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WO2011036957A1 - Oligomethylphosphine compound for amorphous semiconductor film and film deposition gas containing same - Google Patents

Oligomethylphosphine compound for amorphous semiconductor film and film deposition gas containing same Download PDF

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Publication number
WO2011036957A1
WO2011036957A1 PCT/JP2010/063458 JP2010063458W WO2011036957A1 WO 2011036957 A1 WO2011036957 A1 WO 2011036957A1 JP 2010063458 W JP2010063458 W JP 2010063458W WO 2011036957 A1 WO2011036957 A1 WO 2011036957A1
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amorphous semiconductor
semiconductor film
compound
gas
oligomethylphosphine
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PCT/JP2010/063458
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French (fr)
Japanese (ja)
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利久 井手
竜也 入江
健二 田仲
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セントラル硝子株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/504—Organo-phosphines containing a P-P bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5004—Acyclic saturated phosphines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02524—Group 14 semiconducting materials
    • H01L21/02532—Silicon, silicon germanium, germanium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/0257—Doping during depositing
    • H01L21/02573—Conductivity type
    • H01L21/02576—N-type
    • H—ELECTRICITY
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02587—Structure
    • H01L21/0259—Microstructure
    • H01L21/02592—Microstructure amorphous
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
    • 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
    • H01L31/03762—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 including only elements of Group IV of the Periodic Table
    • 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
    • H01L31/06—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 characterised by potential barriers
    • H01L31/075—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 characterised by potential barriers the potential barriers being only of the PIN type, e.g. amorphous silicon PIN solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/20—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials
    • H01L31/202—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof such devices or parts thereof comprising amorphous semiconductor materials including only elements of Group IV of the Periodic Table
    • 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
    • Y02E10/548—Amorphous silicon PV cells
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a compound used for forming an amorphous semiconductor film having a pin junction in a process for producing a photoelectric conversion layer of a photovoltaic device such as a solar cell.
  • a solar cell using an amorphous semiconductor has a transparent electrode such as ITO or SnO 2 on a glass substrate, a p-type, i-type, or n-type amorphous silicon (a-Si) film, A back electrode such as Ag and Au is laminated in order.
  • a transparent electrode such as ITO or SnO 2
  • a p-type, i-type, or n-type amorphous silicon (a-Si) film A back electrode such as Ag and Au is laminated in order.
  • a-Si film is produced by a continuous separation method in which p-type, i-type, and n-type layers are sequentially formed in separate plasma CVD apparatuses (for example, Patent Document 1). Yes.
  • a Group 5 element is doped, and phosphine (PH 3 ) is used as a doping material.
  • PH 3 is a gas having a boiling point of ⁇ 87.7 ° C.
  • high-pressure filling is necessary to transport a large amount.
  • PH 3 is chemically unstable, handling with high concentration PH 3 under high pressure causes a problem in safety, and it is necessary to dilute and fill. Therefore, there is a problem that mass transportation is difficult and transportation cost is increased. For this reason, it is disadvantageous for a process that requires a large amount of gas supply, such as a manufacturing process of a photoelectric conversion layer of a photovoltaic device.
  • diphosphine P 2 H 4 contained in a trace amount of PH 3 in the process chemical stability such as spontaneous ignition and polymerization explosion of PH 3 gas is extremely low, so strict safety measures are required on equipment and handling. It has become indispensable.
  • the present invention is a compound used for an amorphous semiconductor film having a pin junction formed as a photoelectric conversion layer of a photovoltaic device.
  • doping that is chemically safe and easy to transport in large quantities is an alternative to PH 3 gas.
  • the purpose is to provide raw materials.
  • the present inventors have intensively studied to solve the above problems, and as a result, the oligomethylphosphine compound is a chemically stable alternative to PH 3 gas and is a doping material that can be easily transported in large quantities. As a result, they have reached the present invention.
  • the present invention is a general formula (1) used for a pin junction amorphous semiconductor film formed as a photoelectric conversion layer of a photovoltaic device.
  • (CH 3 ) n PH 3-n (1) [Wherein n represents an integer of any one of 1 to 3] is provided.
  • the oligomethylphosphine compound represented by the general formula (1) used as a doping gas for forming the n-type amorphous semiconductor film and the n-type amorphous semiconductor film are formed.
  • n-methylphosphine compound represented by the above general formula (1) is mixed in the film forming gas used in the process as a doping gas within a range of 0.0001 to 10% by volume, n A deposition gas for an amorphous semiconductor film to be a type semiconductor is provided.
  • a chemically stable compound can be provided as a compound used for a pin junction amorphous semiconductor film formed as a photoelectric conversion layer of a photovoltaic device.
  • 1 is a schematic view of a plasma CVD film forming apparatus used in an example.
  • 1 is a schematic view of a cross section of a photovoltaic device created in an example.
  • the oligomethylphosphine compound used in the present invention has the general formula (1) (CH 3 ) n PH 3-n (1) [Wherein n represents any one integer of 1 to 3], specifically, trimethylphosphine (P (CH 3 ) 3 ), dimethylphosphine ((CH 3 ) 2 PH), methyl And phosphine ((CH 3 ) PH 2 ).
  • (CH 3 ) PH 2 is a gaseous compound having a boiling point of ⁇ 15 ° C.
  • (CH 3 ) 2 PH is a boiling point of 25 ° C.
  • P (CH 3 ) 3 is a boiling point of 38 ° C. Therefore, P (CH 3 ) 3 that is liquid at room temperature (25 ° C.) or higher is a particularly preferable compound in terms of safety.
  • P (CH 3 ) 3 is, for example, Inorganic Synthesis 1967, 9, 59.
  • (CH 3 ) 2 PH for example, as described in JP-B No. 54-8658, phosphorous trichloride and methyl chloride in the presence of Zn.
  • (CH 3 ) PH 2 may be obtained by, for example, Journal of Organic Chemistry 1997, 529 (1), 205.
  • the compound of the present invention can be used in a general method for forming a pin junction amorphous semiconductor film such as plasma CVD, thermal CVD, and photo CVD.
  • Examples of the amorphous semiconductor include a-Si, a-SiGe, a-SiN, a-SiC, and a-SiO 2 .
  • Examples of the Si source include monosilane (SiH 4 ); examples of the a-SiGe Ge source include monogermane (GeH 4 ); examples of the a-SiN N source include ammonia, nitrogen and the like as a C source of a-SiC. In this case, a lower alkane such as ethane or propane, or a gas such as oxygen is used as an O source for a-SiO to form an amorphous semiconductor film. At this time, monosilane, monogermane, etc.
  • the compound of the present invention is used for forming an amorphous semiconductor. It is effective to use it as a doping material.
  • a film forming gas in which the compound of the present invention is mixed in the range of 0.0001 to 10% by volume. If it is less than 0.0001% by volume, the doping concentration is too low and the function as an n-type is reduced. If it exceeds 10% by volume, the material forming the semiconductor film is too low and the function as a semiconductor may be reduced. .
  • FIG. 1 is a schematic view of a plasma CVD film forming apparatus used in this example.
  • An upper discharge electrode 2a and a lower discharge electrode 2b incorporating an electrode heater 12 having a temperature control means are arranged to face each other.
  • a glass substrate 3 to be deposited is placed on the lower discharge electrode 2b.
