WO2015083500A1 - Method for producing metal oxide film, metal oxide film, thin-film transistor, display device, image sensor, and x-ray sensor - Google Patents

Method for producing metal oxide film, metal oxide film, thin-film transistor, display device, image sensor, and x-ray sensor 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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French (fr)
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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    • H01L21/02612—Formation types
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    • 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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    • H01L27/144—Devices controlled by radiation
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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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    • 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.

Abstract

The present invention provides a method for producing a metal oxide film by alternatingly repeating the following steps two or more times: a step for coating a substrate with a solution containing a metal nitrate, and forming a metal oxide precursor film by drying the coated film; and a step for changing the metal oxide precursor film into a metal oxide film. During the steps performed two or more times for changing the metal oxide precursor film into the metal oxide film, the metal oxide precursor film is changed into the metal oxide film with a maximum attained substrate temperature of 120-250°C. The present invention further provides a metal oxide film produced by this method, and a device provided with the same.

Description

金属酸化物膜の製造方法、金属酸化物膜、薄膜トランジスタ、表示装置、イメージセンサ及びＸ線センサMetal oxide film manufacturing method, metal oxide film, thin film transistor, display device, image sensor, and X-ray sensor
　本発明は、金属酸化物膜の製造方法、金属酸化物膜、薄膜トランジスタ、表示装置、イメージセンサ及びＸ線センサに関する。 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.
　金属酸化物半導体膜は真空成膜法による製造において実用化がなされ、現在注目を集めている。
　一方で、簡便に、低温で、かつ大気圧下で高い半導体特性を有する金属酸化物膜を形成することを目的とした、液相プロセスによる金属酸化物膜の作製に関して研究開発が盛んに行われている。 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.
On the other hand, 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.
　例えば、硝酸塩等の金属塩を含む溶液を塗布し、金属酸化物半導体層を形成する手法が開示されている（国際公開第２００９／０８１８６２号参照）。 For example, a method of applying a solution containing a metal salt such as nitrate to form a metal oxide semiconductor layer is disclosed (see International Publication No. 2009/081862).
　また、金属アルコキシド又は金属塩を主原料として得られる金属酸化物の前駆体ゾルを被塗布物の表面に塗布して被塗布物表面に金属酸化物ゲルの薄膜を形成する工程と、金属酸化物ゲルの薄膜に対して波長が３６０ｎｍ以下である紫外光を照射して金属酸化物ゲルを結晶化させる工程とを複数回繰り返して行う金属酸化物膜の製造方法が開示されている（特開２０００－２４７６０８号公報参照）。 A step of applying a metal oxide precursor sol obtained from a metal alkoxide or metal salt as a main raw material to the surface of the object to be coated to form a metal oxide gel thin film on the surface of the object to be coated; 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).
　また、有機金属化合物および／または有機金属錯体を含む膜を形成する工程、前記膜にエネルギー線を照射し、照射部位に位置する膜に含まれる有機成分を分解して金属および／または金属酸化物を析出させる工程、を含む方法が開示されている（特開２００５－２１３５６７号公報参照）。 Also, 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).
　また、溶液を基板上に塗布し、紫外線を用いることで１５０℃以下の低温で高い輸送特性を有する薄膜トランジスタ(ＴＦＴ：Ｔｈｉｎ　Ｆｉｌｍ　Ｔｒａｎｓｉｓｔｏｒ）を製造する手法が報告されている（Ｎａｔｕｒｅ，　４８９　（２０１２）　１２８．参照）。 In addition, a method of manufacturing a thin film transistor (TFT: Thin Film Transistor) having a high transport property at a low temperature of 150 ° C. or lower by applying a solution on a substrate and using ultraviolet rays has been reported (Nature, 489 (2012)). 128.).
　本発明は、緻密な金属酸化物膜を比較的低温で、かつ大気圧下で製造することができる金属酸化物膜の製造方法及び金属酸化物膜、並びに、高い移動度を有する薄膜トランジスタ、表示装置、イメージセンサ及びＸ線センサを提供することを目的とする。 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.
　上記目的を達成するため、以下の発明が提供される。
＜１＞　金属硝酸塩を含む溶液を基板上に塗布し、塗布膜を乾燥させて金属酸化物前駆体膜を形成する工程と、金属酸化物前駆体膜を金属酸化物膜に転化する工程とを交互に２回以上繰り返すことを含み、
　金属酸化物前駆体膜を金属酸化物膜に転化する少なくとも２回の工程において、基板の最高到達温度を１２０℃以上２５０℃以下にして金属酸化物前駆体膜を金属酸化物膜に転化する金属酸化物膜の製造方法。
＜２＞　金属酸化物前駆体膜を金属酸化物膜に転化する全ての工程において、基板の最高到達温度を１２０℃以上にして金属酸化物前駆体膜を金属酸化物膜に転化する＜１＞に記載の金属酸化物膜の製造方法。
＜３＞　金属酸化物前駆体膜を金属酸化物膜に転化する全ての工程において、基板の最高到達温度を２００℃以下にする＜１＞又は＜２＞に記載の金属酸化物膜の製造方法。
＜４＞　金属酸化物前駆体膜を金属酸化物膜に転化する工程が、金属酸化物前駆体膜に紫外線を照射する工程を含む＜１＞～＜３＞のいずれか１つに記載の金属酸化物膜の製造方法。
＜５＞　金属酸化物前駆体膜を形成する工程と、金属酸化物前駆体膜を金属酸化物膜に転化する工程とを交互に４回以上繰り返す＜１＞～＜４＞のいずれか１つに記載の金属酸化物膜の製造方法。
＜６＞　金属硝酸塩を含む溶液が、少なくとも硝酸インジウムを含む＜１＞～＜５＞のいずれか１つに記載の金属酸化物膜の製造方法。
＜７＞　硝酸インジウムを含む溶液が、亜鉛、錫、ガリウム及びアルミニウムから選ばれる少なくとも１つの金属原子を含む化合物をさらに含有する＜６＞に記載の金属酸化物膜の製造方法。
＜８＞　金属硝酸塩を含む溶液の金属モル濃度が、０．０１ｍｏｌ／Ｌ以上０．５ｍｏｌ／Ｌ以下である＜１＞～＜７＞のいずれか１つに記載の金属酸化物膜の製造方法。
＜９＞　金属酸化物前駆体膜を形成する工程と、金属酸化物前駆体膜を金属酸化物膜に転化する工程とを各々１回行って得られる金属酸化物膜の平均膜厚が６ｎｍ以下である＜１＞～＜８＞のいずれか１つに記載の金属酸化物膜の製造方法。
＜１０＞　金属酸化物前駆体膜を形成する工程と、金属酸化物前駆体膜を金属酸化物膜に転化する工程とを各々１回行って得られる金属酸化物膜の平均膜厚が２ｎｍ以下である＜９＞に記載の金属酸化物膜の製造方法。
＜１１＞　金属硝酸塩を含む溶液が、メタノール又はメトキシエタノールを含む＜１＞～＜１０＞のいずれか１つに記載の金属酸化物膜の製造方法。
＜１２＞　金属酸化物前駆体膜を金属酸化物膜に転化する工程が、金属酸化物前駆体膜に対し、波長３００ｎｍ以下の紫外線を１０ｍＷ／ｃｍ２以上の強度で照射する工程を含む＜４＞～＜１１＞のいずれか１つに記載の金属酸化物膜の製造方法。
＜１３＞　金属酸化物前駆体膜に紫外線を照射する際に用いる光源が、低圧水銀ランプである＜１２＞に記載の金属酸化物膜の製造方法。
＜１４＞　金属酸化物前駆体膜を形成する工程において、塗布膜を乾燥させる際の基板の温度が３５℃以上１００℃以下である＜１＞～＜１３＞のいずれか１つに記載の金属酸化物膜の製造方法。
＜１５＞　金属酸化物前駆体膜を形成する工程において、金属硝酸塩を含む溶液を、インクジェット法、ディスペンサー法、凸版印刷法、及び凹版印刷法から選択される少なくとも一種の塗布法により塗布する＜１＞～＜１４＞のいずれか１つに記載の金属酸化物膜の製造方法。 In order to achieve the above object, the following invention is provided.
<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.
<2> In all steps of converting a metal oxide precursor film into a metal oxide film, the maximum reached temperature of the substrate is set to 120 ° C. or higher to convert the metal oxide precursor film into a metal oxide film <1> The manufacturing method of the metal oxide film as described in 2.
<3> The method for producing a metal oxide film according to <1> or <2>, wherein the maximum temperature reached by the substrate is 200 ° C. or lower in all steps of converting the metal oxide precursor film into the metal oxide film. .
<4> The metal according to any one of <1> to <3>, wherein 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 rays. Manufacturing method of oxide film.
<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. The manufacturing method of the metal oxide film as described in 2.
<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.
<7> The method for producing a metal oxide film according to <6>, wherein 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 method for producing a metal oxide film according to any one of <1> to <8>, wherein
<10> 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.
<12> 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 The method for producing a metal oxide film according to any one of> to <11>.
<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. or more and 100 ° C. or less. Manufacturing method of oxide film.
<15> In the step of forming a metal oxide precursor film, 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 The method for producing a metal oxide film according to any one of> to <14>.
＜１６＞　＜１＞～＜１５＞のいずれか１つに記載の金属酸化物膜の製造方法を用いて作製された金属酸化物膜。
＜１７＞　金属酸化物半導体膜である＜１６＞に記載の金属酸化物膜。
＜１８＞　＜１７＞に記載の金属酸化物膜を含む活性層と、ソース電極と、ドレイン電極と、ゲート絶縁膜と、ゲート電極とを有する薄膜トランジスタ。
＜１９＞　＜１８＞に記載の薄膜トランジスタを備えた表示装置。
＜２０＞　＜１８＞に記載の薄膜トランジスタを備えたイメージセンサ。
＜２１＞　＜１８＞に記載の薄膜トランジスタを備えたＸ線センサ。 <16> A metal oxide film produced using the method for producing a metal oxide film according to any one of <1> to <15>.
<17> 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.
<19> A display device comprising the thin film transistor according to <18>.
<20> An image sensor comprising the thin film transistor according to <18>.
<21> An X-ray sensor comprising the thin film transistor according to <18>.
　本発明によれば、緻密な金属酸化物膜を比較的低温で、かつ大気圧下で製造することができる金属酸化物膜の製造方法及び金属酸化物膜、並びに、高い移動度を有する薄膜トランジスタ、表示装置、イメージセンサ及びＸ線センサが提供される。 According to the present invention, a metal oxide film manufacturing method and a metal oxide film capable of manufacturing a dense metal oxide film at a relatively low temperature and atmospheric pressure, and a thin film transistor having high mobility, A display device, an image sensor, and an X-ray sensor are provided.
本発明により製造される薄膜トランジスタの一例（トップゲート－トップコンタクト型）の構成を示す概略図である。It is the schematic which shows the structure of an example (top gate-top contact type) of the thin-film transistor manufactured by this invention. 本発明により製造される薄膜トランジスタの一例（トップゲート－ボトムコンタクト型）の構成を示す概略図である。It is the schematic which shows the structure of an example (top gate-bottom contact type) of the thin-film transistor manufactured by this invention. 本発明により製造される薄膜トランジスタの一例（ボトムゲート－トップコンタクト型）の構成を示す概略図である。It is the schematic which shows the structure of an example (bottom gate-top contact type) of the thin-film transistor manufactured by this invention. 本発明により製造される薄膜トランジスタの一例（ボトムゲート－ボトムコンタクト型）の構成を示す概略図である。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. 実施形態の液晶表示装置の一部分を示す概略断面図である。It is a schematic sectional drawing which shows a part of liquid crystal display device of embodiment. 図５に示す液晶表示装置の電気配線の概略構成図である。It is a schematic block diagram of the electrical wiring of the liquid crystal display device shown in FIG. 実施形態の有機ＥＬ表示装置の一部分を示す概略断面図である。It is a schematic sectional drawing which shows a part of organic EL display apparatus of embodiment. 図７に示す有機ＥＬ表示装置の電気配線の概略構成図である。It is a schematic block diagram of the electrical wiring of the organic electroluminescence display shown in FIG. 実施形態のＸ線センサアレイの一部分を示す概略断面図である。It is a schematic sectional drawing which shows a part of X-ray sensor array of embodiment. 図９に示すＸ線センサアレイの電気配線の概略構成図である。It is a schematic block diagram of the electrical wiring of the X-ray sensor array shown in FIG. 実施例１～４及び比較例１で作製した簡易型ＴＦＴのＶｇ－Ｉｄ特性を示す図である。It is a diagram showing, V g -I d characteristics of the simplified TFT fabricated in Examples 1-4 and Comparative Example 1. 前駆体膜形成工程及び転化工程の繰り返し回数と、ＴＦＴの移動度との関係を示す図である。It is a figure which shows the relationship between the repetition frequency of a precursor film | membrane formation process and a conversion process, and the mobility of TFT. 本発明によって金属酸化物膜を製造する装置の一例を示す概略図である。It is the schematic which shows an example of the apparatus which manufactures a metal oxide film by this invention.
