WO2015083500A1 - Procédé pour fabriquer un film d'oxyde métallique, film d'oxyde métallique, transistor en couches minces, dispositif d'affichage, capteur d'image et capteur de rayons x - Google Patents

Procédé pour fabriquer un film d'oxyde métallique, film d'oxyde métallique, transistor en couches minces, dispositif d'affichage, capteur d'image et capteur de rayons x Download PDF

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WO2015083500A1
WO2015083500A1 PCT/JP2014/079768 JP2014079768W WO2015083500A1 WO 2015083500 A1 WO2015083500 A1 WO 2015083500A1 JP 2014079768 W JP2014079768 W JP 2014079768W WO 2015083500 A1 WO2015083500 A1 WO 2015083500A1
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metal oxide
film
oxide film
metal
substrate
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PCT/JP2014/079768
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Japanese (ja)
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真宏 高田
田中　淳
鈴木　真之
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富士フイルム株式会社
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Priority to KR1020167012845A priority Critical patent/KR101897375B1/ko
Publication of WO2015083500A1 publication Critical patent/WO2015083500A1/fr

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    • H01L21/02612—Formation types
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    • 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
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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    • H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
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    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
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    • H01L21/02614—Transformation of metal, e.g. oxidation, nitridation
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    • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
    • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
    • H01L27/1259—Multistep manufacturing methods
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    • H01L27/144—Devices controlled by radiation
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    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
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    • 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
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    • 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

Definitions

  • the present invention relates to a method for producing a metal oxide film, a metal oxide film, a thin film transistor, a display device, an image sensor, and an X-ray sensor.
  • a metal oxide semiconductor film has been put into practical use in the production by a vacuum film forming method and is currently attracting attention.
  • research and development have been actively conducted on the production of metal oxide films by a liquid phase process for the purpose of easily forming metal oxide films having high semiconductor properties at low temperatures and atmospheric pressure. ing.
  • a method for producing a metal oxide film is disclosed in which a gel thin film is irradiated with ultraviolet light having a wavelength of 360 nm or less to crystallize the metal oxide gel by repeating the process a plurality of times (Japanese Patent Laid-Open No. 2000). -247608).
  • a step of forming a film containing an organometallic compound and / or an organometallic complex, irradiating the film with energy rays, decomposing an organic component contained in the film located at the irradiation site, and metal and / or metal oxide has been disclosed (see Japanese Patent Application Laid-Open No. 2005-213567).
  • TFT Thin Film Transistor
  • the present invention relates to a metal oxide film manufacturing method and metal oxide film capable of manufacturing a dense metal oxide film at a relatively low temperature and atmospheric pressure, and a thin film transistor and a display device having high mobility.
  • An object is to provide an image sensor and an X-ray sensor.
  • ⁇ 1> Applying a solution containing metal nitrate on a substrate, drying the coating film to form a metal oxide precursor film, and converting the metal oxide precursor film into a metal oxide film Including repeating two or more times alternately, Metal that converts a metal oxide precursor film into a metal oxide film by converting the metal oxide precursor film into a metal oxide film in at least two steps of converting the metal oxide precursor film into a metal oxide film with a maximum substrate temperature of 120 ° C. to 250 ° C. Manufacturing method of oxide film.
  • the maximum reached temperature of the substrate is set to 120 ° C.
  • ⁇ 5> Any one of ⁇ 1> to ⁇ 4>, wherein the step of forming the metal oxide precursor film and the step of converting the metal oxide precursor film into the metal oxide film are alternately repeated four times or more.
  • ⁇ 6> The method for producing a metal oxide film according to any one of ⁇ 1> to ⁇ 5>, wherein the solution containing the metal nitrate contains at least indium nitrate.
  • the solution containing indium nitrate further contains a compound containing at least one metal atom selected from zinc, tin, gallium, and aluminum.
  • ⁇ 8> The method for producing a metal oxide film according to any one of ⁇ 1> to ⁇ 7>, wherein the metal molar concentration of the solution containing the metal nitrate is 0.01 mol / L or more and 0.5 mol / L or less. . ⁇ 9>
  • the average thickness of the metal oxide film obtained by performing the process of forming the metal oxide precursor film and the process of converting the metal oxide precursor film into a metal oxide film once is 6 nm or less.
  • the average film thickness of the metal oxide film obtained by performing the process of forming the metal oxide precursor film and the process of converting the metal oxide precursor film into a metal oxide film once is 2 nm or less.
  • ⁇ 9> The method for producing a metal oxide film according to the above.
  • ⁇ 11> The method for producing a metal oxide film according to any one of ⁇ 1> to ⁇ 10>, wherein the solution containing the metal nitrate contains methanol or methoxyethanol.
  • the step of converting the metal oxide precursor film into the metal oxide film includes a step of irradiating the metal oxide precursor film with ultraviolet light having a wavelength of 300 nm or less at an intensity of 10 mW / cm 2 or more ⁇ 4
  • ⁇ 13> The method for producing a metal oxide film according to ⁇ 12>, wherein the light source used when the metal oxide precursor film is irradiated with ultraviolet rays is a low-pressure mercury lamp.
  • ⁇ 14> The metal according to any one of ⁇ 1> to ⁇ 13>, wherein in the step of forming the metal oxide precursor film, the temperature of the substrate when the coating film is dried is 35 ° C.
  • a solution containing a metal nitrate is applied by at least one application method selected from an inkjet method, a dispenser method, a relief printing method, and an intaglio printing method ⁇ 1
  • ⁇ 16> A metal oxide film produced using the method for producing a metal oxide film according to any one of ⁇ 1> to ⁇ 15>.
  • the metal oxide film according to ⁇ 16> which is a metal oxide semiconductor film.
  • ⁇ 18> A thin film transistor having an active layer including the metal oxide film according to ⁇ 17>, a source electrode, a drain electrode, a gate insulating film, and a gate electrode.
  • a display device comprising the thin film transistor according to ⁇ 18>.
  • An image sensor comprising the thin film transistor according to ⁇ 18>.
  • An X-ray sensor comprising the thin film transistor according to ⁇ 18>.
  • FIG. 1 is a schematic view showing a configuration of an example (bottom gate-bottom contact type) thin film transistor manufactured according to the present invention.
  • FIG. 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. It is a schematic sectional drawing which shows a part of organic EL display apparatus of embodiment.
  • FIG. It is a schematic block diagram of the electrical wiring of the organic electroluminescence display shown in FIG. It is a schematic sectional drawing which shows a part of X-ray sensor array of embodiment. It is a schematic block diagram of the electrical wiring of the X-ray sensor array shown in FIG. It is a diagram showing, V g -I d characteristics of the simplified TFT fabricated in Examples 1-4 and Comparative Example 1. It is a figure which shows the relationship between the repetition frequency of a precursor film
  • the inventors conducted a plurality of times by alternately applying a solution using a metal nitrate and forming a metal oxide precursor film by drying and converting it into a metal oxide film by heating a plurality of times. It has been found that an effect of improving the density can be obtained.