  • a high frequency voltage of 13.56 MHz is applied to the vacuum chamber 1 by a high frequency power source 4.
  • an exhaust system 5 is connected to the vacuum chamber 1, and the inside thereof is maintained in a vacuum state.
  • a vacuum discharge is generated between the upper discharge electrode 2a and the lower discharge electrode 2b to generate plasma.
  • the vacuum chamber 1 is connected through a pipe 9 to a cylinder 7 filled with a SiH 4 cylinder 6 and PREM ( 3 ) P (CH 3 ) 3 manufactured by STREM.
  • a mass flow controller 8a for controlling the gas flow rate of SiH 4
  • a mass flow controller 8b for controlling the gas amount of P (CH 3 ) 3 .
  • a heater 10 for vaporizing P (CH 3 ) 3 is installed around the P (CH 3 ) 3 cylinder 7 and heated to 50 ° C.
  • a coil heater 11 is wound around the pipe 9 to heat the inside.
  • P (CH 3 ) 3 is a liquid having a vapor pressure of about 460 torr at room temperature, and therefore the pressure inside the cylinder at 50 ° C. is about 0.15 MPa.
  • the glass substrate 3 placed on the lower discharge electrode 2 b in the vacuum chamber 1 is heated to 200 ° C. by the electrode heater 12.
  • the inside of the vacuum chamber 1 is maintained in a vacuum state of about 1 Pa by the exhaust system 5, and a high frequency voltage of 13.56 MHz is applied by the high frequency power source 4 at an output of 30 W.
  • it is introduced into the vacuum chamber 1 through the pipe 9 that maintained internal to about 50 ° C.
  • the SiH 4 gas controlling the flow rate from the SiH 4 gas cylinder 6 by a mass flow controller 8a by energizing the coil heater 11. Further, the flow rate of P (CH 3 ) 3 in the cylinder 7 heated to 50 ° C.
  • the amount of SiH 4 gas and P (CH 3 ) 3 gas introduced is determined by using the mass flow controllers 8a and 8b, the total gas flow rate is 10 sccm, and the gas mixing ratio of P (CH 3 ) 3 gas in the total gas to be introduced.
  • the film is formed at a deposition rate of about 0.8 nm / s by adjusting to 0.1% by volume.
  • the inside of the vacuum chamber 1 at this time is maintained at a pressure of 10 Pa.
  • the dark conductivity of the n-type semiconductor was measured on the film having a thickness of 1000 mm formed on the glass substrate 3 in this way, and a dark conductivity of 0.89 ⁇ 10 ⁇ 3 S / cm was obtained.
  • the same performance as in the case of using phosphine gas (0.95 ⁇ 10 ⁇ 3 S / cm) was exhibited.
  • n-type amorphous semiconductor film was formed in the same manner as in Example 4 except that the mixing ratio of P (CH 3 ) 3 gas was 0.003% by volume.
  • the dark conductivity of the n-type semiconductor was measured for the film having a thickness of 1000 mm formed on the glass substrate 3 in this way, and a dark conductivity of 3.8 ⁇ 10 ⁇ 7 S / cm was obtained.
  • the same performance as that of the phosphine gas (4.0 ⁇ 10 ⁇ 7 S / cm) was used.
  • n-type amorphous semiconductor film was formed in the same manner as in Example 4 except that the P (CH 3 ) 3 gas mixing ratio was 1% by volume.
  • the dark conductivity of the n-type semiconductor was measured for the film having a thickness of 1000 mm formed on the glass substrate 3 in this way, and a dark conductivity of 1.3 ⁇ 10 ⁇ 2 S / cm was obtained.
  • the same performance as that of the phosphine gas (1.0 ⁇ 10 ⁇ 2 S / cm) was used.
  • n-type amorphous semiconductor film was formed in the same manner as in Example 4 except that the P (CH 3 ) 3 gas mixing ratio was 3% by volume.
  • the dark conductivity of the n-type semiconductor was measured for the film having a thickness of 1000 mm formed on the glass substrate 3 in this way, and a dark conductivity of 1.1 ⁇ 10 ⁇ 2 S / cm was obtained.
  • the same performance as that of the phosphine gas (1.0 ⁇ 10 ⁇ 2 S / cm) was used.
  • a quality semiconductor film was formed.
  • the dark conductivity of the n-type semiconductor is measured, and a dark conductivity of 0.9 ⁇ 10 ⁇ 3 S / cm is obtained.
  • the same performance as when used (0.95 ⁇ 10 ⁇ 3 S / cm) was exhibited.
  • FIG. 1 A schematic view of a cross section of the photovoltaic device produced in this example is shown in FIG.
  • a transparent electrode 22 made of ITO and a p-type layer 23 made of a B (boron) -doped a-SiC film constituting the first photovoltaic element are made transparent on the glass substrate 21 by plasma CVD. It is formed on the electrode 22.
  • an i-type layer 24 made of a-Si having a thickness of 1000 mm was formed.
  • an n-type layer 25 made of P (phosphorus) -doped a-Si having a thickness of 100 mm was formed by plasma CVD using the same method as in Example 4.
  • a metal electrode 26 made of Ag metal was laminated in this order to form a photovoltaic device.
  • the a-Si photovoltaic device obtained was irradiated with simulated sunlight according to AM (air mass) 1.5G reference sunlight spectrum generated using a 300 W solar simulator manufactured by Tokyo Instruments at an intensity of 100 W / cm 2 .
  • AM air mass
  • the short-circuit current density was 17.9 mA / cm 2
  • the open circuit voltage was 0.74 V
  • the fill factor was 0.75
  • the photoelectric conversion efficiency was 9.93%
  • the existing phosphine gas was used. The performance was comparable.
  • a photovoltaic device was produced in the same manner as in Example 10 except that an n-type amorphous semiconductor film formed by the same method as in Example 5 was used as the n-type layer 25.
  • the a-Si photovoltaic device obtained was irradiated with simulated sunlight according to AM (air mass) 1.5G reference sunlight spectrum generated using a 300 W solar simulator manufactured by Tokyo Instruments at an intensity of 100 W / cm 2 .
  • AM air mass
  • the short-circuit current density was 18.0 mA / cm 2
  • the open circuit voltage was 0.77 V
  • the fill factor was 0.74
  • the photoelectric conversion efficiency was 10.26%
  • the existing phosphine gas was used. The performance was comparable.
  • a photovoltaic device was produced in the same manner as in Example 10 except that an n-type amorphous semiconductor film formed by the same method as in Example 6 was used as the n-type layer 25.
  • the a-Si photovoltaic device obtained was irradiated with simulated sunlight according to AM (air mass) 1.5G reference sunlight spectrum generated using a 300 W solar simulator manufactured by Tokyo Instruments at an intensity of 100 W / cm 2 .
  • AM air mass
  • the short-circuit current density was 18.0 mA / cm 2
  • the open circuit voltage was 0.74 V
  • the fill factor was 0.75
  • the photoelectric conversion efficiency was 9.99%
  • the existing phosphine gas was used. The performance was comparable.
  • a photovoltaic device was produced in the same manner as in Example 10 except that an n-type amorphous semiconductor film formed by the same method as in Example 7 was used as the n-type layer 25.
