KR20170070179A - Method for manufacturing metal oxide film, metal oxide film, thin-film transistor, method for manufacturing thin-film transistor, electronic device, and ultraviolet irradiation device - Google Patents

Method for manufacturing metal oxide film, metal oxide film, thin-film transistor, method for manufacturing thin-film transistor, electronic device, and ultraviolet irradiation device Download PDF

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KR20170070179A
KR20170070179A KR1020177013093A KR20177013093A KR20170070179A KR 20170070179 A KR20170070179 A KR 20170070179A KR 1020177013093 A KR1020177013093 A KR 1020177013093A KR 20177013093 A KR20177013093 A KR 20177013093A KR 20170070179 A KR20170070179 A KR 20170070179A
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metal oxide
method
film
oxide film
substrate
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KR1020177013093A
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KR101954551B1 (en
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후미히코 모치즈키
마사히로 다카타
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후지필름 가부시키가이샤
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Priority to PCT/JP2015/084178 priority patent/WO2016088882A1/en
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    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G15/00Compounds of gallium, indium or thallium
    • GPHYSICS
    • G02OPTICS
    • G02FDEVICES OR ARRANGEMENTS, THE OPTICAL OPERATION OF WHICH IS MODIFIED BY CHANGING THE OPTICAL PROPERTIES OF THE MEDIUM OF THE DEVICES OR ARRANGEMENTS FOR THE CONTROL OF THE INTENSITY, COLOUR, PHASE, POLARISATION OR DIRECTION OF LIGHT, e.g. SWITCHING, GATING, MODULATING OR DEMODULATING; TECHNIQUES OR PROCEDURES FOR THE OPERATION THEREOF; FREQUENCY-CHANGING; NON-LINEAR OPTICS; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating, or modulating; Non-linear optics
    • G02F1/01Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating, or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating, or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/136Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
    • G02F1/1362Active matrix addressed cells
    • G02F1/1368Active matrix addressed cells in which the switching element is a three-electrode device
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    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02109Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112Forming 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
    • H01L21/02172Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
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    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02109Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
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    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
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    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02296Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02345Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to radiation, e.g. visible light
    • H01L21/02348Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to radiation, e.g. visible light treatment by exposure to UV light
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    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/324Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
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    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/77Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate
    • H01L21/78Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices
    • H01L21/82Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices to produce devices, e.g. integrated circuits, each consisting of a plurality of components
    • H01L21/822Manufacture or treatment of devices consisting of a plurality of solid state components or integrated circuits formed in, or on, a common substrate with subsequent division of the substrate into plural individual devices to produce devices, e.g. integrated circuits, each consisting of a plurality of components the substrate being a semiconductor, using silicon technology
    • H01L21/8232Field-effect technology
    • H01L21/8234MIS technology, i.e. integration processes of field effect transistors of the conductor-insulator-semiconductor type
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    • H01L27/00Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier
    • H01L27/04Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being a semiconductor body
    • H01L27/06Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being a semiconductor body including a plurality of individual components in a non-repetitive configuration
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    • H01L27/00Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier
    • H01L27/04Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being a semiconductor body
    • H01L27/08Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being a semiconductor body including only semiconductor components of a single kind
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    • H01L29/00Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof; Multistep manufacturing processes therefor
    • H01L29/66Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68Types 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
    • H01L29/76Unipolar devices, e.g. field effect transistors
    • H01L29/772Field effect transistors
    • H01L29/78Field effect transistors with field effect produced by an insulated gate
    • H01L29/786Thin film transistors, i.e. transistors with a channel being at least partly a thin film

Abstract

A precursor film forming step of applying a solution containing indium and a solvent on a substrate to form a precursor film of a metal oxide film; and a step of forming a precursor film on the heated precursor film by irradiating ultraviolet rays under an atmosphere of 10 Pa or less to form a precursor film as a metal oxide film A vacuum pump for decompressing the inside of the vacuum chamber to 10 Pa or less, and a vacuum pump for supporting the substrate in the vacuum chamber. And a light source for irradiating the supported substrate with ultraviolet light.

Description

TECHNICAL FIELD The present invention relates to a metal oxide film, a metal oxide film, a thin film transistor, a method of manufacturing a thin film transistor, an electronic device, and an ultraviolet ray irradiating apparatus. , ELECTRONIC DEVICE, AND ULTRAVIOLET IRRADIATION DEVICE}

The present invention relates to a method of manufacturing a metal oxide film, a metal oxide film, a thin film transistor, a method of manufacturing a thin film transistor, an electronic device, and an ultraviolet ray irradiation apparatus.

The metal oxide semiconductor film has been put to practical use by being put to practical use in the production by the vacuum film forming method. On the other hand, research and development have been actively conducted on the fabrication of a metal oxide semiconductor film by a liquid phase process aiming at forming a metal oxide semiconductor film having high semiconductor characteristics under low temperature and atmospheric pressure.

For example, Nature, Vol. 489 (2012) p. 128. It has been reported that a thin film transistor having a high transporting property at a low temperature of 150 캜 or below is produced by coating a solution on a substrate and irradiating it with ultraviolet rays.

Meanwhile, International Publication No. 2009-81862 discloses a method of forming a metal oxide semiconductor precursor film using a solution of a metal salt such as an inexpensive nitrate salt or an acetate salt, and performing a semiconductor conversion process by heat treatment or microwave irradiation to form a metal oxide film Lt; / RTI >

Also, International Publication No. 2009-11224 discloses a method for forming a metal oxide semiconductor film by forming a precursor film of a metal oxide semiconductor using a solution of nitrate, acetate or the like, and irradiating light in the presence of oxygen.

Nature, Vol. 489 (2012) p. In the method disclosed in 128, it is described that nitrate or acetate is heated and stirred in a solvent at 75 ° C for 12 hours to produce a metal methoxyethoxide. However, do. In addition, since alkoxide is produced, hydrolysis is apt to occur in the atmosphere and there is a problem in stability.

On the other hand, in the method disclosed in International Publication No. 2009-81862 or International Publication No. 2009-11224, it is difficult to obtain a metal oxide film having high electric transfer characteristics at a low temperature of less than 200 캜.

The present invention provides a method for producing a metal oxide film which can easily produce a metal oxide film with reduced unnecessary residual components which may hinder the function expected of the metal oxide film by a coating method and a method for producing a metal oxide film in which unnecessary residual components are reduced .

