[go: up one dir, main page]

WO2008108009A1 - Film semi-conducteur de carbone de type n et dispositif semi-conducteur utilisant celui-ci - Google Patents

Film semi-conducteur de carbone de type n et dispositif semi-conducteur utilisant celui-ci Download PDF

Info

Publication number
WO2008108009A1
WO2008108009A1 PCT/JP2007/059821 JP2007059821W WO2008108009A1 WO 2008108009 A1 WO2008108009 A1 WO 2008108009A1 JP 2007059821 W JP2007059821 W JP 2007059821W WO 2008108009 A1 WO2008108009 A1 WO 2008108009A1
Authority
WO
WIPO (PCT)
Prior art keywords
semiconductor film
carbon
type carbon
type
substrate
Prior art date
Application number
PCT/JP2007/059821
Other languages
English (en)
Japanese (ja)
Inventor
Michikazu Hara
Original Assignee
Tokyo Institute Of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2007056652A external-priority patent/JP2007273970A/ja
Application filed by Tokyo Institute Of Technology filed Critical Tokyo Institute Of Technology
Publication of WO2008108009A1 publication Critical patent/WO2008108009A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D62/00—Semiconductor bodies, or regions thereof, of devices having potential barriers
    • H10D62/80—Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials
    • H10D62/83—Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials being Group IV materials, e.g. B-doped Si or undoped Ge
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D62/00—Semiconductor bodies, or regions thereof, of devices having potential barriers
    • H10D62/80—Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials
    • H10D62/881—Semiconductor bodies, or regions thereof, of devices having potential barriers characterised by the materials being a two-dimensional material
    • H10D62/882—Graphene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/16—Photovoltaic cells having only PN heterojunction potential barriers
    • H10F10/164—Photovoltaic cells having only PN heterojunction potential barriers comprising heterojunctions with Group IV materials, e.g. ITO/Si or GaAs/SiGe photovoltaic cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
    • H10D8/00—Diodes
    • 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