  • the a-Si photovoltaic device obtained was irradiated with simulated sunlight according to AM (air mass) 1.5G reference sunlight spectrum generated using a 300 W solar simulator manufactured by Tokyo Instruments at an intensity of 100 W / cm 2 .
  • AM air mass
  • the short-circuit current density was 18.1 mA / cm 2
  • the open circuit voltage was 0.72 V
  • the fill factor was 0.75
  • the photoelectric conversion efficiency was 9.77%
  • the existing phosphine gas was used. The performance was comparable.
  • a photovoltaic device was produced in the same manner as in Example 10 except that an n-type amorphous semiconductor film formed by the same method as in Example 8 was used as the n-type layer 25.
  • the a-Si photovoltaic device obtained was irradiated with simulated sunlight according to AM (air mass) 1.5G reference sunlight spectrum generated using a 300 W solar simulator manufactured by Tokyo Instruments at an intensity of 100 W / cm 2 .
  • AM air mass
  • the short-circuit current density was 18.0 mA / cm 2
  • the open circuit voltage was 0.69 V
  • the fill factor was 0.75
  • the photoelectric conversion efficiency was 9.32%
  • the existing phosphine gas was used. The performance was comparable.
  • a photovoltaic device was produced in the same manner as in Example 10 except that an n-type amorphous semiconductor film formed by the same method as in Example 9 was used as the n-type layer 25.
  • the a-Si photovoltaic device obtained was irradiated with simulated sunlight according to the AM (air mass) 1.5G reference sunlight spectrum generated using a 300 W solar simulator manufactured by Tokyo Instruments at an intensity of 100 W / cm 2 .
  • the short-circuit current density was 17.9 mA / cm 2
  • the open circuit voltage was 0.74 V
  • the fill factor was 0.74
  • the photoelectric conversion efficiency was 9.80%
  • the existing phosphine gas was used. The performance was comparable.
  • the plasma CVD method is used as the film forming method.
  • the same effect can be obtained by using a known photo-CVD method or micro-CVD method.
  • a-Si as an n-type amorphous semiconductor
  • other amorphous semiconductors of a-SiGe, a-SiN, a-SiC, and a-SiO2 can be performed in exactly the same manner. The same effect was obtained.

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Abstract

Provided is a compound for use in depositing a pin-junction amorphous semiconductor film as the photoelectric conversion layer of a photovoltaic device, the compound being chemically safe and easy to mass-transport. The compound, which is for use in depositing a pin-junction amorphous semiconductor film as the photoelectric conversion layer of a photovoltaic device, is an oligomethylphosphine compound represented by general formula (1). (CH3)nPH3-n (1) (wherein n is an integer of 1-3).

Description

非晶質半導体膜用オリゴメチルホスフィン化合物とこれを用いる成膜ガスOligomethylphosphine compound for amorphous semiconductor film and film forming gas using the same
　本発明は太陽電池などの光起電力装置の光電変換層の製造プロセスにおいて、ｐｉｎ接合の非晶質半導体膜の成膜に用いる化合物に関するものである The present invention relates to a compound used for forming an amorphous semiconductor film having a pin junction in a process for producing a photoelectric conversion layer of a photovoltaic device such as a solar cell.
　近年、クリーンなエネルギーとして、太陽光発電が注目されており、その中でも特に非晶質半導体を用いた太陽電池はコスト面において他の種類の太陽電池よりも有望であり、積極的な研究開発が進められている。 In recent years, solar power generation has attracted attention as a clean energy. Among them, solar cells using amorphous semiconductors are more promising than other types of solar cells in terms of cost, and are actively researched and developed. It is being advanced.
　一般的に、非晶質半導体を用いる太陽電池はガラス基板上の上に、ＩＴＯ、ＳｎＯ2、などの透明電極、ｐ型、ｉ型、ｎ型の非晶質シリコン（ａ－Sｉ）膜、Ａｇ、Ａｕなどの裏面電極を順に積層形成して構成されている。例えば、ａ－Ｓｉ膜は、ｐ型、ｉ型、ｎ型の各層を別々のプラズマＣＶＤ装置内で順次形成する、連続分離式にて作製されること（例えば、特許文献１）が知られている。 Generally, a solar cell using an amorphous semiconductor has a transparent electrode such as ITO or SnO 2 on a glass substrate, a p-type, i-type, or n-type amorphous silicon (a-Si) film, A back electrode such as Ag and Au is laminated in order. For example, it is known that an a-Si film is produced by a continuous separation method in which p-type, i-type, and n-type layers are sequentially formed in separate plasma CVD apparatuses (for example, Patent Document 1). Yes.
特開昭６０－３１０８２号公報JP-A-60-31082
　一般的に、プラズマＣＶＤによりｎ型の非晶質半導体膜を得るために、５族の元素をドープするが、このドーピング原料として、ホスフィン（ＰＨ3）を用いる。しかし、ＰＨ3は沸点が－８７．７℃の気体であるため、大量に輸送をするためには高圧充填を行う必要がある。また、化学的に不安定であるため高濃度のＰＨ3を高圧充填して扱うことは安全性に問題が生じ、希釈して充填する必要がある。したがって、大量輸送が難しく、輸送コストが大きくなるという問題がある。このため、光起電力装置の光電変換層の製造プロセスのように大量のガス供給が必要なプロセスには不利である。また、プロセス上ＰＨ3に微量含まれるジホスフィンＰ2Ｈ4などにより自然発火性、ＰＨ3ガスの重合爆発性など化学的安定性が極めて低いことから、設備上および取扱い上厳重な安全対策が必要不可欠となっている。 In general, in order to obtain an n-type amorphous semiconductor film by plasma CVD, a Group 5 element is doped, and phosphine (PH 3 ) is used as a doping material. However, since PH 3 is a gas having a boiling point of −87.7 ° C., high-pressure filling is necessary to transport a large amount. In addition, since it is chemically unstable, handling with high concentration PH 3 under high pressure causes a problem in safety, and it is necessary to dilute and fill. Therefore, there is a problem that mass transportation is difficult and transportation cost is increased. For this reason, it is disadvantageous for a process that requires a large amount of gas supply, such as a manufacturing process of a photoelectric conversion layer of a photovoltaic device. In addition, due to diphosphine P 2 H 4 contained in a trace amount of PH 3 in the process, chemical stability such as spontaneous ignition and polymerization explosion of PH 3 gas is extremely low, so strict safety measures are required on equipment and handling. It has become indispensable.
　本発明は、光起電力装置の光電変換層として成膜されるｐｉｎ接合の非晶質半導体膜に用いられる化合物で、特に、ＰＨ3ガスに代わる化学的に安全で、かつ大量輸送しやすいドーピング原料を提供することを目的としている。 The present invention is a compound used for an amorphous semiconductor film having a pin junction formed as a photoelectric conversion layer of a photovoltaic device. In particular, doping that is chemically safe and easy to transport in large quantities is an alternative to PH 3 gas. The purpose is to provide raw materials.
　このような状況に鑑み、本発明者らは、上記課題を解決すべく鋭意検討した結果、オリゴメチルホスフィン化合物が、ＰＨ3ガスに代わる化学的に安定で、かつ大量輸送しやすいドーピング原料となることを見出し、本発明に至った。 In view of such a situation, the present inventors have intensively studied to solve the above problems, and as a result, the oligomethylphosphine compound is a chemically stable alternative to PH 3 gas and is a doping material that can be easily transported in large quantities. As a result, they have reached the present invention.
