US20030106581A1 - Silicon structure, method for producing the same, and solar battery using the silicon structure - Google Patents
Silicon structure, method for producing the same, and solar battery using the silicon structure Download PDFInfo
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- US20030106581A1 US20030106581A1 US10/322,192 US32219202A US2003106581A1 US 20030106581 A1 US20030106581 A1 US 20030106581A1 US 32219202 A US32219202 A US 32219202A US 2003106581 A1 US2003106581 A1 US 2003106581A1
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- silicon
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- silicon structure
- solar battery
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 179
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 99
- 239000010703 silicon Substances 0.000 claims abstract description 99
- 239000000758 substrate Substances 0.000 claims abstract description 48
- 229910007245 Si2Cl6 Inorganic materials 0.000 claims abstract description 16
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910015844 BCl3 Inorganic materials 0.000 claims abstract description 8
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 37
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 20
- 239000002210 silicon-based material Substances 0.000 claims description 16
- 229910001882 dioxygen Inorganic materials 0.000 claims description 15
- 239000011344 liquid material Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 10
- 239000004065 semiconductor Substances 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 5
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 3
- 230000002093 peripheral effect Effects 0.000 claims description 2
- 239000010453 quartz Substances 0.000 abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 7
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 abstract description 6
- 229910019213 POCl3 Inorganic materials 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 10
- 230000008016 vaporization Effects 0.000 description 10
- 239000011261 inert gas Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000006200 vaporizer Substances 0.000 description 3
- 229910003818 SiH2Cl2 Inorganic materials 0.000 description 2
- 229910003822 SiHCl3 Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910003910 SiCl4 Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
- H01L31/04—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
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
- H01L31/0547—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means comprising light concentrating means of the reflecting type, e.g. parabolic mirrors, concentrators using total internal reflection
-
- 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
- H01L31/02168—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
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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
- H01L31/02—Details
- H01L31/0236—Special surface textures
- H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
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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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0352—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 characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035209—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 characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
- H01L31/035227—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 characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures the quantum structure being quantum wires, or nanorods
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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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/036—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0368—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including polycrystalline semiconductors
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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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/036—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0376—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 characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including amorphous semiconductors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/52—PV systems with concentrators
Definitions
- the present invention relates to a silicon structure which can be usefully applied to a light-emitting device or a solar battery, the method and apparatus for producing the same, and a solar battery using the silicon structure.
- a solar battery using silicon has been provided with an antireflection coating or an unevenness on its surface.
- FIG. 7 is a cross-sectional diagram of a conventional silicon solar battery (textured structure).
- an uneven surface is formed at the photodetecting side of a p type silicon substrate 31 so as to reduce the reflection ratio of the solar beam.
- Methods of forming the unevenness commonly used include a chemical formation method using photolithography and chemical etching, and a mechanical formation method using a dicing machine.
- Examples of silicon substrates include a single crystalline silicon substrate produced by the Czochralski method and a polycrystalline silicon substrate produced with an electromagnetic cast.
- An n type silicon layer 32 is formed on the uneven surface of the p type silicon substrate 31 .
- the n type silicon layer 32 is formed by diffusing P (phosphorus) using a gas such as POCl 3 on the uneven portion of the p type silicon substrate 31 so as to change a part of the p type silicon substrate 31 to the n type.
- An antireflection coating 33 comprising a material such as SiN and MgF 2 is formed on the n type silicon layer 32 .
- a surface electrode 34 is formed on the light accepting side of the p type silicon substrate 31 via an n++ silicon layer 35 , and the surface electrode 34 is exposed on the surface of the antireflection coating 33 .
- a back side electrode 36 is formed on the back side of the p type silicon substrate 31 via a p+ silicon layer 37 .
- the energy conversion efficiency can be improved (the Third “High Efficiency Solar Battery” workshop preliminary reports, hosted by the Institute of Electrical Engineers, Semiconductor Electric Power Conversion Technology Committee, in Toyama, Japan, A5-A6, 28-35 pages, Oct. 5, 1992).
- an object of the present invention is to provide a silicon structure exhibiting little solar light beam reflection, the method and apparatus for producing the same, and a solar battery using the silicon structure.
- a configuration of the silicon structure of the present invention comprises an aggregate of a plurality of columnar silicon members mainly comprising silicon and having random orientations.
- the silicon structure since the light beam incident on one columnar silicon member is reflected thereby and re-enters another columnar silicon member, the solar beam can be absorbed efficiently. That is, according to the configuration of the silicon structure of the present invention, a silicon structure having little solar beam reflection can be obtained.
- the silicon content amount of the columnar silicon members is 95 weight % or more, and in addition to the silicon, about 1 weight % of chlorine, about a few weight % of oxygen can be included.
- a substrate is provided and the silicon structure is formed on the substrate via a film mainly comprising silicon.
- a transparent electrode does not come in contact with a lower electrode in the process of producing a solar battery using the silicon structure.
- the diameter of the columnar silicon member is 0.1 to 10 ⁇ m. According to this embodiment, an adequate strength of the columnar silicon can be maintained and the depth of junction at the time of converting to an n type or a p type does not need to be limited. Further, the light absorption does not deteriorate.
- the periphery of the columnar silicon member is amorphous and the center thereof is polycrystalline.
- the silicon structure comprising an aggregate of a plurality of columnar silicon members mainly comprising silicon having random orientations can be produced by a method, wherein an atomized or vaporized silicon material containing chloride is introduced to a heated substrate with an oxygen gas.
- a silicon material which is less dangerous than a silane gas (SiH 4 ) can be used, the silicon material can be supplied in a great amount.
