WO2015182679A1 - Procédé de fabrication de film d'oxyde métallique, film d'oxyde métallique, transistor à couches minces, procédé de fabrication de transistor à couches minces, et dispositif électronique - Google Patents

Procédé de fabrication de film d'oxyde métallique, film d'oxyde métallique, transistor à couches minces, procédé de fabrication de transistor à couches minces, et dispositif électronique Download PDF

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WO2015182679A1
WO2015182679A1 PCT/JP2015/065320 JP2015065320W WO2015182679A1 WO 2015182679 A1 WO2015182679 A1 WO 2015182679A1 JP 2015065320 W JP2015065320 W JP 2015065320W WO 2015182679 A1 WO2015182679 A1 WO 2015182679A1
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metal oxide
oxide film
substrate
film
producing
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PCT/JP2015/065320
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English (en)
Japanese (ja)
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文彦 望月
真宏 高田
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富士フイルム株式会社
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Priority to KR1020167032567A priority Critical patent/KR101924272B1/ko
Priority to JP2016523545A priority patent/JP6195986B2/ja
Publication of WO2015182679A1 publication Critical patent/WO2015182679A1/fr

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    • 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
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/34—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of sprayed or atomised solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00—Compounds of gallium, indium or thallium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
    • H01L29/51—Insulating materials associated therewith
    • H01L29/517—Insulating materials associated therewith the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
    • H01L29/51—Insulating materials associated therewith
    • H01L29/518—Insulating materials associated therewith the insulating material containing nitrogen, e.g. nitride, oxynitride, nitrogen-doped material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/131—Interconnections, e.g. wiring lines or terminals

Definitions

  • the present invention relates to a method of manufacturing a metal oxide film, a metal oxide film, a thin film transistor, a method of manufacturing a thin film transistor, and an electronic device.
  • Metal oxide semiconductor films have been put to practical use in the manufacture by vacuum film formation and are currently attracting attention.
  • research and development relating to the preparation of metal oxide semiconductor films by a liquid phase process for the purpose of forming metal oxide semiconductor films having high semiconductor characteristics under simple conditions, low temperature and atmospheric pressure is actively conducted.
  • the ink jet method has attracted attention because a necessary film can be formed in a necessary place and patterning is not necessary after the formation.
  • JP-A-2010-283002 discloses a method of forming a metal oxide semiconductor by applying a solution containing a metal salt by an inkjet method.
  • Nitrate can be suitably used in a solution process because it is inexpensive and can form a dense metal oxide film at a low temperature.
  • Japanese Patent Application Laid-Open No. 2013-21289 discloses a method of producing a metal oxide film by applying a solution containing a metal salt onto a substrate by an ink jet method, drying it, and baking it.
  • JP 2010-182852 A and JP 2010-171237 A after a solution or dispersion liquid of a metal oxide semiconductor precursor is coated on a substrate to form a metal oxide semiconductor precursor film, A method of converting into a metal oxide semiconductor film by a UV (ultraviolet) ozone method or the like is disclosed.
  • a so-called coffee stain phenomenon tends to occur, in which the central portion of the film is recessed due to the difference in the drying speed of the coated film and the end is raised (concave shape).
  • the coating film is formed by a coffee stain phenomenon under low humidity at the time of drying after the ink jet application. Has been reported to be concave and to be convex at high humidity.
  • JP 2010-283002 A, JP 2013-21289 A, JP 2010-182852 A or JP 2010-171237 A after a coating film is formed by an inkjet method, although conversion to a metal oxide film is performed by heating in the air or UV irradiation, a thin film transistor having high mobility can not be obtained even if a semiconductor layer is formed by these methods to manufacture a thin film transistor.
  • the present invention provides a method for producing a metal oxide film which can easily produce a metal oxide film having small thickness unevenness and excellent electrical characteristics, and a metal oxide film excellent in electrical characteristics, a thin film transistor, and a thin film transistor It is an object of the present invention to provide a method and an electronic device.
  • a method of producing a metal oxide film comprising: ⁇ 2> The method for producing a metal oxide film according to ⁇ 1>, wherein the metal nitrate contains indium nitrate.
  • coating process ⁇ 4> The method for producing a metal oxide film according to any one of ⁇ 1> to ⁇ 3>, wherein the solvent is methoxyethanol.
  • ⁇ 6> The method for producing a metal oxide film according to any one of ⁇ 1> to ⁇ 5>, wherein the ultraviolet light contains light having a wavelength of 300 nm or less.
  • ⁇ 7> The method for producing a metal oxide film according to any one of ⁇ 1> to ⁇ 6>, wherein ultraviolet irradiation is performed in a state where the substrate is heated in the conversion step.
  • the manufacturing of the metal oxide film as described in any one of ⁇ 1>- ⁇ 7> including the process of surface-treating with respect to the surface in which the coating film of a board
  • Method The manufacturing method of the metal oxide film as described in ⁇ 8> which performs ultraviolet-ray ozone treatment, argon plasma treatment, or nitrogen plasma treatment as surface treatment.
  • the metal oxide film as described in ⁇ 10> which is a ⁇ 11> semiconductor film.
  • the metal oxide film as described in ⁇ 10> which is a ⁇ 12> conductive film.
  • a method for producing a thin film transistor comprising the step of forming a metal oxide film by the method for producing a metal oxide film according to any one of ⁇ 1> to ⁇ 9> to produce an oxide semiconductor layer.
  • the thin-film transistor provided with the metal oxide film as described in ⁇ 14> ⁇ 10>.
  • the electronic device which has a thin-film transistor as described in ⁇ 15> ⁇ 14>.
  • a method for producing a metal oxide film capable of easily producing a metal oxide film having small thickness unevenness and excellent electrical characteristics, and a metal oxide film excellent in electrical characteristics, a thin film transistor, and a thin film transistor A method of manufacturing the same, and an electronic device are provided.