  • a metal oxide semiconductor film by the method of the present invention, a thin film transistor having high transport properties can be produced at a relatively low temperature under atmospheric pressure. Therefore, a display device such as a thin film liquid crystal display or an organic EL, particularly a flexible display. Can be provided.
  • the method for producing a metal oxide film of the present invention includes a step of applying a solution containing a metal nitrate on a substrate, drying the applied film to form a metal oxide precursor film, and forming the metal oxide precursor film into a metal.
  • the metal oxide precursor film is converted into a metal oxide film at a temperature lower than the temperature.
  • a dense metal oxide film can be formed by the present invention.
  • the metal oxide precursor film is converted into the metal oxide film, the nitric acid component and the component coordinated to the metal are desorbed from the film.
  • the solution is impregnated in the detached part, and as a result, a new metal-oxygen bond is formed, and a dense metal oxide film is formed. .
  • Step A First, prepare a solution containing a metal nitrate for forming a metal oxide film and a substrate for forming a metal oxide film, apply a solution containing the metal nitrate on the substrate, and dry the applied film. A metal oxide precursor film is formed.
  • the structure of the substrate may be a single layer structure or a laminated structure.
  • the material constituting the substrate is not particularly limited, and a substrate made of glass, an inorganic material such as YSZ (Yttria-Stabilized Zirconia), a resin, a resin composite material, or the like can be used.
  • a resin substrate or a substrate made of a resin composite material (resin composite material substrate) is preferable in terms of light weight and flexibility.
  • Inorganic materials contained in the composite material of inorganic material and resin include inorganic particles such as silicon oxide particles, metal nanoparticles, inorganic oxide nanoparticles, and inorganic nitride nanoparticles, carbon fibers such as carbon fibers and carbon nanotubes. Examples thereof include glass materials such as materials, glass ferkes, glass fibers, and glass beads. Also, composite plastic material of resin and clay mineral, composite plastic material of resin and particles having mica-derived crystal structure, laminated plastic material having at least one bonding interface between resin and thin glass, inorganic layer and organic Examples include a composite material having barrier performance having at least one bonding interface by alternately laminating layers.
  • a stainless steel substrate or a metal multilayer substrate in which different metals are laminated with stainless steel, an aluminum substrate, an aluminum substrate with an oxide film whose surface insulation is improved by subjecting the surface to an oxidation treatment (for example, anodization treatment), or the like is used.
  • the resin substrate or the resin composite material substrate is preferably excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation, workability, low air permeability, low moisture absorption, and the like.
  • the resin substrate or the resin composite material substrate may include a gas barrier layer for preventing permeation of moisture, oxygen, and the like, an undercoat layer for improving the flatness of the substrate and adhesion with the lower electrode, and the like.
  • the thickness of the substrate used in the present invention is not particularly limited, but is preferably 50 ⁇ m or more and 500 ⁇ m or less.
  • the thickness of the substrate is 50 ⁇ m or more, the flatness of the substrate itself is further improved.
  • 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.
  • a solution containing a metal nitrate is obtained by weighing a solute such as a metal nitrate so that the solution has a desired concentration and stirring and dissolving in a solvent.
  • the stirring time is not particularly limited as long as the solute is sufficiently dissolved.
  • the metal nitrate contained in the solution may be selected according to the metal oxide film to be formed.
  • the metal molar concentration of the solution can be arbitrarily selected according to the viscosity and the film thickness to be obtained. Is preferred. If the metal molar concentration in the solution is 0.01 mol / L or more, the film density can be effectively improved. In addition, when a metal oxide precursor film is formed by applying a solution on the metal oxide film, the lower metal oxide film should be dissolved if the metal molar concentration in the solution is 0.5 mol / L or less. Is also preferable in that it can be effectively suppressed.
  • the metal molar concentration in the present invention means the total amount of molar concentrations (mol / L) of each metal.
  • the solution containing a metal nitrate may contain a metal atom-containing compound other than the metal nitrate.
  • the metal atom-containing compound include metal salts other than metal nitrates, metal halides, and organometallic compounds.
  • metal salts other than metal nitrates include sulfates, phosphates, carbonates, acetates, and oxalates.
  • metal halides include chlorides, iodides, bromides, and the like. Examples thereof include metal alkoxides, organic acid salts, and metal ⁇ -diketonates.
  • the solution containing metal nitrate preferably contains at least indium nitrate.
  • an indium-containing oxide film can be easily formed by using indium nitrate, and high electrical conductivity can be obtained.
  • the step of converting the metal oxide precursor film into the metal oxide film includes a step of irradiating ultraviolet rays, the precursor film can efficiently absorb ultraviolet light, and the indium-containing oxide film can be easily formed. Can be formed.
  • the solution containing a metal nitrate contains a compound containing any one or more metal atoms 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 the electrical stability of the film is also improved.
  • an oxide semiconductor containing a metal element other than indium and indium and an oxide conductor In—Ga—Zn—O (IGZO), In—Zn—O (IZO), and In—Ga—O (IGO) are used.
  • the solvent used for the solution containing the metal nitrate is not particularly limited as long as the metal atom-containing compound containing the metal nitrate to be used is dissolved.
  • 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, etc.
  • examples include heteroatom-containing solvents other than those described above. In particular, from the viewpoint of solubility and paintability, it is preferable to use methanol, methoxyethanol or the like.
  • the method of applying a solution containing metal nitrate (coating solution for forming a metal oxide film) on the substrate is not particularly limited. Spray coating method, spin coating method, blade coating method, dip coating method, casting method, roll coating method , Bar coating method, die coating method, mist method, ink jet method, dispenser method, screen printing method, relief printing method, and intaglio printing method.
  • the coating film is dried to obtain a first metal oxide precursor film.
  • the fluidity of the coating film can be reduced, and the flatness of the finally obtained oxide film can be improved.
  • an appropriate drying temperature for example, the substrate temperature is 35 ° C. or higher and 100 ° C. or lower
  • a denser metal oxide film can be finally obtained.
  • the method of heat treatment for drying is not particularly limited, and can be selected from hot plate heating, electric furnace heating, infrared heating, microwave heating, and the like. Drying is preferably started within 5 minutes after coating from the viewpoint of keeping the flatness of the film uniform.
  • the drying time is not particularly limited, but is preferably 15 seconds or longer and 10 minutes or shorter from the viewpoint of film uniformity and productivity. Moreover, there is no restriction
  • the metal oxide precursor film obtained by drying is converted into a metal oxide film.
  • the method for converting the metal oxide precursor film into the metal oxide film is not particularly limited as long as the maximum temperature of the substrate can be 120 ° C. or more and 250 ° C. or less, such as a heater such as a hot plate, an electric furnace, plasma, A technique using ultraviolet light, microwaves, or the like can be given. If the maximum temperature of the substrate in the conversion step is less than 120 ° C., the effect of improving the film density is insufficient, and if it exceeds 250 ° C., the manufacturing cost increases. From the viewpoint of conversion to a metal oxide film at a lower temperature, a method using ultraviolet (UV) is preferable. Examples of the ultraviolet light source include a UV lamp and a laser, and a UV lamp is preferable from the viewpoint of performing ultraviolet irradiation with a cheap facility uniformly over a large area.