Definitions

  • the present invention relates to an n-type vigorous semiconductor film, a semiconductor element using the same, and a solar cell.
  • Inorganic semiconductor materials are widely used as materials for semiconductor elements.
  • inorganic semiconductors undergo high-temperature processing at 300 ° C or higher during manufacturing and device manufacturing processes under vacuum such as vapor deposition, sputtering, and CVD, so large-area devices can easily be manufactured at low cost. Difficult to manufacture.
  • organic semiconductor materials instead of inorganic semiconductor materials.
  • Organic semiconductors can be manufactured in an easy manufacturing process at low temperatures, and can be easily increased in area.
  • n-type semiconductors which are the carriers responsible for charge
  • p-type semiconductors which are holes.
  • organic p-type semiconductors those having a Penyusen structure, polythiophene structure, and vorphyrin structure are known
  • organic n-type semiconductors fullerenes and fullerene derivatives are known.
  • these materials have special structures, so the raw materials are limited, and the synthesis route is a complicated and expensive material.
  • the present invention provides a semiconductor device and a solar cell that can be easily produced at low cost and easily by preparing an n-type carbon semiconductor or a p-type carbon semiconductor, and that can be used for high performance and a large area.
  • the present invention provides the following inventions in order to solve the above problems.
  • An organic compound containing at least one of nitrogen and sulfur is produced by contacting a substrate in a liquid phase state or a gas phase state under normal pressure, followed by heat treatment.
  • n-type carbon semiconductor film according to (4) which does not substantially contain a nitrile group.
  • (6) The n-type carbon semiconductor film according to any one of the above (3) to (5), wherein the temperature of the heat treatment is 20 ° C to 900 ° C;
  • a solar cell comprising the semiconductor element according to any one of (10) to (12) above.
  • FIG. 1 is a schematic cross-sectional view of a semiconductor device using the n-type carbon semiconductor film obtained in Example 1.
  • the n-type carbon semiconductor film in the present invention is substantially composed of an assembly of six-membered carbon rings, and in the spectrum by Raman spectroscopy, the D band in the vicinity of 1300 cm- 1 (usually from 1200 to 1) 4 0 0 cm- broad band at 1) and 1 6 0 0 cm- 1 near the G band (usually 1 4 5 0 ⁇ 1 7 0 0 cm- broad band at 1) the integrated intensity ratio I (D) / I (G) is 0.3 to 3.0, preferably 0.5 to 2.5.
  • the D band of Raman spectrum is the vibration of Alg breat hing mode in a carbon six-membered ring. This band is forbidden in the graph item, and when the structural disorder increases, the selectivity for this stretching mode is relaxed and peaks are observed. This peak intensity is known to be strongly influenced by the presence of carbon 6-membered aromatic rings (6-membered sp 2 carbocycles).
  • the G band of the Raman spectrum is the E2g mode vibration of the carbon six-membered ring, and is derived from the stretching motion in which the bonds between sp 2 atoms are planar. This is due to vibrations that occur specifically in carbon atoms in the sp 2 state.
  • the Raman spectrum consisting of the sum of the D band and G band is divided into two peaks with Gaussian or Gaussian-Lorentzian, and the integrated intensities I (D) These integrated intensity ratios I (D) / I (G) were calculated as I (G).
  • the integral intensity ratio I (D) / I (G) is less than 0.3, it will not function as a semiconductor because it becomes a semimetal.
  • the hexagonal network structure in which the six-membered carbon atoms forming the benzene ring are connected in a plane is called graph envy, and the structure in which this sheet is stacked in layers is a dullite crystal.
  • delocalized ⁇ -electrons can move through a conjugated system formed along a carbon chain with a hexagonal network structure, so that high electrical conductivity similar to that of metal is shown. is there.
  • the integral intensity ratio I (D) / I (G) exceeds 3.0, the number of assembled carbon six-membered rings is small and insulation is exhibited, and electrical conductivity cannot be obtained. If the integral intensity ratio I (D) / I (G) ratio is less than 0.3 or more than 3.0, at least one of the peak splits may be ambiguous and less than 0.3. It is an insulator, and even if it exceeds 3.0, it may be a semimetal (conductor).
  • the ⁇ -type carbon semiconductor film of the present invention preferably has a graph sheet having a size of about 1 to 5 nm.
  • the elemental ratio (N and / or S) / C of nitrogen and / or nitrogen and carbon by X-ray photoelectron spectroscopy is 0.001 to 0.4. 0, preferably 0.05 to 0.20. If this elemental ratio (N and / or S) / C is less than 0.01, no n-type is shown. On the other hand, if it exceeds 0.40, electrical conductivity is extremely low. Drops to the edge.
  • the n-type carbon semiconductor film in the present invention preferably has 0. 02 diffraction lines in the powder X-ray pattern. This diffraction line indicates the existence of a structure in which multiple layers of dalaphen sheets, which were suggested to exist in the Raman spectroscopic spectrum, were stacked.
  • the n-type carbon semiconductor according to the present invention has a structure in which graph sheets are stacked.
  • the n-type carbon semiconductor of the present invention mainly comprises a carbon six-membered ring, but the elemental ratio of nitrogen and / or nitrogen to carbon (N and / or S) / C is preferably from 0.001 to 0.40, preferably Contains nitrogen and sulfur or sulfur corresponding to 0.05 to 0.20.
  • the n-type carbon semiconductor film is mainly composed of a six-membered carbon ring because elements other than carbon and nitrogen or sulfur are not substantially detected by Raman spectroscopic analysis or X-ray photoelectron spectroscopic measurement. Can be confirmed by
  • the n-type force one-bon semiconductor of the present invention is characterized by the Raman spectroscopic spectrum, the X-ray photoelectron spectroscopic spectrum, the powder X-ray, and the infrared spectroscopic spectrum. The structure is shown.
  • an organic compound containing nitrogen and sulfur which is a precursor of the n-type semiconductor film, is brought into contact with the substrate in a liquid phase state or in a gas phase state under normal pressure, It can be manufactured by heat treatment.