  • FIG. 1 is a schematic view showing a configuration of an example (top gate-top contact type) of a thin film transistor manufactured according to the present invention.
  • FIG. 1 is a schematic view showing a configuration of an example (top gate-bottom contact type) of a thin film transistor manufactured according to the present invention.
  • FIG. 1 is a schematic view showing a configuration of an example (bottom gate-top contact type) of a thin film transistor manufactured according to the present invention.
  • FIG. 1 is a schematic view showing a configuration of an example (bottom gate-bottom contact type) of a thin film transistor manufactured according to the present invention.
  • It is a schematic sectional drawing which shows a part of liquid crystal display device of embodiment. It is a schematic block diagram of the electrical wiring of the liquid crystal display device shown in FIG.
  • FIG. 6 is a graph showing V g -I d characteristics of the simplified TFTs manufactured in Examples 1 to 4 and Comparative Example 1; It is the electron micrograph which planarly viewed the semiconductor layer of TFT produced by the comparative example 1.
  • FIG. It is the electron micrograph which observed the cross section of the edge part (A point) of the semiconductor layer shown in FIG. It is the electron micrograph which observed the cross section of the center part (B point) of the semiconductor layer shown in FIG.
  • the method for producing a metal oxide film of the present disclosure comprises applying a solution containing metal nitrate and a solvent onto a heated substrate by an inkjet method to form a coating film, and oxygen concentration relative to the coating film. And a conversion step of converting into a metal oxide film by performing ultraviolet irradiation under an atmosphere of 80000 ppm or less.
  • a solution (metal nitrate solution) containing metal nitrate and a solvent is applied onto a substrate in a heated state by an ink jet method to form a coating film.
  • the metal nitrate solution used in the present disclosure is obtained, for example, by preparing a predetermined amount of a solute such as metal nitrate, adding a solvent to a predetermined concentration, and stirring and dissolving it.
  • the time for stirring is not particularly limited as long as the solute is sufficiently dissolved.
  • the metal nitrate may be a hydrate.
  • the metal nitrate solution may contain other metal-containing compounds.
  • metal-containing compounds include metal salts other than metal nitrates, metal halides, and organometallic compounds.
  • metal salts other than metal nitrates include sulfates, phosphates, carbonates, acetates, borates and the like, and metal halides include chlorides, iodides, bromides and the like, and as an organic metal compound And metal alkoxides, organic acid salts, metal ⁇ -diketonates and the like.
  • the metal nitrate solution preferably contains at least indium nitrate.
  • indium nitrate By using indium nitrate, an indium-containing oxide film can be easily formed, and high electrical conductivity can be obtained.
  • ultraviolet light is irradiated in the step of converting the metal oxide precursor film into the metal oxide film, indium nitrate is efficiently decomposed by the ultraviolet light, and an indium-containing oxide film can be easily formed.
  • the metal nitrate solution preferably contains a compound (metal-containing compound) containing one or more metal elements selected from zinc, tin, gallium, and aluminum as a metal element other than indium.
  • a compound (metal-containing compound) containing one or more metal elements selected from zinc, tin, gallium, and aluminum as a metal element other than indium.
  • the threshold voltage of the obtained oxide semiconductor film can be controlled to a desired value, and Electrical stability can be improved.
  • an oxide semiconductor or oxide conductor containing indium and a metal element other than indium In—Ga—Zn—O, In—Zn—O, In—Ga—O, In—Sn—O, In—Sn— Zn-O etc. are mentioned.
  • the concentration of the metal nitrate in the solution may be selected according to the viscosity of the solution, the target film thickness, the electrical characteristics, etc., but the content of indium in the solution is 50 atom% of the metal component contained in the solution It is preferable that it is more than.
  • a solution containing indium in the above concentration range a metal oxide film in which 50 atomic% or more of the metal component in the film is indium can be obtained, and a metal oxide film with excellent electrical characteristics can be manufactured.
  • the concentration of the metal component in the solution (the sum of the molar fractions of each metal contained when multiple metals are contained) can be arbitrarily selected according to the viscosity and the desired film thickness, but the metal oxide film
  • the concentration of the metal component in the solution is preferably 0.01 mol / L or more and 1.0 mol / L or less, and is 0.01 mol / L or more and 0.5 mol / L or less from the viewpoint of flatness and productivity of Is more preferred.
  • the solvent used for the metal nitrate solution is not particularly limited as long as it is a solvent in which the metal nitrate to be used and other metal-containing compounds added as necessary can be dissolved, and water, alcohol solvents (methanol, ethanol, propanol, ethylene glycol Etc.), amide solvents (N, N-dimethylformamide etc.), ketone solvents (acetone, N-methylpyrrolidone, sulfolane, N, N-dimethylimidazolidinone etc.), ether solvents (tetrahydrofuran, methoxyethanol etc.), nitrile solvents (Acetonitrile and the like), and other hetero atom-containing solvents other than the above and the like can be mentioned.
  • alcohol solvents methanol, ethanol, propanol, ethylene glycol Etc.
  • amide solvents N, N-dimethylformamide etc.
  • ketone solvents acetone, N-methylpyrrolidone, sulfo
  • methanol and methoxyethanol can be suitably used from the viewpoint of solubility, wettability and boiling point.
  • the structure of the substrate on which the metal oxide film is formed in the present disclosure are not particularly limited, and can be appropriately selected according to the purpose.
  • the structure of the substrate may be a single layer structure or a laminated structure.
  • a substrate made of glass an inorganic material such as YStria (Yttria-Stabilized Zirconia), a resin, a resin composite material, or the like can be used.
  • a substrate made of a resin or a resin composite material is preferable in terms of light weight and flexibility.
  • a substrate comprising a composite plastic material of the aforementioned synthetic resin etc. and metal nanoparticles, inorganic oxide nanoparticles or inorganic nitride nanoparticles, etc.