  • UV ultraviolet
  • 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.
  • Use of a lamp is preferable because conversion from a metal oxide precursor film to a metal oxide film can be easily performed.
  • the film surface of the metal oxide precursor film is preferably irradiated with ultraviolet light having a wavelength of 300 nm or less at an illuminance of 10 mW / cm 2 or more.
  • ultraviolet light having a wavelength of 300 nm or less at an illuminance of 10 mW / cm 2 or more.
  • the illuminance of ultraviolet rays applied to the metal oxide precursor film can be measured using, for example, an ultraviolet light meter (manufactured by Oak Manufacturing Co., Ltd., UV-M10, photoreceiver UV-25).
  • atmosphere in the conversion step there is no limitation on the atmosphere in the conversion step, and it may be under atmospheric pressure or under vacuum, and may be in the air or in any gas, but it is easy to convert. To atmospheric pressure.
  • the maximum temperature reached by the substrate in the conversion step is preferably 200 ° C. or lower. If it is 200 degrees C or less, application to a resin substrate with low heat resistance will become easy. Note that the maximum temperature reached by the substrate in the conversion step can be measured by a thermo label.
  • the temperature of the substrate is not particularly limited as long as it is a method that can be controlled within the above-described temperature range, and the substrate temperature may be controlled by a heater such as a hot plate, an electric furnace, or microwave heating, and from a light source such as an ultraviolet lamp.
  • the radiant heat may be used.
  • the substrate temperature can be controlled by adjusting the lamp-substrate distance and the lamp output.
  • the ultraviolet irradiation time depends on the illuminance of the ultraviolet rays, it is preferably 5 seconds or longer and 120 minutes or shorter from the viewpoint of productivity.
  • Step A and step B After the metal oxide precursor film is converted into a metal oxide film, a solution containing metal nitrate is again applied and dried on the metal oxide film to form a metal oxide precursor thin film, and the metal oxide precursor film A metal oxide film is further formed on the metal oxide film by converting to a metal oxide film.
  • the metal oxide precursor film formation step (step A) and the conversion step to the metal oxide film (step B) are alternately repeated twice or more, and the metal oxide films are stacked and formed integrally.
  • a metal oxide film having a high film density can be obtained.
  • the process A and the process B do not need to be performed continuously and the process A and the process B are the process A.
  • another process such as formation of an electrode or an insulating film may be included between the process B and the process B.
  • the metal oxide precursor film may be converted into a metal oxide film by setting the maximum temperature of the film to 120 ° C. or higher and 250 ° C. or lower. For example, when the formation of the metal oxide precursor film and the conversion to the metal oxide film are alternately repeated three times, the maximum temperature of the substrate is set to 120 ° C. or more and 250 ° C.
  • the maximum temperature of the substrate may be less than 120 ° C.
  • the maximum temperature of the substrate is less than 120 ° C
  • the maximum temperature of the substrate is reached. It is good also as 120 to 250 degreeC.
  • the maximum temperature of the substrate may be 120 ° C. or higher and 250 ° C. or lower in the first conversion step and the third conversion step, and may be performed at less than 120 ° C. in the second conversion step.
  • the maximum reached temperature of the substrate is set to 120 ° C. or more and 250 ° C. or less to convert the metal oxide precursor film into the metal oxide film. Is preferred.
  • Step A and Step B it is preferable to repeat Step A and Step B four or more times alternately on the same substrate (that is, four or more sets of Step A and Step B).
  • Step A and Step B By repeating Step A and Step B alternately four or more times, a high-quality metal oxide film having a higher film density can be obtained.
  • the number of times of repeating the process A and the process B is not particularly limited as long as it is 2 times or more, and may be determined in consideration of the target thickness of the metal oxide film, etc., but is 10 times or less from the viewpoint of productivity. It is preferable to do.
  • FIG. 13 schematically shows an example of an apparatus for producing a metal oxide film according to the present invention.
  • This apparatus has a configuration in which a metal oxide film is formed by a roll-to-roll method, and an application part 2 (2A, 2B, 2C) by ink jet or the like, and a conversion part 3 (3A, 3B, 3C) by ultraviolet irradiation, Are arranged alternately and continuously, and are provided with a transport belt 4 and a transport roll 5 for transporting the substrate 1, a temperature control means 8 for controlling the temperature of the substrate 1, and the like.
  • the substrate 1 arranged at a predetermined interval on the conveyor belt 4 moves in the direction of the arrow A together with the conveyor belt 4 by the rotation of the conveyor roll 5, and the solution 6 containing metal nitrate is applied to the coating unit 2 ⁇ / b> A to apply metal oxidation.
  • a precursor precursor film is formed.
  • the conversion unit 3A is irradiated with ultraviolet rays, and the temperature control means 8 heats the substrate 1 to a maximum temperature of 120 ° C. or more and 250 ° C. or less to convert the metal oxide precursor film into a metal oxide film. .
  • formation of a metal oxide precursor film and conversion into a metal oxide film are repeatedly performed by the second coating part 2B and the conversion part 3B, and further by the third coating part 2C and the conversion part 3C. In this way, the process A and the process B can be repeated efficiently in a short time.
  • the average film thickness of the metal oxide film obtained by performing Step A and Step B once is preferably 6 nm or less, and more preferably 2 nm or less.
  • the average film thickness described here refers to a value obtained by dividing the film thickness of the metal oxide film produced by alternately repeating the process A and the process B a plurality of times by the number of times of application (the number of processes A).
  • the film thickness of the finally obtained metal oxide film can be evaluated by cross-sectional observation of the film with a transmission electron microscope (TEM).
  • Metal oxide film The metal oxide film produced by alternately repeating the process A and the process B a plurality of times becomes a film having a high film density.
  • the metal oxide film of the present invention preferably contains at least indium as a metal component.
  • indium high electrical conductivity can be obtained when a metal oxide semiconductor film or a metal oxide conductor film is formed.
  • the indium content of the metal oxide film is preferably 50 atom% or more of the total metal elements contained in the metal oxide film. If the indium content is 50 atom% or more, high electrical conductivity can be easily obtained at low temperatures.
  • the metal oxide film preferably contains at least one metal component selected from zinc, tin, gallium, and aluminum as a metal element other than indium. By including an appropriate amount of the metal element, an effect of improving electrical conductivity, controlling threshold voltage when an oxide semiconductor film is manufactured, and improving electrical stability can be obtained.
  • In—Ga—Zn—O In—Zn—O
  • IZO In—Zn—O
  • IGO In—Ga—O
  • ITO In—Sn— O
  • ITZO In—Sn—Zn—O
  • the average film density of the metal oxide film measured by X-ray reflectometry is 6 g / cm 3 or more.