　以下、添付の図面を参照しながら、本発明の金属酸化物膜の製造方法、並びに本発明により製造される金属酸化物膜及びそれを備えた薄膜トランジスタ、表示装置、Ｘ線センサ等について具体的に説明する。
　なお、図中、同一又は対応する機能を有する部材（構成要素）には同じ符号を付して適宜説明を省略する。また、本明細書において「～」の記号により数値範囲を示す場合、下限値及び上限値として記載されている数値が含まれる。
　また、本発明に係る金属酸化物膜の導電性は限定されず、本発明は、酸化物半導体膜、酸化物導電膜、又は酸化物絶縁膜の製造に適用することができるが、代表例として、ＴＦＴの活性層（半導体層）に適用することができる金属酸化物半導体膜の製造方法について主に説明する。 Hereinafter, a method for producing a metal oxide film of the present invention, a metal oxide film produced by the present invention, a thin film transistor including the same, a display device, an X-ray sensor, and the like will be specifically described with reference to the accompanying drawings. explain.
In the drawings, members (components) having the same or corresponding functions are denoted by the same reference numerals and description thereof is omitted as appropriate. In the present specification, when a numerical range is indicated by the symbol “˜”, numerical values described as the lower limit and the upper limit are included.
Further, the conductivity of the metal oxide film according to the present invention is not limited, and the present invention can be applied to the manufacture of an oxide semiconductor film, an oxide conductive film, or an oxide insulating film. A method for manufacturing a metal oxide semiconductor film that can be applied to an active layer (semiconductor layer) of a TFT will be mainly described.
　本発明者らは詳細な研究を通して、金属硝酸塩を用いた溶液の塗布及び乾燥による金属酸化物前駆体膜の形成と加熱による金属酸化物膜への転化を交互に複数回実施することにより、膜密度の向上効果が得られることを見出した。
　特に、本発明の方法によって金属酸化物半導体膜を作製することにより、高い輸送特性を有する薄膜トランジスタを大気圧下、比較的低温で作製できることから薄膜液晶ディスプレイや有機ＥＬ等の表示装置、特にフレキシブルディスプレイを提供することが可能となる。 Through detailed research, 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.
In particular, by producing 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.
＜金属酸化物膜の製造方法＞
　本発明の金属酸化物膜の製造方法は、金属硝酸塩を含む溶液を基板上に塗布し、塗布膜を乾燥させて金属酸化物前駆体膜を形成する工程と、金属酸化物前駆体膜を金属酸化物膜に転化する工程とを交互に２回以上繰り返すことを含み、金属酸化物前駆体膜を金属酸化物膜に転化する少なくとも２回の工程において、基板の最高到達温度を１２０℃以上２５０℃以下にして金属酸化物前駆体膜を金属酸化物膜に転化する。 <Method for producing metal oxide film>
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 step of converting to an oxide film alternately and twice or more, and in at least two steps of converting the metal oxide precursor film to the metal oxide film, the maximum temperature of the substrate is 120 ° C. or more and 250 ° C. The metal oxide precursor film is converted into a metal oxide film at a temperature lower than the temperature.
　本発明によって緻密な金属酸化物膜を形成することができる理由は定かでないが、以下のように推測される。
　金属酸化物前駆体膜が金属酸化物膜に転化される際に、膜中から硝酸成分や金属に配位している成分が脱離する。その状態で再度溶液を塗布することで、脱離した部分に溶液が含浸し、結果として新たに金属と酸素の結合が形成されることにより緻密な金属酸化物膜が形成されるものと考えられる。 The reason why a dense metal oxide film can be formed by the present invention is not clear, but is presumed as follows.
When 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. By applying the solution again in this state, 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. .
［金属酸化物前駆体膜の形成工程（工程Ａ）］
　まず、金属酸化物膜を形成するための金属硝酸塩を含む溶液と、金属酸化物膜を形成するための基板を用意し、金属硝酸塩を含む溶液を基板上に塗布し、塗布膜を乾燥させて金属酸化物前駆体膜を形成する。 [Formation Step of Metal Oxide Precursor Film (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.
（基板）
　基板の形状、構造、大きさ等については特に制限はなく、目的に応じて適宜選択することができる。基板の構造は単層構造であってもよいし、積層構造であってもよい。 (substrate)
There is no restriction | limiting in particular about the shape of a board | substrate, a structure, a magnitude | size, It can select suitably according to the objective. The structure of the substrate may be a single layer structure or a laminated structure.
　基板を構成する材料としては特に限定はなく、ガラス、ＹＳＺ（Yttria－Stabilized Zirconia；イットリウム安定化ジルコニウム）等の無機材料、樹脂、樹脂複合材料等からなる基板を用いることができる。中でも軽量である点、可撓性を有する点から樹脂基板又は樹脂複合材料からなる基板（樹脂複合材料基板）が好ましい。
　具体的には、ポリブチレンテレフタレート、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート、ポリスチレン、ポリカーボネート、ポリスルホン、ポリエーテルスルホン、ポリアリレート、アリルジグリコールカーボネート、ポリアミド、ポリイミド、ポリアミドイミド、ポリエーテルイミド、ポリベンズアゾール、ポリフェニレンサルファイド、ポリシクロオレフィン、ノルボルネン樹脂、ポリクロロトリフルオロエチレン等のフッ素樹脂、液晶ポリマー、アクリル樹脂、エポキシ樹脂、シリコーン樹脂、アイオノマー樹脂、シアネート樹脂、架橋フマル酸ジエステル、環状ポリオレフィン、芳香族エーテル、マレイミド・オレフィン、セルロース、エピスルフィド化合物等の合成樹脂基板が挙げられる。
　また、無機材料と樹脂との複合材料に含まれる無機材料としては、酸化珪素粒子、金属ナノ粒子、無機酸化物ナノ粒子、無機窒化物ナノ粒子等の無機粒子、カーボン繊維、カーボンナノチューブ等の炭素材料、ガラスフェレーク、ガラスファイバー、ガラスビーズ等のガラス材料が挙げられる。
　また、樹脂と粘土鉱物との複合プラスチック材料、樹脂と雲母派生結晶構造を有する粒子との複合プラスチック材料、樹脂と薄いガラスとの間に少なくとも１つの接合界面を有する積層プラスチック材料、無機層と有機層を交互に積層することで少なくとも１つの接合界面を有するバリア性能を有する複合材料等が挙げられる。
　また、ステンレス基板又はステンレスと異種金属を積層した金属多層基板、アルミニウム基板又は表面に酸化処理（例えば陽極酸化処理）を施すことで表面の絶縁性を向上させた酸化皮膜付きのアルミニウム基板等を用いることもできる。
　また、樹脂基板又は樹脂複合材料基板は、耐熱性、寸法安定性、耐溶剤性、電気絶縁性、加工性、低通気性、及び低吸湿性等に優れていることが好ましい。樹脂基板又は樹脂複合材料基板は、水分、酸素等の透過を防止するためのガスバリア層や、基板の平坦性や下部電極との密着性を向上するためのアンダーコート層等を備えていてもよい。 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. Of these, 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.
Specifically, polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, Fluorine resin such as polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, Synthetic resin substrates such as aromatic ether, maleimide / olefin, cellulose, episulfide compounds, etc. .
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.
In addition, 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. You can also.
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. .
　本発明で用いる基板の厚みに特に制限はないが、５０μｍ以上５００μｍ以下であることが好ましい。基板の厚みが５０μｍ以上であると、基板自体の平坦性がより向上する。また、基板の厚みが５００μｍ以下であると、基板自体の可撓性がより向上し、フレキシブルデバイス用基板としての使用がより容易となる。 The thickness of the substrate used in the present invention is not particularly limited, but is preferably 50 μm or more and 500 μm or less. When the thickness of the substrate is 50 μm or more, the flatness of the substrate itself is further improved. Further, when the thickness of the substrate is 500 μm or less, the flexibility of the substrate itself is further improved, and the use as a substrate for a flexible device becomes easier.
（金属硝酸塩を含む溶液）
　金属硝酸塩を含む溶液は、金属硝酸塩等の溶質を、溶液が所望の濃度となるように秤量し、溶媒中で攪拌して溶解させて得られる。攪拌を行う時間は溶質が十分に溶解されれば特に制限はない。 (Solution containing metal nitrate)
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.
　溶液に含まれる金属硝酸塩としては、形成する金属酸化物膜に応じて選択すればよく、例えば、硝酸インジウム、硝酸マグネシウム、硝酸アルミニウム、硝酸カルシウム、硝酸スカンジウム、硝酸クロム、硝酸マンガン、硝酸鉄、硝酸コバルト、硝酸ニッケル、硝酸銅、硝酸亜鉛、硝酸ガリウム、硝酸ストロンチウム、硝酸イットリウム、硝酸バリウム、硝酸ランタン、硝酸セリウム、硝酸プラセオジウム、硝酸ネオジウム、硝酸サマリウム、硝酸ユーロピウム、硝酸ガドリニウム、硝酸テルビウム、硝酸ジスプロシウム、硝酸ホルミウム、硝酸エルビウム、硝酸ツリウム、硝酸イッテルビウム、硝酸ルテチウム、硝酸ビスマスが挙げられる。金属硝酸塩は水和物であってもよい。 The metal nitrate contained in the solution may be selected according to the metal oxide film to be formed. For example, indium nitrate, magnesium nitrate, aluminum nitrate, calcium nitrate, scandium nitrate, chromium nitrate, manganese nitrate, iron nitrate, nitric acid Cobalt, nickel nitrate, copper nitrate, zinc nitrate, gallium nitrate, strontium nitrate, yttrium nitrate, barium nitrate, lanthanum nitrate, cerium nitrate, praseodymium nitrate, neodymium nitrate, samarium nitrate, europium nitrate, gadolinium nitrate, terbium nitrate, dysprosium nitrate, Examples include holmium nitrate, erbium nitrate, thulium nitrate, ytterbium nitrate, lutetium nitrate, and bismuth nitrate. The metal nitrate may be a hydrate.
　溶液の金属モル濃度は、粘度や得たい膜厚に応じて任意に選択することができるが、膜の平坦性及び生産性の観点から０．０１ｍｏｌ／Ｌ以上０．５ｍｏｌ／Ｌ以下であることが好ましい。溶液中の金属モル濃度が０．０１ｍｏｌ／Ｌ以上であれば膜密度を効果的に向上させることができる。また、金属酸化物膜上に溶液を塗布して金属酸化物前駆体膜を形成する場合、溶液中の金属モル濃度が０．５ｍｏｌ／Ｌ以下であれば下の金属酸化物膜を溶解することを効果的に抑制することができる点でも好ましい。 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.
　なお、金属硝酸塩を含む溶液が複数種の金属を含む場合は、本発明における金属モル濃度は、各金属のモル濃度（ｍｏｌ／Ｌ）の合計量を意味する。 In addition, when the solution containing a metal nitrate contains multiple types of metals, the metal molar concentration in the present invention means the total amount of molar concentrations (mol / L) of each metal.
　金属硝酸塩を含む溶液は、金属硝酸塩以外の他の金属原子含有化合物を含んでいてもよい。金属原子含有化合物としては金属硝酸塩以外の金属塩、金属ハロゲン化物、有機金属化合物を挙げることができる。
　金属硝酸塩以外の金属塩としては、硫酸塩、燐酸塩、炭酸塩、酢酸塩、蓚酸塩等が挙げられ、金属ハロゲン化物としては、塩化物、ヨウ化物、臭化物等が挙げられ、有機金属化合物としては、金属アルコキシド、有機酸塩、金属βジケトネート等が挙げられる。 The solution containing a metal nitrate may contain a metal atom-containing compound other than the metal nitrate. Examples of the metal atom-containing compound include metal salts other than metal nitrates, metal halides, and organometallic compounds.
Examples of metal salts other than metal nitrates include sulfates, phosphates, carbonates, acetates, and oxalates. Examples of metal halides include chlorides, iodides, bromides, and the like. Examples thereof include metal alkoxides, organic acid salts, and metal β-diketonates.
　金属硝酸塩を含む溶液は、少なくとも硝酸インジウムを含むことが好ましい。酸化物半導体膜又は酸化物導体膜を形成する場合、硝酸インジウムを用いることで、容易にインジウム含有酸化物膜を形成することができ、高い電気伝導性が得られる。
　また、金属酸化物前駆体膜を金属酸化物膜に転化する工程が紫外線を照射する工程を含む場合、前駆体膜が紫外光を効率よく吸収することができ、インジウム含有酸化物膜を容易に形成することができる。 The solution containing metal nitrate preferably contains at least indium nitrate. In the case of forming an oxide semiconductor film or an oxide conductor film, an indium-containing oxide film can be easily formed by using indium nitrate, and high electrical conductivity can be obtained.
Further, when 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.