It is another object of the present invention to provide a thin film transistor, a method of manufacturing a thin film transistor, and an electronic device which have high linear mobility and excellent operation stability.

It is another object of the present invention to provide an ultraviolet irradiation device capable of easily conducting a telephone call from a precursor film to a metal oxide film.

In order to achieve the above object, the following invention is provided.

A precursor film forming step of forming a precursor film of a metal oxide film by applying a solution containing indium and a solvent on a substrate;

Irradiating the heated precursor film with ultraviolet radiation in an atmosphere of 10 Pa or less to convert the precursor film into a metal oxide film.

&Lt; 2 > A method for producing a metal oxide film according to < 1 >, wherein ultraviolet irradiation is performed in an atmosphere of 1 Pa or less.

<3> The method for producing a metal oxide film according to <1> or <2>, wherein the content of indium contained in the solution is 50 atom% or more based on the total amount of metal components contained in the solution.

&Lt; 4 > The method for producing a metal oxide film according to any one of < 1 > to < 3 >, wherein the temperature of the substrate when irradiated with ultraviolet rays is 150 DEG C or lower.

<5> The method for producing a metal oxide film according to any one of <1> to <4>, wherein the solution is a solution of indium nitrate.

<6> The method for producing a metal oxide film according to <5>, wherein the solution of indium nitrate contains at least one of methanol and methoxyethanol as a solvent.

<7> The method for producing a metal oxide film according to any one of <1> to <6>, wherein the solution further contains at least one selected from the group consisting of zinc, tin, gallium and aluminum.

<8> The method for producing a metal oxide film according to any one of <1> to <7>, wherein the concentration of the metal component in the solution is 0.01 mol / L or more and 0.5 mol / L or less.

<9> The method for producing a metal oxide film according to any one of <1> to <8>, wherein the precursor film is irradiated with ultraviolet rays at an illuminance of 10 mW / cm 2 or more with ultraviolet rays containing light having a wavelength of 300 nm or less.

&Lt; 10 > A process for producing a precursor film according to any one of < 1 > to < 9 >, wherein the solution is applied on a substrate by at least one coating method selected from the ink jet method, the dispenser method, the relief printing method, Wherein the metal oxide film is formed on the surface of the metal oxide film.

<11> A metal oxide film produced by the method for producing a metal oxide film according to any one of <1> to <10>.

<12> A metal oxide film containing indium and having a hydrogen content of 1.0 × 10 22 atoms / cm 3 or less.

<13> The metal oxide film according to <11> or <12>, wherein the content of indium contained in the metal oxide film is 50 atom% or more with respect to the total amount of metal components contained in the metal oxide film.

<14> A method of manufacturing a thin film transistor, comprising the step of forming a metal oxide film by the method of manufacturing a metal oxide film according to any one of <1> to <10>.

<15> A thin film transistor comprising a metal oxide film according to any one of <11> to <13>.

&Lt; 16 > An electronic device having the thin film transistor according to <15>.

<17> A pressure-

A support stand for supporting and heating the substrate in the vacuum chamber,

A vacuum pump for reducing the pressure inside the decompression chamber to 10 Pa or less,

And a light source for irradiating the substrate supported on the support with ultraviolet light.

<18> The ultraviolet irradiating apparatus according to <17>, comprising a position adjusting means for adjusting a positional relationship between a light source and a support.

According to the present invention, there is provided a method for producing a metal oxide film, which can easily produce a metal oxide film in which unnecessary residual components that may inhibit the function expected of the metal oxide film are reduced by a coating method, and a method for producing a metal oxide film in which unnecessary residual components are reduced A film is provided.

According to the present invention, there is provided a thin film transistor, a method of manufacturing a thin film transistor, and an electronic device which are high in linear mobility and excellent in operational stability.

Further, according to the present invention, there is provided an ultraviolet irradiation apparatus capable of easily conducting a telephone call from a precursor film to a metal oxide film.

1 is a schematic view showing the structure of an example (top gate-top contact type) of a thin film transistor manufactured by the present invention.
2 is a schematic view showing the structure of an example (top gate-bottom contact type) of a thin film transistor manufactured by the present invention.
3 is a schematic view showing the structure of an example (bottom gate-top contact type) of a thin film transistor manufactured by the present invention.
4 is a schematic view showing the structure of an example (bottom gate-bottom contact type) of a thin film transistor manufactured by the present invention.
5 is a schematic cross-sectional view showing a part of the liquid crystal display device of the embodiment.
6 is a schematic configuration diagram of the electric wiring of the liquid crystal display device shown in Fig.
7 is a schematic cross-sectional view showing a part of the organic EL display device of the embodiment.
8 is a schematic configuration diagram of the electric wiring of the organic EL display device shown in Fig.
9 is a schematic sectional view showing a part of the X-ray sensor array of the embodiment.
10 is a schematic configuration diagram of the electric wiring of the X-ray sensor array shown in Fig.
Fig. 11 is a schematic configuration diagram showing an example of the configuration of an ultraviolet irradiation device used in the telephone process in this disclosure. Fig.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

In the drawings, members (components) having the same or corresponding functions are denoted by the same reference numerals, and a description thereof will be omitted. In the present specification, when numerical ranges are indicated by the symbols "~ ", the lower limit value and the upper limit value are included.

[Method for producing metal oxide film]

The method of manufacturing a metal oxide film of the present disclosure includes a precursor film forming step of forming a precursor film of a metal oxide film by applying a solution containing indium and a solvent on a substrate; And a telephone process in which the precursor film is converted into a metal oxide film by conducting irradiation.

In the case of forming a metal oxide film by a liquid phase method using a solution, there is no need for a large-scale vacuum film forming apparatus as used in the vapor phase method, but an unnecessary component likely to inhibit the function of the metal oxide film is likely to remain, (For example, resistivity and electrical stability).

As a result of repeated research by the present inventors, the precursor film of the metal oxide film formed by coating a solution containing indium is irradiated with ultraviolet light (UV) in an atmosphere close to vacuum, and the hydrogen content in the metal oxide film is greatly reduced , A metal oxide film having good electrical characteristics can be obtained. The reason for this is not clear, but it is considered that when UV irradiation is performed while heating the precursor film under a high degree of reduced pressure, unnecessary components in the film are decomposed to easily escape from the film.

&Lt; Precursor Film Forming Step &

In the precursor film forming step, a solution containing indium and a solvent (hereinafter sometimes referred to as a " metal oxide precursor solution ") is coated on a substrate to form a precursor film of a metal oxide film May be described).