  • XRR X-ray reflectometry
  • the average film density referred to here is a model of a plurality of layers having different densities when performing fitting from the XRR spectrum using the film thickness, film density, and surface roughness as parameters, and the film density of each layer is defined as the film density.
  • the first layer has a film density of 4 g / cm 3 , the film thickness is 1 nm, and the second layer has a film density of 5 g.
  • a dense metal oxide film can be obtained by a low-temperature process at 200 ° C. or lower under atmospheric pressure, and can be applied to the production of various devices. it can.
  • the device manufacturing cost can be greatly reduced because it is not necessary to use a large vacuum device, an inexpensive resin substrate having low heat resistance can be used, and the raw material is inexpensive.
  • the present invention can be applied to a resin substrate having low heat resistance, a flexible electronic device such as a flexible display can be manufactured at low cost.
  • the present invention can obtain a film having extremely high electron transfer characteristics, particularly when used for manufacturing a metal oxide semiconductor film or a metal oxide conductive film.
  • the metal oxide semiconductor film manufactured according to the embodiment of the present invention exhibits high semiconductor characteristics, it can be suitably used for an active layer (oxide semiconductor layer) of a thin film transistor (TFT).
  • TFT thin film transistor
  • an embodiment in which a metal oxide film produced by the production method of the present invention is used as an active layer of a thin film transistor will be described.
  • a top gate type thin film transistor is described as an embodiment, a thin film transistor using a metal oxide semiconductor film manufactured according to the present invention is not limited to a top gate type, and is a bottom gate type thin film transistor. Also good.
  • the element structure of the TFT according to the present invention is not particularly limited, and is either a so-called reverse stagger structure (also referred to as a bottom gate type) or a stagger structure (also referred to as a top gate type) based on the position of the gate electrode. Also good. Further, based on the contact portion between the active layer and the source and drain electrodes (referred to as “source / drain electrodes” as appropriate), either a so-called top contact type or bottom contact type may be used.
  • the top gate type is a form in which a gate electrode is disposed on the upper side of the gate insulating film and an active layer is formed on the lower side of the gate insulating film when the substrate on which the TFT is formed is the lowest layer.
  • the bottom gate type is a form in which a gate electrode is disposed below the gate insulating film and an active layer is formed above the gate insulating film.
  • the bottom contact type is a mode in which the source / drain electrodes are formed before the active layer and the lower surface of the active layer is in contact with the source / drain electrodes.
  • the active layer is formed before the source / drain electrodes, and the upper surface of the active layer is in contact with the source / drain electrodes.
  • FIG. 1 is a schematic diagram showing an example of a top contact type TFT according to the present invention having a top gate structure.
  • the above-described metal oxide film is laminated as an active layer 14 on one main surface of the substrate 12.
  • a source electrode 16 and a drain electrode 18 are disposed on the active layer 14 so as to be separated from each other, and a gate insulating film 20 and a gate electrode 22 are sequentially stacked thereon.
  • FIG. 2 is a schematic view showing an example of a bottom contact type TFT according to the present invention having a top gate structure.
  • the source electrode 16 and the drain electrode 18 are disposed on one main surface of the substrate 12 so as to be separated from each other. Then, the above-described metal oxide film, the gate insulating film 20, and the gate electrode 22 are sequentially stacked as the active layer.
  • FIG. 3 is a schematic view showing an example of a TFT according to the present invention having a bottom gate structure and a top contact type.
  • the gate electrode 22, the gate insulating film 20, and the above-described metal oxide film as the active layer 14 are sequentially stacked on one main surface of the substrate 12.
  • a source electrode 16 and a drain electrode 18 are disposed on the surface of the active layer 14 so as to be separated from each other.
  • FIG. 4 is a schematic view showing an example of a bottom contact type TFT according to the present invention having a bottom gate structure.
  • the gate electrode 22 and the gate insulating film 20 are sequentially stacked on one main surface of the substrate 12.
  • the source electrode 16 and the drain electrode 18 are provided on the surface of the gate insulating film 20 so as to be spaced apart from each other, and the above-described metal oxide semiconductor film is stacked as the active layer 14 thereon.
  • the top gate type thin film transistor 10 shown in FIG. 1 will be mainly described.
  • the thin film transistor of the present invention is not limited to the top gate type and may be a bottom gate type thin film transistor.
  • the thin film transistor 10 of this embodiment When the thin film transistor 10 of this embodiment is manufactured, first, a solution containing a metal nitrate is prepared, and the formation process of the metal oxide precursor film and the conversion process to the metal oxide film are alternately repeated twice or more to form the substrate 12. A metal oxide film is formed thereon.
  • the patterning of the metal oxide film may be performed by the above-described inkjet method, dispenser method, relief printing method, or intaglio printing method, and may be patterned by photolithography and etching after the formation of the metal oxide film.
  • a resist pattern is formed by photolithography on a portion to be left as the active layer 14, and then hydrochloric acid, nitric acid, dilute sulfuric acid, phosphoric acid, nitric acid
  • the pattern of the active layer 14 is formed by etching with an acid solution such as a mixed solution of acetic acid.
  • the thickness of the metal oxide film is preferably 5 nm or more and 50 nm or less from the viewpoint of film flatness and time required for film formation.
  • the indium content in the active layer 14 is preferably 50 atom% or more of the total metal elements contained in the active layer 14, and more preferably 80 atom% or more.
  • a protective layer (not shown) for protecting the active layer 14 is preferably formed on the active layer 14 when the source / drain electrodes 16 and 18 are etched.
  • the method for forming the protective layer is not particularly limited, and may be formed after the metal oxide film is formed and before the patterning, or after the metal oxide film is patterned. Further, the protective layer may be a metal oxide layer or an organic material such as a resin. The protective layer may be removed after the source electrode 15 and the drain electrode 18 (referred to as “source / drain electrodes” as appropriate) are formed.
  • Source / drain electrodes 16 and 18 are formed on the active layer 14 formed of a metal oxide semiconductor film.
  • the source / drain electrodes 16 and 18 have high conductivity so as to function as electrodes, respectively, and metals such as Al, Mo, Cr, Ta, Ti, Au, Au, Al—Nd, Ag alloy, tin oxide
  • metals such as Al, Mo, Cr, Ta, Ti, Au, Au, Al—Nd, Ag alloy, tin oxide
  • a metal oxide conductive film such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), or In—Ga—Zn—O can be used.
  • a wet method such as a printing method and a coating method, a physical method such as a vacuum deposition method, a sputtering method, and an ion plating method, a chemical method such as a CVD method and a plasma CVD method, etc.
  • the film may be formed according to a method appropriately selected in consideration of suitability with the material to be used.
  • 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 properties, patterning properties by etching or lift-off methods, conductivity, and the like. More preferred.
  • the source / drain electrodes 16 and 18 may be formed by patterning into a predetermined shape by, for example, etching or a lift-off method after forming a conductive film, or may be directly formed by an inkjet method or the like. At this time, it is preferable to pattern the source / drain electrodes 16 and 18 and wiring (not shown) connected to these electrodes simultaneously.