  • organic compound containing nitrogen and sulfur which is the precursor of the n-type semiconductor of the present invention, hydrocarbons containing nitrogen and sulfur are preferable.
  • Hydrocarbons containing nitrogen are not particularly limited, but aliphatic amines, aromatic amines, nitriles, aromatic heterocycles, amides, imides, imines, urethanes, Isocyanides, amino acids 7 059821
  • Nitro compounds nitrogen-containing polymer compounds, and the like.
  • the structure of the aliphatic amine is not particularly limited, but an aliphatic amine having 1 to 60 carbon atoms is preferably used.
  • Specific examples include alkylamines such as methylamine, ethylamine, jetylamine, triethylamine, propylamine, isopropylamine, diisopropylamine, ptylamine, isoptilamine, pentylamine, hexylamine, 1,6-diaminohexane, cyclohexylamine and the like.
  • alkylamines such as methylamine, ethylamine, jetylamine, triethylamine, propylamine, isopropylamine, diisopropylamine, ptylamine, isoptilamine, pentylamine, hexylamine, 1,6-diaminohexane, cyclohexylamine and the like.
  • the substituents of amine contain alkyl groups, functional groups other than alkyl groups, and elements other than carbon and hydrogen, such as oxygen, nitrogen, and sulfur, in the substituents, such as alkanolamines. It does not matter. Aliphatic amines can be primary, secondary or tertiary amines.
  • aromatic amines having 1 to 60 carbon atoms are preferably used. Specific examples include aniline and diphenylamine.
  • the substitution group of the alkyl group may have an alkyl group, a functional group other than the alkyl group, or an element other than carbon or hydrogen such as oxygen, nitrogen, or sulfur.
  • Aromatic amines can be primary, secondary or tertiary amines.
  • nitriles having 1 to 30 carbon atoms such as acetonitrile, benzonitrile, hexanenitrile and the like are preferably used.
  • polyacrylonitrile is also preferably used.
  • aromatic heterocycles there is no limitation on the valence and the structure is not particularly limited, but an aromatic heterocycle having 4 to 30 carbon atoms is preferably used. It is. Specific examples include pyridine, pyrimidine, quinoline, isoquinoline, pyrrole, piperidine, pyrimidine, imidazole, and purine. These aromatic rings may have a substituent.
  • the substituent is not particularly limited, and examples thereof include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group.
  • nitrogen-containing hydrocarbons aliphatic amines, aromatic amines, polyacrylonitrile, polyethyleneimine, and aromatic heterocycles are more preferably used.
  • Hydrocarbons containing sulfur are not particularly limited, but thiols such as methane thiol and ethane thiol; sulfides such as dimethyl sulfide and jetyl sulfide; sulfones; chepine, thiophene, thianthrene, etc. Sulfur-containing heterocycles; Sulfur-containing aliphatic cyclic compounds such as tetrahydrothiophene; Sulfur-containing polymer compounds such as polythiophene;
  • nitrogen and sulfur may be contained in the same molecule.
  • These precursors may be used alone or in any combination of two or more kinds and in a ratio.
  • the precursor As a method of bringing the precursor into contact with the substrate in a liquid phase state, the precursor is substantially as it is, or from the state of a solution or dispersion, a coating method, a casting method, a blade coating method, a wire bar method, a spin coating method.
  • Coating methods such as a method, a dip coating method and a spray coating method; publicly known methods can be used. These methods are generally carried out under normal pressure.
  • the precursor solvent is not particularly limited, and a common organic solvent or water can be used as long as it can dissolve or disperse the precursor.
  • organic solvents include aliphatic hydrocarbons such as hexane, heptane, and octane; aromatic hydrocarbons such as toluene, xylene, benzene, and chlorobenzene; alcohols such as methanol, ethanol, propanol, and butanol; Ketones such as acetone, methyl ethyl ketone, cyclobennone, cyclohexanone, etc .; Ethers such as jetyl ether, dioxane, tetrahydrofuran; Nitrogen-containing aromatic hydrocarbons such as pyridine and quinoline; Halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethane, trichloroethane, and trichloroethylene; N, N-dimethylformamide,
  • One of these organic solvents may be used alone, or two or more thereof may be used in any combination and ratio.
  • a general method such as stirring is used.
  • dissolution may be performed while heating.
  • a surfactant may coexist.
  • the surfactant include a cationic system, an anionic system, and a nonionic system.
  • the concentration of the precursor in the solution is not particularly limited, and can be used in any ratio depending on the type of substrate and the method of contacting the substrate.
  • the solvent or the dispersion medium may be removed as necessary.
  • the removal of the solvent or dispersant can be performed by a general method such as heating under normal pressure or reduced pressure, or removing the solvent or dispersant accompanied by an air stream. 2007/059821
  • a method of bringing the precursor into contact with the substrate in a gas phase there is a method of bringing the precursor into contact with the substrate in the state of a gas or a mist containing the precursor.
  • the method of incorporating the precursor into the gas is not particularly limited, and examples thereof include a method of bringing the gas into contact with the precursor by bubbling or the like.
  • the normal pressure generally means atmospheric pressure, and means a state where the pressure is not forcibly increased or decreased.
  • the gas containing the precursor is preferably an inert gas.
  • the inert gas include nitrogen, argon, helium, carbon dioxide, and carbon monoxide.
  • the inert gas may be used alone or in a mixture of two or more.
  • the oxygen concentration in the inert gas is desirably 3% by volume or less, preferably 1% by volume or less, and more preferably 0.5% by volume or less.
  • the precursor in contact with the substrate can be converted into an n-type carbon semiconductor film by heat treatment and immobilized on the substrate.
  • the temperature of the heat treatment is 2100 ° C to 900 ° C, preferably 3200 ° C to 800 ° C. If the temperature becomes too high, the integral intensity ratio I (D) / I (G) ratio of the Raman spectroscopic spectrum decreases. If the temperature is too low, no 0 2 diffraction lines are observed in the powder X-ray pattern, nitrile groups are detected, and the I-band and D-pand of the Raman spectroscopic spectrum tend not to be observed.
  • nitrile groups are generally generated during the heat treatment process. To do.