　また、金属硝酸塩を含む溶液にインジウム以外の金属元素として、亜鉛、錫、ガリウム、及びアルミニウムから選ばれるいずれか１つ以上の金属原子を含む化合物を含有することが好ましい。インジウムとインジウム以外の前記金属元素を適量含むことにより、得られる酸化物半導体膜の閾値電圧を所望の値に制御することができ、且つ膜の電気的安定性も向上する。
　なお、インジウムとインジウム以外の前記金属元素を含む酸化物半導体及び酸化物導電体として、Ｉｎ－Ｇａ－Ｚｎ－Ｏ（ＩＧＺＯ）、Ｉｎ－Ｚｎ－Ｏ（ＩＺＯ）、Ｉｎ－Ｇａ－Ｏ（ＩＧＯ）、Ｉｎ－Ｓｎ－Ｏ（ＩＴＯ）、Ｉｎ－Ｓｎ－Ｚｎ－Ｏ（ＩＴＺＯ）等が挙げられる。 Moreover, it is preferable that 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. By containing an appropriate amount of indium and the 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.
Note that as 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. In-Sn-O (ITO), In-Sn-Zn-O (ITZO), and the like.
　金属硝酸塩を含む溶液に用いる溶媒は、用いる金属硝酸塩を含む金属原子含有化合物が溶解するものであれば特に制限されず、水、アルコール溶媒（メタノール、エタノール、プロパノール、エチレングリコール等）、アミド溶媒（Ｎ，Ｎ－ジメチルホルムアミド等）、ケトン溶媒（アセトン、Ｎ－メチルピロリドン、スルホラン、Ｎ，Ｎ－ジメチルイミダゾリジノン等）、エーテル溶媒（テトラヒドロフラン、メトキシエタノール等）、ニトリル溶媒（アセトニトリル等）、その他上記以外のヘテロ原子含有溶媒等が挙げられる。特に溶解性、塗れ性の観点からメタノール、メトキシエタノール等を用いることが好ましい。 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.), 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.
（塗布）
　金属硝酸塩を含む溶液（金属酸化物膜形成用塗布液）を基板上に塗布する方法は特に限定されず、スプレーコート法、スピンコート法、ブレードコート法、ディップコート法、キャスト法、ロールコート法、バーコート法、ダイコート法、ミスト法、インクジェット法、ディスペンサー法、スクリーン印刷法、凸版印刷法、及び凹版印刷法等が挙げられる。特に、微細パターンを容易に形成する観点から、インクジェット法、ディスペンサー法、凸版印刷法、及び凹版印刷法から選択される少なくとも一種の塗布法を用いることが好ましい。 (Application)
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. In particular, from the viewpoint of easily forming a fine pattern, it is preferable to use at least one coating method selected from an inkjet method, a dispenser method, a relief printing method, and an intaglio printing method.
（乾燥）
　金属酸化物膜形成用塗布液を基板上に塗布した後、塗布膜を乾燥させ、第１の金属酸化物前駆体膜を得る。乾燥によって、塗布膜の流動性を低減させ、最終的に得られる酸化物膜の平坦性を向上させることができる。
　適切な乾燥温度（例えば、基板の温度が３５℃以上１００℃以下）を選択することにより、最終的により緻密な金属酸化物膜を得ることができる。乾燥のための加熱処理の方法は特に限定されず、ホットプレート加熱、電気炉加熱、赤外線加熱、マイクロ波加熱等から選択することができる。
　乾燥は膜の平坦性を均一に保つ観点から、塗布後、５分以内に開始することが好ましい。
　乾燥を行う時間は特に制限はないが、膜の均一性、生産性の観点から１５秒以上１０分以下であることが好ましい。
　また、乾燥における雰囲気に特に制限はないが、製造コスト等の観点から大気圧下、大気中で行うことが好ましい。 (Dry)
After the metal oxide film forming coating solution is applied onto the substrate, the coating film is dried to obtain a first metal oxide precursor film. By drying, the fluidity of the coating film can be reduced, and the flatness of the finally obtained oxide film can be improved.
By selecting 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 | limiting in particular in the atmosphere in drying, but it is preferable to carry out in air | atmosphere under atmospheric pressure from viewpoints, such as manufacturing cost.
［金属酸化物膜への転化工程（工程Ｂ）］
　次いで、乾燥して得た金属酸化物前駆体膜を金属酸化物膜に転化する。金属酸化物前駆体膜を金属酸化物膜に転化する方法は、基板の最高到達温度を１２０℃以上２５０℃以下にすることができれば特に制限はなく、ホットプレート等のヒーター、電気炉、プラズマ、紫外光、マイクロ波等を用いる手法が挙げられる。
　転化工程における基板の最高到達温度が１２０℃未満であると膜密度の向上効果が不十分であり、２５０℃を超えると製造コストが増大する。
　より低温で金属酸化物膜への転化を行う観点から、紫外線（ＵＶ：Ultraviolet）を用いる手法が好ましい。紫外線の光源としては、ＵＶランプやレーザーが挙げられるが、大面積に均一に、安価な設備で紫外線照射を行う観点からＵＶランプが好ましい。 [Conversion Step to Metal Oxide Film (Step B)]
Next, 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ランプとしては、エキシマランプ、重水素ランプ、低圧水銀ランプ、高圧水銀ランプ、超高圧水銀ランプ、メタルハライドランプ、ヘリウムランプ、カーボンアークランプ、カドミウムランプ、無電極放電ランプ等が挙げられ、特に低圧水銀ランプを用いると金属酸化物前駆体膜から金属酸化物膜への転化が容易に行えることから好ましい。 Examples of 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.
　転化工程において、金属酸化物前駆体膜の膜面には波長３００ｎｍ以下の紫外光を１０ｍＷ／ｃｍ２以上の照度で照射することが好ましい。上記波長範囲の紫外光を上記照度範囲で照射することでより短い時間で金属酸化物前駆体膜から金属酸化物膜への転化を行うことができる。
　なお、金属酸化物前駆体膜に照射する紫外線の照度は、例えば、紫外線光量計（オーク製作所社製、ＵＶ－Ｍ１０、受光器ＵＶ－２５）を用いて測定することができる。 In the conversion step, 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. By irradiating ultraviolet light in the above wavelength range within the above illuminance range, conversion from the metal oxide precursor film to the metal oxide film can be performed in a shorter time.
Note that 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).
　転化工程における雰囲気に制限はなく、大気圧下であっても真空下であってもよく、また、大気中であっても、任意のガス中であってもよいが、簡便に転化を行う観点から大気圧下で行うことが好ましい。 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.
　転化工程における基板の最高到達温度は２００℃以下であることが好ましい。２００℃以下であれば耐熱性の低い樹脂基板への適用が容易となる。なお、転化工程における基板の最高到達温度はサーモラベルによって測定することができる。 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.
　基板の温度は、前述した温度範囲に制御可能な手法であれば特に限定されず、ホットプレート等のヒーター、電気炉、マイクロ波加熱で基板温度を制御してもよく、紫外線ランプ等、光源からの輻射熱を用いてもよい。光源からの輻射熱を用いる際には、ランプ－基板間距離やランプ出力を調整することで基板温度を制御することができる。
　紫外線照射時間は紫外線の照度にもよるが、生産性の観点から、５秒以上１２０分以下であることが好ましい。 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. When radiant heat from the light source is used, the substrate temperature can be controlled by adjusting the lamp-substrate distance and the lamp output.
Although 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.
［工程Ａと工程Ｂの繰り返し］
　金属酸化物前駆体膜を金属酸化物膜に転化した後、金属酸化物膜上に金属硝酸塩を含む溶液を再度塗布・乾燥して金属酸化物前駆体薄膜を形成し、金属酸化物前駆体膜を金属酸化物膜に転化することによって金属酸化物膜上に更に金属酸化物膜を形成する。
　このようにして金属酸化物前駆体膜の形成工程（工程Ａ）と金属酸化物膜への転化工程（工程Ｂ）を交互に２回以上繰り返して金属酸化物膜を重ねて一体的に形成することで、膜密度が高い金属酸化物膜を得ることができる。
　尚、工程Ａと工程Ｂは、工程Ａと工程Ｂの順がＡ→Ｂ→Ａ→Ｂの関係になっていればよく、工程Ａと工程Ｂは連続して行わなくてもよく、工程Ａと工程Ｂの間に例えば電極や絶縁膜の形成など別の工程が入っていてもよい。 [Repeat 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.
In this manner, 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. Thus, a metal oxide film having a high film density can be obtained.
In addition, as long as the order of the process A and the process B has become the relationship of A->B->A-> B, 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. For example, another process such as formation of an electrode or an insulating film may be included between the process B and the process B.
　また、金属酸化物前駆体膜を形成する工程と、金属酸化物前駆体膜を金属酸化物膜に転化する工程を交互にＮ回（Ｎは２以上の整数）繰り返す場合、金属酸化物前駆体膜を金属酸化物膜に転化するＮ回の転化工程全てにおいて基板の最高到達温度を１２０℃以上２５０℃以下にする必要はなく、Ｎ回の転化工程のうち少なくとも２回の転化工程において、基板の最高到達温度を１２０℃以上２５０℃以下にして金属酸化物前駆体膜を金属酸化物膜に転化すればよい。例えば、金属酸化物前駆体膜の形成と金属酸化物膜への転化を交互に３回繰り返す場合、１回目と２回目の転化工程では基板の最高到達温度を１２０℃以上２５０℃以下とし、３回目の転化工程では基板の最高到達温度を１２０℃未満としてもよいし、１回目の転化工程では基板の最高到達温度を１２０℃未満とし、２回目と３回目の転化工程では基板の最高到達温度を１２０℃以上２５０℃以下としもよい。あるいは１回目の転化工程と３回目の転化工程では基板の最高到達温度を１２０℃以上２５０℃以下とし、２回目の転化工程では１２０℃未満で行ってもよい。
　ただし、金属酸化物前駆体膜を金属酸化物膜に転化する全ての工程において、基板の最高到達温度を１２０℃以上２５０℃以下にして金属酸化物前駆体膜を金属酸化物膜に転化することが好ましい。 When 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 repeated N times (N is an integer of 2 or more), the metal oxide precursor It is not necessary to set the maximum temperature of the substrate to 120 ° C. or more and 250 ° C. or less in all N conversion steps for converting the film into a metal oxide film, and in at least two conversion steps among the N conversion steps, 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. or less in the first and second conversion steps. In the second conversion process, the maximum temperature of the substrate may be less than 120 ° C. In the first conversion process, the maximum temperature of the substrate is less than 120 ° C, and in the second and third conversion processes, the maximum temperature of the substrate is reached. It is good also as 120 to 250 degreeC. Alternatively, 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.
However, in all the steps for converting the metal oxide precursor film into the metal oxide film, 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.
　本発明の金属酸化物膜の製造方法は、工程Ａと工程Ｂを同一基板上で交互に４回以上（すなわち、工程Ａと工程Ｂのセットを４セット以上）繰り返すことが好ましい。工程Ａと工程Ｂを交互に４回以上繰り返すことで、膜密度がより高い良質な金属酸化物膜を得ることができる。
　なお、工程Ａと工程Ｂを繰り返す回数は２回以上であれば特に制限されず、目標とする金属酸化物膜の厚み等を考慮して決めればよいが、生産性の観点から１０回以下とすることが好ましい。 In the method for producing a metal oxide film of the present invention, 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). 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.
In addition, 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.
　工程Ａ及び工程Ｂを交互に２回以上繰り返して金属酸化物膜を形成する好ましい製造形態として、例えば以下のような形態が挙げられる。図１３は本発明によって金属酸化物膜を製造する装置の一例を概略的に示している。この装置はロールツーロール方式にて金属酸化物膜を形成する構成を有し、インクジェット等による塗布部２（２Ａ，２Ｂ，２Ｃ）と、紫外線照射による転化部３（３Ａ，３Ｂ，３Ｃ）とが交互に連続して配置され、基板１を搬送する搬送ベルト４及び搬送ロール５、基板１の温度を制御する温度制御手段８などを備えている。搬送ベルト４上に所定の間隔で配置された基板１は、搬送ロール５の回転によって搬送ベルト４とともに矢印Ａの方向に移動し、塗布部２Ａにおいて金属硝酸塩を含む溶液６が付与されて金属酸化物前駆体膜が形成される。次いで、転化部３Ａにおいて紫外線照射されるとともに温度制御手段８により基板１の最高到達温度が１２０℃以上２５０℃以下の範囲に加熱されて金属酸化物前駆体膜が金属酸化物膜に転化される。同様にして２番目の塗布部２Ｂと転化部３Ｂ、さらに３番目の塗布部２Ｃと転化部３Ｃによって金属酸化物前駆体膜の形成と金属酸化物膜への転化が繰り返し行われる。このようにして工程Ａと工程Ｂの繰り返しを短時間で効率的に行うことが可能となる。 As a preferable production form in which the metal oxide film is formed by alternately repeating the process A and the process B twice or more, the following forms are exemplified. 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. Next, 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. . Similarly, 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.