(solution)

In this disclosure, the solution (metal oxide precursor solution) for forming the precursor film of the metal oxide film contains at least indium as a metal component. Here, the "metal component" means a metal atom (including an ion) contained in a metal oxide precursor solution.

The metal oxide precursor solution is obtained by weighing a solute such as a metal salt serving as a raw material so that the solution reaches a desired concentration and dissolving it by stirring in a solvent. The stirring time is not particularly limited as long as the solute is sufficiently dissolved.

The indium content in the metal oxide precursor solution is preferably 50 atom% or more based on the total amount of the metal components contained in the solution. By using the metal oxide precursor solution containing indium in the above concentration range, a metal oxide film in which 50 atom% or more of the total amount of metal components in the film becomes indium can be obtained, and a metal oxide film having high electron transfer characteristics can be obtained. Here, examples of the metal component (metal element) other than indium that can be contained in the metal oxide film include Ga, Zn, Mg, Al, Sn, Sb, Cd and Ge,

As the compound (raw material) derived from the metal component contained in the metal oxide precursor solution, a metal atom-containing compound such as a metal salt, a metal halide, or an organometallic compound can be used.

Examples of the metal salt include nitrates, sulfates, phosphates, carbonates, acetates and oxalates. Examples of the metal halides include chloride, iodide and bromine. Examples of the metal compounds include metal alkoxides , An organic acid salt, and a metal beta-diketonate.

The metal oxide precursor solution is preferably a solution (indium nitrate solution) in which at least nitric acid is dissolved in a solvent. The metal oxide precursor film obtained by applying the metal oxide precursor solution in which indium nitrate is dissolved can be efficiently decomposed by the ultraviolet light in the indium nitrate in the telephone process and can be easily dialed into the indium containing oxide film. In addition, indium nitrate may be a hydrate.

The metal oxide precursor solution is preferably a metal element other than indium and further preferably at least one selected from the group consisting of zinc, tin, gallium, and aluminum. When the metal oxide precursor solution contains an appropriate amount of the metal element other than indium, the electrical stability of the resulting metal oxide film is improved. For example, in the metal oxide semiconductor film, it is possible to control the threshold voltage to a desired value by including an appropriate amount of the above-described metal element other than indium.

(IGO), In-Zn-O (IZO), In-Ga-O (IGO), or the like can be used as the metal oxide (oxide semiconductor or oxide conductor) ), In-Sn-O (ITO), and In-Sn-Zn-O (ITZO).

The solvent used for the metal oxide precursor solution containing indium nitrate is not particularly limited as long as it dissolves the metal atom-containing compound to be used, and may be selected from water, an alcohol solvent (methanol, ethanol, propanol, ethylene glycol and the like) , N-dimethylformamide and the like), ketone solvents (acetone, N-methylpyrrolidone, sulfolane, N, N-dimethylimidazolidinone, etc.), ether solvents (tetrahydrofuran, methoxyethanol, etc. ), Nitrile solvents (acetonitrile and the like), and other hetero atom-containing solvents other than the above. These solvents may be used alone or in combination of two or more.

Particularly, at least one of methanol and methoxyethanol can be suitably used from the viewpoints of solubility and applicability.

The concentration of the metal component in the metal oxide precursor solution (the sum of the mole fractions of the respective metals when a plurality of metals are included) can be arbitrarily selected depending on the viscosity of the solution and the desired film thickness. L or more and 1.0 mol / L or less, and more preferably 0.01 mol / L or more and 0.5 mol / L or less, from the viewpoints of productivity and productivity.

(Board)

The shape, structure, size, etc. of the substrate for forming the metal oxide film in the present disclosure are not particularly limited and can be appropriately selected according to the purpose.

For example, the substrate may have a single-layer structure or a stacked structure.

The material constituting the substrate is not particularly limited, and a substrate made of an inorganic material such as glass or YSZ (Yttria-Stabilized Zirconia), resin, resin composite material or the like can be used. Among these, a resin substrate or a substrate made of a resin composite material (resin composite substrate) is preferable in that it is lightweight and has flexibility.

Specific examples thereof include polystyrene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polystyrene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide , Fluoropolymers such as polyimide, polyamideimide, polyetherimide, polybenzazole, polyphenylene sulfide, polycycloolefin, norbornene resin and polychlorotrifluoroethylene, liquid crystal polymers, acrylic resins, epoxy resins, Synthetic resin substrates such as silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic ether, maleimide-olefin, cellulose, and episulfide compound.

Examples of the inorganic material contained in the composite material of the inorganic material and the resin include inorganic particles such as silicon oxide particles, metal nanoparticles, inorganic oxide nanoparticles and inorganic nitride nanoparticles, carbon materials such as carbon fibers and carbon nanotubes, Glass materials such as flakes, glass fibers and glass beads.

It is also possible to use a composite plastic material of a resin and a clay mineral, a composite plastic material of a particle having a resin and a mica-derived crystal structure, a laminated plastic material having at least one bonding interface between the resin and the thin glass, And a composite material having barrier performance with at least one bonded interface by lamination.

It is also possible to use a metal substrate such as a stainless steel substrate or a metal multilayer substrate formed by laminating stainless and dissimilar metals, an aluminum substrate or an aluminum substrate with an oxide film having an improved surface insulating property by performing oxidation treatment (for example, anodizing treatment) Silicon substrate or the like may be used.

The resin substrate or resin composite substrate preferably has excellent heat resistance, dimensional stability, solvent resistance, electrical insulation, workability, low air permeability, and low hygroscopicity. The resin substrate or the resin composite substrate may be provided with a gas barrier layer for preventing permeation of moisture and oxygen, an undercoat layer for improving the flatness of the substrate or the adhesion with the lower electrode, and the like.

Although the thickness of the substrate used in the present disclosure is not particularly limited, it is preferably 50 μm or more and 500 μm or less. When the thickness of the substrate is 50 m or more, the flatness of the substrate itself is further improved. When the thickness of the substrate is 500 m or less, the flexibility of the substrate itself is further improved, and the substrate is more easily used as a substrate for a flexible device.

In addition, a lower electrode, an insulating film, and the like may be provided on the substrate. In this case, a metal oxide film is formed on the lower electrode or the insulating film on the substrate.