　すなわち本発明は、光起電力装置の光電変換層として成膜されるｐｉｎ接合の非晶質半導体膜に用いられる、一般式（１）
　　　　　　　　　（ＣＨ3）nＰＨ3-n　　　（１）
［式中、ｎは１～３のいずれか一つの整数を表す］で表されるオリゴメチルホスフィン化合物を提供するものである。さらには、ｎ型の該非晶質半導体膜を形成するためのドーピングガスとして用いられる、上記一般式（１）で表されるオリゴメチルホスフィン化合物、また、ｎ型の該非晶質半導体膜を成膜するのに用いられる成膜ガスに、上記一般式（１）で表されるオリゴメチルホスフィン化合物がドーピングガスとして０．０００１～１０体積%の範囲内で混合されていることを特徴とする、ｎ型半導体となる非晶質半導体膜の成膜ガスを提供するものである。 That is, the present invention is a general formula (1) used for a pin junction amorphous semiconductor film formed as a photoelectric conversion layer of a photovoltaic device.
(CH 3 ) n PH 3-n (1)
[Wherein n represents an integer of any one of 1 to 3] is provided. Further, the oligomethylphosphine compound represented by the general formula (1) used as a doping gas for forming the n-type amorphous semiconductor film and the n-type amorphous semiconductor film are formed. An n-methylphosphine compound represented by the above general formula (1) is mixed in the film forming gas used in the process as a doping gas within a range of 0.0001 to 10% by volume, n A deposition gas for an amorphous semiconductor film to be a type semiconductor is provided.
　本発明により、光起電力装置の光電変換層として成膜されるｐｉｎ接合の非晶質半導体膜に用いられる化合物として、化学的に安定な化合物を提供することができる。 According to the present invention, a chemically stable compound can be provided as a compound used for a pin junction amorphous semiconductor film formed as a photoelectric conversion layer of a photovoltaic device.
実施例に用いたプラズマＣＶＤの成膜装置の該略図である。1 is a schematic view of a plasma CVD film forming apparatus used in an example. 実施例で作成した光起電力装置の断面の該略図である。1 is a schematic view of a cross section of a photovoltaic device created in an example.
　以下に本発明を詳細に説明する。 The present invention will be described in detail below.
　本発明で用いられるオリゴメチルホスフィン化合物は一般式（１）
　　　　　　　　　（ＣＨ3）nＰＨ3-n　　　（１）
　［式中、ｎは１～３のいずれか一つの整数を表す］で表され、具体的には、トリメチルホスフィン（Ｐ（ＣＨ3）3）、ジメチルホスフィン（（ＣＨ3）2ＰＨ）、メチルホスフィン（（ＣＨ3）ＰＨ2）が挙げられる。この中で、（ＣＨ3）ＰＨ2は沸点－１５℃のガス状化合物であり、（ＣＨ3）2ＰＨは沸点２５℃、Ｐ（ＣＨ3）3は沸点３８℃である。このため室温（２５℃）以上の温度で液体であるＰ（ＣＨ3）3が、安全面で特に好ましい化合物である。 The oligomethylphosphine compound used in the present invention has the general formula (1)
(CH 3 ) n PH 3-n (1)
[Wherein n represents any one integer of 1 to 3], specifically, trimethylphosphine (P (CH 3 ) 3 ), dimethylphosphine ((CH 3 ) 2 PH), methyl And phosphine ((CH 3 ) PH 2 ). Among them, (CH 3 ) PH 2 is a gaseous compound having a boiling point of −15 ° C., (CH 3 ) 2 PH is a boiling point of 25 ° C., and P (CH 3 ) 3 is a boiling point of 38 ° C. Therefore, P (CH 3 ) 3 that is liquid at room temperature (25 ° C.) or higher is a particularly preferable compound in terms of safety.
　本発明の化合物のうち、Ｐ（ＣＨ3）3は、例えばＩｎｏｒｇａｎｉｃ　Ｓｙｍｔｈｅｓｉｓ　１９６７，　９，　５９．に記載されるように、トリメチルホスファイトとメチルグリニア試薬との反応、(ＣＨ3)2ＰＨは、例えば特公昭５４－８６５８号公報に記載されるように、三塩化リンと塩化メチルをＺｎ存在下でガス状で反応させる方法、（ＣＨ3）ＰＨ2は、例えばＪｏｕｒｎａｌ　ｏｆ Ｏｒｇａｎｏｍｅｔａｌｉｃ　Ｃｈｅｍｉｓｔｒｙ　１９９７，　５２９（１），　２０５．に記載されるように、ジメトキシメチルホスフィンをＬｉＡｌＨ4などの還元剤により水素化する方法など、公知の方法で得ることができ、本発明は、該化合物を得る方法に限定されない。 Among the compounds of the present invention, P (CH 3 ) 3 is, for example, Inorganic Synthesis 1967, 9, 59. (CH 3 ) 2 PH, for example, as described in JP-B No. 54-8658, phosphorous trichloride and methyl chloride in the presence of Zn. (CH 3 ) PH 2 may be obtained by, for example, Journal of Organic Chemistry 1997, 529 (1), 205. Can be obtained by a known method such as a method of hydrogenating dimethoxymethylphosphine with a reducing agent such as LiAlH 4, and the present invention is not limited to the method of obtaining the compound.
　本発明の化合物は、プラズマＣＶＤ、熱ＣＶＤ、光ＣＶＤなどｐｉｎ接合の非晶質半導体膜を成膜する一般的な方法に用いることができる。 The compound of the present invention can be used in a general method for forming a pin junction amorphous semiconductor film such as plasma CVD, thermal CVD, and photo CVD.
　非晶質半導体としては、ａ－Ｓｉ、ａ－ＳｉＧｅ、ａ－ＳｉＮ、ａ－ＳｉＣ、ａ－ＳｉＯ2などが挙げられる。Ｓｉ源としては、モノシラン（ＳｉＨ4）など、ａ－ＳｉＧｅのＧｅ源としては、モノゲルマン（ＧｅＨ4）など、ａ－ＳｉＮのＮ源としては、アンモニア、窒素など、ａ－ＳｉＣのＣ源としては、エタン、プロパンなどの低級アルカン、ａ－ＳｉＯのＯ源としては、酸素などのガスが非晶質半導体膜の成膜に用いられる。またこの際、モノシラン、モノゲルマンなどは希釈された状態で成膜装置内に供給され、キャリアガスとして水素、ヘリウム、窒素などが用いられる
　特に本発明の化合物は、非晶質半導体の成膜時のドーピング原料として用いることが有効である。また、ドーピング原料として用いる場合、本発明の化合物を０．０００１～１０体積％の範囲内で混合させた成膜ガスを用いることが好ましい。０．０００１体積％未満ではドーピング濃度が低濃度すぎてｎ型としての機能が低下し、１０体積％超では、半導体膜を形成する材料が低濃度すぎて半導体としての機能が低下する虞がある。 Examples of the amorphous semiconductor include a-Si, a-SiGe, a-SiN, a-SiC, and a-SiO 2 . Examples of the Si source include monosilane (SiH 4 ); examples of the a-SiGe Ge source include monogermane (GeH 4 ); examples of the a-SiN N source include ammonia, nitrogen and the like as a C source of a-SiC. In this case, a lower alkane such as ethane or propane, or a gas such as oxygen is used as an O source for a-SiO to form an amorphous semiconductor film. At this time, monosilane, monogermane, etc. are supplied into the film forming apparatus in a diluted state, and hydrogen, helium, nitrogen, etc. are used as a carrier gas. Particularly, the compound of the present invention is used for forming an amorphous semiconductor. It is effective to use it as a doping material. In addition, when used as a doping raw material, it is preferable to use a film forming gas in which the compound of the present invention is mixed in the range of 0.0001 to 10% by volume. If it is less than 0.0001% by volume, the doping concentration is too low and the function as an n-type is reduced. If it exceeds 10% by volume, the material forming the semiconductor film is too low and the function as a semiconductor may be reduced. .