  • the gate insulating film 20 preferably has a high insulating property.
  • 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 is used.
  • An insulating film including two or more kinds may be used.
  • the gate insulating film 20 is a material used from a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method or an ion plating method, or a chemical method such as CVD or plasma CVD method.
  • the film may be formed according to a method appropriately selected in consideration of the suitability of
  • the gate insulating film 20 needs to have a thickness for reducing leakage current and improving voltage resistance. On the other hand, if the gate insulating film 20 is too thick, the driving voltage is 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 made of highly conductive metal such as Al, Mo, Cr, Ta, Ti, Au, Au, Al—Nd, Ag alloy, tin oxide, zinc oxide, indium oxide, indium tin oxide ( It can be formed using a metal oxide conductive film such as ITO), zinc indium oxide (IZO), or IGZO. As the gate electrode 22, these conductive films can be used as a single layer structure or a stacked structure of two or more layers.
  • the gate electrode 22 is made of a material used from a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method or an ion plating method, or a chemical method such as a CVD or plasma CVD method.
  • the film is formed according to a method appropriately selected in consideration of the suitability of the above.
  • the film thickness of the metal film for forming the gate electrode 22 is preferably 10 nm or more and 1000 nm or less, preferably 50 nm or more and 200 nm or less in consideration of film forming properties, patterning properties by etching or lift-off methods, conductivity, and the like. More preferably.
  • the gate electrode 22 may be formed by patterning into a predetermined shape by an etching or lift-off method, or the pattern may be directly formed by an inkjet method or the like. At this time, it is preferable to pattern the gate electrode 22 and the gate wiring (not shown) at the same time.
  • the application of the thin film transistor 10 of the present embodiment described above is not particularly limited. However, since it exhibits high transport characteristics, for example, an electro-optical device, specifically, a liquid crystal display device, an organic EL (Electro Luminescence) display device. It is suitable as a drive element in a display device such as an inorganic EL display device, and is particularly suitable for production of a flexible display using a resin substrate having low heat resistance. Further, the thin film transistor manufactured according to the present invention is suitably used as a driving element (driving circuit) in various electronic devices such as various sensors such as an X-ray sensor and an image sensor, and a micro electro mechanical system (MEMS).
  • driving element driving circuit
  • various electronic devices such as various sensors such as an X-ray sensor and an image sensor, and a micro electro mechanical system (MEMS).
  • MEMS micro electro mechanical system
  • FIG. 5 shows a schematic 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 includes a top contact type TFT 10 having the top gate structure shown in FIG. 1 and a pixel lower electrode on the gate electrode 22 protected by the passivation layer 102 of the TFT 10. 104 and a liquid crystal layer 108 sandwiched between the counter upper electrode 106 and an R (red) G (green) B (blue) color filter 110 for developing different colors corresponding to each pixel.
  • the polarizing plate 112a and 112b are provided on the substrate 12 side and the RGB color filter 110, respectively.
  • the liquid crystal display device 100 of the present embodiment includes a plurality of gate wirings 112 parallel to each other and data wirings 114 intersecting with the gate wirings 112 and parallel to each other.
  • the gate wiring 112 and the data wiring 114 are electrically insulated.
  • the TFT 10 is provided in the vicinity of the intersection between the gate wiring 112 and the data wiring 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.
  • the drain electrode 18 of the TFT 10 is connected to the pixel lower electrode 104 through a contact hole 116 provided in the gate insulating film 20 (a conductor is embedded in the contact hole 116).
  • the pixel lower electrode 104 forms a capacitor 118 together with the grounded counter upper electrode 106.
  • FIG. 7 shows a schematic sectional view of a part of an active matrix organic EL display device according to an embodiment of the present invention
  • FIG. 8 shows a schematic configuration diagram of electrical wiring.
  • the active matrix organic EL display device 200 of the present embodiment includes the TFT 10 having the top gate structure shown in FIG. 1 as a driving TFT 10a and a switching TFT 10b on a substrate 12 having a passivation layer 202.
  • 10b is provided with an organic EL light emitting element 214 composed 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 gate wirings 220 that are parallel to each other, and a data wiring 222 and a driving wiring 224 that are parallel to each other and intersect the gate wiring 220.
  • 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 driving TFT 10a is kept on by using the capacitor 226.
  • 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 the bottom electrode 208 and each TFT electrode may be a transparent electrode.
  • FIG. 9 shows a schematic sectional view of a part of an X-ray sensor according to an embodiment of the present invention
  • FIG. 10 shows a schematic configuration diagram of its electrical wiring.
  • the X-ray sensor 300 of this embodiment 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. Composed.
  • a passivation film 308 is provided on the TFT 10.
  • the capacitor 310 has a structure in which an insulating film 316 is sandwiched between a capacitor lower electrode 312 and a 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 so as 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 of this embodiment includes a plurality of gate wirings 320 that are parallel to each other and a plurality of data wirings 322 that intersect with the gate wirings 320 and are parallel to each other.
  • 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 collecting electrode 302, and the charge collecting electrode 302 is connected to the capacitor 310.
  • X-rays enter from the upper electrode 306 side in FIG. 9 and generate electron-hole pairs in the X-ray conversion layer 304.
  • the generated charge is accumulated in the capacitor 310 and read out by sequentially scanning the TFT 10.
  • a TFT having a top gate structure is provided in the liquid crystal display device 100, the organic EL display device 200, and the X-ray sensor 300 of the above embodiment.
  • the TFT is not limited to this, and FIGS. A TFT having the structure shown in FIG.
  • Example 1 Comparative Example 1> The following evaluation devices were produced and evaluated. Indium nitrate (In (NO 3 ) 3 ⁇ H 2 O, 4N, manufactured by High Purity Chemical Research Laboratories) was dissolved in 2-methoxyethanol (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) and shown in Table 1 below. Solutions with different indium nitrate concentrations were prepared.
  • In (NO 3 ) 3 ⁇ H 2 O, 4N manufactured by High Purity Chemical Research Laboratories
  • 2-methoxyethanol special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.
  • a simple TFT using a thermal oxide film as a gate insulating film was prepared using a p-type Si substrate with a thermal oxide film (film thickness 100 nm) as the substrate.
  • Each of the prepared solutions was spin-coated on a p-type Si 1 inch square substrate with a thermal oxide film at a rotational speed of 1500 rpm for 30 seconds, and then dried on a hot plate heated to 60 ° C. for 1 minute to obtain a metal oxide.
  • a semiconductor precursor film was obtained.
  • the obtained metal oxide semiconductor precursor film was converted into a metal oxide semiconductor film by heat treatment by ultraviolet irradiation under the following conditions.
  • a UV ozone cleaner manufactured by Filgen, UV253H
  • a low-pressure mercury lamp was used as an ultraviolet irradiation device.
  • the sample was set on a glass plate having a thickness of 40 mm, and the distance between the lamp and the sample was 5 mm.