  • the film is substantially free of nitrile groups. This Therefore, it is important to prevent the nitrile group from being contained in the product by controlling the heat treatment conditions according to the structure of the raw material.
  • the fact that nitrile groups are not substantially contained in the film is, for example, an absorption band of nitrile groups in infrared spectroscopic measurement.
  • the heat treatment is preferably performed in an inert gas atmosphere.
  • the inert gas include nitrogen, argon, helium, carbon dioxide, carbon monoxide and the like.
  • the inert gas may be used alone or in a mixture of two or more.
  • the oxygen concentration in the inert gas is desirably 3% by volume or less, preferably 1% by volume or less, and more preferably 0.5% by volume or less.
  • an inert gas atmosphere containing molecular oxygen such as air may be used.
  • the inert gas include nitrogen, argon, helium, carbon dioxide, and carbon monoxide.
  • the concentration of molecular oxygen is 0.5% by volume or more, preferably 1% by volume or more, and more preferably 3% by volume or more.
  • heat treatment may be performed while the gas containing the precursor is kept in contact with the substrate.
  • the heat treatment time depends on the film thickness of the n-type carbon semiconductor film, the type of organic compound, and the temperature, it is usually about 0.1 seconds to 100 hours.
  • the film thickness can be selected according to the purpose, but is usually 1 to 100 nm, and preferably 5 to 500 nm.
  • the substrate can be appropriately selected according to the purpose.
  • Semiconductor substrates such as copper substrates, metal substrates such as stainless steel and nickel, insulating substrates such as glass, alumina, gallium nitride, indium oxide, and zinc oxide, and ceramic substrates can be used.
  • Another compound or the like may be coated on these substrates, and the n-type force-bon semiconductor film of the present invention may be formed thereon. It is desirable to treat the substrate with hydrofluoric acid before use.
  • n-type carbon semiconductor film of the present invention it is not necessary to add a commonly used n-type dopant, but it is not excluded to add it as appropriate.
  • the electrical conductivity of the n-type carbon semiconductor of the present invention is usually 100 S / cm or more.
  • the P-type carbon semiconductor in the present invention is produced by contacting a hydrocarbon, which is a precursor of a p-type semiconductor film, with a substrate in a liquid phase state or a gas phase state under normal pressure, followed by heat treatment.
  • a P-type carbon semiconductor film mainly composed of an aggregate of carbon six-membered rings is used.
  • the D band near 1 30 0 c nr 1 normally a broad band in 1 2 0 0 to 1 4 0 0 cm- 1
  • the integrated intensity ratio I (D) / I (G) of the G band near 0 cm— 1 is 0.3 to 3.0, preferably A p-type force single-bon semiconductor film having a thickness of 0.5 to 2.5 can be used.
  • the integrated intensity ratio I (D) II (G) is less than 0.3, it will be a semi-metal and will not function as a semiconductor, while the integrated intensity ratio I (D) / I (G) will be 3.0. If exceeded, the number of aggregated carbon six-membered rings is small and insulation is exhibited, and electrical conductivity cannot be obtained. Further, the P-type carbon semiconductor film in the present invention preferably has 0. 02 diffraction lines in the powder X-ray pattern. PT / JP2007 / 059821
  • Precursor hydrocarbons are not particularly limited, but aliphatic chain hydrocarbons such as methane, ethane, propane, butane, butene, pentane, hexane, and octane, cyclopentane, cyclohexane, cyclooctane, etc.
  • Non-heterocyclic monocyclic or polycyclic aromatic hydrocarbons such as aliphatic cyclic hydrocarbons, benzene, toluene, xylene, ethylbenzene, styrene, naphthenolene, anthracene, naphtha, gasolin, light oil, heavy oil, petroleum Can be widely used, such as tar or pitch based on coal or coal. These precursors may be used alone or in any combination and ratio of two or more.
  • the precursor As a method of bringing the precursor into contact with the substrate in a liquid phase state, the precursor is substantially as it is, or from the state of a solution or dispersion, a coating method, a casting method, a blade coating method, a wire bar method, a spin coating method. Coating methods such as a method, a dip coating method, and a spray coating method; publicly known methods can be used.
  • the precursor solvent is not particularly limited, and a common organic solvent or water can be used as long as it can dissolve or disperse the precursor.
  • organic solvents examples include aliphatic hydrocarbons such as hexane, heptane and octane; aromatic hydrocarbons such as toluene, xylene, benzene and black benzene; alcohols such as methanol, ethanol, propanol and butyl alcohol Ketones such as acetone, methyl ethyl ketone, cyclobennone, cyclohexanone, etc .; Ethers such as jetyl ether, dioxane, tetrahydrofuran, etc .; Ethyl acetate, butyl acetate, propylene glycol methyl ether, etc.
  • aliphatic hydrocarbons such as hexane, heptane and octane
  • aromatic hydrocarbons such as toluene, xylene, benzene and black benzene
  • alcohols such as methanol, ethanol, propanol and
  • Nitrogen-containing aromatic hydrocarbons such as pyridine and quinoline; Halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethane, trichloroethane, and trichloroethylene; N, N —dimethylformamide, Amides such as N, N-dimethylacetamide, N-methylpyrrolidone, N, N-dimethylimidazolidinone, sulfur-containing solvents such as dimethylsulfoxide and carbon disulfide can be used.
  • Halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethane, trichloroethane, and trichloroethylene
  • Amides such as N, N-dimethylacetamide, N-methylpyrrolidone, N, N-dimethylimidazolidinone
  • sulfur-containing solvents such as dimethylsulfoxide and carbon disulfide can be used.
  • One of these organic solvents may be used alone, or two or more thereof may be used in any combination and ratio.
  • a general method such as stirring is used.
  • dissolution may be performed while heating.
  • a surfactant may coexist.
  • the surfactant include a cationic system, an anionic system, and a nonionic system.
  • the concentration of the precursor in the solution is not particularly limited, and can be used in any ratio depending on the type of substrate and the method of contacting the substrate.
  • the solvent or the dispersion medium may be removed as necessary.
  • the removal of the solvent or dispersant can be performed by a general method such as heating under normal pressure or reduced pressure, or removing the solvent or dispersant accompanied by an air stream.