  • Substrate comprising composite plastic material of synthetic resin etc. and carbon fiber or carbon nanotube, substrate composed of composite plastic material of synthetic resin etc.
  • the surface insulation property is improved by performing oxidation treatment (for example, anodizing treatment) on a substrate made of a composite material having the barrier performance, a stainless steel substrate or a metal multilayer substrate in which stainless steel and a dissimilar metal are laminated, an aluminum substrate or the surface.
  • oxidation treatment for example, anodizing treatment
  • An aluminum substrate with an oxide film, a silicon substrate with an oxide film, or the like can be used.
  • the resin substrate is preferably excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation, processability, low air permeability, low hygroscopicity, and the like.
  • the resin substrate may be provided with a gas barrier layer for preventing permeation of moisture and oxygen, and an undercoat layer for improving the flatness of the resin substrate and the adhesion with the lower electrode.
  • a lower electrode or an insulating film may be provided on the substrate, in which case the metal oxide film of the present disclosure is formed on the lower electrode on the substrate or the insulating film.
  • the metal nitrate solution is applied by the inkjet method in a state where the substrate is heated, but may include a step of performing surface treatment on the surface of the substrate on which the coating film is to be formed, before the application step.
  • the substrate is preferably subjected to surface treatment for removing moisture and dirt.
  • UV ozone treatment examples include ultraviolet (UV) ozone treatment, argon plasma treatment, nitrogen plasma treatment and the like.
  • the UV ozone treatment is performed, for example, using a UV ozone treatment apparatus (Model 144AX-100 manufactured by Jelight-company-Inc) under the following conditions and wavelength for about 1 to 3 minutes. Conditions: atmospheric pressure, in air, wavelength: 254 nm (30 mW / cm 2 ), 185 nm (3.3 mW / cm 2 )
  • the heating temperature of the substrate is selected according to the heat resistance of the substrate, the solvent contained in the metal nitrate solution to be applied, the target thickness unevenness and the like, but it is preferable to make it equal to or higher than the boiling point of the solvent contained in the metal nitrate solution.
  • the thickness of the active layer composed of the semiconductor film is particularly likely to adversely affect the electrical characteristics, but the solution is discharged by the ink jet method onto the substrate heated to the boiling point or more of the solvent, and drying is performed substantially simultaneously with landing. The time can be shortened and the thickness unevenness of the coating film can be suppressed, and a semiconductor film with improved electrical characteristics can be formed in the next conversion step.
  • the present invention is not limited to the active layer, and is suitable for forming a film having conductivity other than the active layer.
  • the configuration of the bottom gate TFT shown in FIG. 3 has a configuration in which the gate electrode 22, the gate insulating film 20, the active layer 14, and the source / drain electrodes 16 and 18 are stacked on the substrate 12. Furthermore, a channel protective layer, an interlayer insulating film and the like are formed on the TFT. Therefore, for example, in the case where the gate electrode 22 is formed by inkjet, when the thickness of the gate electrode 22 is large due to the coffee stain phenomenon, the coverage of the gate insulating film 20 to be formed next or the deterioration of the insulation characteristics due to the coffee stain shape. There is a high possibility that a short will occur.
  • the gate electrode 22 by forming the gate electrode 22 according to the present disclosure, thickness unevenness can be reduced, and the occurrence of deterioration in insulation characteristics, short circuit, and the like can be suppressed.
  • the present disclosure by applying the present disclosure to the formation of the source / drain electrode and the gate electrode in TFTs having other structures, thickness unevenness is suppressed and the influence on the upper layer is suppressed, so that the same effect can be obtained.
  • the heating temperature of the substrate is, for example, about 65 ° C. or more when the solvent contained in the metal nitrate solution is methanol (boiling point: 64.7 ° C.), and about 125 ° C. or more when methoxyethanol (boiling point: 124 ° C.)
  • the temperature is preferably lower than the heat resistance temperature of the substrate, for example, lower than the softening point when using a resin substrate. If the surface temperature of the substrate is too high, the shape may be disturbed when droplets of the metal nitrate solution are discharged onto the substrate, and the energy cost required for heating also increases, so the surface temperature of the substrate is
  • the boiling point of the solvent is preferably + 20 ° C. or less, and more preferably the boiling point of the solvent + 10 ° C. or less.
  • the temperature of the substrate is measured by measuring the surface temperature of the substrate with a thermocouple-attached Si wafer.
  • the heating time of the substrate there is no restriction on the heating time of the substrate, and the heat conduction of the substrate may be taken into consideration.
  • the substrate may be disposed on a heated stage, a heater may be installed separately from the stage, and lamp heating may be performed. It is preferable that the substrate be in direct contact with the heating portion in order to shorten the heating time.
  • the atmosphere in the coating step is not particularly limited, but is preferably an inert atmosphere (nitrogen, argon or the like) from the viewpoint of excluding influences other than the solution of water and oxygen.
  • a metal nitrate solution is applied by an inkjet method.
  • the solvent in the coating solution formed on the substrate is quickly volatilized, and the shape of the semiconductor film formed after conversion is determined and thickness unevenness is suppressed. .
  • the inkjet method it is not necessary to perform a photolithography process, and it is possible to form a coating film at a necessary place.
  • the inkjet method it is possible to cope with misalignment of pattern alignment due to a thermal factor during the process when using a flexible substrate, and to form a coating film with high accuracy by confirming the formation position in advance. it can.
  • the solution is applied by the inkjet method in a heated state of the substrate, discharge and drying of the droplets of the metal nitrate solution are performed almost simultaneously, and it is not necessary to separately perform a drying step after application.
  • the solvent may evaporate little by little and shape control may become difficult.
  • the pattern accuracy before and after application may be deteriorated.
  • the UV irradiation is performed under heating without performing the drying process, the film may be damaged.