  • the ultraviolet illuminance at the sample position at a wavelength of 254 nm was measured using an ultraviolet light meter (manufactured by Oak Manufacturing Co., Ltd., UV-M10, photoreceiver UV-25). The maximum value was reached in 3 minutes after the lamp was turned on, and was 15 mW / cm 2 .
  • ultraviolet irradiation was performed for 90 minutes. During UV irradiation, nitrogen was always flowed at 6 L / min. When the substrate temperature at the time of ultraviolet irradiation treatment was monitored with a thermolabel, it showed 160 ° C.
  • the source / drain electrodes were formed by vapor deposition on the obtained oxide semiconductor film.
  • the source / drain electrodes were formed by pattern deposition using a metal mask, and Ti was deposited to a thickness of 50 nm.
  • the source / drain electrode size was 1 mm square, and the distance between the electrodes was 0.2 mm.
  • the measurement of the V g -I d characteristic is performed by fixing the drain voltage (V d ) to +1 V, changing the gate voltage (V g ) within a range of ⁇ 15 V to +15 V, and drain current (I d ) at each gate voltage. It was performed by measuring.
  • Figure 11 shows a, V g -I d characteristics of the Examples 1 to 4 and Comparative Example 1. Also, the linear mobility was estimated from, V g -I d characteristics of the Examples 1 to 4 and Comparative Example 1 (hereinafter, sometimes referred to as "mobility”.) Shown in Table 2.
  • FIG. 12 shows a plot of the relationship between the number of repetitions and mobility. The effect of improving the characteristics can be obtained when the number of repetitions is 2 times or more. Particularly, in Examples 2 to 4 in which the number of repetitions is 4 times or more, the characteristics of 5 times or more are obtained as compared with Comparative Example 1 of 1 time.
  • Example 5 Using the solution A, the spin coat rotation speed is increased and repeated twice> A simple TFT using a solution A, a p-type Si substrate with a thermal oxide film (film thickness 100 nm) as a substrate, and using the thermal oxide film as a gate insulating film was fabricated.
  • a solution A is spin-coated at a rotational speed of 5000 rpm for 30 seconds on a p-type Si 1 inch square substrate with a thermal oxide film, and then dried for 1 minute on a hot plate heated to 60 ° C. A precursor film was obtained.
  • the obtained metal oxide semiconductor precursor film was converted into a metal oxide semiconductor film by performing an ultraviolet irradiation treatment under the following conditions.
  • an ultraviolet irradiation device a UV ozone cleaner (manufactured by Filgen, UV253H) using a low-pressure mercury lamp was used.
  • the sample was set on a glass plate having a thickness of 40 mm, and the distance between the lamp and the sample was 5 mm.
  • the ultraviolet illuminance at the sample position at a wavelength of 254 nm was measured using an ultraviolet light meter (manufactured by Oak Manufacturing Co., Ltd., UV-M10, photoreceiver UV-25). The maximum value was reached in 3 minutes after the lamp was turned on, and was 15 mW / cm 2 .
  • ultraviolet irradiation was performed for 90 minutes. During UV irradiation, nitrogen was always flowed at 6 L / min. When the substrate temperature at the time of ultraviolet irradiation treatment was monitored with a thermolabel, it showed 160 ° C.
  • a source / drain electrode was formed on the obtained oxide semiconductor film by vapor deposition.
  • the source / drain electrodes were formed by pattern deposition using a metal mask, and Ti was deposited to a thickness of 50 nm.
  • the source / drain electrode size was 1 mm square, and the distance between the electrodes was 0.2 mm.
  • V g -I d characteristics transistor characteristics (V g -I d characteristics).
  • the measurement of the V g -I d characteristic is performed by fixing the drain voltage (V d ) to +1 V, changing the gate voltage (V g ) within a range of ⁇ 15 V to +15 V, and drain current (I d ) at each gate voltage. It was performed by measuring.
  • Example 5 The mobility of Example 5 is 1.9 cm 2 / Vs, and even when the same solution A as in Comparative Example 1 is used, formation of a metal oxide semiconductor precursor film by coating and drying of a solution containing metal nitrate The transistor characteristic improvement effect was confirmed by performing the process and the process of converting the metal oxide semiconductor precursor film into the metal oxide semiconductor film a plurality of times.
  • ⁇ Comparative Example 2 Application / drying once using solution A, and UV irradiation treatment twice> A simple TFT using a solution A, a p-type Si substrate with a thermal oxide film (film thickness 100 nm) as a substrate, and using the thermal oxide film as a gate insulating film was fabricated.
  • a solution A is spin-coated for 30 seconds at a rotational speed of 1500 rpm on this p-type Si 1 inch square substrate with a thermal oxide film, and then dried for 1 minute on a hot plate heated to 60 ° C. A precursor film was obtained.
  • the obtained metal oxide semiconductor precursor film was converted into a metal oxide semiconductor film by performing an ultraviolet irradiation treatment under the following conditions.
  • an ultraviolet irradiation device a UV ozone cleaner (manufactured by Filgen, UV253H) using a low-pressure mercury lamp was used.
  • the sample was set on a glass plate having a thickness of 40 mm, and the distance between the lamp and the sample was 5 mm.
  • the ultraviolet illuminance at the sample position at a wavelength of 254 nm was measured using an ultraviolet light meter (manufactured by Oak Manufacturing Co., Ltd., UV-M10, photoreceiver UV-25). The maximum value was reached in 3 minutes after the lamp was turned on, and was 15 mW / cm 2 .
  • ultraviolet irradiation was performed for 90 minutes. During UV irradiation, nitrogen was always flowed at 6 L / min. When the substrate temperature at the time of ultraviolet irradiation treatment was monitored with a thermolabel, it showed 160 ° C.
  • the ultraviolet irradiation treatment was again performed under the same conditions.
  • the film thickness of the metal oxide semiconductor film of the comparative example 2 was confirmed by cross-sectional TEM observation, it was 10.2 nm, and it was confirmed that there was no big difference in film thickness with respect to the Example and the comparative example mentioned above.
  • a source / drain electrode was formed on the obtained oxide semiconductor film by vapor deposition.
  • the source / drain electrodes were formed by pattern deposition using a metal mask, and Ti was deposited to a thickness of 50 nm.
  • the source / drain electrode size was 1 mm square, and the distance between the electrodes was 0.2 mm.
  • V g -I d characteristics transistor characteristics (V g -I d characteristics).
  • the measurement of the V g -I d characteristic is performed by fixing the drain voltage (V d ) to +1 V, changing the gate voltage (V g ) within a range of ⁇ 15 V to +15 V, and drain current (I d ) at each gate voltage. It was performed by measuring.
  • the mobility of Comparative Example 2 was 0.5 cm 2 / Vs, and it was confirmed that the effect of improving the characteristics could not be obtained even if the coating / drying was performed once and the ultraviolet irradiation treatment was performed several times.
  • the obtained metal oxide semiconductor precursor film was converted into a metal oxide semiconductor film by performing an ultraviolet irradiation treatment under the following conditions.