  • a method of bringing the precursor into contact with the substrate in a gas phase state there is a method in which the precursor is brought into contact with the substrate in the state of a gas or a mist containing the precursor.
  • the method of incorporating the precursor into the gas is not particularly limited, and examples thereof include a method of bringing the gas into contact with the precursor by bubbling or the like.
  • the normal pressure when the substrate is brought into contact with the substrate in the gas phase under normal pressure, the normal pressure generally refers to the atmospheric pressure, and refers to the state where the pressure is not forcibly increased or decreased.
  • the gas is preferably an inert gas.
  • the inert gas include nitrogen, argon, helium, carbon dioxide, and carbon monoxide.
  • the inert gas may be used alone or in a mixture of two or more. T / JP2007 / 059821
  • the oxygen concentration in the inert gas is desirably 3% by volume or less, preferably 1% by volume or less, and more preferably 0.5% by volume or less.
  • the precursor in contact with the substrate can be converted into a P-type carbon semiconductor film by heat treatment and immobilized on the substrate.
  • the temperature for the heat treatment is from 200 ° C. to 90 ° C., preferably from 300 ° C. to 80 ° C. If the temperature gets too high, the integrated intensity ratio I (D) / I (G) ratio of the Raman spectrum will become smaller.
  • the temperature can be selected according to the value of the desired integral intensity ratio I (D) / I (G).
  • the heat treatment is preferably performed in an inert gas atmosphere.
  • the inert gas include nitrogen, argon, helium, carbon dioxide, carbon monoxide and the like.
  • the inert gas may be used alone or in a mixture of two or more.
  • the oxygen concentration in the inert gas is desirably 3% by volume or less, preferably 1% by volume or less, and more preferably 0.5% by volume or less.
  • an inert gas atmosphere containing molecular oxygen such as air may be used.
  • the inert gas include nitrogen, argon, helium, carbon dioxide, and carbon monoxide.
  • the concentration of molecular oxygen is 0.5% by volume or more, preferably 1% by volume or more, and more preferably 3% by volume or more.
  • heat treatment may be performed while the gas containing the precursor is kept in contact with the substrate.
  • the treatment time depends on the film thickness of the n-type carbon semiconductor film, the type of organic compound, and the temperature, but is usually about 0.1 seconds to 100 hours.
  • the film thickness can be selected according to the purpose, but is usually 1 to 100 nm, preferably 5 to 500 nm.
  • the substrate can be appropriately selected according to the purpose. For example, a semiconductor substrate such as a silicon substrate, a metal substrate such as stainless steel or nickel, an insulating substrate such as glass, alumina, gallium nitride, indium oxide, or zinc oxide.
  • a ceramic substrate can be used.
  • Another compound or the like may be coated on these substrates, and the P-type force-bon semiconductor film of the present invention may be formed thereon. It is desirable to treat the substrate with hydrofluoric acid before use.
  • the p-type semiconductor film of the present invention may be formed after the n-type carbon semiconductor film of the present invention is formed on the substrate.
  • the n-type force-bon semiconductor film of the present invention may be formed after forming the p-type force-bon semiconductor film of the present invention on the substrate.
  • the n-type force semiconductor film and the p-type carbon semiconductor film of the present invention can be prepared from a liquid phase state such as a precursor solution by various known coating methods.
  • the precursor can be prepared from a gas phase under normal pressure without requiring pressurization or decompression.
  • a general heating furnace or the like can be used for the heat treatment. According to the method of the present invention, a semiconductor film having a large area can be easily produced at a low cost.
  • the n-type carbon semiconductor film of the present invention is used as a material for semiconductor elements.
  • it can be suitably used as an n-type semiconductor film of a semiconductor element having a pn junction composed of a p-type semiconductor film and an n-type semiconductor film.
  • a p n junction is a part of a semiconductor where a p-type region and an n-type region are in contact.
  • the formation of the pn conjugate itself can be performed by a conventional method.
  • it can also be a pin junction.
  • the p-type semiconductor film a known p-type semiconductor film such as Si can be used, but preferably the P-type carbon semiconductor film of the present invention mainly composed of an aggregate of carbon six-membered rings. Is used.
  • the method for forming the P n bonded body is not particularly limited.
  • the n-type of the present invention is formed thereon.
  • the p-type carbon semiconductor film may be formed.
  • the semiconductor device using the n-type carbon semiconductor film of the present invention is a device such as a diode, a transistor, a photoelectric conversion device, or various sensors as a pn junction which is a junction structure of a p-type semiconductor and an n-type semiconductor as described above.
  • a semiconductor element particularly for solar cells it can be suitably used as a semiconductor element particularly for solar cells. That is, for example, the above-mentioned n-type carbon semiconductor film and p-type carbon semiconductor film are stacked on a silicon substrate, and a pn junction is formed as a photoelectric conversion layer, which is incorporated into a solar cell having a known configuration having electrodes and the like.
  • a hole having ten electricity a hole from which an electron has escaped
  • an electron having one electricity are generated, which are separated by a pn junction and become a current.
  • the solar cell using the semiconductor element using the n-type carbon semiconductor film according to the present invention has, for example, a performance with an energy efficiency of 0.05% or more when measured in a solar simulator AM 1.5 G mode. Is obtained.
  • P-type Si (100) substrate (2 X 2 cm) (Mitsubishi Materials Co., Ltd.) surface-treated with dilute hydrofluoric acid was placed in a quartz annular electric furnace, and nitrogen gas containing pyridine vapor was distributed. Under heating at 700 ° C. for 10 hours. As the nitrogen gas containing pyridine vapor, pyridine was introduced, nitrogen gas was blown into the container kept at 20 ° C, and 50 ml / min was blown into the container. 2007/059821