- SiH 4 silane gas
- a silicon structure comprising an aggregate of a plurality of columnar silicon members mainly comprising silicon can be obtained.
- an inert gas can be introduced to the substrate at the same time in order to convey a silicon material containing chloride.
- the amount of chloride in the silicon structure can be reduced. Further, since a complicated process to form an uneven shape is not necessary unlike the conventional textured structure, the production cost can be reduced.
- the silicon material containing chloride is Si 2 Cl 6 .
- the decomposition temperature is approximately 350° C., which is low and the decomposition can be conducted by radiating an ultraviolet ray beam (188 nm)
- a silicon structure comprising an aggregate of a plurality of columnar silicon members mainly comprising silicon and having random orientations can be easily obtained.
- an n type or p type silicon structure is formed using a liquid material containing PCl 3 or BCl 3 as the silicon material comprising Si 2 Cl 6 .
- the oxygen gas is introduced so that the oxygen content of the vicinity of the centers of the columnar silicon members becomes 3% or less.
- the resistance of the silicon structure can be kept at a low level and thus the silicon structure can be used in an electronic device.
- an apparatus for producing the silicon structure of the present invention comprises a chamber, means to supply an atomized or vaporized liquid material comprising silicon and oxygen gas to the chamber, a support for a substrate to be treated by the apparatus, a heater for a substrate to be treated by the apparatus and a filter having an area that is at least as large as the area of a substrate to be treated by the apparatus, through which the atomized or vaporized liquid material and oxygen gas are introduced to a substrate to be treated by the apparatus.
- a silicon substrate can be formed uniformly on the substrate.
- the filter comprises a stainless steel fiber.
- a filter having a large area and a very large void ratio of from 70 to 90% and a uniform pore size can be formed at a low cost. And by dividing the vaporizing chamber and the process chamber with the filter, the pressure difference between the vaporizing chamber and the process chamber is unlikely to be generated and thus the condensation of the material caused by the adiabatic expansion can be prevented.
- the pore size of the filter is 1 to 30 ⁇ m. According to this embodiment, a material gas and an oxygen gas can be sprayed on the substrate uniformly.
- a solar battery of the present invention is a solar battery comprising a semiconductor layer to generate an electron-hole pair by light radiation, wherein the semiconductor layer includes a silicon structure comprising an aggregate of a plurality of columnar silicon members mainly comprising silicon and having random orientations. According to the configuration of the solar battery, since the solar beam reflection is reduced, power generation can be conducted efficiently.
- a substrate is provided and a silicon structure is formed on the substrate via a film mainly comprising silicon.
- the diameter of the columnar silicon member is 0.1 to 10 ⁇ m.
- the periphery of the columnar silicon member is amorphous and the center portion is polycrystalline.
- the silicon structure is formed on the surface of the semiconductor layer at the side on which the light beam enters.
- a pn junction is formed inside the columnar silicon. According to this embodiment, the following advantage can be achieved. That is, since the area of the pn junction portion can be increased in the case of a silicon structure comprising a plurality of columnar silicon members compared with the case of a conventional flat film, power generation can be conducted efficiently.
- FIG. 1 is a diagram illustrating the silicon film formation device used in the first embodiment of the present invention.
- FIGS. 2A and 2B are tracings of a scanning electron microscope photograph (SEM) of the silicon structure formed in the first embodiment of the present invention.
- FIGS. 3A to 3 C are tracings of a laser microscope photograph of the surface shapes of the silicon films formed with different oxygen amounts in the first embodiment of the present invention.
- FIG. 4 is a graph to illustrate the visible absorption spectrum of the silicon structure formed on the quartz substrate in the first embodiment of the present invention.
- FIGS. 5A to 5 C are diagrams illustrating the process for producing the solar battery using the silicon structure in the second embodiment of the present invention.
- FIG. 6 is a cross-sectional view illustrating the configuration of the solar battery of the second embodiment of the present invention.
- FIG. 7 is a cross-sectional diagram illustrating the configuration of the silicon solar battery (textured structure) of a conventional silicon solar battery.
- FIG. 1 is a diagram illustrating the silicon film formation device used in the first embodiment of the present invention.
- a process chamber 11 having an air-tight structure is divided with a horizontal filter 26 .
- the filter 26 is formed by sintering many stainless steel fibers having a few ⁇ m diameter and the pore size is about 10 ⁇ m.
- the process chamber 11 has a material gas supply orifice 18 at the side wall beneath the filter 26 (the vaporizing chamber 14 ) so as to supply an atomized or vaporized liquid material 15 to the process chamber 11 from a vaporizer 23 , with the flow rate being adjusted by a flow control device 22 as needed.
- the vaporizer 23 can be supplied with an oxygen gas 24 so as to supply a liquid material 15 containing the oxygen gas 24 to the process chamber 11 .
- An exhaustion orifice 17 is arranged at the upper wall above the filter 26 in the process chamber 11 .
- a substrate holder 12 in which a heater for heating the substrate 21 is stored is located horizontally above the filter 26 in the process chamber 11 so as to hold a substrate 13 on the lower side thereof. Further, a vaporization aid heater 27 is arranged under the filming chamber 11 .
- a quartz substrate was used for the substrate 13 .
- the substrate 13 was heated with the heater for heating the substrate 21 to approximately 680° C.
- And (Si 2 Cl 6 +BCl 3 ) was used as the liquid material 15 .
- the inside of the process chamber 11 was kept at an ordinary pressure (1 atomospheric pressure).