(Surface treatment)

And a step of performing surface treatment on the surface of the substrate on which the coating film (precursor film) is formed, before applying the metal oxide precursor solution onto the substrate. For example, in the case of manufacturing a thin film transistor, foreign matter such as moisture, carbon, organic component adheres to the surface of the insulating film adversely affects the transistor characteristics (operational stability) if left for a long time under the indoor environment after formation of the gate insulating film. There is a possibility. Therefore, as the pretreatment for applying the metal oxide precursor solution to the substrate, it is preferable to perform surface treatment for removing water and contamination to the substrate. Examples of the surface treatment of the substrate include ultraviolet (UV) ozone treatment, argon plasma treatment, nitrogen plasma treatment and the like.

As the UV ozone treatment, for example, a UV ozone treatment apparatus (Model 144AX-100 made by Jelight-company-Inc) is used for 1 to 3 minutes under the following conditions and wavelength .

· Conditions: atmospheric pressure, in air

Wavelength: 254 nm (30 mW / cm 2 ), 185 nm (3.3 mW / cm 2 )

(apply)

Examples of the method of applying the metal oxide precursor solution on a substrate include spray coating, spin coating, blade coating, dip coating, casting, roll coating, bar coating, die coating, mist, A dispenser method, a screen printing method, a convex printing method, a concave printing method, and the like. In particular, from the viewpoint of easily forming a fine pattern, it is preferable to use at least one coating method selected from an ink jet method, a dispenser method, a convex printing method, and a concave printing method.

(dry)

After the metal oxide precursor solution is coated on the substrate, the coating film is preferably dried by heat treatment to obtain a metal oxide precursor film. By drying, the fluidity of the coating film can be reduced, and the flatness of the finally obtained metal oxide film can be improved. In addition, by selecting an appropriate drying temperature (preferably 35 DEG C or more and 100 DEG C or less), a more dense metal oxide film can be finally obtained.

The method of the heat treatment is not particularly limited and can be selected from hot plate heating, electric furnace heating, infrared heating, microwave heating and the like.

The initiation of the drying is not particularly limited, but it is preferable that the drying is started within 5 minutes from the viewpoint of keeping the flatness of the film uniform.

<Telephone process>

In the telephone process, the precursor film in a heated state is irradiated with ultraviolet rays in an atmosphere of 10 Pa or less to convert the precursor film into a metal oxide film.

From the standpoint of further reducing the hydrogen content in the metal oxide film, the pressure at the time of dialysis is preferably 1 Pa or less, more preferably 0.1 Pa or less. A metal oxide film having a hydrogen content of 1.0 x 10 &lt; 22 &gt; atoms / cm &lt; 3 &gt; or less can be obtained by setting the pressure when the precursor film is converted to a metal oxide film to 1 Pa or less. In addition, the hydrogen content in the metal oxide film in this disclosure is calculated from secondary ion mass spectrometry (SIMS).

The temperature of the substrate at the time of ultraviolet irradiation is preferably less than 200 占 폚. When the substrate temperature in the telephone process is less than 200 DEG C, application to a resin substrate having low heat resistance is facilitated, and increase in heat energy can be suppressed, and manufacturing cost can be suppressed to a low level. It is more preferable that the substrate temperature in the telephone process is 150 DEG C or less from the viewpoint that it is possible to cope with more various resin substrates.

On the other hand, from the standpoint of conducting a telephone call from the precursor film to the metal oxide film in a short time, the substrate temperature in the telephone process is preferably 120 ° C or higher. The substrate temperature in the telephone process can be measured by a thermo-label.

Although the process of converting into a metal oxide film is different depending on the illuminance of the ultraviolet ray, it is preferably from 5 seconds to 120 minutes from the viewpoint of productivity.

The heating means for the substrate in the telephone process is not particularly limited and may be selected from hot plate heating, electric furnace heating, infrared heating, microwave heating, and the like.

The heating of the substrate during the ultraviolet ray treatment may be performed using radiation heat from a light source such as an ultraviolet lamp used for ultraviolet ray irradiation, or the temperature of the substrate may be controlled by a heater or the like. When radiant heat from an ultraviolet lamp or the like is used, it can be controlled by adjusting the distance between the lamp and the substrate and / or the lamp output.

In the telephone process, it is preferable to irradiate the film surface of the metal oxide precursor film with ultraviolet light containing light having a wavelength of 300 nm or less at an illuminance of 10 mW / cm 2 or more. By irradiating ultraviolet light in a wavelength range of 300 nm or less at an illuminance of 10 mW / cm 2 or more, it is possible to perform a telephone call from the metal oxide precursor film to the metal oxide film in a shorter time.

As ultraviolet light sources, UV lamps and lasers can be mentioned. UV lamps are preferable from the standpoint of ultraviolet ray irradiation with a uniform and inexpensive facility in a large area.

Examples of the UV lamp include an excimer lamp, a deuterium lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a helium lamp, a carbon arc lamp, a cadmium lamp and an electrodeless discharge lamp. The use of a low-pressure mercury lamp is preferable in that a call is easily made from the metal oxide precursor film to the metal oxide film.

(Ultraviolet irradiation apparatus)

Here, an apparatus used in the telephone process in the present disclosure will be described.

The apparatus used for the telephone process is not limited. For example, the apparatus for use in the telephone process is not limited, but may be a vacuum chamber, a supporting stand for supporting the substrate in the vacuum chamber, a vacuum pump for reducing the pressure inside the vacuum chamber to 10 Pa or less, An ultraviolet irradiating device having a light source for irradiating ultraviolet rays can be suitably used.

In addition, when the structure further includes the position adjusting means for adjusting the positional relationship between the light source and the support base, the distance between the light source and the substrate on the support base is adjusted to adjust the UV irradiation power (illumination) irradiated to the substrate.

Fig. 11 schematically shows an example of the configuration of an apparatus used in the telephone process in this disclosure. The apparatus 400 shown in Fig. 11 is provided with a stage 412 having a heater function in a vacuum chamber (decompression chamber) 410 to adjust the temperature of the substrate on the stage (support table) 412, The stage 412 can be moved up and down by turning a handle (position adjustment means) 418 from the stage 412. (Vacuum pump) 414 for vacuum evacuation, an N 2 gas introduction port (MFC) 424, a vacuum gauge 422, a UV irradiation unit (light source) 416, and a vent valve 426, respectively. A pressure regulating valve 420 is provided between the vacuum chamber 410 and the turbo mechanical pump 414 so that the pressure in the chamber 410 can be adjusted to 10 Pa or less.