  • FIG. 1 is a schematic cross-sectional view of this structure.
  • a tens of nanometer gold sputtering film (3) is formed on a carbon film (2) on a substrate (1) ( (4) is the lead wire)
  • this device has been confirmed to have photovoltaic and photocurrent against the forward bias of pn, and it is clear that the carbon thin film functions as an n-type semiconductor. Became.
  • n-type Si (100) substrate (2 X 2 cm) (Mitsubishi Materials Co., Ltd.) surface-treated with dilute hydrofluoric acid was placed in a quartz annular electric furnace under nitrogen gas flow containing benzene vapor. And heated at 600 ° C. for 10 hours. As nitrogen gas containing this benzene vapor, benzene is introduced, 2007/059821
  • Nitrogen gas was blown into the container held at 2 Ot: at 50 mL / min, and nitrogen-benzene gas derived from the container was used.
  • the Si substrate surface side of the obtained sample substrate was polished to construct the same device as in Example 1.
  • photovoltaic power and photocurrent were observed for the forward bias of pn in this device, and it became clear that the carbon thin film functions as a P-type semiconductor.
  • this device was confirmed to operate as a solar cell with 0 CV: 20 OmV, Jsc: 13.9 mA / cm 2, energy conversion efficiency: 1.8% .
  • a polished Ni substrate (0.1 X 2 X 2 cm) was placed in a quartz annular electric furnace and heated at 70 ° C. for 10 hours under a nitrogen gas flow containing pyridine vapor as in Example 1. did. Thereafter, the sample was heated at 60 ° C. for 10 hours under a nitrogen gas flow containing benzene vapor in the same manner as in Example 2.
  • Example 2 The Ni substrate side of the obtained sample substrate was polished, and a device similar to Example 1 was constructed. As a result of electrical measurement, photovoltaic power and photocurrent were observed for this device in the forward direction of pn, and it became clear that this device functions as a pn junction. As measured by solar simulator AM I .5 G mode, this device operates as 0 CV: lOOmV, Jsc: 10. OmA / cm 2 , energy conversion efficiency: 1.2% solar cell It was done.
  • P-type Si (1 0 0) substrate (2 X 2 cm) (Mitsubishi Materials Co., Ltd.) surface-treated with dilute hydrofluoric acid was placed in a quartz annular electric furnace under nitrogen gas flow containing pyridine vapor And heated at 100 ° C. for 10 hours.
  • nitrogen gas containing pyridine vapor pyridine was introduced, nitrogen gas of 5 O mL / min was blown into a container maintained at 20 ° C., and nitrogen-pyridine gas derived from the container was used.
  • the carbon thin film showed 0 0 2 diffraction lines in the powder X-ray pattern, and no absorption peak in the vicinity of 2 1 30 cm -1 was observed in the infrared spectrum.
  • Example 4 One side of the obtained sample substrate was polished to construct a device similar to Example 1. As a result of electrical measurement, it was confirmed that the carbon thin film functions as a conductor, and it was confirmed that it does not function as a solar cell.
  • Example 4
  • One side of a polished Ni substrate (0.1 X 2 X 2 cm) was spin-coated with C heavy oil at 3 00 rpm, and 7 0 0 ° under nitrogen gas flow in a quartz tubular electric furnace. Heated at C for 5 hours. It was confirmed with a scanning electron microscope that a carbon thin film of about 30 nm was formed on the heated substrate. Further, 5 wt% polyacrylonitrile N, N-dimethylformamide solution was spin-coated three times on this striking thin film, and nitrogen gas was circulated in a stone electric tube furnace manufactured by Ishiei. Heated at ° C for 5 hours. A scanning electron microscope confirmed that a carbon thin film of about 100 nm was formed on the heated substrate.
  • P-type S i (1 0 0) substrate X 22 cm, manufactured by Mitsubishi Materials surface-treated with dilute hydrofluoric acid was placed in a quartz tubular electric furnace, and under a nitrogen gas flow containing normal butylamine vapor, 7 0 Heated at 0 ° C for 5 hours. Nitrogen gas containing normal-peptylamine vapor was blown with nitrogen gas at 10 m 1 / m 1 n into a container containing normal-peptylamine kept at 15 ° C, and nitrogen normal n-butylamine exiting from the container Gas was used.
  • the Si substrate surface side of the obtained sample substrate was polished to construct the same device as in Example 1.
  • photovoltaic power and photocurrent were observed against the forward bias of pn, and it was revealed that the obtained carbon thin film functions as an n-type semiconductor.
  • this device is: ⁇ CV: 20 00 mV, J sc: l 1. 9 mA / cm 2 , energy conversion efficiency T / JP2007 / 059821
  • Heating under the flow of nitrogen gas containing normal butylamine vapor was carried out in the same manner as in Example 4 except that the heating was performed at 150 ° C. for 5 hours and the flow rate of nitrogen gas was 5 O ml / min.
  • the carbon thin film obtained by heating was not able to obtain a clear absorption spectrum in either the D band or the G band in the Raman spectroscopic spectrum. Also, no X-ray diffraction line was observed in the powder X-ray pattern, and no clear absorption was observed in the vicinity of 2 2500 cm- 1 corresponding to the nitrile group in the infrared spectrum. I was not able to admit.
  • the obtained sample substrate was constructed with the same device as in Example 1 and subjected to electrochemical measurements, but was found to be an insulator. As a result of measurement in AM I .5 G mode, it was found that the solar cell does not function as a solar cell.
  • a quartz glass substrate (2 ⁇ 2 cm) was placed in a quartz tubular electric furnace and heated at 700 ° C. for 5 hours under a nitrogen gas flow containing normal-pylamine vapor.
  • a nitrogen gas flow containing normal-pylamine vapor 10 m 1 Zmin of nitrogen gas was blown into a container containing pyridine maintained at 15 ° C., and nitrogen one-normal ptylamamine gas exiting from the container was used. It was confirmed with a scanning electron microscope that a thin film of about 30 nm was formed on the substrate obtained by heating.
  • the electric conductivity of the carbon thin film on this substrate is calculated by van der Pauw method. It was measured. As a result, it was confirmed that the electrical conductivity of this carbon thin film was 40 0 S / Cm.
  • the present invention it is possible to provide a semiconductor element and a solar cell that can produce an n-type power single semiconductor at low cost and that can be used for high performance and a large area.