- the liquid material 15 was propelled by an inert gas such as Ar and the flow rate was controlled at a proper level by a flow control device 22 . Then the liquid material 15 was atomized or vaporized and mixed with the inert gas and an oxygen gas 24 in a vaporizer 23 , and was supplied to the vaporizing chamber 14 from the material gas supply orifice 18 . At the same time, a reducing gas 25 such as H 2 was supplied to the vaporizing chamber 14 . It is preferable that the flow rate of the oxygen gas 24 is 1 to 10 cc/minute with respect to a flow rate of Si 2 Cl 6 of 10 g/hour (H 2 O calibration).
- Methods for atomizing the liquid material 15 include a method of using an ultrasonic vibration.
- the silicon material can be supplied to the process chamber 11 in a great amount.
- a silicon structure comprising an aggregate of a plurality of columnar silicon members mainly comprising silicon and having random orientations can be obtained.
- the oxygen content amount in the vicinity of the center of a columnar silicon is 3% or less.
- the 3% or less of the oxygen content amount in the vicinity of the center of the columnar silicon member enables maintaining the resistance of the silicon structure to be maintained at a low level so that the silicon structure can be used in an electronic device.
- the “vicinity of the center of the columnar silicon member” herein denotes the region excluding the region from the surface to about 50 nm depth of the columnar silicon member.
- Si 2 Cl 6 was used as the silicon material containing chlorine in this embodiment, it is not limited thereto but other materials can be used as well.
- the silicon materials containing chlorine include SiCl 4 , SiH 2 Cl 2 , SiHCl 3 , Si 3 Cl 8 and Si 4 Cl 10 .
- SiCl 4 SiH 2 Cl 2
- SiHCl 3 Si 3 Cl 8
- Si 4 Cl 10 Si 4 Cl 10 .
- Si 2 Cl 6 has a decomposition temperature of approximately 350° C., which is low, and is decomposed by radiation of an ultraviolet ray (188 nm), a silicon structure can be formed easily.
- Ar was used as the inert gas for spraying in this embodiment, it is not limited thereto but other gases such as He and N 2 can be used as well.
- a so-called bubbling method namely, a method to introduce the liquid material 15 to the process chamber 11 as bubbles, can be used.
- H 2 gas was used as the reducing gas 25 in this embodiment, it is not limited thereto but other gases such as CO can be used as well.
- a silicon structure can be formed without introducing a reducing gas. Besides, by conveying the silicon material only with an H 2 gas without using an inert gas, the amount of chlorine contained in the silicon structure can be reduced.
- a quartz is used as the substrate 13 in this embodiment, it is not limited thereto but other materials such as a ceramic material or a metallic material such as stainless steel can be used as well.
- the film formation was conducted in the chamber with an ordinary pressure (1 atomospheric pressure) in this embodiment, it is not limited thereto but the film formation can be conducted in a vacuum state (0.1 to 760 Torr) or in a pressurized state (1 to 10 atomospheric pressure). In particular, by conducting the film formation in the pressurized state, the deposition rate can be further increased.
- a filter 26 comprising stainless steel fibers was used in this embodiment, it is not limited thereto but a filter 26 of other materials such as quartz can be used as well.
- a filter 26 by sintering many stainless steel fibers, a filter having a large area and a very large void ratio of from 70 to 90% can be provided at a low cost. By dividing the vaporizing chamber 14 and the process chamber 11 with the filter, the pressure difference between the vaporizing chamber 14 and the process chamber 11 is unlikely to be generated.
- the pore size of the filter 26 was set to be 10 ⁇ m, the pore size is not limited thereto but any filter 26 having a pore size of 1 to 30 ⁇ m can allow uniform spraying of a material gas or an oxygen gas to the substrate 13 .
- FIGS. 2A, 2B are tracings of scanning electron microscope photographs (SEM) of the silicon structure formed in this embodiment.
- FIG. 2A and FIG. 2B illustrate the same sample in different magnifications.
- a silicon structure comprising an aggregate of a plurality of columnar silicon members having a diameter of approximately 0.5 ⁇ m, mainly comprising silicon and having different orientations was formed.
- the silicon structure since a light beam entered into and reflected by a columnar silicon member enters another columnar silicon member, the solar beam can be absorbed efficiently. That is, a silicon structure having little solar light beam reflection can be obtained.
- FIGS. 3A to 3 C are tracings of laser microscope photographs illustrating the surface shape of the silicon film formed with different oxygen amounts.
- the FIGS. 3A to 3 C are described with the black portion and the white portion reversed with respect to the actual laser microscope photographs in 1,000 magnification.
- Film formation conditions are as per Table 1.
- Pressure Ordinary pressure
- FIG. 3A when the oxygen flow rate was 0 cc/min, an approximately flat film (black portion) was formed.
- FIG. 3B when the oxygen flow rate was 1 cc/min, although a silicon structure (white portion) was partially formed, a flat portion (black portion) still remains.
- FIG. 3C when the oxygen flow rate was 3 cc/min, a silicon structure (white portion) was formed almost completely.
- FIG. 4 illustrates a visible absorption spectrum of the silicon structure formed on a quartz substrate in this embodiment. As shown in FIG. 4, a silicon structure formed in this embodiment barely permeates a light beam having a wavelength of 200 to 800 nm.
- the silicon structure comprises columnar silicon members having a diameter of approximately 0.5 ⁇ m in this embodiment
- the diameter of columnar silicons can vary as long as it is in the range of 0.1 to 10 ⁇ m.