The UV irradiation unit 416 can irradiate the substrate on the stage 412 with ultraviolet light through the quartz glass 417 and adjust the height of the stage 412 to irradiate the substrate on the stage 412 with UV irradiation Power (illumination) can be adjusted. The configuration may be such that the position of the UV irradiation unit 416 is moved and the UV irradiation power irradiated to the substrate on the stage 412 is adjusted or the output of the ultraviolet lamp of the UV irradiation unit 416 is changed And the UV irradiation power (illumination) to be irradiated on the substrate may be adjusted.

The film thickness of the metal oxide film produced by this disclosure is not particularly limited and may be selected depending on the application. For example, in the case of forming the semiconductor layer of the thin film transistor according to the present disclosure, the film thickness is preferably 50 nm or less, and more preferably about 10 nm.

The method for producing a metal oxide film of the present disclosure can easily obtain a metal oxide film in which unnecessary residual components are reduced even in a low-temperature process of less than 200 캜 by the liquid phase method. In addition, it is possible to greatly reduce the manufacturing cost of the device from the point that there is no need to use a large-scale vacuum device, the use of an inexpensive resin substrate with low heat resistance, and the availability of a cheap raw material.

In addition, a flexible electronic device such as a flexible display can be manufactured at low cost because it can be applied to a resin substrate having low heat resistance.

[Thin Film Transistor]

In the present disclosure, a method for producing a metal oxide film of the present disclosure is characterized in that an oxide semiconductor layer (active layer) of, for example, a thin film transistor (TFT) And an electrode. For example, by forming the oxide semiconductor layer as the semiconductor layer (active layer) by the method for producing a metal oxide film of the present disclosure, a thin film transistor having high linear mobility and excellent operation stability can be obtained.

Hereinafter, the method of manufacturing the metal oxide film of the present disclosure will be mainly described with respect to the application of the method for forming the semiconductor layer (oxide semiconductor film) of the TFT, but the present invention is not limited to the formation of the semiconductor layer of the TFT.

The device structure of the TFT according to the present disclosure is not particularly limited, and may be any of a so-called reverse stagger structure (also referred to as bottom gate type) and a stagger structure (also referred to as top gate type) based on the position of the gate electrode. It is also possible to use any of top contact type and bottom contact type based on the contact portion between the semiconductor layer and the source electrode and the drain electrode (appropriately referred to as "source / drain electrode").

The term " top gate type "means a type in which a gate electrode is disposed on the gate insulating film and a semiconductor 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. A gate electrode is disposed below the insulating film, and a semiconductor layer is formed above the gate insulating film. The term " bottom contact type "means that the source / drain electrode is formed before the semiconductor layer so that the lower surface of the semiconductor layer contacts the source / drain electrode. And the top surface of the semiconductor layer is in contact with the source / drain electrodes.

1 is a schematic diagram showing an example of a top-gate type top-gate TFT according to the present disclosure. In the TFT 10 shown in Fig. 1, the above-described oxide semiconductor film is stacked as the semiconductor layer 14 on one main surface of the substrate 12. [ A source electrode 16 and a drain electrode 18 are disposed apart from each other on the semiconductor layer 14 and a gate insulating film 20 and a gate electrode 22 are stacked in this order.

2 is a schematic diagram showing an example of a bottom-contact type TFT according to the present disclosure, which is a top gate structure. In the TFT 30 shown in Fig. 2, the source electrode 16 and the drain electrode 18 are provided apart from each other on one main surface of the substrate 12. The above-described oxide semiconductor film, the gate insulating film 20, and the gate electrode 22 are laminated in this order as the semiconductor layer 14.

3 is a schematic view showing an example of a bottom-gate structure and top contact type TFT according to the present disclosure. In the TFT 40 shown in Fig. 3, the gate electrode 22, the gate insulating film 20, and the oxide semiconductor film described above as the semiconductor layer 14 are sequentially stacked on one main surface of the substrate 12. On the surface of the semiconductor layer 14, the source electrode 16 and the drain electrode 18 are provided apart from each other.

4 is a schematic view showing an example of a bottom-gate type TFT of the present disclosure having a bottom gate structure. In the TFT 50 shown in Fig. 4, the gate electrode 22 and the gate insulating film 20 are stacked in this order on one main surface of the substrate 12. The source electrode 16 and the drain electrode 18 are provided apart from each other on the surface of the gate insulating film 20 and the oxide semiconductor film described above is laminated as the semiconductor layer 14. [

In the following embodiments, the bottom gate type thin film transistor shown in Fig. 3 will be mainly described as a representative example, but the thin film transistor according to the present disclosure is not limited to the bottom gate type and may be a top gate type thin film transistor.

(Board)

The shape, structure, size, and the like of the substrate 12 on which the TFTs are formed are not particularly limited. For example, the substrate 12 may be appropriately selected according to the purpose from the substrate.

The thickness of the substrate used in the present disclosure is not particularly limited, but is preferably 50 μm or more and 500 μm or less.

When the thickness of the substrate is 50 m or more, the flatness of the substrate itself is further improved. When the thickness of the substrate is 500 탆 or less, the flexibility of the substrate itself is further improved, and the substrate is more easily used as a substrate for a flexible device. In a manufacturing process of a flexible device, for example, a flexible substrate may be peeled from a glass substrate after a thin film transistor is formed on a flexible substrate temporarily fixed on a glass substrate.

(Gate electrode)

After the substrate 12 is cleaned, the gate electrode 22 is formed on the substrate 12 subjected to, for example, UV ozone treatment. The gate electrode 22 may be formed of a material having high conductivity, for example, a metal such as Al, Cu, Mo, Cr, Ta, Ti, Ag, or Au, a metal such as an Al-Nd, Ag alloy, tin oxide, A metal oxide conductive film such as indium tin oxide (In-Sn-O), zinc oxide indium (In-Zn-O), or In-Ga-Zn-O can be used. As the gate electrode 22, these conductive films can be used as a single layer structure or a laminated structure of two or more layers.

The gate electrode 22 may be formed by 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, a chemical method such as a CVD method or a plasma CVD method, And the film is formed according to a method selected appropriately.

The film thickness of the metal film for forming the gate electrode 22 is preferably 10 nm or more and 1000 nm or less and more preferably 50 nm or more and 200 nm or less in consideration of the film forming property, the patterning property by the etching or lift- Is more preferable.