  • the substrate is applied by the inkjet method in a heated state, it is possible to form a pattern with high uniformity of dimensions (particularly thickness) between the first applied portion and the last applied portion.
  • an atmosphere having an oxygen concentration of 80000 ppm or less may be applied to the coating film (hereinafter referred to as "under low oxygen concentration atmosphere” ) To convert to a metal oxide film by ultraviolet irradiation.
  • the coating film can be converted to a metal oxide film at a lower temperature by irradiating ultraviolet light in a low oxygen concentration atmosphere, and a conductor film or a semiconductor film having excellent electrical characteristics can be formed. .
  • UV lamp and a laser As a light source of ultraviolet light, a UV lamp and a laser may be mentioned, and a UV lamp is preferable from the viewpoint of performing ultraviolet irradiation uniformly on a large area and inexpensive equipment.
  • UV lamps include excimer lamps, deuterium lamps, low pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, helium lamps, carbon arc lamps, cadmium lamps, electrodeless discharge lamps, etc. It is preferable to use a mercury lamp because conversion from a precursor film to an oxide film can be easily performed.
  • a laser beam with a wavelength of 266 nm may be used.
  • the film surface of the metal oxide precursor film is preferably irradiated with ultraviolet light containing light with a wavelength of 300 nm or less at an illuminance of 10 mW / cm 2 or more.
  • ultraviolet light containing light with a wavelength of 300 nm or less at an illuminance of 10 mW / cm 2 or more.
  • the ultraviolet irradiation in the conversion step is performed under a low oxygen concentration atmosphere having an oxygen concentration of 80000 ppm (8%) or less.
  • the carrier density of the oxide semiconductor can be easily controlled by performing UV irradiation on the coating film on the substrate in a low oxygen concentration atmosphere of 80000 ppm or less, and a metal oxide film with high electron transfer characteristics can be obtained. It is preferable that the oxygen concentration in the atmosphere which performs said ultraviolet irradiation from a viewpoint of improving an electron transfer characteristic is 30000 ppm or less (3% or less).
  • the oxygen concentration in the atmosphere at the time of ultraviolet irradiation for example, nitrogen gas supplied into a processing chamber in which heating and ultraviolet irradiation are performed on a metal oxide precursor film on a substrate
  • nitrogen gas supplied into a processing chamber in which heating and ultraviolet irradiation are performed on a metal oxide precursor film on a substrate There are a method of adjusting the flow rate of inert gas, a method of adjusting the oxygen concentration in the gas supplied into the processing chamber, and a method of evacuating the processing chamber in advance and filling the gas with the desired oxygen concentration.
  • ultraviolet irradiation When UV irradiation is performed on the coating film on the substrate in a low oxygen concentration atmosphere in the conversion step, ultraviolet irradiation may be performed in a state where the substrate is heated. If UV irradiation and heating of the substrate are performed, conversion to a metal oxide film can be performed in a shorter time, and processing time can be shortened.
  • UV irradiation is performed by heating the substrate in the conversion step, it is preferable that the highest temperature reached of the substrate be heated to 120 ° C. or higher. If the temperature is 120 ° C. or higher, a dense metal oxide film can be easily obtained.
  • the substrate temperature in the conversion step is maintained at 200 ° C. or less, the increase in thermal energy can be suppressed to suppress the manufacturing cost low, and the application to a resin substrate with low heat resistance becomes easy.
  • the means for heating the substrate in the conversion step is not particularly limited, and may be selected from hot plate heating, electric furnace heating, infrared heating, microwave heating and the like.
  • the substrate temperature at the time of the ultraviolet treatment radiation heat from the ultraviolet lamp to be used may be used, or the temperature of the substrate may be controlled by a heater or the like.
  • the radiant heat from the ultraviolet lamp it is possible to control by adjusting the lamp-substrate distance and the lamp output.
  • the ultraviolet irradiation time depends on the illuminance of the ultraviolet light, but is preferably 5 seconds or more and 120 minutes or less from the viewpoint of productivity.
  • the film thickness of the metal oxide film produced according to the present disclosure is not particularly limited and may be selected according to the application, but when the semiconductor layer of the thin film transistor according to the present disclosure is formed, the film thickness is preferably 50 nm or less More preferably, it is about 10 nm.
  • a metal oxide film having conductor or semiconductor characteristics can be easily manufactured.
  • the method for producing a metal oxide film of the present disclosure can easily obtain a metal oxide film having conductor or semiconductor characteristics in a low temperature process at 200 ° C. or less.
  • an inexpensive resin substrate with low heat resistance can be used, and the raw materials are inexpensive, etc., it is possible to significantly reduce the device manufacturing cost.
  • the method for producing a metal oxide film of the present disclosure can be applied to a resin substrate with low heat resistance, it becomes possible to produce a flexible electronic device such as a flexible display at low cost.
  • a conductive film or a semiconductor film having small thickness unevenness and excellent electrical characteristics can be formed.
  • the process suitability is excellent and the electron mobility is high.
  • a semiconductor element exhibiting electrical characteristics can be manufactured inexpensively.
  • the method for producing a metal oxide film of the present disclosure comprises an electrode (source electrode of a thin film transistor (TFT), It can use suitably for formation of a drain electrode or a gate electrode) or an oxide semiconductor layer (active layer).
  • TFT thin film transistor
  • the element structure of the TFT according to the present disclosure is not particularly limited, and any aspect of so-called reverse stagger structure (also called bottom gate type) and stagger structure (also called top gate type) based on the position of the gate electrode It is also good.
  • any aspect of so-called top contact type or bottom contact type may be adopted.
  • the top gate type is a form in which the gate electrode is disposed on the upper side of the gate insulating film and the semiconductor layer is formed on the lower side of the gate insulating film, when the substrate on which the TFT is formed is the lower layer.
  • the gate electrode is disposed below the gate insulating film, and the semiconductor layer is formed above the gate insulating film.