- the diameter of the columns within the above mentioned range provides the columns with a proper strength and also does not limit the depth of junction in changing the surface of the silicon to an n type or a p type by a diffusion. Further, if the diameter of the columns is in the above mentioned range, light absorption is not deteriorated.
- FIGS. 5A to 5 C are diagrams illustrating the production process of the solar battery using the silicon structure in the second embodiment.
- FIG. 6 illustrates the confuguration of the solar battery of this embodiment.
- a p type silicon structure 43 comprising an aggregate of a plurality of columnar silicon members 48 on the lower electrode 41 via a film 47 mainly comprising silicon 47 , there is no risk of contacting a transparent electrode 45 to the lower electrode 41 in forming the transparent electrode 45 as explained below.
- amorphous silicons have a resistance higher than that of polycrystalline silicons, it is preferable to have a polycrystalline region in a large area. Specifically speaking, with respect to a diameter of 0.5 ⁇ m of the columnar silicons 48 , a preferable thickness of the n type region (amorphous) 44 is approximately 0.1 ⁇ m.
- a transparent electrode 45 comprising indium-tin oxide having a thickness of approximately 30 to 40 ⁇ m on the entire surface of the p type silicon structure 43
- an upper electrode 46 comprising Al was formed at approximately 1 ⁇ m thickness on the transparent electrode 45 .
- the transparent electrode is formed so as to fill in the gap among a plurality of columnar silicon members 48 of the p type silicon structure 43 .
- a solar battery produced by the above mentioned procedure contains a silicon structure comprising an aggregate of a plurality of columnar silicon members 48 mainly comprising silicon and having random orientations in the semiconductor layer, the solar battery does not have the solar light beam reflection and thus power generation can be conducted efficiently.
- the formation of the texture which requires complicated processes is unneccesary whereas a silicon structure which can provide the effects equivalent to the texture can be realized. Accordingly, by using the silicon structure in a solar battery, a solar battery having little solar light beam reflection, namely, a high energy conversion efficiency, can be provided at a low cost.
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Abstract
A silicon structure having little solar light beam reflection, which is suitable for a solar battery. On the entire surface of a quartz substrate, Mo is deposited at a thickness of approximately 1 μm to form a lower electrode. On the entire surface of the lower electrode, a p type silicon structure having a thickness of 30 to 40 μm comprising an aggregate of a plurality of columnar silicon members mainly comprising silicon and having random orientations is formed via a film mainly comprising silicon, using Si2Cl6 mixed with BCl3. On the surface of the p type silicon structure, P is diffused by a thermal diffusion method using POCl3 to form an n type region at the periphery of the columnar silicon members. On the entire surface of the p type silicon structure, a transparent electrode comprising indium-tin oxide having a thickness of 30 to 40 μm is formed, and an upper electrode comprising Al having a thickness of approximately 1 μm is formed on the transparent electrode.
Description
- 1. Field of the Invention
- The present invention relates to a silicon structure which can be usefully applied to a light-emitting device or a solar battery, the method and apparatus for producing the same, and a solar battery using the silicon structure.
- 2. Disclosure of the Prior Art
- In order to reduce the reflection of solar beams at its surface, a solar battery using silicon has been provided with an antireflection coating or an unevenness on its surface.
- Hereinafter the structure of a conventional solar battery will be explained with reference to a drawing. FIG. 7 is a cross-sectional diagram of a conventional silicon solar battery (textured structure). As FIG. 7 illustrates, an uneven surface is formed at the photodetecting side of a p
type silicon substrate 31 so as to reduce the reflection ratio of the solar beam. Methods of forming the unevenness commonly used include a chemical formation method using photolithography and chemical etching, and a mechanical formation method using a dicing machine. Examples of silicon substrates include a single crystalline silicon substrate produced by the Czochralski method and a polycrystalline silicon substrate produced with an electromagnetic cast. An ntype silicon layer 32 is formed on the uneven surface of the ptype silicon substrate 31. The ntype silicon layer 32 is formed by diffusing P (phosphorus) using a gas such as POCl3 on the uneven portion of the ptype silicon substrate 31 so as to change a part of the ptype silicon substrate 31 to the n type. Anantireflection coating 33 comprising a material such as SiN and MgF2 is formed on the ntype silicon layer 32. Further asurface electrode 34 is formed on the light accepting side of the ptype silicon substrate 31 via ann++ silicon layer 35, and thesurface electrode 34 is exposed on the surface of theantireflection coating 33. On the other hand, aback side electrode 36 is formed on the back side of the ptype silicon substrate 31 via ap+ silicon layer 37. By forming ap+ silicon layer 37 between theback side electrode 36 and the ptype silicon substrate 31, the energy conversion efficiency can be improved (the Third “High Efficiency Solar Battery” workshop preliminary reports, hosted by the Institute of Electrical Engineers, Semiconductor Electric Power Conversion Technology Committee, in Toyama, Japan, A5-A6, 28-35 pages, Oct. 5, 1992). - Although the above mentioned conventional silicon solar battery configuration enables an efficient collection of the solar beam, the method includes complicated processes to form the unevenness. This increases the production cost and thus the method is not suitable for the practical use.
- In order to solve the above mentioned problems in the conventional technology, an object of the present invention is to provide a silicon structure exhibiting little solar light beam reflection, the method and apparatus for producing the same, and a solar battery using the silicon structure.