After the film formation, the gate electrode 22 may be formed by patterning in a predetermined shape by an etching or lift-off method, or may be directly pattern-formed by an inkjet method, a printing method, or the like. At this time, it is preferable to simultaneously pattern the gate electrode 22 and the gate wiring (not shown).

(Gate insulating film)

After the gate electrode 22 and the wiring (not shown) are formed, the gate insulating film 20 is formed. The gate insulating film 20 is preferably made of a material having high insulating properties, and may be 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 may be a single-layer structure or a stacked-layer structure.

The formation of the gate insulating film 20 can be performed by a physical method such as a wet method such as a printing method or a coating method, a vacuum evaporation method, a sputtering method, and an ion plating method, a chemical method such as a CVD method or a plasma CVD method, The film may be formed according to a method appropriately selected. The gate insulating film 20 may be an organic insulating film or an inorganic insulating film as long as it has a gate insulating property. Examples of the inorganic insulating film formed by the wet process include an SiO 2 film, a SiON film, a SiN film, and the like using a compound solution that is a polysilazane.

In addition, the gate insulating film 20 needs to have a thickness for improving the leak current and the voltage resistance, while if the thickness of the gate insulating film 20 is too large, the driving voltage is increased. Though depending on the material of the gate insulating film 20, the thickness of the gate insulating film 20 is preferably 10 nm or more and 10 m or less, more preferably 50 nm or more and 1000 nm or less, and particularly preferably 100 nm or more and 400 nm or less.

(Semiconductor layer)

After the gate insulating film 20 is formed, the semiconductor layer 14 is formed on the gate insulating film 20. After the precursor film of the metal oxide semiconductor film is formed by applying and drying a solution containing indium on the gate insulating film 20 by the above-described method for producing a metal oxide film of the present disclosure, the precursor film is heated in an atmosphere of 10 Pa or less Under irradiation with ultraviolet rays.

The metal oxide semiconductor film is patterned into the shape of the semiconductor layer 14. [ The patterning of the semiconductor layer 14 may be performed by forming the semiconductor layer 14 patterned by the inkjet method, the dispenser method, the convex printing method, and the concave printing method described above, and the metal oxide semiconductor film may be patterned by photolithography and etching, (14).

In order to perform pattern formation by photolithography and etching, a resist pattern is formed by photolithography on a portion where the metal oxide semiconductor film is left, and a resist pattern is formed by an acid solution such as hydrochloric acid, nitric acid, dilute sulfuric acid, or a mixture of phosphoric acid, nitric acid and acetic acid Thereby forming a pattern of the semiconductor layer 14.

The thickness of the semiconductor layer 14 is preferably 5 nm or more and 50 nm or less from the viewpoints of flatness and time required for film formation.

(Protective layer)

It is preferable to form a protective layer (not shown) on the semiconductor layer 14 for protecting the semiconductor layer 14 at the time of etching the source / drain electrodes 16 and 18. The method of forming the protective layer is not particularly limited, and the film may be formed continuously on the metal oxide semiconductor film. The protective layer may be formed before patterning the metal oxide semiconductor film, or may be formed after patterning.

The protective layer is preferably an insulator, and the material constituting the protective layer may be an inorganic material or an organic material such as a resin. Further, the protective layer may be removed after formation of the source electrode 16 and the drain electrode 18 (source / drain electrodes 16 and 18).

(Source and drain electrodes)

Source and drain electrodes 16 and 18 are formed on the semiconductor layer 14 formed of a metal oxide semiconductor film. The source and drain electrodes 16 and 18 are made of a material having high conductivity such as Al, Mo, Cr, Ta, Ti, Ag and Au, A metal oxide conductive film such as zinc oxide, indium oxide, indium tin oxide (In-Sn-O), zinc oxide indium (In-Zn-O), or In-Ga-Zn-O can be used .

In the case of forming the source / drain electrodes 16 and 18, a physical method such as a wet method such as a printing method or a coating method, a vacuum evaporation method, a sputtering method, an ion plating method, a CVD (Chemical Vapor Deposition) A chemical method or the like depending on suitability with a 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, and more preferably 50 nm or more and 100 nm or less in consideration of film forming property, patterning property by etching or lift- More preferable.

The source / drain electrodes 16 and 18 may be formed by patterning in a predetermined shape by, for example, etching or lift-off after forming a conductive film, or may be formed by direct patterning by an inkjet method or the like. At this time, it is preferable to simultaneously pattern the source / drain electrodes 16 and 18 and wirings (not shown) connected to these electrodes.

The use of the thin film transistor of the present embodiment as described above is not particularly limited, but various electronic devices, particularly a resin substrate with low heat resistance, can be used as the thin film transistor at a low temperature because a thin film transistor showing high semiconductor characteristics and stability at low temperatures can be manufactured at a relatively low temperature The present invention can be applied to the production of a flexible electronic device using the same. Specifically, it is suitable for manufacturing a flexible display using a driving element in a display device such as a liquid crystal display device, an organic EL (Electro Luminescence) display device, an inorganic EL display device, or a resin substrate with low heat resistance.

The thin film transistor manufactured by the present disclosure 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 MEMS (Micro Electro Mechanical System).

Hereinafter, an example of an electronic device to which the thin film transistor manufactured according to the present disclosure is applied will be described.

<Liquid Crystal Display Device>

5 is a schematic sectional view of a liquid crystal display device according to an embodiment of the present disclosure, and Fig. 6 is a schematic structural view of an electric wiring.

As shown in Fig. 5, the liquid crystal display device 100 of the present embodiment has a top-gate type TFT 10 shown in Fig. 1 and a top contact type TFT 10 and a passivation layer 102 A liquid crystal layer 108 interposed between the pixel lower electrode 104 and the opposing upper electrode 106 on the gate electrode 22 and R (red) G (green) B (Blue) color filter 110 and polarizing plates 112a and 112b on the substrate 12 side of the TFT 10 and the RGB color filter 110, respectively.

6, the liquid crystal display 100 according to the present embodiment includes a plurality of gate wirings 112 parallel to each other and a plurality of data wirings 114 crossing the gate wirings 112 and parallel to each other. . Here, the gate wiring 112 and the data wiring 114 are electrically insulated. A TFT 10 is provided near the intersection of 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 buried in the contact hole 116). The pixel lower electrode 104 constitutes a capacitor 118 together with the grounded opposing upper electrode 106.