Abstract

L'invention concerne un semi-conducteur de carbone de type n à coût faible ainsi qu'un dispositif semi-conducteur et une cellule solaire à performance élevée et surface importante utilisant celui-ci. L'invention concerne un film semi-conducteur de carbone de type n composé principalement d'un agrégat de noyaux à 6 chaînons de carbone, présentant dans son spectre, selon une spectroscopie Raman, un rapport d'intensité intégrale de bande D au voisinage de 1300 cm-1 à la bande G au voisinage de 1600 cm-1, I(D)/I(G), de 0,3 à 3,0, et présentant un rapport d'élément d'azote et/ou de soufre sur carbone selon une spectroscopie photoélectronique aux rayons X, (N et/ou S)/C, de 0,01 à 0,40. Ledit film semi-conducteur de carbone de type n est obtenu en amenant un composé organique contenant de l'azote et/ou du soufre sous la forme d'une phase liquide ou d'une phase vapeur à des pressions normales en contact avec une partie supérieure d'un substrat et en réalisant un traitement thermique à 200° à 900°C.
PCT/JP2007/059821 2007-03-07 2007-05-08 Film semi-conducteur de carbone de type n et dispositif semi-conducteur utilisant celui-ci WO2008108009A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2007-056652 2007-03-07
JP2007056652A JP2007273970A (ja) 2006-03-07 2007-03-07 ｎ型カーボン半導体膜およびそれを用いた半導体素子

Publications (1)

Publication Number Publication Date
WO2008108009A1 true WO2008108009A1 (fr) 2008-09-12

Family

ID=39737912

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/059821 WO2008108009A1 (fr) 2007-03-07 2007-05-08 Film semi-conducteur de carbone de type n et dispositif semi-conducteur utilisant celui-ci

Country Status (1)

Country Link
WO (1) WO2008108009A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012246215A (ja) * 2011-05-27 2012-12-13 Pohang Univ Of Science & Technology Academy-Industry Cooperation 炭素薄膜の製造方法、炭素薄膜を含んだ電子素子及び炭素薄膜を含んだ電気化学素子
KR20150129108A (ko) * 2014-05-08 2015-11-19 주식회사 포스코 그래핀 박막의 제조방법 및 이를 이용하여 제조된 그래핀 박막