　以下、実施例および比較例を挙げ、本発明をより具体的に詳細に説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, although an example and a comparative example are given and the present invention is explained more concretely in detail, the present invention is not limited to the following examples.
　磁製カップの上にろ紙を置き、ＳＴＲＥＭ社製Ｐ（ＣＨ3）3を注射器で０．５ｍＬ滴下し、その様子を観察した。５分後においても、ろ紙が燃えた形跡も焦げた形跡も観測されなかった。この実験を繰り返し３回実施したが同様の結果となった。このことから、自然発火性はないものと考えられる。 A filter paper was placed on the porcelain cup, and 0.5 mL of P (CH 3 ) 3 made by STREM was dropped with a syringe, and the state was observed. Even after 5 minutes, no evidence of burning or scorching of the filter paper was observed. This experiment was repeated three times with similar results. From this, it is considered that there is no spontaneous ignition.
　磁製カップの上にろ紙を置き、特公昭５４－８６５８号公報に記載されている方法を用いて得られた（ＣＨ3）2ＰＨを注射器で０．５ｍＬ滴下し、その様子を観察した。５分後においても、ろ紙が燃えた形跡も焦げた形跡も観測されなかった。この実験を繰り返し３回実施したが同様の結果となった。このことから、自然発火性はないものと考えられる。 A filter paper was placed on a porcelain cup, and 0.5 mL of (CH 3 ) 2 PH obtained by using the method described in JP-B-54-8658 was dropped with a syringe and the state was observed. Even after 5 minutes, no evidence of burning or scorching of the filter paper was observed. This experiment was repeated three times with similar results. From this, it is considered that there is no spontaneous ignition.
　真空引きした１ＬのＳＵＳ製シリンダーにＪｏｕｒｎａｌ ｏｆ　Ｏｒｇａｎｏｍｅｔａｌｉｃ　Ｃｈｅｍｉｓｔｒｙ　１９９７，　５２９（１），　２０５．に記載されている方法を用いて得られた（ＣＨ3）ＰＨ2を室温で入れ、その後空気を所定量入れ、全体で１０００ｔｏｒｒとなるようにした。その後室温で圧力変化の様子を観察した。空気の濃度０～１００％のいずれの場合においても５分後における圧力変動は観測されなかった。このことから、自然発火性はないものと考えられる。 In a 1 L SUS cylinder evacuated, Journal of Organic Chemistry 1997, 529 (1), 205. (CH 3 ) PH 2 obtained using the method described in 1 ) was introduced at room temperature, and then a predetermined amount of air was introduced so that the total amount was 1000 torr. Thereafter, the pressure change was observed at room temperature. No pressure fluctuation was observed after 5 minutes at any air concentration of 0 to 100%. From this, it is considered that there is no spontaneous ignition.
　図１は、本実施例に用いたプラズマＣＶＤの成膜装置の概略図である。上部放電電極２ａ、及び温度制御手段を備えた電極ヒータ１２を内蔵した下部放電電極２ｂが対向して配置されている。下部放電電極２ｂ上には成膜対象のガラス基板３が載置されている。真空チャンバ１には高周波電源４により、１３．５６ＭＨｚの高周波電圧が印加される。また、真空チャンバ１には排気システム５が接続されており、その内部が真空状態に維持されている。そして、上部放電電極２ａ、下部放電電極２ｂ間に真空放電が生じてプラズマが発生するようになっている。 FIG. 1 is a schematic view of a plasma CVD film forming apparatus used in this example. An upper discharge electrode 2a and a lower discharge electrode 2b incorporating an electrode heater 12 having a temperature control means are arranged to face each other. A glass substrate 3 to be deposited is placed on the lower discharge electrode 2b. A high frequency voltage of 13.56 MHz is applied to the vacuum chamber 1 by a high frequency power source 4. Further, an exhaust system 5 is connected to the vacuum chamber 1, and the inside thereof is maintained in a vacuum state. A vacuum discharge is generated between the upper discharge electrode 2a and the lower discharge electrode 2b to generate plasma.
　真空チャンバ１は、配管９を介してＳｉＨ4ボンベ６及びＳＴＲＥＭ社製Ｐ（ＣＨ3）3を充填したボンベ７に連結されている。配管９の中途にはＳｉＨ4のガス流量を制御するマスフローコントローラ８ａとＰ（ＣＨ3）3のガス量を制御するマスフローコントローラ８ｂとが設けられている。Ｐ（ＣＨ3）3ボンベ７の周囲にはＰ（ＣＨ3）3を気化するためのヒータ１０が設置され、５０℃に加温されている。また、配管９には、その内部を加温するためのコイルヒータ１１が巻きつけられている。なお、１０ＭＰａ以上の高圧充填されたＰＨ3とは異なり、Ｐ（ＣＨ3）3は室温で４６０ｔｏｒｒ程度の蒸気圧をもつ液体であるため、５０℃におけるボンベ内圧力は略０．１５ＭＰａである。 The vacuum chamber 1 is connected through a pipe 9 to a cylinder 7 filled with a SiH 4 cylinder 6 and PREM ( 3 ) P (CH 3 ) 3 manufactured by STREM. In the middle of the pipe 9, there are provided a mass flow controller 8a for controlling the gas flow rate of SiH 4 and a mass flow controller 8b for controlling the gas amount of P (CH 3 ) 3 . A heater 10 for vaporizing P (CH 3 ) 3 is installed around the P (CH 3 ) 3 cylinder 7 and heated to 50 ° C. A coil heater 11 is wound around the pipe 9 to heat the inside. Unlike PH 3 filled with a high pressure of 10 MPa or more, P (CH 3 ) 3 is a liquid having a vapor pressure of about 460 torr at room temperature, and therefore the pressure inside the cylinder at 50 ° C. is about 0.15 MPa.