　工程Ａと工程Ｂを各々１回ずつ行って得られる金属酸化物膜の平均膜厚が６ｎｍ以下であることが好ましく、２ｎｍ以下であることがより好ましい。工程Ａと工程Ｂを各々１回ずつ行って得られる金属酸化物膜の平均膜厚を６ｎｍ以下にすることによって、最終的に得られる膜密度が高い金属酸化物膜を得ることができ、２ｎｍ以下であればその効果がより高く得られる。尚、ここで述べる平均膜厚とは、工程Ａ及び工程Ｂを交互に複数回繰り返して作製した金属酸化物膜の膜厚を塗布回数（工程Ａの回数）で除した値を指す。例えば工程Ａ及び工程Ｂを交互に２回繰り返し、最終的に得られる膜厚が１０ｎｍの場合、平均膜厚は１０／２＝５ｎｍとなる。最終的に得られる金属酸化物膜の膜厚は膜の透過型電子顕微鏡（Ｔｒａｎｓｍｉｓｓｉｏｎ　Ｅｌｅｃｔｒｏｎ　Ｍｉｃｒｏｓｃｏｅ：ＴＥＭ）による断面観察によって評価することができる。 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. By making the average film thickness of the metal oxide film obtained by performing Step A and Step B once each 6 nm or less, a metal oxide film having a high film density finally obtained can be obtained. The effect will be higher if it is below. 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). For example, when the step A and the step B are alternately repeated twice and the finally obtained film thickness is 10 nm, the average film thickness is 10/2 = 5 nm. 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).
＜金属酸化物膜＞
　上記工程Ａ及び工程Ｂを交互に複数回繰り返して製造された金属酸化物膜は、膜密度が高い膜となる。 <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.
　本発明の金属酸化物膜は金属成分として少なくともインジウムを含むことが好ましい。インジウムを含むことで金属酸化物半導体膜や金属酸化物導電体膜とした際に高い電気伝導性が得られる。
　金属酸化物膜のインジウムの含有量が、金属酸化物膜に含まれる全金属元素の５０ａｔｏｍ％以上であることが好ましい。インジウム含有量が５０ａｔｏｍ％以上であれば低温で容易に高い電気伝導性が得られる。
　金属酸化物膜は、インジウム以外の金属元素として、亜鉛，錫，ガリウム及びアルミニウムから選ばれる少なくとも１種の金属成分を含むことが好ましい。金属元素を適量含むことにより、電気伝導性の向上や、酸化物半導体膜を作製した際の閾値電圧制御や電気的安定性の向上効果が得られる。インジウムと前記金属元素を含む酸化物半導体及び酸化物導電体として、Ｉｎ－Ｇａ－Ｚｎ－Ｏ（ＩＧＺＯ）、Ｉｎ－Ｚｎ－Ｏ（ＩＺＯ）、Ｉｎ－Ｇａ－Ｏ（ＩＧＯ）、Ｉｎ－Ｓｎ－Ｏ（ＩＴＯ）、Ｉｎ－Ｓｎ－Ｚｎ－Ｏ（ＩＴＺＯ）等が挙げられる。 The metal oxide film of the present invention preferably contains at least indium as a metal component. By containing 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. As an oxide semiconductor and an oxide conductor containing indium and the above metal elements, In—Ga—Zn—O (IGZO), In—Zn—O (IZO), In—Ga—O (IGO), In—Sn— O (ITO), In—Sn—Zn—O (ITZO), and the like can be given.
　金属酸化物膜のＸ線反射率法（Ｘ－ｒａｙ　Ｒｅｆｌｅｃｔｏｍｅｔｅｒ：ＸＲＲ）によって測定した平均膜密度が６ｇ／ｃｍ３以上であることが好ましい。上記平均膜密度の範囲であれば金属酸化物半導体膜又は金属酸化物導電体膜とした際に高い電気伝導性が得られる。ここで言うところの平均膜密度とはＸＲＲスペクトルから膜厚、膜密度、表面ラフネスをパラメータとしてフィッティングを行う際に、金属酸化物膜を密度の異なる複数層のモデルとし、各層の膜密度を膜厚で乗じた値を加算した後に、金属酸化物膜の全膜厚で除した値をいう。例えば、金属酸化物膜を３層とした場合にシミュレーション結果と良い一致を示す金属酸化物膜であって、１層目が膜密度４ｇ／ｃｍ３で膜厚１ｎｍ、２層目が膜密度５ｇ／ｃｍ３で膜厚８ｎｍ、３層目が膜密度４ｇ／ｃｍ３で膜厚１ｎｍとすると、この金属酸化物膜の平均膜密度は（４×１＋５×８＋４×１）／（１＋８＋１）＝４．８ｇ／ｃｍ３となる。尚、実測スペクトルとシミュレーション結果が良い一致を示すか否かは信頼性因子（Ｒ値）で見積もることができ、良い一致を示すものは、Ｒ値が０．０１５以下であることを意味する。 It is preferable that the average film density of the metal oxide film measured by X-ray reflectometry (XRR) is 6 g / cm 3 or more. When the average film density is within the above range, high electrical conductivity can be obtained when a metal oxide semiconductor film or a metal oxide conductor film is used. 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. A value obtained by adding the value multiplied by the thickness and then dividing by the total thickness of the metal oxide film. For example, when the metal oxide film has three layers, the metal oxide film shows a good agreement with the simulation result. 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. When the film thickness is 8 nm at / cm 3 and the film density of the third layer is 4 g / cm 3 and the film thickness is 1 nm, the average film density of this metal oxide film is (4 × 1 + 5 × 8 + 4 × 1) / (1 + 8 + 1) = 4 8 g / cm 3 . Whether or not the measured spectrum and the simulation result show a good match can be estimated by a reliability factor (R value). A good match means that the R value is 0.015 or less.
　本発明の金属酸化物膜の製造方法を用いることで、例えば、大気圧下、２００℃以下の低温プロセスで緻密な金属酸化物膜を得ることができ、種々のデバイスの作製に適用することができる。本発明では、大掛かりな真空装置を用いる必要がない点、耐熱性の低い安価な樹脂基板を用いることができる点、原料が安価である点等からデバイス作製コストを大幅に低減可能となる。
　また、本発明は、耐熱性の低い樹脂基板に適用できることからフレキシブルディスプレイ等のフレキシブル電子デバイスを安価に作製することが可能となる。本発明は、特に金属酸化物半導体膜や金属酸化物導電膜の作製に用いた際に極めて電子伝達特性が高い膜を得ることができる。 By using the method for producing a metal oxide film of the present invention, for example, 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. In the present invention, 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.
In addition, since 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.
＜薄膜トランジスタ＞
　本発明の実施形態により作製された金属酸化物半導体膜は高い半導体特性を示すことから、薄膜トランジスタ（ＴＦＴ）の活性層（酸化物半導体層）に好適に用いることができる。以下、本発明の製造方法により作製された金属酸化物膜を薄膜トランジスタの活性層として用いる実施形態について説明する。
　尚、実施形態としてはトップゲート型の薄膜トランジスタについて記述するが、本発明により製造される金属酸化物半導体膜を用いた薄膜トランジスタはトップゲート型に限定されることなく、ボトムゲート型の薄膜トランジスタであってもよい。 <Thin film transistor>
Since 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). Hereinafter, 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.
Although 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.
　本発明に係るＴＦＴの素子構造は特に限定されず、ゲート電極の位置に基づいた、いわゆる逆スタガ構造（ボトムゲート型とも呼ばれる）及びスタガ構造（トップゲート型とも呼ばれる）のいずれの態様であってもよい。また、活性層とソース電極及びドレイン電極（適宜、「ソース・ドレイン電極」という。）との接触部分に基づき、いわゆるトップコンタクト型、ボトムコンタクト型のいずれの態様であってもよい。
　トップゲート型とは、ＴＦＴが形成されている基板を最下層としたときに、ゲート絶縁膜の上側にゲート電極が配置され、ゲート絶縁膜の下側に活性層が形成された形態である。ボトムゲート型とは、ゲート絶縁膜の下側にゲート電極が配置され、ゲート絶縁膜の上側に活性層が形成された形態である。また、ボトムコンタクト型とは、ソース・ドレイン電極が活性層よりも先に形成されて活性層の下面がソース・ドレイン電極に接触する形態である。トップコンタクト型とは、活性層がソース・ドレイン電極よりも先に形成されて活性層の上面がソース・ドレイン電極に接触する形態である。 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. In the top contact type, 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.
　図１は、トップゲート構造でトップコンタクト型の本発明に係るＴＦＴの一例を示す模式図である。図１に示すＴＦＴ１０では、基板１２の一方の主面上に活性層１４として上述の金属酸化物膜が積層されている。そして、活性層１４上にソース電極１６及びドレイン電極１８が互いに離間して設置され、更にこれらの上にゲート絶縁膜２０と、ゲート電極２２とが順に積層されている。 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. In the TFT 10 shown in FIG. 1, 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.
　図２は、トップゲート構造でボトムコンタクト型の本発明に係るＴＦＴの一例を示す模式図である。図２に示すＴＦＴ３０では、基板１２の一方の主面上にソース電極１６及びドレイン電極１８が互いに離間して設置されている。そして、活性層１４として上述の金属酸化物膜と、ゲート絶縁膜２０と、ゲート電極２２と、が順に積層されている。 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. In the TFT 30 shown in FIG. 2, 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.
　図３は、ボトムゲート構造でトップコンタクト型の本発明に係るＴＦＴの一例を示す模式図である。図３に示すＴＦＴ４０では、基板１２の一方の主面上にゲート電極２２と、ゲート絶縁膜２０と、活性層１４として上述の金属酸化物膜と、が順に積層されている。そして、活性層１４の表面上にソース電極１６及びドレイン電極１８が互いに離間して設置されている。 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. In the TFT 40 shown in FIG. 3, 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.
　図４は、ボトムゲート構造でボトムコンタクト型の本発明に係るＴＦＴの一例を示す模式図である。図４に示すＴＦＴ５０では、基板１２の一方の主面上にゲート電極２２と、ゲート絶縁膜２０と、が順に積層されている。そして、ゲート絶縁膜２０の表面上にソース電極１６及びドレイン電極１８が互いに離間して設置され、更にこれらの上に、活性層１４として上述の金属酸化物半導体膜が積層されている。 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. In the TFT 50 shown in FIG. 4, 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 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.
　以下の実施形態としては図１に示すトップゲート型の薄膜トランジスタ１０について主に説明するが、本発明の薄膜トランジスタはトップゲート型に限定されることなく、ボトムゲート型の薄膜トランジスタであってもよい。 In the following embodiment, the top gate type thin film transistor 10 shown in FIG. 1 will be mainly described. However, 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.
（活性層）
　本実施形態の薄膜トランジスタ１０を製造する場合、まず、金属硝酸塩を含む溶液を準備し、金属酸化物前駆体膜の形成工程及び金属酸化物膜への転化工程を交互に２回以上繰り返して基板１２上に金属酸化物膜を形成する。
　金属酸化物膜のパターンニングは前述したインクジェット法、ディスペンサー法、凸版印刷法、又は凹版印刷法によって行ってもよく、金属酸化物膜の形成後にフォトリソグラフィー及びエッチングによりパターニングを行ってもよい。
　フォトリソグラフィー及びエッチングによりパターン形成を行うには、金属酸化物膜を形成した後、活性層１４として残存させる部分にフォトリソグラフィーによりレジストパターンを形成した後、塩酸、硝酸、希硫酸、又は燐酸、硝酸及び酢酸の混合液等の酸溶液によりエッチングすることにより活性層１４のパターンを形成する。 (Active layer)
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.
In order to form a pattern by photolithography and etching, after forming a 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.
　金属酸化物膜の膜厚は膜の平坦性及び膜形成に要する時間の観点から５ｎｍ以上５０ｎｍ以下であることが好ましい。 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.
　また、高い移動度を得る観点から、活性層１４におけるインジウムの含有量は、活性層１４に含まれる全金属元素の５０ａｔｏｍ％以上であることが好ましく、８０ａｔｏｍ％以上であることがより好ましい。 Further, from the viewpoint of obtaining high mobility, 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.
（保護層）
　活性層１４上にはソース・ドレイン電極１６，１８のエッチング時に活性層１４を保護するための保護層（不図示）を形成することが好ましい。保護層の成膜方法に特に限定はなく、金属酸化物膜を形成した後、パターニングする前に形成してもよいし、金属酸化物膜のパターニング後に形成してもよい。
　また、保護層としては金属酸化物層であってもよく、樹脂のような有機材料であってもよい。なお、保護層はソース電極１５及びドレイン電極１８（適宜「ソース・ドレイン電極」と記す）の形成後に除去しても構わない。 (Protective layer)
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.