  • the source / drain electrode is formed before the semiconductor layer, and the lower surface of the semiconductor layer is in contact with the source / drain electrode.
  • the semiconductor layer is the source / drain It is formed prior to the electrode, and the upper surface of the semiconductor layer is in contact with the source / drain electrode.
  • FIG. 1 is a schematic view showing an example of a top gate type and top contact type TFT according to the present disclosure according to the present disclosure.
  • the above-described oxide semiconductor film is stacked as the semiconductor layer 14 on one main surface of the substrate 12. Then, the source electrode 16 and the drain electrode 18 are provided separately from each other on the semiconductor layer 14, and the gate insulating film 20 and the gate electrode 22 are further stacked in order.
  • FIG. 2 is a schematic view showing an example of a top gate structure and a bottom contact type TFT according to the present disclosure.
  • the source electrode 16 and the drain electrode 18 are disposed apart from each other on one main surface of the substrate 12. Then, the above-described oxide semiconductor film, the gate insulating film 20, and the gate electrode 22 are sequentially stacked as the semiconductor layer 14.
  • FIG. 3 is a schematic view showing an example of a bottom gate structure and a top contact type TFT according to the present disclosure.
  • the gate electrode 22, the gate insulating film 20, and the above-described oxide semiconductor film as the semiconductor layer 14 are sequentially stacked on one main surface of the substrate 12. Then, the source electrode 16 and the drain electrode 18 are provided apart from each other on the surface of the semiconductor layer 14.
  • FIG. 4 is a schematic view showing an example of a bottom gate type bottom contact TFT according to the present disclosure.
  • the gate electrode 22 and the gate insulating film 20 are sequentially stacked on one main surface of the substrate 12. Then, the source electrode 16 and the drain electrode 18 are provided apart from each other on the surface of the gate insulating film 20, and the above-described oxide semiconductor film is further stacked as the semiconductor layer 14.
  • the top gate thin film transistor 10 shown in FIG. 1 will be mainly described as the following embodiment, the thin film transistor according to the present disclosure is not limited to the top gate type, and may be a bottom gate thin film transistor.
  • the thickness of the substrate used in the present disclosure is not particularly limited, but is preferably 50 ⁇ m or more and 500 ⁇ m or less. When the thickness of the substrate is 50 ⁇ m or more, the flatness of the substrate itself is further improved. In addition, when the thickness of the substrate is 500 ⁇ m or less, the flexibility of the substrate itself is further improved, and the use as a substrate for a flexible device becomes easier. Alternatively, for example, in the manufacturing process of the flexible device, after the thin film transistor is formed over the flexible substrate temporarily fixed to the glass substrate, the flexible substrate may be peeled from the glass substrate.
  • the surface of the substrate 12 on which the TFT is to be formed is subjected to UV ozone treatment as necessary, and then the metal nitrate solution is made into a semiconductor layer by the inkjet method Is applied to form a coating film, and then ultraviolet irradiation is performed in an atmosphere having an oxygen concentration of 80000 ppm or less to convert the coating film into a metal oxide semiconductor film.
  • the thickness of the semiconductor layer 14 is preferably 5 nm or more and 50 nm or less from the viewpoint of flatness and time required for film formation.
  • a protective layer (not shown) for protecting the semiconductor layer 14 on the semiconductor layer 14 when the source / drain electrodes 16 and 18 are etched.
  • the metal oxide semiconductor film may be formed successively.
  • the protective layer an insulator is preferable, and the material constituting the protective layer may be an inorganic material or an organic material such as a resin. Note that the protective layer may be removed after the formation of the source electrode 16 and the drain electrode 18 (referred to as “source / drain electrode” as appropriate).
  • Source / drain electrodes 16 and 18 are formed on the semiconductor layer 14 formed of the metal oxide semiconductor film.
  • the source and drain electrodes 16 and 18 are materials having high conductivity which function as electrodes, for example, metals such as Al, Mo, Cr, Ta, Ti, Ag and Au, Al-Nd, Ag alloy, tin oxide, oxide
  • the conductive film can be formed using a metal oxide conductive film such as zinc, indium oxide, indium tin oxide (ITO), zinc indium oxide (IZO), In—Ga—Zn—O, or the like.
  • a wet method such as a printing method or a coating method, a physical method such as a vacuum evaporation method, a sputtering method or an ion plating method, CVD (chemical vapor deposition), plasma CVD method
  • CVD chemical vapor deposition
  • the film formation may be carried out according to a method appropriately selected in consideration of the suitability with the material to be used from among chemical methods such as, etc.
  • the film thickness of the source / drain electrodes 16 and 18 is preferably 10 nm or more and 1000 nm or less, preferably 50 nm or more and 100 nm or less, in consideration of film forming property, patterning property by etching or lift-off method, conductivity and the like. More preferable.
  • the source / drain electrodes 16 and 18 may be formed by patterning in a predetermined shape by, for example, an etching or lift-off method, or may be directly patterned by an inkjet method or the like. At this time, it is preferable to simultaneously pattern the source / drain electrodes 16 and 18 and wires (not shown) connected to these electrodes.
  • the gate insulating film 20 is preferably a material having high insulating properties, for example, an insulating film such as SiO 2 , SiN x , SiON, Al 2 O 3 , Y 2 O 3 , Ta 2 O 5 , HfO 2 or a compound thereof.
  • the insulating film may include two or more types, and may have a single-layer structure or a stacked structure.
  • the gate insulating film 20 can be formed from a printing method, a wet method such as a coating method, a physical method such as vacuum evaporation, sputtering, ion plating, or a chemical method such as CVD or plasma CVD.
  • the film may be formed according to a method appropriately selected in consideration of the suitability with the material to be used.
  • the gate insulating film 20 may be an organic insulating film or an inorganic insulating film as long as it has a gate insulating property.