- In order to achieve the above mentioned object, a configuration of the silicon structure of the present invention comprises an aggregate of a plurality of columnar silicon members mainly comprising silicon and having random orientations. According to the configuration of the silicon structure, since the light beam incident on one columnar silicon member is reflected thereby and re-enters another columnar silicon member, the solar beam can be absorbed efficiently. That is, according to the configuration of the silicon structure of the present invention, a silicon structure having little solar beam reflection can be obtained. Herein it is preferable that the silicon content amount of the columnar silicon members is 95 weight % or more, and in addition to the silicon, about 1 weight % of chlorine, about a few weight % of oxygen can be included.
- In the above mentioned configuration of the silicon structure of the present invention, it is preferable that a substrate is provided and the silicon structure is formed on the substrate via a film mainly comprising silicon. According to the preferable embodiment, a transparent electrode does not come in contact with a lower electrode in the process of producing a solar battery using the silicon structure.
- In the above mentioned configuration of the silicon structure of the present invention, it is more preferable that the diameter of the columnar silicon member is 0.1 to 10 μm. According to this embodiment, an adequate strength of the columnar silicon can be maintained and the depth of junction at the time of converting to an n type or a p type does not need to be limited. Further, the light absorption does not deteriorate.
- According to the configuration of the silicon structure of the present invention, it is further preferable that the periphery of the columnar silicon member is amorphous and the center thereof is polycrystalline.
- Further, the silicon structure comprising an aggregate of a plurality of columnar silicon members mainly comprising silicon having random orientations can be produced by a method, wherein an atomized or vaporized silicon material containing chloride is introduced to a heated substrate with an oxygen gas. According to this production method, since a silicon material which is less dangerous than a silane gas (SiH4) can be used, the silicon material can be supplied in a great amount. As a consequence, since the silicon formation rate can be improved, a silicon structure comprising an aggregate of a plurality of columnar silicon members mainly comprising silicon can be obtained. In this case, an inert gas can be introduced to the substrate at the same time in order to convey a silicon material containing chloride. Besides, by conveying a silicon material with an inert gas including hydrogen, or with only hydrogen, the amount of chloride in the silicon structure can be reduced. Further, since a complicated process to form an uneven shape is not necessary unlike the conventional textured structure, the production cost can be reduced.
- According to the production method of the silicon structure of the present invention, it is preferable that the silicon material containing chloride is Si2Cl6. According to the preferable embodiment, since the decomposition temperature is approximately 350° C., which is low and the decomposition can be conducted by radiating an ultraviolet ray beam (188 nm), a silicon structure comprising an aggregate of a plurality of columnar silicon members mainly comprising silicon and having random orientations can be easily obtained. In this case, it is more preferable that an n type or p type silicon structure is formed using a liquid material containing PCl3 or BCl3 as the silicon material comprising Si2Cl6.
- In the above mentioned production method, it is more preferable that the oxygen gas is introduced so that the oxygen content of the vicinity of the centers of the columnar silicon members becomes 3% or less. According to this embodiment, the resistance of the silicon structure can be kept at a low level and thus the silicon structure can be used in an electronic device.
- Further, an apparatus for producing the silicon structure of the present invention comprises a chamber, means to supply an atomized or vaporized liquid material comprising silicon and oxygen gas to the chamber, a support for a substrate to be treated by the apparatus, a heater for a substrate to be treated by the apparatus and a filter having an area that is at least as large as the area of a substrate to be treated by the apparatus, through which the atomized or vaporized liquid material and oxygen gas are introduced to a substrate to be treated by the apparatus. According to the configuration of this apparatus, since the atomized or vaporized liquid material is uniformly diffused in the area of approximately the size of the filter at the time of passing through the filter and introduced to the surface of the substrate, a silicon substrate can be formed uniformly on the substrate.
- In the above mentioned production apparatus of the silicon structure of the present invention, it is preferable that the filter comprises a stainless steel fiber. According to this embodiment, a filter having a large area and a very large void ratio of from 70 to 90% and a uniform pore size can be formed at a low cost. And by dividing the vaporizing chamber and the process chamber with the filter, the pressure difference between the vaporizing chamber and the process chamber is unlikely to be generated and thus the condensation of the material caused by the adiabatic expansion can be prevented.
- In the above mentioned production apparatus of the silicon structure of the present invention, it is more preferable that the pore size of the filter is 1 to 30 μm. According to this embodiment, a material gas and an oxygen gas can be sprayed on the substrate uniformly.
- Further, a solar battery of the present invention is a solar battery comprising a semiconductor layer to generate an electron-hole pair by light radiation, wherein the semiconductor layer includes a silicon structure comprising an aggregate of a plurality of columnar silicon members mainly comprising silicon and having random orientations. According to the configuration of the solar battery, since the solar beam reflection is reduced, power generation can be conducted efficiently.
- In the above mentioned configuration of the solar battery of the present invention, it is preferable that a substrate is provided and a silicon structure is formed on the substrate via a film mainly comprising silicon.
- In the above mentioned configuration of the solar battery of the present invention, it is more preferable that the diameter of the columnar silicon member is 0.1 to 10 μm.
- In the above mentioned configuration of the solar battery of the present invention, it is further preferable that the periphery of the columnar silicon member is amorphous and the center portion is polycrystalline.
- In the above mentioned configuration of the solar battery of the present invention, it is more preferable that the silicon structure is formed on the surface of the semiconductor layer at the side on which the light beam enters.
- In the above mentioned configuration of the solar battery of the present invention, it is further preferable that a pn junction is formed inside the columnar silicon. According to this embodiment, the following advantage can be achieved. That is, since the area of the pn junction portion can be increased in the case of a silicon structure comprising a plurality of columnar silicon members compared with the case of a conventional flat film, power generation can be conducted efficiently.