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62103367A (ja) * 1985-10-28 1987-05-13 Nippon Telegr & Teleph Corp <Ntt> 炭素膜の合成方法
JPH0790588A (ja) * 1993-09-24 1995-04-04 Res Dev Corp Of Japan 窒素含有炭素膜の製造方法
JPH07232978A (ja) * 1993-12-29 1995-09-05 Nippon Tungsten Co Ltd ダイアモンドライクカーボン膜を被覆した材料とその形成方法
JP2980546B2 (ja) * 1994-11-09 1999-11-22 科学技術振興事業団 半導体素子と太陽電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62103367A (ja) * 1985-10-28 1987-05-13 Nippon Telegr & Teleph Corp <Ntt> 炭素膜の合成方法
JPH0790588A (ja) * 1993-09-24 1995-04-04 Res Dev Corp Of Japan 窒素含有炭素膜の製造方法
JPH07232978A (ja) * 1993-12-29 1995-09-05 Nippon Tungsten Co Ltd ダイアモンドライクカーボン膜を被覆した材料とその形成方法
JP2980546B2 (ja) * 1994-11-09 1999-11-22 科学技術振興事業団 半導体素子と太陽電池

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012246215A (ja) * 2011-05-27 2012-12-13 Pohang Univ Of Science & Technology Academy-Industry Cooperation 炭素薄膜の製造方法、炭素薄膜を含んだ電子素子及び炭素薄膜を含んだ電気化学素子
KR20150129108A (ko) * 2014-05-08 2015-11-19 주식회사 포스코 그래핀 박막의 제조방법 및 이를 이용하여 제조된 그래핀 박막
KR101585767B1 (ko) 2014-05-08 2016-01-15 주식회사 포스코 그래핀 박막의 제조방법 및 이를 이용하여 제조된 그래핀 박막

Similar Documents

Publication Publication Date Title
Yang et al. Ultra‐broadband flexible photodetector based on topological crystalline insulator SnTe with high responsivity
US8598569B2 (en) Pentacene-carbon nanotube composite, method of forming the composite, and semiconductor device including the composite
US8187915B2 (en) Aryl dicarboxylic acid diimidazole-based compounds as n-type semiconductor materials for thin film transistors
US8030127B2 (en) Methods of making carbon-containing semiconducting devices by pyrolyzing a polymer including asphalt or petroleum pitch
EP1872416B1 (fr) Matériaux semi-conducteurs pour des transistors à couche mince
JP2009231810A (ja) 半導体カーボン膜、半導体素子、及び半導体カーボン膜の製造方法
Yin et al. Substrate‐Free Chemical Vapor Deposition of Large‐Scale III–V Nanowires for High‐Performance Transistors and Broad‐Spectrum Photodetectors
JP5856008B2 (ja) パラジウム前駆体組成物
US20090312553A1 (en) N-type semiconductor materials for thin film transistors
US20060131564A1 (en) Fluorine-containing N,N&#39;-diaryl perylene-based tetracarboxylic diimide compounds as N-type semiconductor materials for thin film transistors
US20110266523A1 (en) Semiconducting devices and methods of preparing
JP2007273970A (ja) ｎ型カーボン半導体膜およびそれを用いた半導体素子
KR101629697B1 (ko) 그래핀 적층 구조체의 제조방법 및 이로 제조된 그래핀 적층 구조체
WO2014156773A1 (fr) Composé hétérocyclique aromatique, son procédé de fabrication, matière semi-conductrice organique et dispositif semi-conducteur organique
TWI516490B (zh) 有機薄膜電晶體
WO2008108009A1 (fr) Film semi-conducteur de carbone de type n et dispositif semi-conducteur utilisant celui-ci
US10566539B2 (en) Organic semiconductor compounds and methods of use
Zou et al. Synthesis, characterization, and field-effect transistor performance of a two-dimensional starphene containing sulfur
JP6647106B2 (ja) 有機半導体材料及び有機半導体デバイス
US20200332133A1 (en) Solvent and method of forming organic film using solvent
Kim et al. Solution-Processable Diketopyrrolopyrrole Derivatives as organic semiconductors for organic thin-film transistors
Song et al. SYNTHESIS OF Tin (IV) DICHLORIDE HEXADECAFLUOROPHTHALOCYANINE (SnPcCl2F16) AS SEMICONDUCTOR MATERIAL FOR ORGANIC THIN FILM TRANSISTORS
JP2007194557A (ja) 複合光電変換素子及びその製造方法
Song et al. SYNTHESIS AND CHARACTERIZATION OF COBALT (II) PERFLUOROPHTHALOCYANINE
Chang et al. High-mobility and solution-processable organic field-effect transistors based on carbazole-dihexylquaterthiophenes with controllable morphology

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07743256

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07743256

Country of ref document: EP

Kind code of ref document: A1