  • the gate insulating film 20 needs to have a thickness for reducing the leak current and improving the voltage resistance, but if the thickness of the gate insulating film 20 is too large, the driving voltage will be increased.
  • the thickness of the gate insulating film 20 is preferably 10 nm to 10 ⁇ m, more preferably 50 nm to 1000 nm, and particularly preferably 100 nm to 400 nm.
  • the gate electrode 22 is a material having high conductivity, for example, a metal such as Al, Cu, Mo, Cr, Ta, Ti, Ag, Au, Al-Nd, Ag alloy, tin oxide, zinc oxide, indium oxide, indium oxide
  • the conductive film can be formed using a metal oxide conductive film such as tin (ITO), indium zinc oxide (IZO), In—Ga—Zn—O, or the like. As the gate electrode 22, these conductive films can be used as a single-layer structure or a stacked-layer structure of two or more layers.
  • the gate electrode 22 may be formed of a printing method, a wet method such as a coating method, a physical method such as vacuum evaporation, sputtering, ion plating, or a chemical method such as CVD or plasma CVD.
  • the film is formed according to a method appropriately selected in consideration of the suitability of the above.
  • the thickness of the metal film for forming the gate electrode 22 is preferably 10 nm to 1000 nm, preferably 50 nm to 200 nm, in consideration of film forming property, patterning property by etching or lift-off method, conductivity and the like. It is more preferable to do.
  • the gate electrode 22 may be formed by patterning in a predetermined shape by etching or lift-off method, or direct pattern formation may be performed by an inkjet method, a printing method, or the like. At this time, it is preferable to simultaneously pattern the gate electrode 22 and the gate wiring (not shown).
  • the application of the thin film transistor 10 of the present embodiment described above is not particularly limited, but it can be applied to the production of various electronic devices, particularly flexible electronic devices, because thin film transistors having high transport characteristics can be produced at low temperatures. it can. Specifically, it is suitable for manufacturing a flexible display using a driving element in a display device such as a liquid crystal display device, an organic EL (Electro Luminescence) display device, an inorganic EL display device, and a resin substrate with low heat resistance. Furthermore, the thin film transistor manufactured according to the present disclosure is suitably used as a drive element (drive circuit) in various electronic devices such as various sensors such as an X-ray sensor and an image sensor, and MEMS (Micro Electro Mechanical System).
  • FIG. 5 shows a schematic cross-sectional view of a part of a liquid crystal display device according to an embodiment of the present invention
  • FIG. 6 shows a schematic configuration diagram of electrical wiring.
  • the liquid crystal display device 100 of this embodiment has a top gate structure shown in FIG. 1 and a top contact type TFT 10, and a pixel lower electrode on the gate electrode 22 protected by the passivation layer 102 of the TFT 10. And a color filter 110 for R (red), G (green) and B (blue) for coloring different colors corresponding to respective pixels.
  • Polarizers 112a and 112b are provided on the substrate 12 side and on the RGB color filter 110, respectively.
  • the liquid crystal display device 100 of the present embodiment includes a plurality of parallel gate lines 112 parallel to each other, and parallel data lines 114 intersecting the gate lines 112.
  • the gate wiring 112 and the data wiring 114 are electrically insulated.
  • a TFT 10 is provided in the vicinity of the intersection between the gate line 112 and the data line 114.
  • the gate electrode 22 of the TFT 10 is connected to the gate wiring 112, and the source electrode 16 of the TFT 10 is connected to the data wiring 114. Further, the drain electrode 18 of the TFT 10 is connected to the pixel lower electrode 104 (with a conductor embedded in the contact hole 116) through the contact hole 116 provided in the gate insulating film 20.
  • the pixel lower electrode 104 constitutes a capacitor 118 together with the opposed upper electrode 106 grounded.
  • the organic EL display device 200 of the active matrix system is provided with the top gate TFT 10 shown in FIG. 1 as a driving TFT 10 a and a switching TFT 10 b on the substrate 12 provided with the passivation layer 202.
  • 10b are provided with an organic EL light emitting element 214 consisting of an organic light emitting layer 212 sandwiched between a lower electrode 208 and an upper electrode 210, and the upper surface is also protected by a passivation layer 216.
  • the organic EL display device 200 includes a plurality of parallel gate lines 220 parallel to one another, and parallel data lines 222 and drive lines 224 intersecting the gate lines 220. ing.
  • the gate wiring 220, the data wiring 222, and the drive wiring 224 are electrically insulated.
  • the gate electrode 22 of the switching TFT 10 b is connected to the gate wiring 220, and the source electrode 16 of the switching TFT 10 b is connected to the data wiring 222.
  • the drain electrode 18 of the switching TFT 10b is connected to the gate electrode 22 of the driving TFT 10a, and the use of the capacitor 226 keeps the driving TFT 10a in the on state.
  • the source electrode 16 of the driving TFT 10 a is connected to the driving wiring 224, and the drain electrode 18 is connected to the organic EL light emitting element 214.
  • the upper electrode 210 may be a top emission type using a transparent electrode, or may be a bottom emission type by using lower electrodes 208 and TFT electrodes as transparent electrodes.
  • the X-ray sensor 300 includes the TFT 10 and the capacitor 310 formed on the substrate 12, the charge collection electrode 302 formed on the capacitor 310, the X-ray conversion layer 304, and the upper electrode 306. Configured A passivation film 308 is provided on the TFT 10.
  • the capacitor 310 has a structure in which the insulating film 316 is sandwiched between the capacitor lower electrode 312 and the capacitor upper electrode 314.
  • the capacitor upper electrode 314 is connected to one of the source electrode 16 and the drain electrode 18 (the drain electrode 18 in FIG. 9) of the TFT 10 through a contact hole 318 provided in the insulating film 316.
  • the charge collection electrode 302 is provided on the capacitor upper electrode 314 in the capacitor 310 and is in contact with the capacitor upper electrode 314.