　次に動作について説明する。真空チャンバ１内の下部放電電極２ｂ上に載置されているガラス基板３を電極ヒータ１２により２００℃に加熱する。排気システム５により真空チャンバ１内を略１Ｐａの真空状態に維持し、高周波電源４により１３．５６ＭＨｚの高周波電圧を出力３０Ｗで印加する。一方、ＳｉＨ4ボンベ６からマスフローコントローラ８ａにてその流量を制御したＳｉＨ4ガスをコイルヒータ１１への通電により内部を５０℃程度に維持した配管９を介して真空チャンバ１内に導入する。また、ヒータ１０にて５０℃に加温して気化させたボンベ７内のＰ（ＣＨ3）3を、マスフローコントローラ８ｂにてその流量を制御し、配管９を介して真空チャンバ１内に導入する。ＳｉＨ4ガスとＰ（ＣＨ3）3ガスの導入量は各マスフローコントローラ８ａおよび８ｂを用いて、トータルガス流量を１０ｓｃｃｍ、導入されるトータルガス中のＰ（ＣＨ3）3ガスのガス混合率を０．１体積％に調節し、０．８ｎｍ／ｓ程度の蒸着速度にて成膜する。このときの真空チャンバ１内を圧力１０Ｐａに維持されている。 Next, the operation will be described. The glass substrate 3 placed on the lower discharge electrode 2 b in the vacuum chamber 1 is heated to 200 ° C. by the electrode heater 12. The inside of the vacuum chamber 1 is maintained in a vacuum state of about 1 Pa by the exhaust system 5, and a high frequency voltage of 13.56 MHz is applied by the high frequency power source 4 at an output of 30 W. On the other hand, it is introduced into the vacuum chamber 1 through the pipe 9 that maintained internal to about 50 ° C. The SiH 4 gas controlling the flow rate from the SiH 4 gas cylinder 6 by a mass flow controller 8a by energizing the coil heater 11. Further, the flow rate of P (CH 3 ) 3 in the cylinder 7 heated to 50 ° C. by the heater 10 and vaporized is controlled by the mass flow controller 8 b and introduced into the vacuum chamber 1 through the pipe 9. To do. The amount of SiH 4 gas and P (CH 3 ) 3 gas introduced is determined by using the mass flow controllers 8a and 8b, the total gas flow rate is 10 sccm, and the gas mixing ratio of P (CH 3 ) 3 gas in the total gas to be introduced. The film is formed at a deposition rate of about 0.8 nm / s by adjusting to 0.1% by volume. The inside of the vacuum chamber 1 at this time is maintained at a pressure of 10 Pa.
　このようにしてガラス基板３上に成膜された膜厚１０００Åの膜について、ｎ型半導体の暗導電率測定を行い、０．８９×１０-3Ｓ／ｃｍの暗導電率が得られ、既存のホスフィンガスを用いた場合（０．９５×１０-3Ｓ／ｃｍ）と同程度の性能を示した。 The dark conductivity of the n-type semiconductor was measured on the film having a thickness of 1000 mm formed on the glass substrate 3 in this way, and a dark conductivity of 0.89 × 10 −3 S / cm was obtained. The same performance as in the case of using phosphine gas (0.95 × 10 −3 S / cm) was exhibited.
　Ｐ（ＣＨ3）3ガス混合率を０．００３体積％とした以外は実施例４と同じようにｎ型非晶質半導体膜を成膜した。このようにしてガラス基板３上に成膜された膜厚１０００Åの膜について、ｎ型半導体の暗導電率測定を行い、３．８×１０-7Ｓ／ｃｍの暗導電率が得られ、既存のホスフィンガスを用いた場合（４．０×１０-7Ｓ／ｃｍ）と同程度の性能を示した。 An n-type amorphous semiconductor film was formed in the same manner as in Example 4 except that the mixing ratio of P (CH 3 ) 3 gas was 0.003% by volume. The dark conductivity of the n-type semiconductor was measured for the film having a thickness of 1000 mm formed on the glass substrate 3 in this way, and a dark conductivity of 3.8 × 10 −7 S / cm was obtained. The same performance as that of the phosphine gas (4.0 × 10 −7 S / cm) was used.
　Ｐ（ＣＨ3）3ガス混合率を１体積％とした以外は実施例４と同じようにｎ型非晶質半導体膜を成膜した。このようにしてガラス基板３上に成膜された膜厚１０００Åの膜について、ｎ型半導体の暗導電率測定を行い、１．３×１０-2Ｓ／ｃｍの暗導電率が得られ、既存のホスフィンガスを用いた場合（１．０×１０-2Ｓ／ｃｍ）と同程度の性能を示した。 An n-type amorphous semiconductor film was formed in the same manner as in Example 4 except that the P (CH 3 ) 3 gas mixing ratio was 1% by volume. The dark conductivity of the n-type semiconductor was measured for the film having a thickness of 1000 mm formed on the glass substrate 3 in this way, and a dark conductivity of 1.3 × 10 −2 S / cm was obtained. The same performance as that of the phosphine gas (1.0 × 10 −2 S / cm) was used.
　Ｐ（ＣＨ3）3ガス混合率を３体積％とした以外は実施例４と同じようにｎ型非晶質半導体膜を成膜した。このようにしてガラス基板３上に成膜された膜厚１０００Åの膜について、ｎ型半導体の暗導電率測定を行い、１．１×１０-2Ｓ／ｃｍの暗導電率が得られ、既存のホスフィンガスを用いた場合（１．０×１０-2Ｓ／ｃｍ）と同程度の性能を示した。 An n-type amorphous semiconductor film was formed in the same manner as in Example 4 except that the P (CH 3 ) 3 gas mixing ratio was 3% by volume. The dark conductivity of the n-type semiconductor was measured for the film having a thickness of 1000 mm formed on the glass substrate 3 in this way, and a dark conductivity of 1.1 × 10 −2 S / cm was obtained. The same performance as that of the phosphine gas (1.0 × 10 −2 S / cm) was used.
　Ｐ(ＣＨ3)3を、特公昭５４－８６５８号公報に記載されている方法を用いて得られた（ＣＨ3）2ＰＨに代えた以外は、実施例４と同じようにｎ型非晶質半導体膜を成膜した。このようにしてガラス基板３上に成膜された膜について、ｎ型半導体の暗導電率測定を行い、０．９×１０-3Ｓ／ｃｍの暗導電率が得られ、既存のホスフィンガスを用いた場合（０．９５×１０-3Ｓ／ｃｍ）と同程度の性能を示した。 N-type amorphous as in Example 4 except that P (CH 3 ) 3 was replaced with (CH 3 ) 2 PH obtained by using the method described in JP-B-54-8658. A quality semiconductor film was formed. For the film formed on the glass substrate 3 in this way, the dark conductivity of the n-type semiconductor is measured, and a dark conductivity of 0.9 × 10 −3 S / cm is obtained. The same performance as when used (0.95 × 10 −3 S / cm) was exhibited.
　Ｐ(ＣＨ3)3を、Ｊｏｕｒｎａｌ ｏｆ　Ｏｒｇａｎｏｍｅｔａｌｉｃ　Ｃｈｅｍｉｓ
ｔｒｙ　１９９７，　５２９（１），　２０５．に記載されている方法を用いて得られた（ＣＨ3）ＰＨ2に代え、ヒータ１０およびヒータ１１をはずした以外は、実施例５と同じようにｎ型非晶質半導体膜を形成した。このようにしてガラス基板３上に成膜された膜について、ｎ型半導体の暗導電率測定を行い、１．９×１０-7Ｓ／ｃｍの暗導電率が得られ、既存のホスフィンガスを用いた場合（４．０×１０-7Ｓ／ｃｍ）と同程度の性能を示した。 P (CH 3 ) 3 is replaced by Journal of Organicometric Chemis
try 1997, 529 (1), 205. An n-type amorphous semiconductor film was formed in the same manner as in Example 5 except that the heater 10 and the heater 11 were removed in place of the (CH 3 ) PH 2 obtained by using the method described in 1 ). The film thus formed on the glass substrate 3 was measured for dark conductivity of the n-type semiconductor, and a dark conductivity of 1.9 × 10 −7 S / cm was obtained. The performance was similar to that when used (4.0 × 10 −7 S / cm).