（ソース・ドレイン電極）
　金属酸化物半導体膜で形成される活性層１４上にソース・ドレイン電極１６，１８を形成する。ソース・ドレイン電極１６，１８はそれぞれ電極として機能するように高い導電性を有するものを用い、Ａｌ，Ｍｏ，Ｃｒ，Ｔａ，Ｔｉ，Ａｕ，Ａｕ等の金属、Ａｌ－Ｎｄ、Ａｇ合金、酸化錫、酸化亜鉛、酸化インジウム、酸化インジウム錫（ＩＴＯ）、酸化亜鉛インジウム（ＩＺＯ）、Ｉｎ－Ｇａ－Ｚｎ－Ｏ等の金属酸化物導電膜等を用いて形成することができる。 (Source / drain electrodes)
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 Alternatively, 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.
　ソース・ドレイン電極１６，１８を形成する場合、印刷方式、コーティング方式等の湿式方式、真空蒸着法、スパッタリング法、イオンプレーティング法等の物理的方式、ＣＶＤ、プラズマＣＶＤ法等の化学的方式等の中から使用する材料との適性を考慮して適宜選択した方法に従って成膜すればよい。 When the source / drain electrodes 16 and 18 are formed, 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.
　ソース・ドレイン電極１６，１８の膜厚は、成膜性、エッチング又はリフトオフ法によるパターンニング性、導電性等を考慮すると、１０ｎｍ以上１０００ｎｍ以下とすることが好ましく、５０ｎｍ以上１００ｎｍ以下とすることがより好ましい。 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.
　ソース・ドレイン電極１６，１８は、導電膜を形成した後、例えば、エッチング又はリフトオフ法により所定の形状にパターンニングして形成してもよく、インクジェット法等により直接パターン形成してもよい。この際、ソース・ドレイン電極１６，１８及びこれらの電極に接続する配線（不図示）を同時にパターンニングすることが好ましい。 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.
（ゲート絶縁膜）
　ソース・ドレイン電極１６，１８及び配線（不図示）を形成した後、ゲート絶縁膜２０を形成する。ゲート絶縁膜２０は高い絶縁性を有するものが好ましく、例えばＳｉＯ２、ＳｉＮｘ、ＳｉＯＮ、Ａｌ２Ｏ３、Ｙ２Ｏ３、Ｔａ２Ｏ５、ＨｆＯ２等の絶縁膜、又はこれらの化合物を２種以上含む絶縁膜としてもよい。
　ゲート絶縁膜２０は、印刷方式、コーティング方式等の湿式方式、真空蒸着法、スパッタリング法、イオンプレーティング法等の物理的方式、ＣＶＤ、プラズマＣＶＤ法等の化学的方式等の中から使用する材料との適性を考慮して適宜選択した方法に従って成膜すればよい。 (Gate insulation film)
After the source / drain electrodes 16 and 18 and the wiring (not shown) are formed, the gate insulating film 20 is formed. The gate insulating film 20 preferably has a high insulating property. 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 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
　尚、ゲート絶縁膜２０はリーク電流の低下及び電圧耐性の向上のための厚みを有する必要がある一方、ゲート絶縁膜２０の厚みが大きすぎると駆動電圧の上昇を招いてしまう。ゲート絶縁膜２０は材質にもよるが、ゲート絶縁膜２０の厚みは１０ｎｍ以上１０μｍ以下が好ましく、５０ｎｍ以上１０００ｎｍ以下がより好ましく、１００ｎｍ以上４００ｎｍ以下が特に好ましい。 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. Although the gate insulating film 20 depends on the material, the thickness of the gate insulating film 20 is preferably 10 nm to 10 μm, more preferably 50 nm to 1000 nm, and particularly preferably 100 nm to 400 nm.
（ゲート電極）
　ゲート絶縁膜２０を形成した後、ゲート電極２２を形成する。ゲート電極２２は高い導電性を有するものを用い、Ａｌ，Ｍｏ，Ｃｒ，Ｔａ，Ｔｉ，Ａｕ，Ａｕ等の金属、Ａｌ－Ｎｄ、Ａｇ合金、酸化錫、酸化亜鉛、酸化インジウム、酸化インジウム錫（ＩＴＯ）、酸化亜鉛インジウム（ＩＺＯ）、ＩＧＺＯ等の金属酸化物導電膜等を用いて形成することができる。ゲート電極２２としてはこれらの導電膜を単層構造又は２層以上の積層構造として用いることができる。 (Gate electrode)
After forming the gate insulating film 20, a gate electrode 22 is formed. 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.
　ゲート電極２２は、印刷方式、コーティング方式等の湿式方式、真空蒸着法、スパッタリング法、イオンプレーティング法等の物理的方式、ＣＶＤ、プラズマＣＶＤ法等の化学的方式等の中から使用する材料との適性を考慮して適宜選択した方法に従って成膜する。
　ゲート電極２２を形成するための金属膜の膜厚は、成膜性、エッチングやリフトオフ法によるパターンニング性、導電性等を考慮すると、１０ｎｍ以上１０００ｎｍ以下とすることが好ましく、５０ｎｍ以上２００ｎｍ以下とすることがより好ましい。
　成膜後、エッチング又はリフトオフ法により所定の形状にパターンニングすることにより、ゲート電極２２を形成してもよく、インクジェット法等により直接パターン形成してもよい。この際、ゲート電極２２及びゲート配線（不図示）を同時にパターンニングすることが好ましい。 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.
After the film formation, 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.
　以上で説明した本実施形態の薄膜トランジスタ１０の用途には特に限定はないが、高い輸送特性を示すことから、例えば電気光学装置、具体的には、液晶表示装置、有機ＥＬ（Ｅｌｅｃｔｒｏ　Ｌｕｍｉｎｅｓｃｅｎｃｅ）表示装置、無機ＥＬ表示装置等の表示装置における駆動素子として好適であり、耐熱性の低い樹脂基板を用いたフレキシブルディスプレイの作製に特に好適である。
　更に本発明により製造される薄膜トランジスタは、Ｘ線センサ、イメージセンサ等の各種センサ、ＭＥＭＳ（Ｍｉｃｒｏ　Ｅｌｅｃｔｒｏ　Ｍｅｃｈａｎｉｃａｌ　Ｓｙｓｔｅｍ）等、種々の電子デバイスにおける駆動素子（駆動回路）として好適に用いられる。 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).
＜液晶表示装置＞
　本発明の一実施形態である液晶表示装置について、図５にその一部分の概略断面図を示し、図６に電気配線の概略構成図を示す。 <Liquid crystal display device>
FIG. 5 shows a schematic sectional view of a part of a liquid crystal display device according to an embodiment of the present invention, and FIG. 6 shows a schematic configuration diagram of electrical wiring.
　図５に示すように、本実施形態の液晶表示装置１００は、図１に示したトップゲート構造でトップコンタクト型のＴＦＴ１０と、ＴＦＴ１０のパッシベーション層１０２で保護されたゲート電極２２上に画素下部電極１０４およびその対向上部電極１０６で挟まれた液晶層１０８と、各画素に対応させて異なる色を発色させるためのＲ（赤）Ｇ（緑）Ｂ（青）のカラーフィルタ１１０とを備え、ＴＦＴ１０の基板１２側およびＲＧＢカラーフィルタ１１０上にそれぞれ偏光板１１２ａ、１１２ｂを備えた構成である。 As shown in FIG. 5, the liquid crystal display device 100 according to the present embodiment 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.
　また、図６に示すように、本実施形態の液晶表示装置１００は、互いに平行な複数のゲート配線１１２と、該ゲート配線１１２と交差する、互いに平行なデータ配線１１４とを備えている。ここでゲート配線１１２とデータ配線１１４は電気的に絶縁されている。ゲート配線１１２とデータ配線１１４との交差部付近に、ＴＦＴ１０が備えられている。 Further, as shown in FIG. 6, 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. Here, 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.
　ＴＦＴ１０のゲート電極２２は、ゲート配線１１２に接続されており、ＴＦＴ１０のソース電極１６はデータ配線１１４に接続されている。また、ＴＦＴ１０のドレイン電極１８はゲート絶縁膜２０に設けられたコンタクトホール１１６を介して（コンタクトホール１１６に導電体が埋め込まれて）画素下部電極１０４に接続されている。この画素下部電極１０４は、接地された対向上部電極１０６とともにキャパシタ１１８を構成している。 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.
＜有機ＥＬ表示装置＞
　本発明の一実施形態に係るアクティブマトリックス方式の有機ＥＬ表示装置について、図７に一部分の概略断面図を示し、図８に電気配線の概略構成図を示す。 <Organic EL display device>
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, and FIG. 8 shows a schematic configuration diagram of electrical wiring.
　本実施形態のアクティブマトリックス方式の有機ＥＬ表示装置２００は、図１に示したトップゲート構造のＴＦＴ１０が、パッシベーション層２０２を備えた基板１２上に、駆動用ＴＦＴ１０ａおよびスイッチング用ＴＦＴ１０ｂとして備えられ、ＴＦＴ１０ａ，１０ｂ上に下部電極２０８および上部電極２１０に挟まれた有機発光層２１２からなる有機ＥＬ発光素子２１４を備え、上面もパッシベーション層２１６により保護された構成となっている。 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.
　また、図８に示すように、本実施形態の有機ＥＬ表示装置２００は、互いに平行な複数のゲート配線２２０と、該ゲート配線２２０と交差する、互いに平行なデータ配線２２２および駆動配線２２４とを備えている。ここで、ゲート配線２２０とデータ配線２２２、駆動配線２２４とは電気的に絶縁されている。スイッチング用ＴＦＴ１０ｂのゲート電極２２は、ゲート配線２２０に接続されており、スイッチング用ＴＦＴ１０ｂのソース電極１６はデータ配線２２２に接続されている。また、スイッチング用ＴＦＴ１０ｂのドレイン電極１８は駆動用ＴＦＴ１０ａのゲート電極２２に接続されるとともに、キャパシタ２２６を用いることで駆動用ＴＦＴ１０ａをオン状態に保つ。駆動用ＴＦＴ１０ａのソース電極１６は駆動配線２２４に接続され、ドレイン電極１８は有機ＥＬ発光素子２１４に接続される。 As shown in FIG. 8, the organic EL display device 200 according to the present embodiment 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. I have. Here, 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.
　なお、図７に示した有機ＥＬ表示装置において、上部電極２１０を透明電極としてトップエミッション型としてもよいし、下部電極２０８およびＴＦＴの各電極を透明電極とすることによりボトムエミッション型としてもよい。 In the organic EL display device shown in FIG. 7, 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.
＜Ｘ線センサ＞
　本発明の一実施形態であるＸ線センサについて、図９にその一部分の概略断面図を示し、図１０にその電気配線の概略構成図を示す。 <X-ray sensor>
FIG. 9 shows a schematic sectional view of a part of an X-ray sensor according to an embodiment of the present invention, and FIG. 10 shows a schematic configuration diagram of its electrical wiring.
　本実施形態のＸ線センサ３００は基板１２上に形成されたＴＦＴ１０およびキャパシタ３１０と、キャパシタ３１０上に形成された電荷収集用電極３０２と、Ｘ線変換層３０４と、上部電極３０６とを備えて構成される。ＴＦＴ１０上にはパッシベーション膜３０８が設けられている。 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.
　キャパシタ３１０は、キャパシタ用下部電極３１２とキャパシタ用上部電極３１４とで絶縁膜３１６を挟んだ構造となっている。キャパシタ用上部電極３１４は絶縁膜３１６に設けられたコンタクトホール３１８を介し、ＴＦＴ１０のソース電極１６およびドレイン電極１８のいずれか一方（図９においてはドレイン電極１８）と接続されている。 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.
　電荷収集用電極３０２は、キャパシタ３１０におけるキャパシタ用上部電極３１４上に設けられており、キャパシタ用上部電極３１４に接している。
　Ｘ線変換層３０４はアモルファスセレンからなる層であり、ＴＦＴ１０およびキャパシタ３１０を覆うように設けられている。
　上部電極３０６はＸ線変換層３０４上に設けられており、Ｘ線変換層３０４に接している。 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.
　図１０に示すように、本実施形態のＸ線センサ３００は、互いに平行な複数のゲート配線３２０と、ゲート配線３２０と交差する、互いに平行な複数のデータ配線３２２とを備えている。ここでゲート配線３２０とデータ配線３２２は電気的に絶縁されている。ゲート配線３２０とデータ配線３２２との交差部付近に、ＴＦＴ１０が備えられている。 As shown in FIG. 10, 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. Here, 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.
　ＴＦＴ１０のゲート電極２２は、ゲート配線３２０に接続されており、ＴＦＴ１０のソース電極１６はデータ配線３２２に接続されている。また、ＴＦＴ１０のドレイン電極１８は電荷収集用電極３０２に接続されており、さらに電荷収集用電極３０２は、キャパシタ３１０に接続されている。 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.