  • the X-ray conversion layer 304 is a layer made of amorphous selenium, and is provided to cover the TFT 10 and the capacitor 310.
  • the upper electrode 306 is provided on the X-ray conversion layer 304 and is in contact with the X-ray conversion layer 304.
  • the X-ray sensor 300 includes a plurality of gate wirings 320 parallel to each other, and a plurality of data wirings 322 parallel to each other intersecting the gate wirings 320.
  • the gate wiring 320 and the data wiring 322 are electrically insulated.
  • the TFT 10 is provided in the vicinity of the intersection between the gate wiring 320 and the data wiring 322.
  • the gate electrode 22 of the TFT 10 is connected to the gate wiring 320, and the source electrode 16 of the TFT 10 is connected to the data wiring 322.
  • the drain electrode 18 of the TFT 10 is connected to the charge collection electrode 302, and the charge collection electrode 302 is connected to the capacitor 310.
  • X-rays are incident from the upper electrode 306 side in FIG. 9 to generate electron-hole pairs in the X-ray conversion layer 304.
  • the generated charge is stored in the capacitor 310 and is read out by sequentially scanning the TFT 10.
  • the liquid crystal display device 100, the organic EL display device 200, and the X-ray sensor 300 include the top gate TFT, the present invention is not limited to the top gate TFT, and FIGS. It may be a TFT having a structure shown in FIG.
  • Example 1 (Metal nitrate solution) Dissolve indium nitrate (In (NO 3 ) 3 x H 2 O, purity: 4 N, manufactured by High Purity Chemical Laboratory Co., Ltd.) in 2-methoxyethanol (special grade reagent, boiling point: 124 ° C., manufactured by Wako Pure Chemical Industries, Ltd.) To prepare a solution with an indium nitrate concentration of 0.5 mol / L.
  • a p-type Si substrate with a thermal oxide film (film thickness 100 nm) was used as a substrate.
  • the gate electrode is p-type Si
  • the gate insulating film is a thermal oxide film Si.
  • UV ozone treatment was performed for about 3 minutes on the substrate using a UV ozone treatment apparatus (Model 144AX-100 manufactured by Jelight-company-Inc).
  • a material printer DMP-2831 manufactured by Fujifilm Corporation was used as an inkjet apparatus.
  • the temperature of the ink cartridge and the stage can be adjusted independently, and the temperature of the ink cartridge is 25 ° C.
  • a silicon rubber heater was mounted on the substrate stage so as to heat the substrate on the stage at a higher temperature, and a mechanism capable of heating to 60 degrees or more was provided. The temperature calibration was performed on a Si wafer with a thermocouple, and was adjusted to an accurate substrate surface temperature.
  • the substrate was placed on a stage set at 60 ° C. and heated for 5 minutes, and then a line-shaped coating film of about 3 mm in length was formed on the substrate by ink jet (sometimes abbreviated as “IJ”).
  • IJ ink jet
  • UV irradiation apparatus VUE-3400-F manufactured by Oak Manufacturing Co., Ltd. was used as a UV irradiation apparatus.
  • This UV irradiation apparatus comprises a substrate heating mechanism (maximum 300 ° C.), gas (N 2 , O 2 ) introduction port, and a UV irradiation mechanism (low pressure mercury lamp: peak wavelength 254 nm). The conditions for the conversion step are shown below.
  • Substrate heating temperature 150 ° C (temperature-calibrated: TC wafer with thermocouple) Peak wavelength: 254 nm
  • Irradiation power 20mW / cm 2 (measured with Oak-manufactured UV-M10)
  • Irradiation time 30 minutes
  • Atmosphere N 2 , 1 atm (1013.25 hPa)
  • the stage Before setting the sample on the stage in the UV irradiation apparatus, the stage was previously heated to 150 ° C., and after the stage temperature reached 150 ° C., the sample was placed on the stage.
  • UV irradiation was started.
  • the N 2 flow was continued even during UV irradiation.
  • the sample was taken out of the apparatus.
  • source / drain electrodes were formed on the semiconductor film.
  • a metal mask having two 1 mm square holes (distance 0.2 mm) for source and drain electrodes is used to easily manufacture a TFT and to eliminate the influence on the semiconductor film by photolithography or the like.
  • Ti was sputter-deposited to a thickness of about 50 nm to form a source / drain electrode.
  • Examples 2 to 4 A TFT was produced in the same manner as in Example 1 except that the substrate surface temperature in the coating step was changed as shown in Table 1.
  • Comparative Example 1 After the coating step was performed in the same manner as in Example 1 except that the substrate was not heated, drying was performed at 60 ° C. for 1 minute using a hot plate. After drying, the conversion step was carried out in the same manner as in Example 1.
  • Comparative Example 2 The coating step was performed in the same manner as in Example 1 except that the substrate was not heated, and the conversion step was performed without drying. In the conversion step, since the coating film of the sample was cracked, the subsequent evaluation could not be performed (described as “NG” in Table 1). The crack of the coating film in Comparative Example 2 is estimated to be caused by heating and UV irradiation in a state where the coating film formed by the ink jet is not sufficiently dried.
  • the transistor characteristics were measured using a semiconductor parameter analyzer 4156C (manufactured by Agilent Technologies) for the TFTs manufactured in the above examples and comparative examples.
  • the measurement of the V g -I d characteristics is such that the drain voltage (V d ) is fixed at +1 V, the gate voltage (V g ) is changed within the range of -15 V to +15 V, and the drain current (I d ) at each gate voltage
  • the transistor characteristics are shown in FIG. 11 and the mobility calculated from FIG. 11 is shown in Table 1. From FIG. 11 and Table 1, the mobility showing the transistor characteristics is increased in Examples 1 to 4 as compared with Comparative Example 1, and it is confirmed that the characteristics are improved.
  • the film thickness of the semiconductor layer in the manufactured TFT was observed and measured by a transmission electron microscope (Hitachi H-9000 NAR).