- FIG. 1 is a diagram illustrating the silicon film formation device used in the first embodiment of the present invention.
- FIGS. 2A and 2B are tracings of a scanning electron microscope photograph (SEM) of the silicon structure formed in the first embodiment of the present invention.
- FIGS. 3A to3C are tracings of a laser microscope photograph of the surface shapes of the silicon films formed with different oxygen amounts in the first embodiment of the present invention.
- FIG. 4 is a graph to illustrate the visible absorption spectrum of the silicon structure formed on the quartz substrate in the first embodiment of the present invention.
- FIGS. 5A to5C are diagrams illustrating the process for producing the solar battery using the silicon structure in the second embodiment of the present invention.
- FIG. 6 is a cross-sectional view illustrating the configuration of the solar battery of the second embodiment of the present invention.
- FIG. 7 is a cross-sectional diagram illustrating the configuration of the silicon solar battery (textured structure) of a conventional silicon solar battery.
- Hereinafter the present invention will be further explained with reference to preferred embodiments.
- (First Embodiment)
- FIG. 1 is a diagram illustrating the silicon film formation device used in the first embodiment of the present invention. As shown in FIG. 1, the inside of a
process chamber 11 having an air-tight structure is divided with ahorizontal filter 26. Thefilter 26 is formed by sintering many stainless steel fibers having a few μm diameter and the pore size is about 10 μm. Theprocess chamber 11 has a materialgas supply orifice 18 at the side wall beneath the filter 26 (the vaporizing chamber 14) so as to supply an atomized or vaporizedliquid material 15 to theprocess chamber 11 from avaporizer 23, with the flow rate being adjusted by aflow control device 22 as needed. Herein thevaporizer 23 can be supplied with anoxygen gas 24 so as to supply aliquid material 15 containing theoxygen gas 24 to theprocess chamber 11. Anexhaustion orifice 17 is arranged at the upper wall above thefilter 26 in theprocess chamber 11. Asubstrate holder 12 in which a heater for heating thesubstrate 21 is stored is located horizontally above thefilter 26 in theprocess chamber 11 so as to hold asubstrate 13 on the lower side thereof. Further, avaporization aid heater 27 is arranged under thefilming chamber 11. - A method for producing the silicon structure of the present invention using the above mentioned silicon film formation device will be explained hereinafter.
- In this embodiment, a quartz substrate was used for the
substrate 13. Thesubstrate 13 was heated with the heater for heating thesubstrate 21 to approximately 680° C. And (Si2Cl6+BCl3) was used as theliquid material 15. The inside of theprocess chamber 11 was kept at an ordinary pressure (1 atomospheric pressure). - The
liquid material 15 was propelled by an inert gas such as Ar and the flow rate was controlled at a proper level by aflow control device 22. Then theliquid material 15 was atomized or vaporized and mixed with the inert gas and anoxygen gas 24 in avaporizer 23, and was supplied to the vaporizingchamber 14 from the materialgas supply orifice 18. At the same time, a reducinggas 25 such as H2 was supplied to the vaporizingchamber 14. It is preferable that the flow rate of theoxygen gas 24 is 1 to 10 cc/minute with respect to a flow rate of Si2Cl6 of 10 g/hour (H2O calibration). After being heated by thevaporization aid heater 27, all the gases supplied to the vaporizingchamber 14 were uniformly diffused as passing through thefilter 26 and sprayed to thesubstrate 13. Then Si2Cl6 in the atomized or vaporized state was reacted to be thermally decomposed to form a p type silicon structure on thesubstrate 13. Methods for atomizing theliquid material 15 include a method of using an ultrasonic vibration. - According to the above mentioned production method for a silicon structure, since a silicon material such as Si2Cl6, which is less dangerous than a silane gas (SiH4), can be used, the silicon material can be supplied to the
process chamber 11 in a great amount. As a consequence, since the silicon formation rate can be improved, a silicon structure comprising an aggregate of a plurality of columnar silicon members mainly comprising silicon and having random orientations can be obtained. In this case, it is preferable that the oxygen content amount in the vicinity of the center of a columnar silicon is 3% or less. By setting the flow rate of theoxygen gas 24 as mentioned above, the oxygen content amount in the vicinity of the center of a columnar silicon member can be made 3% or less. The 3% or less of the oxygen content amount in the vicinity of the center of the columnar silicon member enables maintaining the resistance of the silicon structure to be maintained at a low level so that the silicon structure can be used in an electronic device. The “vicinity of the center of the columnar silicon member” herein denotes the region excluding the region from the surface to about 50 nm depth of the columnar silicon member. - Although Si2Cl6 was used as the silicon material containing chlorine in this embodiment, it is not limited thereto but other materials can be used as well. Examples of the silicon materials containing chlorine include SiCl4, SiH2Cl2, SiHCl3, Si3Cl8 and Si4 Cl10. When a silicon material having a comparatively high vapor pressure such as SiH2Cl2 and SiHCl3 is used, the material itself needs to be liquefied by pressing or cooling. By using Si2Cl6 as the silicon material containing chlorine as in this embodiment, since Si2Cl6 has a decomposition temperature of approximately 350° C., which is low, and is decomposed by radiation of an ultraviolet ray (188 nm), a silicon structure can be formed easily.