　本実施例で作成した光起電力装置の断面の概略図を図２に示す。ガラス基板２１上に、ＩＴＯからなる透明電極２２、１層目の光起電力素子を構成する膜厚１００ÅのＢ（ボロン）ドープのａ－ＳｉＣ膜からなるｐ型層２３をプラズマＣＶＤ法により透明電極２２上に形成する。続いて、膜厚１０００Åのａ－Ｓｉからなるｉ型層２４を形成した。その後、実施例４と同様の手法により膜厚１００ÅのＰ（リン）ドープのａ－Ｓｉからなるｎ型層２５をプラズマＣＶＤ法により形成した。引き続きＡｇの金属から成る金属電極２６をこの順序で積層して光起電力装置を形成した。得られたａ－Ｓｉ光起電力装置に東京インスツルメンツ製３００Ｗソーラーシミュレータを用い発生させたＡＭ（エアマス）１．５Ｇの基準太陽光のスペクトルに準じた擬似太陽光を、強度１００Ｗ／ｃｍ2で照射し、その光電変換特性を測定したところ、短絡電流密度１７．９ｍＡ／ｃｍ2、開放電圧０．７４Ｖ、フィルファクター０．７５、光電変換効率９．９３％となり、既存のホスフィンガスを用いた場合と同程度の性能を示した。 A schematic view of a cross section of the photovoltaic device produced in this example is shown in FIG. A transparent electrode 22 made of ITO and a p-type layer 23 made of a B (boron) -doped a-SiC film constituting the first photovoltaic element are made transparent on the glass substrate 21 by plasma CVD. It is formed on the electrode 22. Subsequently, an i-type layer 24 made of a-Si having a thickness of 1000 mm was formed. Thereafter, an n-type layer 25 made of P (phosphorus) -doped a-Si having a thickness of 100 mm was formed by plasma CVD using the same method as in Example 4. Subsequently, a metal electrode 26 made of Ag metal was laminated in this order to form a photovoltaic device. The a-Si photovoltaic device obtained was irradiated with simulated sunlight according to AM (air mass) 1.5G reference sunlight spectrum generated using a 300 W solar simulator manufactured by Tokyo Instruments at an intensity of 100 W / cm 2 . When the photoelectric conversion characteristics were measured, the short-circuit current density was 17.9 mA / cm 2 , the open circuit voltage was 0.74 V, the fill factor was 0.75, the photoelectric conversion efficiency was 9.93%, and the existing phosphine gas was used. The performance was comparable.
　実施例５と同じ手法で成膜したｎ型非晶質半導体膜をｎ型層２５として用いた以外は実施例１０と同じように光起電力装置を作製した。得られたａ－Ｓｉ光起電力装置に東京インスツルメンツ製３００Ｗソーラーシミュレータを用い発生させたＡＭ（エアマス）１．５Ｇの基準太陽光のスペクトルに準じた擬似太陽光を、強度１００Ｗ／ｃｍ2で照射し、その光電変換特性を測定したところ、短絡電流密度１８.０ｍＡ／ｃｍ2、開放電圧０．７７Ｖ、フィルファクター０．７４、光電変換効率１０．２６％となり、既存のホスフィンガスを用いた場合と同程度の性能を示した。 A photovoltaic device was produced in the same manner as in Example 10 except that an n-type amorphous semiconductor film formed by the same method as in Example 5 was used as the n-type layer 25. The a-Si photovoltaic device obtained was irradiated with simulated sunlight according to AM (air mass) 1.5G reference sunlight spectrum generated using a 300 W solar simulator manufactured by Tokyo Instruments at an intensity of 100 W / cm 2 . When the photoelectric conversion characteristics were measured, the short-circuit current density was 18.0 mA / cm 2 , the open circuit voltage was 0.77 V, the fill factor was 0.74, the photoelectric conversion efficiency was 10.26%, and the existing phosphine gas was used. The performance was comparable.
　実施例６と同じ手法で成膜したｎ型非晶質半導体膜をｎ型層２５として用いた以外は実施例１０と同じように光起電力装置を作製した。得られたａ－Ｓｉ光起電力装置に東京インスツルメンツ製３００Ｗソーラーシミュレータを用い発生させたＡＭ（エアマス）１．５Ｇの基準太陽光のスペクトルに準じた擬似太陽光を、強度１００Ｗ／ｃｍ2で照射し、その光電変換特性を測定したところ、短絡電流密度１８.０ｍＡ／ｃｍ2、開放電圧０．７４Ｖ、フィルファクター０．７５、光電変換効率９．９９％となり、既存のホスフィンガスを用いた場合と同程度の性能を示した。 A photovoltaic device was produced in the same manner as in Example 10 except that an n-type amorphous semiconductor film formed by the same method as in Example 6 was used as the n-type layer 25. The a-Si photovoltaic device obtained was irradiated with simulated sunlight according to AM (air mass) 1.5G reference sunlight spectrum generated using a 300 W solar simulator manufactured by Tokyo Instruments at an intensity of 100 W / cm 2 . When the photoelectric conversion characteristics were measured, the short-circuit current density was 18.0 mA / cm 2 , the open circuit voltage was 0.74 V, the fill factor was 0.75, the photoelectric conversion efficiency was 9.99%, and the existing phosphine gas was used. The performance was comparable.
　実施例７と同じ手法で成膜したｎ型非晶質半導体膜をｎ型層２５として用いた以外は実施例１０と同じように光起電力装置を作製した。得られたａ－Ｓｉ光起電力装置に東京インスツルメンツ製３００Ｗソーラーシミュレータを用い発生させたＡＭ（エアマス）１．５Ｇの基準太陽光のスペクトルに準じた擬似太陽光を、強度１００Ｗ／ｃｍ2で照射し、その光電変換特性を測定したところ、短絡電流密度１８.１ｍＡ／ｃｍ2、開放電圧０．７２Ｖ、フィルファクター０．７５、光電変換効率９．７７％となり、既存のホスフィンガスを用いた場合と同程度の性能を示した。 A photovoltaic device was produced in the same manner as in Example 10 except that an n-type amorphous semiconductor film formed by the same method as in Example 7 was used as the n-type layer 25. The a-Si photovoltaic device obtained was irradiated with simulated sunlight according to AM (air mass) 1.5G reference sunlight spectrum generated using a 300 W solar simulator manufactured by Tokyo Instruments at an intensity of 100 W / cm 2 . When the photoelectric conversion characteristics were measured, the short-circuit current density was 18.1 mA / cm 2 , the open circuit voltage was 0.72 V, the fill factor was 0.75, the photoelectric conversion efficiency was 9.77%, and the existing phosphine gas was used. The performance was comparable.