<Organic EL Display Device>

FIG. 7 is a schematic cross-sectional view of an active matrix type organic EL display device according to an embodiment of the present disclosure, and FIG. 8 is a schematic structural view of an electric wiring.

The active matrix type organic EL display device 200 of the present embodiment is configured such that the TFT 10 of the top gate structure shown in Fig. 1 is formed on the substrate 12 provided with the passivation layer 202, And an organic EL light emitting element 214 which is provided as a switching TFT 10b and is composed of an organic light emitting layer 212 sandwiched between the lower electrode 208 and the upper electrode 210 on the TFTs 10a and 10b And the upper surface thereof is protected by the passivation layer 216.

8, the organic EL display device 200 of the present embodiment includes a plurality of gate wirings 220 parallel to each other and a plurality of data wirings 222 And a driving wiring 224. [0064] Here, the gate wiring 220, the data wiring 222, and the driving wiring 224 are electrically insulated. The gate electrode 22 of the switching TFT 10b is connected to the gate wiring 220 and the source electrode 16 of the switching TFT 10b 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 turned on by using the capacitor 226 do. The source electrode 16 of the driving TFT 10a is connected to the driving wiring 224 and the drain electrode 18 is connected to the organic EL light emitting element 214. [

In the organic EL display device shown in Fig. 7, the upper electrode 210 may be a top electrode with a transparent electrode, or the bottom electrode 208 and each electrode of the TFT may be a transparent electrode, do.

<X-ray sensor>

9 is a schematic cross-sectional view of an X-ray sensor according to an embodiment of the present disclosure, and Fig. 10 is a schematic configuration diagram of an electric wiring.

The X-ray sensor 300 of the present embodiment includes a TFT 10 and a capacitor 310 formed on a substrate 12, a charge collecting electrode 302 formed on the capacitor 310, an X-ray converting layer 304, and an upper electrode 306. On the TFT 10, a passivation film 308 is provided.

The capacitor 310 has a structure in which the insulating film 316 is interposed between the capacitor lower electrode 312 and the capacitor upper electrode 314. The capacitor upper electrode 314 is connected to either the source electrode 16 or the drain electrode 18 of the TFT 10 through the contact hole 318 provided in the insulating film 316 ).

The charge collecting 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 covers 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.

10, the X-ray sensor 300 of the present embodiment includes a plurality of gate wirings 320 parallel to each other, a plurality of data wirings 322 parallel to each other and intersecting the gate wirings 320, . Here, the gate wiring 320 and the data wiring 322 are electrically insulated. A TFT 10 is provided near the intersection of 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 electrically connected to the charge collecting electrode 302 and the charge collecting electrode 302 is connected to the capacitor 310.

In the X-ray sensor 300 of the present embodiment, an X-ray is incident from the side of the upper electrode 306 in FIG. 9 to generate an electron-hole pair 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 electric charge is accumulated in the capacitor 310 and read out by sequentially scanning the TFT 10.

The liquid crystal display device 100, the organic EL display device 200, and the X-ray sensor 300 of the above embodiments are provided with the TFTs of the top gate structure shown in Fig. 1, The present invention is not limited to the TFT having the gate structure, and the TFT having the structure shown in Figs. 2 to 4 may be used.

Example

EXAMPLES Hereinafter, examples will be described, but the present invention is not limited to the following examples.

&Lt; Examples and Comparative Examples in which a metal oxide film containing In is formed >

In order to more simply explain the effect of the present invention, a TFT device was manufactured as described below to evaluate electric characteristics.

Indium nitrate: by dissolving (In (NO 3) 3 · xH 2 O, the purity 4N, gojun FIG Kagaku Gen kyusyo Co.) to 2-methoxyethanol (special reagent grade, Wako Pure Chemical Industries, Ltd.), 0.1mol / L Was prepared. The indium nitrate solution for the semiconductor layer formation was prepared.

A simple TFT using a silicon substrate as a gate electrode and a thermal oxide film as a gate insulating film was fabricated using a p-type silicon substrate with a thermally oxidized film as a substrate. The prepared indium nitrate solution was spin-coated on a p-type silicon substrate with 1 inch square thermal oxide film at a rotation speed of 1,500 rpm for 30 seconds and then dried on a hot plate heated to 60 占 폚 for 1 minute. Thus, an oxide semiconductor precursor film (thickness: 10 nm) was formed.

Next, the precursor film is irradiated with ultraviolet rays in an atmosphere in which the pressure is adjusted in the state of heating, whereby the metal oxide film is called.

In the telephone process, an ultraviolet irradiation device having the above-described schematic configuration shown in Fig. 11 was used. (Pressure of the chamber: atmospheric to 1 x 10 &lt; -4 &gt; Pa; sample substrate temperature: room temperature to 600 deg. C); UV irradiation power (Illuminance): 1 to 30 mW / cm 2 . The irradiation power can be changed by adjusting the height of the sample stage (support table) 412. [

In the apparatus shown in Figure 11, the ultraviolet rays UV illumination with a wavelength of 254nm light amount meter (Oak Seisakusho Co., Ltd., UV-M10, a light receiver UV-25) to measure and, 10mW / cm 2 is adjusted on the stage positioned so that by using the And the film of the oxide semiconductor precursor film was formed under the conditions shown in Table 1. [

Condition 1 is a telephone treatment in the atmosphere, Condition 2 is vacuum evacuation from the atmosphere to 1 x 10 &lt; -4 &gt; Pa, N 2 gas is introduced after the evacuation is stopped, Respectively, and then subjected to telephone processing. The condition 9 was the telephone processing while reducing the pressure from the atmosphere to 0.8 atm (about 0.081 MPa).

Further, under all conditions, the substrate temperature in the telephone process was fixed at 150 占 폚, and the UV treatment time was fixed at 30 minutes. In addition, the substrate temperature during ultraviolet irradiation treatment was monitored by thermo-labeling.

Source and drain electrodes were formed on the metal oxide semiconductor film by sputtering film formation after the telephone treatment. The source and drain electrodes were formed by patterning using a metal mask, and Ti was deposited to a thickness of 50 nm. The sizes of the source and drain electrodes were 1 mm x 1 mm and the interelectrode distance was 0.2 mm.

Here, the fabrication of the simple type TFT element is completed.

The transistor characteristics V g -I d were measured for the obtained simple type TFT by using a semiconductor parameter analyzer 4156C (manufactured by Agilent Technologies).