- Although Ar was used as the inert gas for spraying in this embodiment, it is not limited thereto but other gases such as He and N2 can be used as well. As a method to introduce the inert gas into the
process chamber 11, a so-called bubbling method, namely, a method to introduce theliquid material 15 to theprocess chamber 11 as bubbles, can be used. - Although H2 gas was used as the reducing
gas 25 in this embodiment, it is not limited thereto but other gases such as CO can be used as well. Further, a silicon structure can be formed without introducing a reducing gas. Besides, by conveying the silicon material only with an H2 gas without using an inert gas, the amount of chlorine contained in the silicon structure can be reduced. - Although a quartz is used as the
substrate 13 in this embodiment, it is not limited thereto but other materials such as a ceramic material or a metallic material such as stainless steel can be used as well. - Although the film formation was conducted in the chamber with an ordinary pressure (1 atomospheric pressure) in this embodiment, it is not limited thereto but the film formation can be conducted in a vacuum state (0.1 to 760 Torr) or in a pressurized state (1 to 10 atomospheric pressure). In particular, by conducting the film formation in the pressurized state, the deposition rate can be further increased.
- Although a mixture liquid of Si2Cl6 and BCl3 was used for the p type silicon structure formation in this embodiment, by using only Si2Cl6, a nearly intrinsic silicon structure can be obtained. And by using PCl3 in place of BCl3, an n type silicon structure can be formed. In this case, by supplying Si2Cl6 and BCl3 or PCl3 separately without preparing a material mixture liquid, a silicon structure can be formed as well.
- Although a
filter 26 comprising stainless steel fibers was used in this embodiment, it is not limited thereto but afilter 26 of other materials such as quartz can be used as well. In particular, by forming afilter 26 by sintering many stainless steel fibers, a filter having a large area and a very large void ratio of from 70 to 90% can be provided at a low cost. By dividing the vaporizingchamber 14 and theprocess chamber 11 with the filter, the pressure difference between the vaporizingchamber 14 and theprocess chamber 11 is unlikely to be generated. Further, although the pore size of thefilter 26 was set to be 10 μm, the pore size is not limited thereto but anyfilter 26 having a pore size of 1 to 30 μm can allow uniform spraying of a material gas or an oxygen gas to thesubstrate 13. - FIGS. 2A, 2B are tracings of scanning electron microscope photographs (SEM) of the silicon structure formed in this embodiment. FIG. 2A and FIG. 2B illustrate the same sample in different magnifications. As described in FIGS. 2A and 2B, a silicon structure comprising an aggregate of a plurality of columnar silicon members having a diameter of approximately 0.5 μm, mainly comprising silicon and having different orientations was formed. By using the silicon structure, since a light beam entered into and reflected by a columnar silicon member enters another columnar silicon member, the solar beam can be absorbed efficiently. That is, a silicon structure having little solar light beam reflection can be obtained.
- FIGS. 3A to3C are tracings of laser microscope photographs illustrating the surface shape of the silicon film formed with different oxygen amounts. The FIGS. 3A to 3C are described with the black portion and the white portion reversed with respect to the actual laser microscope photographs in 1,000 magnification. Film formation conditions are as per Table 1.
TABLE 1 Si2Cl6 flow rate 10 g/hour (H2O calibration) Ar (3% H2) flow rate 400 cc/minute O2 flow rate 0, 1, 3 cc/minute Substrate temperature 675° C. Pressure Ordinary pressure - As illustrated in FIG. 3A, when the oxygen flow rate was 0 cc/min, an approximately flat film (black portion) was formed. As illustrated in FIG. 3B, when the oxygen flow rate was 1 cc/min, although a silicon structure (white portion) was partially formed, a flat portion (black portion) still remains. As illustrated in FIG. 3C, when the oxygen flow rate was 3 cc/min, a silicon structure (white portion) was formed almost completely. By these results, it was learned that oxygen plays a key role in the silicon structure formation.
- FIG. 4 illustrates a visible absorption spectrum of the silicon structure formed on a quartz substrate in this embodiment. As shown in FIG. 4, a silicon structure formed in this embodiment barely permeates a light beam having a wavelength of 200 to 800 nm.
- Although the silicon structure comprises columnar silicon members having a diameter of approximately 0.5 μm in this embodiment, the diameter of columnar silicons can vary as long as it is in the range of 0.1 to 10 μm. The diameter of the columns within the above mentioned range provides the columns with a proper strength and also does not limit the depth of junction in changing the surface of the silicon to an n type or a p type by a diffusion. Further, if the diameter of the columns is in the above mentioned range, light absorption is not deteriorated.
- (Second Embodiment)
- FIGS. 5A to5C are diagrams illustrating the production process of the solar battery using the silicon structure in the second embodiment. FIG. 6 illustrates the confuguration of the solar battery of this embodiment.