  • the microscope picture of TFT produced by the comparative example 1 in FIG. 12 is shown. When viewed at the same density, it may be considered as the same thickness.
  • the concentration is different between the edge and the center of the semiconductor layer, the color is darker at the edge and the lower thermal oxide film (black) is seen through in the center. This is due to the difference in the film thickness of the semiconductor layer, and it can be seen that the central portion is thinner than the two edge portions.
  • each cross-sectional observation of the edge (point A) and the center (point B) of the semiconductor layer in FIG. 12 was performed by a transmission electron microscope (Hitachi H-9000NAR).
  • the part A is shown in FIG. 13 and the part B is shown in FIG.
  • the film thickness of the location A of the semiconductor layer was about 30 nm, and the film thickness of the location B was about 2 nm.
  • a portion presumed to be a defect was observed.
  • the semiconductor layer of Comparative Example 1 had a large difference in film thickness (uneven thickness). Further, a defect which is considered to cause the deterioration of the transistor characteristics is present at the edge (point A), and the location of the defect is not at the thermal oxide film interface but at about 10 nm from the thermal oxide film interface. It is considered that this is because impurities and the like can not be completely removed in the conversion process to the semiconductor film. That is, it can be estimated that reducing the unevenness in thickness of the semiconductor film to about 10 nm or less (after conversion) is a factor to reduce defects.
  • the film thickness difference (uneven thickness) at the locations A and B is smaller in Examples 1 to 4 than in Comparative Example 1, and in particular, the substrate surface temperature in the coating step In Examples 3 and 4 in which the boiling point (124 ° C.) or higher was used, the difference was 1 nm or less.
  • Example 5 Indium nitrate (In (NO 3 ) 3 x H 2 O, purity: 4 N, manufactured by High Purity Chemical Laboratory Co., Ltd.) is dissolved in methanol (special grade reagent, boiling point: 64.7 ° C., manufactured by Wako Pure Chemical Industries, Ltd.) A solution with an indium nitrate concentration of 0.5 mol / L was prepared. A coating film was formed on the thermally oxidized film-attached Si substrate whose substrate surface temperature was adjusted to 65 ° C. by ink jet using the above-mentioned indium nitrate solution in the same manner as in Example 1.
  • Examples 6 to 8 and Comparative Example 3 A TFT was produced and evaluated in the same manner as in Example 5 except that the substrate surface temperature in the coating step was changed as shown in Table 2. The results are summarized in Table 2.
  • Examples 9, 10, Comparative Examples 4, 5> A TFT was produced in the same manner as in Example 4 except that the oxygen concentration in the atmosphere at the time of UV irradiation in the conversion step of Example 4 was changed as shown in Table 3 below, and the mobility was evaluated. The results are shown in Table 3 together with Example 4.
  • a high mobility was obtained when the oxygen concentration in the atmosphere at the time of UV irradiation in the conversion step was 80000 ppm or less, but the mobility was low in Comparative Example 4 of 110,000 ppm, and the TFT characteristics were not shown in Comparative Example 5 of 200,000 ppm.

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Abstract

　L'invention concerne un procédé de fabrication d'un film d'oxyde métallique, et une application pour ledit procédé, le procédé comportant : une étape de revêtement consistant à appliquer une solution contenant un nitrate métallique et un solvant sur un substrat chauffé, au moyen d'un procédé de jet d'encre, pour former un film de revêtement; et une étape de conversion consistant à exposer le film de revêtement à des rayons ultraviolets dans une atmosphère dans laquelle la concentration d'oxygène est de 80.000 ppm ou moins, moyennant quoi le film de revêtement est converti en un film d'oxyde métallique.
PCT/JP2015/065320 2014-05-30 2015-05-27 Procédé de fabrication de film d'oxyde métallique, film d'oxyde métallique, transistor à couches minces, procédé de fabrication de transistor à couches minces, et dispositif électronique WO2015182679A1 (fr)

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JP2016523545A JP6195986B2 (ja) 2014-05-30 2015-05-27 金属酸化物半導体膜の製造方法及び薄膜トランジスタの製造方法

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CN113289617A (zh) * 2021-05-21 2021-08-24 北京邮电大学 一种集热策略制备超薄贵金属类薄膜催化剂的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010106920A1 (fr) * 2009-03-18 2010-09-23 コニカミノルタホールディングス株式会社 Procédé de fabrication d'un transistor à couches minces et transistor à couches minces
JP2010258058A (ja) * 2009-04-22 2010-11-11 Konica Minolta Holdings Inc 金属酸化物半導体の製造方法、金属酸化物半導体および薄膜トランジスタ
WO2013157715A1 (fr) * 2012-04-16 2013-10-24 전자부품연구원 Procédé de production d'un film d'oxyde par traitement à basse température, film d'oxyde et dispositif électronique

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* Cited by examiner, † Cited by third party
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JP2010258057A (ja) * 2009-04-22 2010-11-11 Konica Minolta Holdings Inc 金属酸化物半導体、その製造方法、及びそれを用いた薄膜トランジスタ

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010106920A1 (fr) * 2009-03-18 2010-09-23 コニカミノルタホールディングス株式会社 Procédé de fabrication d'un transistor à couches minces et transistor à couches minces
JP2010258058A (ja) * 2009-04-22 2010-11-11 Konica Minolta Holdings Inc 金属酸化物半導体の製造方法、金属酸化物半導体および薄膜トランジスタ
WO2013157715A1 (fr) * 2012-04-16 2013-10-24 전자부품연구원 Procédé de production d'un film d'oxyde par traitement à basse température, film d'oxyde et dispositif électronique

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113289617A (zh) * 2021-05-21 2021-08-24 北京邮电大学 一种集热策略制备超薄贵金属类薄膜催化剂的方法

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JPWO2015182679A1 (ja) 2017-04-27
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