　本実施形態のＸ線センサ３００において、Ｘ線は図９中、上部電極３０６側から入射してＸ線変換層３０４で電子－正孔対を生成する。Ｘ線変換層３０４に上部電極３０６によって高電界を印加しておくことにより、生成した電荷はキャパシタ３１０に蓄積され、ＴＦＴ１０を順次走査することによって読み出される。 In the X-ray sensor 300 of this embodiment, X-rays enter from the upper electrode 306 side in FIG. 9 and generate electron-hole pairs in the X-ray conversion layer 304. By applying a high electric field to the X-ray conversion layer 304 by the upper electrode 306, the generated charge is accumulated in the capacitor 310 and read out by sequentially scanning the TFT 10.
　なお、上記実施形態の液晶表示装置１００、有機ＥＬ表示装置２００、及びＸ線センサ３００においては、トップゲート構造のＴＦＴを備えるものとしたが、ＴＦＴはこれに限定されず、図２～図４に示す構造のＴＦＴであってもよい。 In the liquid crystal display device 100, the organic EL display device 200, and the X-ray sensor 300 of the above embodiment, a TFT having a top gate structure is provided. However, the TFT is not limited to this, and FIGS. A TFT having the structure shown in FIG.
　以下に実施例を説明するが、本発明はこれら実施例により何ら限定されるものではない。
＜実施例１～４、比較例１＞
　以下のような評価用デバイスを作製し、評価を行った。
　硝酸インジウム（Ｉｎ（ＮＯ３）３・ｘＨ２Ｏ、４Ｎ、高純度化学研究所社製）を２－メトキシエタノール（試薬特級、和光純薬工業社製）中に溶解させ、下記表１に示す硝酸インジウム濃度の異なる溶液を作製した。 Examples will be described below, but the present invention is not limited to these examples.
<Examples 1 to 4, 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.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　基板として熱酸化膜（膜厚１００ｎｍ）付ｐ型Ｓｉ基板を用い、熱酸化膜をゲート絶縁膜として用いる簡易型のＴＦＴを作製した。
　熱酸化膜付ｐ型Ｓｉ １ｉｎｃｈ角の基板上に、作製した各溶液を１５００ｒｐｍの回転速度で３０秒スピンコートした後、６０℃に加熱されたホットプレート上で１分間乾燥を行い、金属酸化物半導体前駆体膜を得た。 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.
　得られた金属酸化物半導体前駆体膜に対し、下記条件で紫外線照射による加熱処理を行うことで金属酸化物半導体膜への転化を行った。
　紫外線照射装置としては、低圧水銀ランプを用いたＵＶオゾンクリーナー（フィルジェン社製、ＵＶ２５３Ｈ）を用いた。試料を厚さ４０ｍｍのガラス板上にセットし、ランプ－試料間距離を５ｍｍとした。試料位置での波長２５４ｎｍの紫外照度は、紫外線光量計（オーク製作所社製、ＵＶ－Ｍ１０、受光器ＵＶ－２５）を用いて測定した。ランプ点灯から３分間で最大値に達し、１５ｍＷ／ｃｍ２であった。
　紫外線照射処理室内に窒素を６Ｌ／ｍｉｎで１０分間フローさせた後、９０分間、紫外線照射を行った。紫外線照射中は常に６Ｌ／ｍｉｎで窒素をフローさせた。紫外線照射処理時の基板温度をサーモラベルでモニターしたところ、１６０℃を示した。 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.
As 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 .
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.
　溶液Ａを用いたものは上記溶液の塗布・乾燥及び紫外線照射による金属酸化物半導体膜への転化を各１回行った（比較例１）。 In the case of using the solution A, the above solution was applied and dried and converted into a metal oxide semiconductor film by ultraviolet irradiation once (Comparative Example 1).
　上記溶液の塗布・乾燥及び紫外線照射による金属酸化物半導体膜への転化を、溶液Ｂを用いたものは交互に各２回（実施例１）、溶液Ｃを用いたものは交互に各４回（実施例２）、溶液Ｄを用いたものは交互に各７回（実施例３）、溶液Ｅを用いたものは交互に各１２回（実施例４）それぞれ繰り返した。 Application and drying of the above solution and conversion to a metal oxide semiconductor film by ultraviolet irradiation are performed twice each for the solution B using the solution B (Example 1) and four times each for the solution C using the solution C. (Example 2), those using the solution D were alternately repeated 7 times each (Example 3), and those using the solution E were alternately repeated 12 times (Example 4).
　実施例１～４及び比較例１の金属酸化物半導体膜の膜厚を断面ＴＥＭ観察によって確認したところ、全て１０．５ｎｍ±１．０ｎｍの範囲に収まっており、試料間で膜厚に大きな差がないことが確認された。また、全ての試料において、膜中に明瞭な界面層は確認されなかった。 When the film thicknesses of the metal oxide semiconductor films of Examples 1 to 4 and Comparative Example 1 were confirmed by cross-sectional TEM observation, they were all within the range of 10.5 nm ± 1.0 nm, and there was a large difference in film thickness between samples. It was confirmed that there was no. In all samples, no clear interface layer was observed in the film.
　上記得られた酸化物半導体膜上にソース・ドレイン電極を蒸着により成膜した。ソース・ドレイン電極はメタルマスクを用いたパターン成膜にて作製し、Ｔｉを５０ｎｍの厚さに成膜した。ソース・ドレイン電極サイズは各々１ｍｍ角とし、電極間距離は０．２ｍｍとした。 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.
　上記で得られた簡易型ＴＦＴについて、半導体パラメータ・アナライザー４１５６Ｃ（アジレントテクノロジー社製）を用い、トランジスタ特性（Ｖｇ－Ｉｄ特性）の測定を行った。 For simplified TFT obtained above, using a semiconductor parameter analyzer 4156C (manufactured by Agilent Technologies), it was measured transistor characteristics (V g -I d characteristics).
　Ｖｇ－Ｉｄ特性の測定は、ドレイン電圧（Ｖｄ）を＋１Ｖに固定し、ゲート電圧（Ｖｇ）を－１５Ｖ～＋１５Ｖの範囲内で変化させ、各ゲート電圧におけるドレイン電流（Ｉｄ）を測定することにより行った。 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.
　図１１に実施例１～４及び比較例１のＶｇ－Ｉｄ特性を示す。また、実施例１～４及び比較例１のＶｇ－Ｉｄ特性から見積もった線形移動度（以下、「移動度」と記す場合がある。）を表２に示す。 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.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　金属硝酸塩を含む溶液の塗布・乾燥による金属酸化物半導体前駆体膜形成工程と、金属酸化物半導体前駆体膜を金属酸化物半導体膜に転化する工程を交互に複数回行うことで、低温で、高いトランジスタ動作が確認された。
　図１２に繰り返し回数と移動度の関係のプロットを示す。繰り返し回数が２回以上で特性向上効果が得られ、特に４回以上の実施例２～４では１回の比較例１と比較して５倍以上の特性が得られる。 By performing a metal oxide semiconductor precursor film forming step by applying and drying a solution containing a metal nitrate and a step of converting the metal oxide semiconductor precursor film into a metal oxide semiconductor film alternately several times, at a low temperature, High transistor operation was confirmed.
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.
＜実施例５：溶液Ａを用いてスピンコート回転数を上げて繰り返し２回＞
　溶液Ａを用い、基板として熱酸化膜（膜厚１００ｎｍ）付ｐ型Ｓｉ基板を用い、熱酸化膜をゲート絶縁膜として用いる簡易型のＴＦＴを作製した。
　この熱酸化膜付ｐ型Ｓｉ １ｉｎｃｈ角の基板上に、溶液Ａを５０００ｒｐｍの回転速度で３０秒スピンコートした後、６０℃に加熱されたホットプレート上で１分間乾燥を行い、金属酸化物半導体前駆体膜を得た。 <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.
　得られた金属酸化物半導体前駆体膜に対し、下記条件で紫外線照射処理を行うことで金属酸化物半導体膜への転化を行った。
　紫外線照射装置としては、低圧水銀ランプを用いたＵＶオゾンクリーナー（フィルジェン社製、ＵＶ２５３Ｈ）を用いた。試料を厚さ４０ｍｍのガラス板上にセットし、ランプ－試料間距離を５ｍｍとした。試料位置での波長２５４ｎｍの紫外照度は、紫外線光量計（オーク製作所製、ＵＶ－Ｍ１０、受光器ＵＶ－２５）を用いて測定した。ランプ点灯から３分間で最大値に達し、１５ｍＷ／ｃｍ２であった。
　紫外線照射処理室内に窒素を６Ｌ／ｍｉｎで１０分間フローさせた後、９０分間、紫外線照射を行った。紫外線照射中は常に６Ｌ／ｍｉｎで窒素をフローさせた。紫外線照射処理時の基板温度をサーモラベルでモニターしたところ、１６０℃を示した。 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.
As 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 .
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.
　上記溶液Ａの塗布・乾燥及び紫外線照射による金属酸化物半導体膜への転化を交互に２回繰り返した。実施例５の金属酸化物半導体膜の膜厚を断面ＴＥＭ観察によって確認したところ、１０．７ｎｍであり、前述した実施例１～４及び比較例１に対して膜厚に大きな差がないことが確認された。また、膜中に明瞭な界面層は確認されなかった。
　上記得られた酸化物半導体膜上にソース・ドレイン電極を蒸着により成膜した。ソース・ドレイン電極はメタルマスクを用いたパターン成膜にて作製し、Ｔｉを５０ｎｍの厚さに成膜した。ソース・ドレイン電極サイズは各々１ｍｍ角とし、電極間距離は０．２ｍｍとした。 Application / drying of the solution A and conversion to a metal oxide semiconductor film by ultraviolet irradiation were alternately repeated twice. When the film thickness of the metal oxide semiconductor film of Example 5 was confirmed by cross-sectional TEM observation, it was 10.7 nm, and there was no significant difference in film thickness with respect to Examples 1 to 4 and Comparative Example 1 described above. confirmed. Further, a clear interface layer was not confirmed in the film.
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.
　上記で得られた簡易型ＴＦＴについて、半導体パラメータ・アナライザー４１５６Ｃ（アジレントテクノロジー社製）を用い、トランジスタ特性（Ｖｇ－Ｉｄ特性）の測定を行った。
　Ｖｇ－Ｉｄ特性の測定は、ドレイン電圧（Ｖｄ）を＋１Ｖに固定し、ゲート電圧（Ｖｇ）を－１５Ｖ～＋１５Ｖの範囲内で変化させ、各ゲート電圧におけるドレイン電流（Ｉｄ）を測定することにより行った。 For simplified TFT obtained above, using a semiconductor parameter analyzer 4156C (manufactured by Agilent Technologies), it was measured 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.
　実施例５の移動度は１．９ｃｍ２／Ｖｓであり、比較例１と同じ溶液Ａを用いた場合であっても、金属硝酸塩を含む溶液の塗布・乾燥による金属酸化物半導体前駆体膜形成工程と、金属酸化物半導体前駆体膜を金属酸化物半導体膜に転化する工程を複数回行うことで、トランジスタ特性向上効果が確認された。 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.
＜比較例２：溶液Ａを用いて塗布・乾燥を１回、紫外線照射処理を２回＞
　溶液Ａを用い、基板として熱酸化膜（膜厚１００ｎｍ）付ｐ型Ｓｉ基板を用い、熱酸化膜をゲート絶縁膜として用いる簡易型のＴＦＴを作製した。
　この熱酸化膜付ｐ型Ｓｉ １ｉｎｃｈ角の基板上に、溶液Ａを１５００ｒｐｍの回転速度で３０秒スピンコートした後、６０℃に加熱されたホットプレート上で１分間乾燥を行い、金属酸化物半導体前駆体膜を得た。 <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.
　得られた金属酸化物半導体前駆体膜に対し、下記条件で紫外線照射処理を行うことで金属酸化物半導体膜への転化を行った。
　紫外線照射装置としては、低圧水銀ランプを用いたＵＶオゾンクリーナー（フィルジェン社製、ＵＶ２５３Ｈ）を用いた。試料を厚さ４０ｍｍのガラス板上にセットし、ランプ－試料間距離を５ｍｍとした。試料位置での波長２５４ｎｍの紫外照度は、紫外線光量計（オーク製作所製、ＵＶ－Ｍ１０、受光器ＵＶ－２５）を用いて測定した。ランプ点灯から３分間で最大値に達し、１５ｍＷ／ｃｍ２であった。
　紫外線照射処理室内に窒素を６Ｌ／ｍｉｎで１０分間フローさせた後、９０分間、紫外線照射を行った。紫外線照射中は常に６Ｌ／ｍｉｎで窒素をフローさせた。紫外線照射処理時の基板温度をサーモラベルでモニターしたところ、１６０℃を示した。 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.
As 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 .
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.
　紫外線照射処理後、再び同一条件で紫外線照射処理を実施した。比較例２の金属酸化物半導体膜の膜厚を断面ＴＥＭ観察によって確認したところ、１０．２ｎｍであり、前述した実施例及び比較例に対して膜厚に大きな差がないことが確認された。
　上記得られた酸化物半導体膜上にソース・ドレイン電極を蒸着により成膜した。ソース・ドレイン電極はメタルマスクを用いたパターン成膜にて作製し、Ｔｉを５０ｎｍの厚さに成膜した。ソース・ドレイン電極サイズは各々１ｍｍ角とし、電極間距離は０．２ｍｍとした。 After the ultraviolet irradiation treatment, the ultraviolet irradiation treatment was again performed under the same conditions. When 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.