- As shown in FIG. 5A, on the entire surface of a
quartz substrate 42 having a 0.5 mm thickness, Mo was deposited at approximately 1 μm thickness to form alower electrode 41. Then a ptype silicon structure 43 of 30 to 40 μm thickness was formed on the entire surface of thelower electrode 41 using Si2 Cl6 including BCl3. In this case, as shown in FIG. 6, a ptype silicon structure 43 comprising an aggregate of a plurality ofcolumnar silicon members 48 mainly comprising silicon and having random orientations was formed on thelower electrode 41 via afilm 47 mainly comprising silicon (hereinbefore related to FIG. 5A). By forming a ptype silicon structure 43 comprising an aggregate of a plurality ofcolumnar silicon members 48 on thelower electrode 41 via afilm 47 mainly comprisingsilicon 47, there is no risk of contacting atransparent electrode 45 to thelower electrode 41 in forming thetransparent electrode 45 as explained below. - As shown in FIG. 5B, on the surface of the p
type silicon structure 43, P was diffused by a thermal diffusion method using POCl3 to form ann type region 44 at the periphery of the columnar silicons 48 (see FIG. 6). By this operation, a pn junction is formed inside thecolumnar silicons 48. Since thepresent silicon structure 43 comprising a plurality ofcolumnar silicon members 48 has a pn junction in an area larger than that of a conventional flat film, power generation can be conducted efficiently. In this case, although the center portion of thecolumnar silicon members 48 remain polycrystalline, the peripheral portions of thecolumnar silicon members 48 become amorphous. Since amorphous silicons have a resistance higher than that of polycrystalline silicons, it is preferable to have a polycrystalline region in a large area. Specifically speaking, with respect to a diameter of 0.5 μm of thecolumnar silicons 48, a preferable thickness of the n type region (amorphous) 44 is approximately 0.1 μm. - As shown in FIG. 5C, after forming a
transparent electrode 45 comprising indium-tin oxide having a thickness of approximately 30 to 40 μm on the entire surface of the ptype silicon structure 43, anupper electrode 46 comprising Al was formed at approximately 1 μm thickness on thetransparent electrode 45. In this case, the transparent electrode is formed so as to fill in the gap among a plurality ofcolumnar silicon members 48 of the ptype silicon structure 43. By the above mentioned operation, a solar battery can be obtained. - Since a solar battery produced by the above mentioned procedure contains a silicon structure comprising an aggregate of a plurality of
columnar silicon members 48 mainly comprising silicon and having random orientations in the semiconductor layer, the solar battery does not have the solar light beam reflection and thus power generation can be conducted efficiently. - In the below mentioned Table 2, properties of the solar battery this embodiment are shown in comparison with a solar battery of a conventional technology.
TABLE 2 Open end Short circuit voltage (mV) light current (mA/cm2) Solar battery 602 39.1 of the second embodiment of the present invention Solar battery of 600 or less 37 or less a conventional method - As shown in Table 2, although the open end voltages were almost the same, the short circuit light current was greater in the second embodiment than in the conventional method.
- As heretofore mentioned, according to the present invention, the formation of the texture, which requires complicated processes is unneccesary whereas a silicon structure which can provide the effects equivalent to the texture can be realized. Accordingly, by using the silicon structure in a solar battery, a solar battery having little solar light beam reflection, namely, a high energy conversion efficiency, can be provided at a low cost.
- While the invention has been described in its preferred embodiments, it is to be understood that the words which have been used are words of description rather than limitation and that changes within the purview of the appended claims may be made without departing from the true scope and spirit of the invention in its broader aspects.
Claims (17)
1. A silicon structure comprising an aggregate of a plurality of columnar silicon members mainly comprising silicon and having random orientations.
2. A substrate having a first surface on which the silicon structure of claim 1 is formed via a vilm mainly comprising silicon.
3. The silicon structure according to claim 1 , wherein the diameter of the columnar silicon members is from 0.1 to 10 μm.
4. The silicon structure according to claim 1 , wherein the periphery of the columnar silicon members is amorphous and the center portion of the columnar silicon members is polycrystalline.
5. A method for producing a silicon structure comprising an aggregate of a plurality of columnar silicon members mainly comprising silicon and having random orientations, wherein an atomized or vaporized silicon material containing chlorine is introduced to a heated substrate with an oxygen gas.
6. The method according to claim 5 , wherein the silicon material containing chlorine is Si2Cl6.
7. The method according to claim 6 , wherein an n type or p type silicon structure is formed by using a liquid material prepared by mixing PCl3 or BCl3 into the Si2Cl6.
8. The method according to claim 5 , wherein the oxygen gas is introduced so as to provide an oxygen content in the vicinity of the center of the columnar siliconmembers of 3% or less.
9. An apparatus for producing a silicon structure comprising an aggregate of a plurality of columnar silicon members mainly comprising silicon and having random orientations on a substrate, the apparatus comprising:
a chamber;
means to supply an atomized or vaporized liquid material comprising silicon and oxygen gas to the chamber;
a support for a substrate to be treated by the apparatus;
a heater for a substrate to be treated by the apparatus; and
a filter having an area that is at least as large as the area of a substrate to be treated by the apparatus, through which the atomized or vaporized liquid material and oxygen gas are introduced to a substrate to be treated by the apparatus.
10. The apparatus according to claim 9 , wherein the filter comprises a stainless steel fiber.
11. The apparatus according to claim 9 , wherein the pore size of the filter is from 1 to 30 μm.
12. A solar battery comprising a semiconductor layer to generate an electron-hole pair by a light radiation, wherein the semiconductor layer comprises a silicon structure comprising an aggregate of a plurality of columnar silicon members mainly comprising silicon and having random orientations.
13. The solar battery according to claim 12 , further comprising a substrate, on which the silicon structure is formed via a film mainly comprising silicon.
14. The solar battery according to claim 12 , wherein the diameter of the columnar silicon members is 0.1 to 10 μm.
15. The solar battery according to claim 12 , wherein the peripheral portion of the columnar silicon members is amorphous and the center portion of the columnar silicon members is polycrystalline.
16. The solar battery according to claim 12 , wherein the silicon structure is formed on the surface of the side of the semiconductor layer at which a light beam enters.
17. The solar battery according to claim 12 , wherein a pn junction is formed inside the columnar silicon members
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Also Published As
Publication number | Publication date |
---|---|
KR100294057B1 (en) | 2001-09-17 |
US6518494B1 (en) | 2003-02-11 |
CN1082254C (en) | 2002-04-03 |
KR970013435A (en) | 1997-03-29 |
CN1147156A (en) | 1997-04-09 |
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