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 PDF

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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
columnar
substrate
silicon structure
solar battery
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Munehiro Shibuya
Masatoshi Kitagawa
Yuuji Mukai
Akihisa Yoshida
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/04Semiconductor 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
    • H01L31/054Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H01L31/0547Optical 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/02Details
    • H01L31/0216Coatings
    • H01L31/02161Coatings for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/02167Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H01L31/02168Coatings 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/02Details
    • H01L31/0236Special surface textures
    • H01L31/02363Special surface textures of the semiconductor body itself, e.g. textured active layers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/0248Semiconductor 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
    • H01L31/0352Semiconductor 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
    • H01L31/035209Semiconductor 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
    • H01L31/035227Semiconductor 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/0248Semiconductor 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
    • H01L31/036Semiconductor 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
    • H01L31/0368Semiconductor 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00Semiconductor 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
    • H01L31/0248Semiconductor 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
    • H01L31/036Semiconductor 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
    • H01L31/0376Semiconductor 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
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/52PV 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.

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

    BACKGROUND OF THE INVENTION
  • 1. Field of the Invention [0001]
  • 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. [0002]
  • 2. Disclosure of the Prior Art [0003]
  • 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. [0004]
  • 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 [0005] 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 POCl3 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 MgF2 is formed on the n type silicon layer 32. Further 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. On the other hand, a back side electrode 36 is formed on the back side of the p type silicon substrate 31 via a p+ silicon layer 37. By forming a p+ silicon layer 37 between the back side electrode 36 and the p type 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. [0006]
  • SUMMARY OF THE INVENTION
  • 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. [0007]
  • 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. [0008]
  • 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. [0009]
  • 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. [0010]
  • 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. [0011]
  • 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 (SiH[0012] 4) 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 Si[0013] 2Cl6. 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. [0014]
  • 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. [0015]
  • 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. [0016]
  • 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. [0017]
  • 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. [0018]
  • 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. [0019]
  • 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. [0020]
  • 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. [0021]
  • 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. [0022]
  • 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.[0023]
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 is a diagram illustrating the silicon film formation device used in the first embodiment of the present invention. [0024]
  • 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. [0025]
  • FIGS. 3A to [0026] 3C 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. [0027]
  • FIGS. 5A to [0028] 5C 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. [0029]
  • FIG. 7 is a cross-sectional diagram illustrating the configuration of the silicon solar battery (textured structure) of a conventional silicon solar battery.[0030]
  • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • Hereinafter the present invention will be further explained with reference to preferred embodiments. [0031]
  • (First Embodiment) [0032]
  • 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 [0033] 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 μm diameter and the pore size is about 10 μm. 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. Herein 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 method for producing the silicon structure of the present invention using the above mentioned silicon film formation device will be explained hereinafter. [0034]
  • In this embodiment, a quartz substrate was used for the [0035] substrate 13. The substrate 13 was heated with the heater for heating the substrate 21 to approximately 680° C. And (Si2Cl6+BCl3) was used as the liquid material 15. The inside of the process chamber 11 was kept at an ordinary pressure (1 atomospheric pressure).
  • The [0036] 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 H2 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 Si2Cl6 of 10 g/hour (H2O calibration). After being heated by the vaporization aid heater 27, all the gases supplied to the vaporizing chamber 14 were uniformly diffused as passing through the filter 26 and sprayed to the substrate 13. Then Si2Cl6 in the atomized or vaporized state was reacted to be thermally decomposed to form a p type silicon structure on the substrate 13. Methods for atomizing the liquid 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 Si[0037] 2Cl6, 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 the oxygen 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 Si[0038] 2Cl6 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 N[0039] 2 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 the liquid material 15 to the process chamber 11 as bubbles, can be used.
  • Although H[0040] 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. 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 [0041] 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. [0042]
  • Although a mixture liquid of Si[0043] 2Cl6 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 [0044] 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. In particular, by forming 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. Further, although the pore size of the filter 26 was set to be 10 μm, the pore size is not limited thereto but any filter 26 having a pore size of 1 to 30 μm 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. 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. [0045]
  • FIGS. 3A to [0046] 3C 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. [0047]
  • 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. [0048]
  • 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. [0049]
  • (Second Embodiment) [0050]
  • FIGS. 5A to [0051] 5C 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 [0052] quartz substrate 42 having a 0.5 mm thickness, Mo was deposited at approximately 1 μm thickness to form a lower electrode 41. Then a p type silicon structure 43 of 30 to 40 μm thickness was formed on the entire surface of the lower electrode 41 using Si2 Cl6 including BCl3. In this case, as shown in FIG. 6, a p type silicon structure 43 comprising an aggregate of a plurality of columnar silicon members 48 mainly comprising silicon and having random orientations was formed on the lower electrode 41 via a film 47 mainly comprising silicon (hereinbefore related to FIG. 5A). By forming 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.
  • As shown in FIG. 5B, on the surface of the p [0053] type silicon structure 43, P was diffused by a thermal diffusion method using POCl3 to form an n type region 44 at the periphery of the columnar silicons 48 (see FIG. 6). By this operation, a pn junction is formed inside the columnar silicons 48. Since the present silicon structure 43 comprising a plurality of columnar 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 the columnar silicon members 48 remain polycrystalline, the peripheral portions of the columnar 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 the columnar 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 [0054] transparent electrode 45 comprising indium-tin oxide having a thickness of approximately 30 to 40 μm on the entire surface of the p type silicon structure 43, an upper electrode 46 comprising Al was formed at approximately 1 μm thickness on the transparent electrode 45. In this case, 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. 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 [0055] 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. [0056]
    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. [0057]
  • 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. [0058]
  • 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. [0059]

Claims (17)

What is claimed is:
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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