The V g -I d characteristic was measured by fixing the drain voltage V d to +1 V and changing the gate voltage V g within the range of -15 V to +15 V to determine the drain current I d ). The atmosphere of the measurement was set at an atmospheric pressure (a flow for 60 minutes in advance) in a dry air atmosphere, and the influence of moisture at the time of measurement was excluded, and measurement was repeated five times to obtain a linear mobility (initial mobility) and a Vth shift Voltage shift).

Table 1 shows the amount of hydrogen in the semiconductor film, calculated from the linear mobility obtained from the V g -I d characteristic, the Vth shift (ΔV th) after the fifth repetition measurement, and the secondary ion mass analysis (SIMS). SIMS was performed using "PHI ADEPT 1010" manufactured by Physical Electronics.

[Table 1]

Figure pct00001

Conditions 1 and 9 did not operate as TFTs. As a factor, it is considered that the oxygen deficiency of the semiconductor layer is terminated by the residual oxygen at the time of the telephone process, the carrier is lost, and it does not function as a semiconductor film.

In the conditions 2 and 3, although the transistor characteristics can be confirmed, when? Vth exceeds 2.0 V, there is a problem in operation stability. In condition 2, although the initial mobility is the greatest, since the amount of residual hydrogen is also greatest, it is considered that hydrogen acts as a surplus carrier and deteriorates operation stability.

In conditions 4 to 8,? Vth becomes less than 2.0 V, and in the case of conditions 6 to 8 where the pressure in the telephone process is 1 Pa or less, the amount of hydrogen in the semiconductor film is lowered to 1.0 × 10 22 / cm 3 or less, Small amounts were roughly the same. From these results, the influence of oxygen and the like on the semiconductor film is eliminated, and the amount of hydrogen in the semiconductor film depends on the pressure in the telephone process, and the smaller the amount of hydrogen in the film, the smaller? Vth, .

&Lt; Comparative Examples and Examples in which a metal oxide film containing In and Zn was formed >

The following samples were prepared and evaluated.

Indium nitrate (In (NO 3) 3 · xH 2 O, purity: 4N, gojun FIG Kagaku Gen kyusyo Co., Ltd.), zinc nitrate (Zn (NO 3) 2 · 6H 2 O, purity: 3N, gojun FIG Kagaku Gen Was dissolved in 2-methoxyethanol (reagent grade, Wako Pure Chemical Industries, Ltd.) to prepare an indium nitrate / zinc nitrate mixed solution having an indium nitrate concentration of 0.095 mol / L and a zinc nitrate concentration of 0.005 mol / L did.

An oxide semiconductor precursor film was formed on the p-type silicon substrate with a thermal oxide film using the prepared zinc nitrate / zinc nitrate mixed solution, and the oxide semiconductor film was formed in the same manner as in Condition 1 or Condition 4, And evaluated.

When the telephone process was performed in the same manner as the condition 1, the TFT did not operate as a TFT.

In the case of performing the telephone process in the same manner as the condition 4, the initial mobility of the TFT was 5.4 cm 2 / Vs, the Vth was 1.7 V, and the amount of hydrogen in the film was 1.77 × 10 22 / cm 3 .

The disclosure of Japanese Patent Application No. 2014-247074 filed on December 5, 2014 is incorporated herein by reference in its entirety.

All publications, patents, patent applications, and technical specifications described in this specification are herein incorporated by reference to the same extent as if each individual document, patent, patent application, and technical specification were specifically and individually indicated to be incorporated by reference. Is used.

Claims (18)

  1. A precursor film forming step of forming a precursor film of a metal oxide film by applying a solution containing indium and a solvent on a substrate,
    Irradiating ultraviolet rays to the precursor film in a heated state in an atmosphere of 10 Pa or less to cause the precursor film to be converted into a metal oxide film.
  2. The method according to claim 1,
    Wherein the ultraviolet irradiation is performed in an atmosphere of 1 Pa or less.
  3. The method according to claim 1 or 2,
    Wherein a content of indium contained in said solution is 50 atom% or more based on a total amount of metal components contained in said solution.
  4. The method according to any one of claims 1 to 3,
    Wherein a temperature of the substrate when irradiating the ultraviolet ray is 150 DEG C or less.
  5. The method according to any one of claims 1 to 4,
    Wherein the solution is a solution of indium nitrate.
  6. The method of claim 5,
    Wherein the solution of indium nitrate comprises at least one of methanol and methoxyethanol as the solvent.
  7. The method according to any one of claims 1 to 6,
    Wherein the solution further contains at least one selected from the group consisting of zinc, tin, gallium, and aluminum.
  8. The method according to any one of claims 1 to 7,
    Wherein the concentration of the metal component in the solution is 0.01 mol / L or more and 0.5 mol / L or less.
  9. The method according to any one of claims 1 to 8,
    Wherein the ultraviolet irradiation is performed by irradiating ultraviolet rays containing light having a wavelength of 300 nm or less to the precursor film at an illuminance of 10 mW / cm 2 or more.
  10. The method according to any one of claims 1 to 9,
    In the precursor film forming step, the solution is coated on the substrate by at least one coating method selected from the ink jet method, the dispenser method, the convex printing method, and the concave printing method.
  11. A metal oxide film produced by the method for manufacturing a metal oxide film according to any one of claims 1 to 10.
  12. And a hydrogen content of 1.0 x 10 &lt; 22 &gt; atoms / cm &lt; 3 &gt; or less.
  13. The method according to claim 11 or 12,
    Wherein a content of indium contained in said metal oxide film is 50 atom% or more with respect to a total amount of metal components contained in said metal oxide film.
  14. A method of manufacturing a thin film transistor, comprising the step of forming a metal oxide film by the method of manufacturing a metal oxide film according to any one of claims 1 to 10.
  15. A thin film transistor comprising the metal oxide film according to any one of claims 11 to 13.
  16. An electronic device having the thin film transistor according to claim 15.
  17. A decompression chamber,
    A support table for supporting and heating the substrate in the vacuum chamber,
    A vacuum pump for reducing the pressure within the vacuum chamber to 10 Pa or less,
    And a light source that emits ultraviolet light to the substrate supported by the support.
  18. 18. The method of claim 17,
    And position adjusting means for adjusting a positional relationship between the light source and the support base.
KR1020177013093A 2014-12-05 2015-12-04 Method for manufacturing metal oxide film, metal oxide film, thin-film transistor, method for manufacturing thin-film transistor, electronic device, and ultraviolet irradiation device KR101954551B1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
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