  • an ultraviolet irradiation device a UV ozone cleaner (manufactured by Filgen, UV253H) using a low-pressure mercury lamp was used.
  • the sample was set on a glass plate having a thickness of 40 mm, and the distance between the lamp and the sample was 5 mm.
  • the ultraviolet illuminance at the sample position at a wavelength of 254 nm was measured using an ultraviolet light meter (manufactured by Oak Manufacturing Co., Ltd., UV-M10, photoreceiver UV-25). The maximum value was reached in 3 minutes after the lamp was turned on, and was 15 mW / cm 2 .
  • ultraviolet irradiation was performed for 90 minutes. During UV irradiation, nitrogen was always flowed at 6 L / min. When the substrate temperature at the time of ultraviolet irradiation treatment was monitored with a thermolabel, it showed 160 ° C. When the film thickness of the metal oxide semiconductor film of the comparative example 3 was confirmed by cross-sectional TEM observation, it was 5.2 nm.
  • the source / drain electrodes were formed by vapor deposition on the obtained oxide semiconductor film.
  • the source / drain electrodes were formed by pattern deposition using a metal mask, and Ti was deposited to a thickness of 50 nm.
  • the source / drain electrode size was 1 mm square, and the distance between the electrodes was 0.2 mm.
  • V g -I d characteristics transistor characteristics (V g -I d characteristics).
  • the measurement of the V g -I d characteristic is performed by fixing the drain voltage (V d ) to +1 V, changing the gate voltage (V g ) within a range of ⁇ 15 V to +15 V, and drain current (I d ) at each gate voltage. It was performed by measuring.
  • the mobility of Comparative Example 3 was 0.2 cm 2 / Vs, and it was confirmed that even if a low-concentration solution was used, the effect of improving the characteristics could not be obtained unless coating / drying and ultraviolet irradiation treatment were performed alternately several times. It was done.
  • Example 1-5 XRR analysis was performed on the metal oxide semiconductor films of Example 1-5 and Comparative Example 1-3.
  • the measurement was carried out with ATX-G manufactured by Rigaku Corporation, a scanning speed of 0.2 ° / min and a step width of 0.001 °.
  • the range of 0.3 to 4.0 ° of the obtained XRR spectrum was set as the analysis range.
  • Example 1-5 and Comparative Example 1-3 have good R values of 0.01 or less by fitting using model simulation results in which the indium oxide layer has 3 to 5 layers. Showed a match.
  • Table 3 below shows the average film density of Example 1-5 and Comparative Example 1-3.
  • Example 6> Using the solution F (indium nitrate concentration: 0.035 mol / L), a p-type Si substrate with a thermal oxide film (film thickness 100 nm) was used as a substrate, and a simple TFT using a thermal oxide film as a gate insulating film was produced. .
  • a solution F is spin-coated for 30 seconds at a rotation speed of 1500 rpm on this p-type Si 1 inch square substrate with a thermal oxide film, and then dried for 1 minute on a hot plate heated to 60 ° C. A precursor film was obtained.
  • the obtained metal oxide semiconductor precursor film was converted into a metal oxide semiconductor film by performing an ultraviolet irradiation treatment under the following conditions.
  • a UV ozone cleaner manufactured by Filgen, UV253H
  • a low-pressure mercury lamp was used as an ultraviolet irradiation device.
  • the sample was set on a glass plate having a thickness of 40 mm, and the distance between the lamp and the sample was 5 mm.
  • the ultraviolet illuminance at the sample position at a wavelength of 254 nm was measured using an ultraviolet light meter (manufactured by Oak Manufacturing Co., Ltd., UV-M10, photoreceiver UV-25). The maximum value was reached in 3 minutes after the lamp was turned on, and was 15 mW / cm 2 .
  • ultraviolet irradiation was performed for 90 minutes. During UV irradiation, nitrogen was always flowed at 6 L / min. When the substrate temperature at the time of ultraviolet irradiation treatment was monitored with a thermolabel, it showed 160 ° C. After the application and drying of the solution F and the conversion to the metal oxide semiconductor film by UV irradiation are repeated twice, the solution F is further applied and dried under the condition that the maximum substrate temperature is 100 ° C. Conversion to a metal oxide semiconductor film by ultraviolet irradiation was performed. A source / drain electrode was formed on the obtained oxide semiconductor film by vapor deposition.
  • the source / drain electrodes were formed by pattern deposition using a metal mask, and Ti was deposited to a thickness of 50 nm.
  • the source / drain electrode size was 1 mm square, and the distance between the electrodes was 0.2 mm.
  • the mobility of Example 6 was 2.5 cm 2 / Vs.
  • Example 7 Using the solution F (indium nitrate concentration: 0.035 mol / L), a p-type Si substrate with a thermal oxide film (film thickness 100 nm) was used as a substrate, and a simple TFT using a thermal oxide film as a gate insulating film was produced. .
  • a solution F is spin-coated for 30 seconds at a rotation speed of 1500 rpm on this p-type Si 1 inch square substrate with a thermal oxide film, and then dried for 1 minute on a hot plate heated to 60 ° C. A precursor film was obtained.
  • the obtained metal oxide semiconductor precursor film was converted into a metal oxide semiconductor film by performing an ultraviolet irradiation treatment under the following conditions.
  • a UV ozone cleaner manufactured by Filgen, UV253H
  • a low-pressure mercury lamp was used as an ultraviolet irradiation device.
  • the sample was set on a glass plate having a thickness of 40 mm, and the distance between the lamp and the sample was 5 mm.
  • the ultraviolet illuminance at the sample position at a wavelength of 254 nm was measured using an ultraviolet light meter (manufactured by Oak Manufacturing Co., Ltd., UV-M10, photoreceiver UV-25). The maximum value was reached in 3 minutes after the lamp was turned on, and was 15 mW / cm 2 .
  • UV irradiation After flowing nitrogen at 6 L / min for 10 minutes in the ultraviolet irradiation treatment chamber, ultraviolet irradiation was performed for 90 minutes. During UV irradiation, nitrogen was always flowed at 6 L / min. When the substrate temperature at the time of ultraviolet irradiation treatment was monitored with a thermolabel, it showed 160 ° C. Application / drying of the solution F and conversion to a metal oxide semiconductor film by ultraviolet irradiation were repeated three times alternately. A source / drain electrode was formed on the obtained oxide semiconductor film by vapor deposition. The source / drain electrodes were formed by pattern deposition using a metal mask, and Ti was deposited to a thickness of 50 nm. The source / drain electrode size was 1 mm square, and the distance between the electrodes was 0.2 mm. The mobility of Example 7 was 3.0 cm 2 / Vs.
  • ⁇ Comparative example 4> Using the solution F (indium nitrate concentration: 0.035 mol / L), a p-type Si substrate with a thermal oxide film (film thickness 100 nm) was used as a substrate, and a simple TFT using a thermal oxide film as a gate insulating film was produced. . A solution F is spin-coated for 30 seconds at a rotation speed of 1500 rpm on this p-type Si 1 inch square substrate with a thermal oxide film, and then dried for 1 minute on a hot plate heated to 60 ° C. A precursor film was obtained. The obtained metal oxide semiconductor precursor film was converted into a metal oxide semiconductor film by performing an ultraviolet irradiation treatment under the following conditions.