　上記で得られた簡易型ＴＦＴについて、半導体パラメータ・アナライザー４１５６Ｃ（アジレントテクノロジー社製）を用い、トランジスタ特性（Ｖｇ－Ｉｄ特性）の測定を行った。
　Ｖｇ－Ｉｄ特性の測定は、ドレイン電圧（Ｖｄ）を＋１Ｖに固定し、ゲート電圧（Ｖｇ）を－１５Ｖ～＋１５Ｖの範囲内で変化させ、各ゲート電圧におけるドレイン電流（Ｉｄ）を測定することにより行った。
　比較例２の移動度は０．５ｃｍ２／Ｖｓが得られ、塗布・乾燥を１回、紫外線照射処理を複数回行っても特性向上効果が得られないことが確認された。 For simplified TFT obtained above, using a semiconductor parameter analyzer 4156C (manufactured by Agilent Technologies), it was measured 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.
＜比較例３：溶液Ｂを用いて塗布・乾燥を１回、紫外線照射処理を１回＞
　溶液Ｂを用い、基板として熱酸化膜（膜厚１００ｎｍ）付ｐ型Ｓｉ基板を用い、熱酸化膜をゲート絶縁膜として用いる簡易型のＴＦＴを作製した。
　この熱酸化膜付ｐ型Ｓｉ １ｉｎｃｈ角の基板上に、溶液Ｂを１５００ｒｐｍの回転速度で３０秒スピンコートした後、６０℃に加熱されたホットプレート上で１分間乾燥を行い、金属酸化物半導体前駆体膜を得た。 <Comparative Example 3: Application / drying once using solution B, and UV irradiation treatment once>
A simple TFT using a solution B, 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 B is spin-coated at a rotational speed of 1500 rpm for 30 seconds on the p-type Si 1 inch square substrate with the thermal oxide film, and then dried on a hot plate heated to 60 ° C. for 1 minute, thereby obtaining a metal oxide semiconductor. A precursor film was obtained.
　得られた金属酸化物半導体前駆体膜に対し、下記条件で紫外線照射処理を行うことで金属酸化物半導体膜への転化を行った。
　紫外線照射装置としては、低圧水銀ランプを用いたＵＶオゾンクリーナー（フィルジェン社製、ＵＶ２５３Ｈ）を用いた。試料を厚さ４０ｍｍのガラス板上にセットし、ランプ－試料間距離を５ｍｍとした。試料位置での波長２５４ｎｍの紫外照度は、紫外線光量計（オーク製作所製、ＵＶ－Ｍ１０、受光器ＵＶ－２５）を用いて測定した。ランプ点灯から３分間で最大値に達し、１５ｍＷ／ｃｍ２であった。
　紫外線照射処理室内に窒素を６Ｌ／ｍｉｎで１０分間フローさせた後、９０分間、紫外線照射を行った。紫外線照射中は常に６Ｌ／ｍｉｎで窒素をフローさせた。紫外線照射処理時の基板温度をサーモラベルでモニターしたところ、１６０℃を示した。
　比較例３の金属酸化物半導体膜の膜厚を断面ＴＥＭ観察によって確認したところ、５．２ｎｍであった。 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.
As 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 .
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.
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.
　上記得られた酸化物半導体膜上にソース・ドレイン電極を蒸着により成膜した。ソース・ドレイン電極はメタルマスクを用いたパターン成膜にて作製し、Ｔｉを５０ｎｍの厚さに成膜した。ソース・ドレイン電極サイズは各々１ｍｍ角とし、電極間距離は０．２ｍｍとした。 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.
　上記で得られた簡易型ＴＦＴについて、半導体パラメータ・アナライザー４１５６Ｃ（アジレントテクノロジー社製）を用い、トランジスタ特性（Ｖｇ－Ｉｄ特性）の測定を行った。
　Ｖｇ－Ｉｄ特性の測定は、ドレイン電圧（Ｖｄ）を＋１Ｖに固定し、ゲート電圧（Ｖｇ）を－１５Ｖ～＋１５Ｖの範囲内で変化させ、各ゲート電圧におけるドレイン電流（Ｉｄ）を測定することにより行った。
　比較例３の移動度は０．２ｃｍ２／Ｖｓが得られ、低濃度の溶液を用いても塗布・乾燥及び紫外線照射処理を交互に複数回行わなければ特性向上効果が得られないことが確認された。 For simplified TFT obtained above, using a semiconductor parameter analyzer 4156C (manufactured by Agilent Technologies), it was measured 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.
　次に実施例１－５及び比較例１－３の金属酸化物半導体膜についてＸＲＲ分析を行った。測定装置はリガク社製ＡＴＸ－Ｇ、走査速度０．２°／ｍｉｎ、ステップ幅０．００１°で測定を行った。得られたＸＲＲスペクトルの０．３～４．０°の範囲を解析範囲とした。 Next, 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.
　実施例１－５及び比較例１－３の金属酸化物半導体膜は、酸化インジウム層を３～５層としたモデルのシミュレーション結果でフィッティングを行うことで、Ｒ値が全て０．０１以下の良い一致を示した。下記表３に実施例１－５及び比較例１－３の平均膜密度を示す。 The metal oxide semiconductor films of 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.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　繰り返し回数が増えるほど、平均膜密度が高くなることが確認された。 It was confirmed that the average film density increased as the number of repetitions increased.
＜実施例６＞
　溶液Ｆ（硝酸インジウム濃度：０．０３５ｍｏｌ／Ｌ）を用い、基板として熱酸化膜（膜厚１００ｎｍ）付ｐ型Ｓｉ基板を用い、熱酸化膜をゲート絶縁膜として用いる簡易型のＴＦＴを作製した。
　この熱酸化膜付ｐ型Ｓｉ １ｉｎｃｈ角の基板上に、溶液Ｆを１５００ｒｐｍの回転速度で３０秒スピンコートした後、６０℃に加熱されたホットプレート上で１分間乾燥を行い、金属酸化物半導体前駆体膜を得た。
　得られた金属酸化物半導体前駆体膜に対し、下記条件で紫外線照射処理を行うことで金属酸化物半導体膜への転化を行った。
　紫外線照射装置としては、低圧水銀ランプを用いたＵＶオゾンクリーナー（フィルジェン社製、ＵＶ２５３Ｈ）を用いた。試料を厚さ４０ｍｍのガラス板上にセットし、ランプ－試料間距離を５ｍｍとした。試料位置での波長２５４ｎｍの紫外照度は、紫外線光量計（オーク製作所製、ＵＶ－Ｍ１０、受光器ＵＶ－２５）を用いて測定した。ランプ点灯から３分間で最大値に達し、１５ｍＷ／ｃｍ２であった。
　紫外線照射処理室内に窒素を６Ｌ／ｍｉｎで１０分間フローさせた後、９０分間、紫外線照射を行った。紫外線照射中は常に６Ｌ／ｍｉｎで窒素をフローさせた。紫外線照射処理時の基板温度をサーモラベルでモニターしたところ、１６０℃を示した。
　上記溶液Ｆの塗布・乾燥及び紫外線照射による金属酸化物半導体膜への転化を交互に２回繰り返した後、更に溶液Ｆの塗布・乾燥を実施し、基板最高到達温度が１００℃となる条件で紫外線照射による金属酸化物半導体膜への転化を行った。
　上記得られた酸化物半導体膜上にソース・ドレイン電極を蒸着により成膜した。ソース・ドレイン電極はメタルマスクを用いたパターン成膜にて作製し、Ｔｉを５０ｎｍの厚さに成膜した。ソース・ドレイン電極サイズは各々１ｍｍ角とし、電極間距離は０．２ｍｍとした。
　実施例６の移動度は２．５ｃｍ２／Ｖｓであった。 <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.
As 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 .
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.
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.
＜実施例７＞
　溶液Ｆ（硝酸インジウム濃度：０．０３５ｍｏｌ／Ｌ）を用い、基板として熱酸化膜（膜厚１００ｎｍ）付ｐ型Ｓｉ基板を用い、熱酸化膜をゲート絶縁膜として用いる簡易型のＴＦＴを作製した。
　この熱酸化膜付ｐ型Ｓｉ １ｉｎｃｈ角の基板上に、溶液Ｆを１５００ｒｐｍの回転速度で３０秒スピンコートした後、６０℃に加熱されたホットプレート上で１分間乾燥を行い、金属酸化物半導体前駆体膜を得た。
　得られた金属酸化物半導体前駆体膜に対し、下記条件で紫外線照射処理を行うことで金属酸化物半導体膜への転化を行った。
　紫外線照射装置としては、低圧水銀ランプを用いたＵＶオゾンクリーナー（フィルジェン社製、ＵＶ２５３Ｈ）を用いた。試料を厚さ４０ｍｍのガラス板上にセットし、ランプ－試料間距離を５ｍｍとした。試料位置での波長２５４ｎｍの紫外照度は、紫外線光量計（オーク製作所製、ＵＶ－Ｍ１０、受光器ＵＶ－２５）を用いて測定した。ランプ点灯から３分間で最大値に達し、１５ｍＷ／ｃｍ２であった。
　紫外線照射処理室内に窒素を６Ｌ／ｍｉｎで１０分間フローさせた後、９０分間、紫外線照射を行った。紫外線照射中は常に６Ｌ／ｍｉｎで窒素をフローさせた。紫外線照射処理時の基板温度をサーモラベルでモニターしたところ、１６０℃を示した。
　上記溶液Ｆの塗布・乾燥及び紫外線照射による金属酸化物半導体膜への転化を交互に３回繰り返した。
　上記得られた酸化物半導体膜上にソース・ドレイン電極を蒸着により成膜した。ソース・ドレイン電極はメタルマスクを用いたパターン成膜にて作製し、Ｔｉを５０ｎｍの厚さに成膜した。ソース・ドレイン電極サイズは各々１ｍｍ角とし、電極間距離は０．２ｍｍとした。
　実施例７の移動度は３．０ｃｍ２／Ｖｓであった。 <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.
As 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 .
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.
＜比較例４＞
　溶液Ｆ（硝酸インジウム濃度：０．０３５ｍｏｌ／Ｌ）を用い、基板として熱酸化膜（膜厚１００ｎｍ）付ｐ型Ｓｉ基板を用い、熱酸化膜をゲート絶縁膜として用いる簡易型のＴＦＴを作製した。
　この熱酸化膜付ｐ型Ｓｉ １ｉｎｃｈ角の基板上に、溶液Ｆを１５００ｒｐｍの回転速度で３０秒スピンコートした後、６０℃に加熱されたホットプレート上で１分間乾燥を行い、金属酸化物半導体前駆体膜を得た。
　得られた金属酸化物半導体前駆体膜に対し、下記条件で紫外線照射処理を行うことで金属酸化物半導体膜への転化を行った。
　紫外線照射装置としては、低圧水銀ランプを用いたＵＶオゾンクリーナー（フィルジェン社製、ＵＶ２５３Ｈ）を用いた。試料を厚さ４０ｍｍのガラス板上にセットし、ランプ－試料間距離を５ｍｍとした。試料位置での波長２５４ｎｍの紫外照度は、紫外線光量計（オーク製作所製、ＵＶ－Ｍ１０、受光器ＵＶ－２５）を用いて測定した。ランプ点灯から３分間で最大値に達し、１５ｍＷ／ｃｍ２であった。
　紫外線照射処理室内に窒素を６Ｌ／ｍｉｎで１０分間フローさせた後、３０分間、紫外線照射を行った。紫外線照射中は常に６Ｌ／ｍｉｎで窒素をフローさせた。紫外線照射処理時の基板温度をサーモラベルでモニターしたところ、１００℃を示した。
　上記溶液Ｆの塗布・乾燥及び紫外線照射による金属酸化物半導体膜への転化を交互に２回繰り返した後、更に溶液Ｆの塗布・乾燥を実施し、基板最高到達温度が１６０℃となる条件で紫外線照射による金属酸化物半導体膜への転化を行った。
　上記得られた酸化物半導体膜上にソース・ドレイン電極を蒸着により成膜した。ソース・ドレイン電極はメタルマスクを用いたパターン成膜にて作製し、Ｔｉを５０ｎｍの厚さに成膜した。ソース・ドレイン電極サイズは各々１ｍｍ角とし、電極間距離は０．２ｍｍとした。
　比較例４の移動度は０．５ｃｍ２／Ｖｓであった。 <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.
As 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 .
After flowing nitrogen at 6 L / min for 10 minutes in the ultraviolet irradiation treatment chamber, 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.
