18 | Polycrystalline silicon material and preparation method thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4301323A (en) * | 1979-05-30 | 1981-11-17 | Siemens Aktiengesellschaft | Lead-doped silicon with enhanced semiconductor properties |
| US20020078992A1 (en) * | 2000-11-15 | 2002-06-27 | Peter Woditsch | Multicrystalline silicon having a low proportion of active grain borders |
| US20070006916A1 (en) * | 2005-07-07 | 2007-01-11 | Kyojiro Kaneko | Solar-cell polycrystalline silicon and method for producing the same |
| US20120135590A1 (en) * | 2010-11-30 | 2012-05-31 | Advanced Technology Materials, Inc. | Silicon removal from surfaces and method of forming high k metal gate structures using same |
| CN104229802A (en) * | 2013-06-24 | 2014-12-24 | 潘龙祥 | Preparation method of polycrystalline silicon |
| CN109867287A (en) * | 2019-03-16 | 2019-06-11 | 浙江海顺新能源有限公司 | A kind of solar energy polycrystalline silicon sheet preparation method |
-
2020
- 2020-11-18 CN CN202011293081.0A patent/CN112410872A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4301323A (en) * | 1979-05-30 | 1981-11-17 | Siemens Aktiengesellschaft | Lead-doped silicon with enhanced semiconductor properties |
| US20020078992A1 (en) * | 2000-11-15 | 2002-06-27 | Peter Woditsch | Multicrystalline silicon having a low proportion of active grain borders |
| US20070006916A1 (en) * | 2005-07-07 | 2007-01-11 | Kyojiro Kaneko | Solar-cell polycrystalline silicon and method for producing the same |
| US20120135590A1 (en) * | 2010-11-30 | 2012-05-31 | Advanced Technology Materials, Inc. | Silicon removal from surfaces and method of forming high k metal gate structures using same |
| CN104229802A (en) * | 2013-06-24 | 2014-12-24 | 潘龙祥 | Preparation method of polycrystalline silicon |
| CN109867287A (en) * | 2019-03-16 | 2019-06-11 | 浙江海顺新能源有限公司 | A kind of solar energy polycrystalline silicon sheet preparation method |
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