  • solution F indium nitrate concentration: 0.035 mol / L
  • a solution F is spin-coated for 30 seconds at a rotation speed of 1500 rpm on this p-type Si 1 inch square substrate with a thermal oxide film, and then dried for 1 minute on a hot plate heated to 60
  • a UV ozone cleaner manufactured by Filgen, UV253H
  • a low-pressure mercury lamp was used as an ultraviolet irradiation device.
  • the sample was set on a glass plate having a thickness of 40 mm, and the distance between the lamp and the sample was 5 mm.
  • the ultraviolet illuminance at the sample position at a wavelength of 254 nm was measured using an ultraviolet light meter (manufactured by Oak Manufacturing Co., Ltd., UV-M10, photoreceiver UV-25). The maximum value was reached in 3 minutes after the lamp was turned on, and was 15 mW / cm 2 .
  • ultraviolet irradiation was performed for 30 minutes. During UV irradiation, nitrogen was always flowed at 6 L / min. When the substrate temperature at the time of ultraviolet irradiation treatment was monitored with a thermolabel, it showed 100 ° C. After the application and drying of the solution F and the conversion to the metal oxide semiconductor film by ultraviolet irradiation were repeated twice, the solution F was further applied and dried, under the condition that the maximum substrate temperature reached 160 ° C. Conversion to a metal oxide semiconductor film by ultraviolet irradiation was performed. A source / drain electrode was formed on the obtained oxide semiconductor film by vapor deposition.
  • the source / drain electrodes were formed by pattern deposition using a metal mask, and Ti was deposited to a thickness of 50 nm.
  • the source / drain electrode size was 1 mm square, and the distance between the electrodes was 0.2 mm.
  • the mobility of Comparative Example 4 was 0.5 cm 2 / Vs.
  • Table 4 below shows the average film densities of Examples 6 and 7 and Comparative Example 4.
  • a simple TFT using a thermal oxide film as a gate insulating film was prepared using a p-type Si substrate with a thermal oxide film (film thickness 100 nm) as the substrate.
  • the prepared solution A was spin-coated on a p-type Si 1 inch square substrate with a thermal oxide film at a rotational speed of 1500 rpm for 30 seconds, and then dried for 1 minute on a hot plate heated to 60 ° C.
  • a semiconductor precursor film was obtained.
  • the obtained metal oxide semiconductor precursor film was converted into a metal oxide semiconductor film by performing a heat treatment with a hot plate at 250 ° C. for 90 minutes in the air.
  • a source / drain electrode was formed on the obtained oxide semiconductor film by vapor deposition.
  • the source / drain electrodes were formed by pattern deposition using a metal mask, and Ti was deposited to a thickness of 50 nm.
  • the source / drain electrode size was 1 mm square, and the distance between the electrodes was 0.2 mm.
  • V g -I d characteristics transistor characteristics (V g -I d characteristics).
  • the measurement of the V g -I d characteristic is performed by fixing the drain voltage (V d ) to +1 V, changing the gate voltage (V g ) within a range of ⁇ 15 V to +15 V, and drain current (I d ) at each gate voltage. It was performed by measuring.
  • the mobility of Comparative Example 5 was 0.5 cm 2 / Vs.
  • Example 8> A simple TFT using a thermal oxide film as a gate insulating film was prepared using a p-type Si substrate with a thermal oxide film (film thickness 100 nm) as the substrate.
  • the prepared solution E was spin-coated at a rotational speed of 1500 rpm for 30 seconds on a p-type Si 1 inch square substrate with a thermal oxide film, and then dried for 1 minute on a hot plate heated to 60 ° C.
  • a semiconductor precursor film was obtained.
  • the obtained metal oxide semiconductor precursor film was converted into a metal oxide semiconductor film by performing a heat treatment with a hot plate at 250 ° C. for 90 minutes in the air.
  • the application / drying of the solution and the conversion to the metal oxide semiconductor film were alternately repeated 12 times.
  • a source / drain electrode was formed on the obtained oxide semiconductor film by vapor deposition.
  • the source / drain electrodes were formed by pattern deposition using a metal mask, and Ti was deposited to a thickness of 50 nm.
  • the source / drain electrode size was 1 mm square, and the distance between the electrodes was 0.2 mm.
  • V g -I d characteristics transistor characteristics (V g -I d characteristics).
  • the measurement of the V g -I d characteristic is performed by fixing the drain voltage (V d ) to +1 V, changing the gate voltage (V g ) within a range of ⁇ 15 V to +15 V, and drain current (I d ) at each gate voltage. It was performed by measuring.
  • the mobility of Example 8 was 8.3 cm 2 / Vs.
  • Table 5 shows the average film density of Example 8 and Comparative Example 5.

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Abstract

La présente invention porte sur un procédé pour fabriquer un film d'oxyde métallique par répétition de manière alternée des étapes suivantes au moins deux fois : une étape pour enrober un substrat avec une solution contenant un nitrate métallique, et former un film de précurseur d'oxyde métallique par séchage du film enrobé ; et une étape pour modifier le film de précurseur d'oxyde métallique en un film d'oxyde métallique. Durant les étapes réalisées au moins deux fois pour modifier le film de précurseur d'oxyde métallique en le film d'oxyde métallique, le film de précurseur d'oxyde métallique est modifié en le film d'oxyde métallique avec une température de substrat atteinte maximale de 120-250°C. La présente invention porte en outre sur un film d'oxyde métallique fabriqué par ce procédé, et un dispositif le comportant.
PCT/JP2014/079768 2013-12-06 2014-11-10 Procédé pour fabriquer un film d'oxyde métallique, film d'oxyde métallique, transistor en couches minces, dispositif d'affichage, capteur d'image et capteur de rayons x WO2015083500A1 (fr)

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TWI567805B (zh) * 2015-07-03 2017-01-21 友達光電股份有限公司 薄膜電晶體及其製作方法
JP2019098282A (ja) * 2017-12-06 2019-06-24 株式会社Ｓｃｒｅｅｎホールディングス 光照射装置および薄膜形成装置
CN111088484A (zh) * 2019-11-14 2020-05-01 Tcl华星光电技术有限公司 金属氧化物薄膜的制备方法
CN115522184B (zh) * 2022-10-09 2024-03-19 华能国际电力股份有限公司 一种ysz涂层、镍铁基高温合金及其制备方法

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WO2010044332A1 (fr) * 2008-10-14 2010-04-22 コニカミノルタホールディングス株式会社 Transistor à film mince et son procédé de fabrication
JP2010182852A (ja) * 2009-02-05 2010-08-19 Konica Minolta Holdings Inc 金属酸化物半導体、その製造方法及び薄膜トランジスタ
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