　実施例６、７及び比較例４の平均膜密度を下記表４に示す。 Table 4 below shows the average film densities of Examples 6 and 7 and Comparative Example 4.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
＜比較例５＞
　基板として熱酸化膜（膜厚１００ｎｍ）付ｐ型Ｓｉ基板を用い、熱酸化膜をゲート絶縁膜として用いる簡易型のＴＦＴを作製した。
　熱酸化膜付ｐ型Ｓｉ １ｉｎｃｈ角の基板上に、作製した溶液Ａを１５００ｒｐｍの回転速度で３０秒スピンコートした後、６０℃に加熱されたホットプレート上で１分間乾燥を行い、金属酸化物半導体前駆体膜を得た。
　得られた金属酸化物半導体前駆体膜を、大気中、２５０℃で９０分間、ホットプレートによる加熱処理を行うことで金属酸化物半導体膜への転化を行った。
　比較例５の金属酸化物半導体膜の膜厚を断面ＴＥＭ観察によって確認したところ、１１．４ｎｍであった。
　上記得られた酸化物半導体膜上にソース・ドレイン電極を蒸着により成膜した。ソース・ドレイン電極はメタルマスクを用いたパターン成膜にて作製し、Ｔｉを５０ｎｍの厚さに成膜した。ソース・ドレイン電極サイズは各々１ｍｍ角とし、電極間距離は０．２ｍｍとした。 <Comparative Example 5>
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.
When the film thickness of the metal oxide semiconductor film of the comparative example 5 was confirmed by cross-sectional TEM observation, it was 11.4 nm.
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.
　上記で得られた簡易型ＴＦＴについて、半導体パラメータ・アナライザー４１５６Ｃ（アジレントテクノロジー社製）を用い、トランジスタ特性（Ｖｇ－Ｉｄ特性）の測定を行った。
　Ｖｇ－Ｉｄ特性の測定は、ドレイン電圧（Ｖｄ）を＋１Ｖに固定し、ゲート電圧（Ｖｇ）を－１５Ｖ～＋１５Ｖの範囲内で変化させ、各ゲート電圧におけるドレイン電流（Ｉｄ）を測定することにより行った。
　比較例５の移動度は０．５ｃｍ２／Ｖｓであった。 For simplified TFT obtained above, using a semiconductor parameter analyzer 4156C (manufactured by Agilent Technologies), it was measured 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.
＜実施例８＞
　基板として熱酸化膜（膜厚１００ｎｍ）付ｐ型Ｓｉ基板を用い、熱酸化膜をゲート絶縁膜として用いる簡易型のＴＦＴを作製した。
　熱酸化膜付ｐ型Ｓｉ １ｉｎｃｈ角の基板上に、作製した溶液Ｅを１５００ｒｐｍの回転速度で３０秒スピンコートした後、６０℃に加熱されたホットプレート上で１分間乾燥を行い、金属酸化物半導体前駆体膜を得た。
　得られた金属酸化物半導体前駆体膜を、大気中、２５０℃で９０分間、ホットプレートによる加熱処理を行うことで金属酸化物半導体膜への転化を行った。
　上記溶液の塗布・乾燥及び金属酸化物半導体膜への転化を、交互に各１２回繰り返した。
　実施例８の金属酸化物半導体膜の膜厚を断面ＴＥＭ観察によって確認したところ、１０．３ｎｍであった。
　上記得られた酸化物半導体膜上にソース・ドレイン電極を蒸着により成膜した。ソース・ドレイン電極はメタルマスクを用いたパターン成膜にて作製し、Ｔｉを５０ｎｍの厚さに成膜した。ソース・ドレイン電極サイズは各々１ｍｍ角とし、電極間距離は０．２ｍｍとした。 <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.
It was 10.3 nm when the film thickness of the metal oxide semiconductor film of Example 8 was confirmed by cross-sectional TEM observation.
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.
　上記で得られた簡易型ＴＦＴについて、半導体パラメータ・アナライザー４１５６Ｃ（アジレントテクノロジー社製）を用い、トランジスタ特性（Ｖｇ－Ｉｄ特性）の測定を行った。
　Ｖｇ－Ｉｄ特性の測定は、ドレイン電圧（Ｖｄ）を＋１Ｖに固定し、ゲート電圧（Ｖｇ）を－１５Ｖ～＋１５Ｖの範囲内で変化させ、各ゲート電圧におけるドレイン電流（Ｉｄ）を測定することにより行った。
　実施例８の移動度は８．３ｃｍ２／Ｖｓであった。 For simplified TFT obtained above, using a semiconductor parameter analyzer 4156C (manufactured by Agilent Technologies), it was measured 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.
　実施例８及び比較例５の平均膜密度を下記表５に示す。 Table 5 shows the average film density of Example 8 and Comparative Example 5.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　日本特許出願２０１３－２５３１９０の開示はその全体が参照により本明細書に取り込まれる。
　本明細書に記載された全ての文献、特許、特許出願、および技術規格は、個々の文献、特許、特許出願、および技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。 The entire disclosure of Japanese Patent Application 2013-253190 is incorporated herein by reference.
All documents, patents, patent applications, and technical standards mentioned in this specification are specifically and individually described as individual documents, patents, patent applications, and technical standards are incorporated by reference. To the same extent, it is incorporated herein by reference.

Claims (21)

  1. 　金属硝酸塩を含む溶液を基板上に塗布し、塗布膜を乾燥させて金属酸化物前駆体膜を形成する工程と、前記金属酸化物前駆体膜を金属酸化物膜に転化する工程とを交互に２回以上繰り返すことを含み、
    　前記金属酸化物前駆体膜を前記金属酸化物膜に転化する少なくとも２回の工程において、前記基板の最高到達温度を１２０℃以上２５０℃以下にして前記金属酸化物前駆体膜を前記金属酸化物膜に転化する金属酸化物膜の製造方法。     A step of applying a solution containing a metal nitrate on a substrate and drying the coating film to form a metal oxide precursor film and a step of converting the metal oxide precursor film into a metal oxide film alternately Including repeating twice or more,
    In at least two steps of converting the metal oxide precursor film to the metal oxide film, a 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 to the metal oxide. A method for producing a metal oxide film to be converted into a film.
  2. 　前記金属酸化物前駆体膜を前記金属酸化物膜に転化する全ての工程において、前記基板の最高到達温度を１２０℃以上２５０℃以下にして前記金属酸化物前駆体膜を前記金属酸化物膜に転化する請求項１に記載の金属酸化物膜の製造方法。 In all the steps of converting the metal oxide precursor film into the metal oxide film, the substrate reaches a maximum temperature of 120 ° C. or more and 250 ° C. or less, and the metal oxide precursor film is converted into the metal oxide film. The method for producing a metal oxide film according to claim 1 to be converted.
  3. 　前記金属酸化物前駆体膜を前記金属酸化物膜に転化する全ての工程において、前記基板の最高到達温度を２００℃以下にする請求項１又は請求項２に記載の金属酸化物膜の製造方法。 3. The method for producing a metal oxide film according to claim 1, wherein a maximum temperature of the substrate is set to 200 ° C. or lower in all steps of converting the metal oxide precursor film to the metal oxide film. .
  4. 　前記金属酸化物前駆体膜を前記金属酸化物膜に転化する工程が、前記金属酸化物前駆体膜に紫外線を照射する工程を含む請求項１～請求項３のいずれか一項に記載の金属酸化物膜の製造方法。 The metal according to any one of claims 1 to 3, wherein 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 rays. Manufacturing method of oxide film.
  5. 　前記金属酸化物前駆体膜を形成する工程と、前記金属酸化物前駆体膜を前記金属酸化物膜に転化する工程とを交互に４回以上繰り返す請求項１～請求項４のいずれか一項に記載の金属酸化物膜の製造方法。 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. The manufacturing method of the metal oxide film as described in 2.
  6. 　前記金属硝酸塩を含む溶液が、少なくとも硝酸インジウムを含む請求項１～請求項５のいずれか一項に記載の金属酸化物膜の製造方法。 The method for producing a metal oxide film according to any one of claims 1 to 5, wherein the solution containing the metal nitrate contains at least indium nitrate.
  7. 　前記硝酸インジウムを含む溶液が、亜鉛、錫、ガリウム及びアルミニウムから選ばれる少なくとも１つの金属原子を含む化合物をさらに含有する請求項６に記載の金属酸化物膜の製造方法。 The method for producing a metal oxide film according to claim 6, wherein the solution containing indium nitrate further contains a compound containing at least one metal atom selected from zinc, tin, gallium and aluminum.
  8. 　前記金属硝酸塩を含む溶液の金属モル濃度が、０．０１ｍｏｌ／Ｌ以上０．５ｍｏｌ／Ｌ以下である請求項１～請求項７のいずれか一項に記載の金属酸化物膜の製造方法。 The method for producing a metal oxide film according to any one of claims 1 to 7, wherein a 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. 　前記金属酸化物前駆体膜を形成する工程と、前記金属酸化物前駆体膜を前記金属酸化物膜に転化する工程とを各々１回行って得られる金属酸化物膜の平均膜厚が６ｎｍ以下である請求項１～請求項８のいずれか一項に記載の金属酸化物膜の製造方法。 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 the metal oxide film once is 6 nm or less. The method for producing a metal oxide film according to any one of claims 1 to 8, wherein:
  10. 　前記金属酸化物前駆体膜を形成する工程と、前記金属酸化物前駆体膜を前記金属酸化物膜に転化する工程とを各々１回行って得られる金属酸化物膜の平均膜厚が２ｎｍ以下である請求項９に記載の金属酸化物膜の製造方法。 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 the metal oxide film once is 2 nm or less. The method for producing a metal oxide film according to claim 9.
  11. 　前記金属硝酸塩を含む溶液が、メタノール又はメトキシエタノールを含む請求項１～請求項１０のいずれか一項に記載の金属酸化物膜の製造方法。 The method for producing a metal oxide film according to any one of claims 1 to 10, wherein the solution containing the metal nitrate contains methanol or methoxyethanol.
  12. 　前記金属酸化物前駆体膜を前記金属酸化物膜に転化する工程が、前記金属酸化物前駆体膜に対し、波長３００ｎｍ以下の紫外線を１０ｍＷ／ｃｍ２以上の強度で照射する工程を含む請求項４～請求項１１のいずれか一項に記載の金属酸化物膜の製造方法。 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 rays having a wavelength of 300 nm or less at an intensity of 10 mW / cm 2 or more. The method for producing a metal oxide film according to any one of claims 4 to 11.
  13. 　前記金属酸化物前駆体膜に前記紫外線を照射する際に用いる光源が、低圧水銀ランプである請求項１２に記載の金属酸化物膜の製造方法。 The method for producing a metal oxide film according to claim 12, wherein a light source used when irradiating the metal oxide precursor film with the ultraviolet light is a low-pressure mercury lamp.
  14. 　前記金属酸化物前駆体膜を形成する工程において、前記塗布膜を乾燥させる際の前記基板の温度が３５℃以上１００℃以下である請求項１～請求項１３のいずれか一項に記載の金属酸化物膜の製造方法。 The metal according to any one of claims 1 to 13, wherein in the step of forming the metal oxide precursor film, a temperature of the substrate when the coating film is dried is 35 ° C or more and 100 ° C or less. Manufacturing method of oxide film.
  15. 　前記金属酸化物前駆体膜を形成する工程において、前記金属硝酸塩を含む溶液を、インクジェット法、ディスペンサー法、凸版印刷法、及び凹版印刷法から選択される少なくとも一種の塗布法により塗布する請求項１～請求項１４のいずれか一項に記載の金属酸化物膜の製造方法。 2. In the step of forming the metal oxide precursor film, the solution containing the 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. The method for producing a metal oxide film according to any one of claims 14 to 14.
  16. 　請求項１～請求項１５のいずれか一項に記載の金属酸化物膜の製造方法を用いて作製された金属酸化物膜。 A metal oxide film produced using the method for producing a metal oxide film according to any one of claims 1 to 15.
  17. 　金属酸化物半導体膜である請求項１６に記載の金属酸化物膜。 The metal oxide film according to claim 16, which is a metal oxide semiconductor film.
  18. 　請求項１７に記載の金属酸化物膜を含む活性層と、ソース電極と、ドレイン電極と、ゲート絶縁膜と、ゲート電極とを有する薄膜トランジスタ。 A thin film transistor having an active layer including the metal oxide film according to claim 17, a source electrode, a drain electrode, a gate insulating film, and a gate electrode.
  19. 　請求項１８に記載の薄膜トランジスタを備えた表示装置。 A display device comprising the thin film transistor according to claim 18.
  20. 　請求項１８に記載の薄膜トランジスタを備えたイメージセンサ。 An image sensor comprising the thin film transistor according to claim 18.
  21. 　請求項１８に記載の薄膜トランジスタを備えたＸ線センサ。 An X-ray sensor comprising the thin film transistor according to claim 18.
PCT/JP2014/079768 2013-12-06 2014-11-10 Method for producing metal oxide film, metal oxide film, thin-film transistor, display device, image sensor, and x-ray sensor WO2015083500A1 (en)

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