　実施例８と同じ手法で成膜したｎ型非晶質半導体膜をｎ型層２５として用いた以外は実施例１０と同じように光起電力装置を作製した。得られたａ－Ｓｉ光起電力装置に東京インスツルメンツ製３００Ｗソーラーシミュレータを用い発生させたＡＭ（エアマス）１．５Ｇの基準太陽光のスペクトルに準じた擬似太陽光を、強度１００Ｗ／ｃｍ2で照射し、その光電変換特性を測定したところ、短絡電流密度１８.０ｍＡ／ｃｍ2、開放電圧０．６９Ｖ、フィルファクター０．７５、光電変換効率９．３２％となり、既存のホスフィンガスを用いた場合と同程度の性能を示した。 A photovoltaic device was produced in the same manner as in Example 10 except that an n-type amorphous semiconductor film formed by the same method as in Example 8 was used as the n-type layer 25. The a-Si photovoltaic device obtained was irradiated with simulated sunlight according to AM (air mass) 1.5G reference sunlight spectrum generated using a 300 W solar simulator manufactured by Tokyo Instruments at an intensity of 100 W / cm 2 . When the photoelectric conversion characteristics were measured, the short-circuit current density was 18.0 mA / cm 2 , the open circuit voltage was 0.69 V, the fill factor was 0.75, the photoelectric conversion efficiency was 9.32%, and the existing phosphine gas was used. The performance was comparable.
　実施例９と同じ手法で成膜したｎ型非晶質半導体膜をｎ型層２５として用いた以外は実施例１０と同じように光起電力装置を作製した。得られたａ－Ｓｉ光起電力装置に東京インスツルメンツ製３００Ｗソーラーシミュレータを用い発生させたＡＭ（エアマス）１.５Ｇの基準太陽光のスペクトルに準じた擬似太陽光を、強度１００Ｗ／ｃｍ2で照射し、その光電変換特性を測定したところ、短絡電流密度１７．９ｍＡ／ｃｍ2、開放電圧０．７４Ｖ、フィルファクター０．７４、光電変換効率９．８０％となり、既存のホスフィンガスを用いた場合と同程度の性能を示した。 A photovoltaic device was produced in the same manner as in Example 10 except that an n-type amorphous semiconductor film formed by the same method as in Example 9 was used as the n-type layer 25. The a-Si photovoltaic device obtained was irradiated with simulated sunlight according to the AM (air mass) 1.5G reference sunlight spectrum generated using a 300 W solar simulator manufactured by Tokyo Instruments at an intensity of 100 W / cm 2 . When the photoelectric conversion characteristics were measured, the short-circuit current density was 17.9 mA / cm 2 , the open circuit voltage was 0.74 V, the fill factor was 0.74, the photoelectric conversion efficiency was 9.80%, and the existing phosphine gas was used. The performance was comparable.
　なお、上述の実施例では、成膜方法としてプラズマＣＶＤ法を用いたが、公知の光ＣＶＤ法またはマイクロＣＶＤ法等を用いても同様の効果が得られた。 In the above-described embodiment, the plasma CVD method is used as the film forming method. However, the same effect can be obtained by using a known photo-CVD method or micro-CVD method.
　また、ｎ型非晶質半導体としてａ－Ｓｉの場合について説明したが、ａ－ＳｉＧｅ、ａ－ＳｉＮ、ａ－ＳｉＣ、ａ－ＳｉＯ２の他の非晶質半導体についても全く同様に行うことができ、同様の効果が得られた。 Although the case of a-Si as an n-type amorphous semiconductor has been described, other amorphous semiconductors of a-SiGe, a-SiN, a-SiC, and a-SiO2 can be performed in exactly the same manner. The same effect was obtained.
１・・・真空チャンバ
２ａ・・・上部放電電極
２ｂ・・・下部放電電極
３・・・ガラス基板
４・・・高周波電源
５・・・排気システム
６・・・ＳｉＨ4ボンベ
７・・・ボンベ
８ａ、８ｂ・・・マスフローコントローラ
９・・・配管
１０・・・ヒータ
１１・・・コイルヒータ
１２・・・電極ヒータ
２１・・・ガラス基板
２２・・・透明電極
２３・・・ｐ型層
２４・・・ｉ型層
２５・・・ｎ型層
２６・・・金属電極 1 ... vacuum chamber 2a ... upper discharge electrode 2b ... lower discharge electrode 3 ... glass substrate 4 ... high-frequency power supply 5 ... exhaust system 6 ... SiH 4 gas cylinder 7 ... bomb 8a, 8b ... mass flow controller 9 ... piping 10 ... heater 11 ... coil heater 12 ... electrode heater 21 ... glass substrate 22 ... transparent electrode 23 ... p-type layer 24 ... i-type layer 25 ... n-type layer 26 ... metal electrode

Claims (3)

  1. 光起電力装置の光電変換層として成膜されるｐｉｎ接合の非晶質半導体膜に用いられる、一般式（１）
    　　　　　　　　　（ＣＨ3）ｎＰＨ3-n　　　（１）
    　［式中、ｎは１～３のいずれか一つの整数を表す。］で表されるオリゴメチルホスフィン化合物。     General formula (1) used for a pin junction amorphous semiconductor film formed as a photoelectric conversion layer of a photovoltaic device
    (CH 3 ) nPH 3-n (1)
    [Wherein n represents any one integer of 1 to 3. ] The oligomethylphosphine compound represented by this.
  2. ｎ型の該非晶質半導体膜を形成するためのドーピングガスとして用いられる、請求項１に記載のオリゴメチルホスフィン化合物。 The oligomethylphosphine compound according to claim 1, which is used as a doping gas for forming the n-type amorphous semiconductor film.
  3. ｎ型の該非晶質半導体膜を成膜するのに用いられる成膜ガスに、請求項１に記載のオリゴメチルホスフィン化合物がドーピングガスとして０．０００１～１０体積%の範囲内で混合されていることを特徴とする、ｎ型半導体となる非晶質半導体膜の成膜ガス。 The oligomethylphosphine compound according to claim 1 is mixed as a doping gas in a range of 0.0001 to 10% by volume in a deposition gas used to form the n-type amorphous semiconductor film. A film forming gas for an amorphous semiconductor film to be an n-type semiconductor.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6444014A (en) * 1987-08-12 1989-02-16 Seiko Epson Corp Manufacture of silicon thin film
JPH0649644A (en) * 1992-04-11 1994-02-22 Licentia Patent Verwalt Gmbh Method of doping amorphous silicon and method of producing electrophotographic recording material
JP2005086135A (en) * 2003-09-11 2005-03-31 Nippon Telegr & Teleph Corp <Ntt> Epitaxial wafer for hetero bipolar transistor and its manufacturing method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6444014A (en) * 1987-08-12 1989-02-16 Seiko Epson Corp Manufacture of silicon thin film
JPH0649644A (en) * 1992-04-11 1994-02-22 Licentia Patent Verwalt Gmbh Method of doping amorphous silicon and method of producing electrophotographic recording material
JP2005086135A (en) * 2003-09-11 2005-03-31 Nippon Telegr & Teleph Corp <Ntt> Epitaxial wafer for hetero bipolar transistor and its manufacturing method

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Title
J. SCHMAL ET AL.: "Defect density and photoelectrical properties of alternative doped amorphous silicon", JOURNAL OF NON-CRYSTALLINE SOLIDS, vol. 164-166, no. 1, 1993, pages 415 - 418 *

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