TW201939756A - Semiconductor film, semiconductor element using the same, and dispersion liquid - Google Patents

Abstract

A semiconductor film comprises metal oxide particles and an organic compound, with respect to 100% by mass of the entire semiconductor film, the content of the metal oxide is 55% by mass or more and 95% by mass or less, the content of the organic compound is 5% by mass or more and 45% by mass or less, the ratio (S2/S1) of the area S1 of the peak attributed to the O<SP>2-</SP> ion of the metal oxide and the area S2 of the peak attributed to the O<SP>2-</SP> ion of the oxygen deficiency in the O1s spectrum in the XPS measurement of the semiconductor film is 0.25 or more and 0.60 or less. Provided are a semiconductor film which can be manufactured by a vacuum system process and a low temperature process and can exhibit higher mobility, a semiconductor element using the same, and a dispersion liquid.

Description

Semiconductor film, semiconductor element using the semiconductor film, and dispersion liquid

The present invention relates to a semiconductor film, a semiconductor element using the semiconductor film, and a dispersion liquid.

In recent years, with the development of thin and light-weight display elements such as organic electroluminescence (organic EL) elements, semiconductor elements have been required to develop materials with high mobility (hereinafter referred to as mobility) of carriers. A metal oxide of indium / gallium / zinc oxide having a high mobility metal oxide has been developed (Patent Document 1).

In addition, today's semiconductor devices are centered on silicon, and the manufacturing process must be expensive vacuum equipment and high temperature processes. Further, in order to use photolithography, a plurality of steps must be performed. Therefore, there is a problem that the manufacturing cost of the semiconductor element is high. Therefore, a non-vacuum-based process such as a coating method is actively studied as a method for forming a layer composed of inorganic semiconductor particles having a high mobility.

[Prior technical literature] [Patent Literature]

Patent Document 1: International Publication No. 2005/088726.

In the case of an inorganic semiconductor film, the film formation temperature of the thin film must be as high as about 300 degrees or more. Therefore, glass substrates and silicon wafers must be used as substrates for the formation of inorganic semiconductor films, and it is extremely difficult to apply them to resin substrates that require impact resistance and flexibility.

Therefore, an object of the present invention is to provide a semiconductor film which can be manufactured in a non-vacuum-based process and a low-temperature process and exhibits high mobility, a semiconductor element using the semiconductor film, and a dispersion liquid.

The present inventors have worked hard to solve the above-mentioned problems, and have completed the present invention.

That is, the present invention is a semiconductor film containing metal oxide particles and an organic compound, and the content of the metal oxide is 55 mass% to 95 mass% with respect to 100 mass% of the entire semiconductor film, and the content of the organic compound The ratio of the peak area S1 of O ² ions belonging to metal oxides to the peak area S ² of O ² ions belonging to anoxic oxygen in the O1s spectrum of the aforementioned semiconductor film in XPS measurement is 5 mass% to 45 mass% ( S2 / S1) is 0.25 or more and 0.60 or less.

The present invention is a semiconductor film containing indium oxide particles and an organic compound, and the content of the indium oxide is 55% by mass or more and 95% by mass or less, and the content of the organic compound is 5% by mass or more with respect to 100% by mass of the entire semiconductor film. Below 45 mass%, the O1s spectrum of the aforementioned semiconductor film in the XPS measurement exists in a wave of 528eV to 530eV The ratio (S2 / S1) of the peak area S1 to the peak area S2 existing between 530eV and 533eV is 0.25 or more and 0.60 or less.

The present invention is a semiconductor film containing zinc oxide particles and an organic compound, and the content of the zinc oxide is 55% by mass or more and 95% by mass or less, and the content of the organic compound is 5% by mass or more relative to 100% by mass of the entire semiconductor film. Below 45% by mass, the ratio (S2 / S1) of the peak area S1 of O ² ions belonging to zinc oxide to the peak area S ² of O ² ions belonging to hypoxia in the O1s spectrum of the aforementioned semiconductor film in the XPS measurement is 0.25 Above 0.60.

In the present invention, it is preferable that the organic compound is a dielectric substance, and a specific permittivity thereof is 5 or more and 100 or less.

In the present invention, the organic compound is preferably a cyano-containing organic compound.

In the present invention, the relative element concentration of Na in the XPS measurement of the semiconductor film is preferably 1.0 atomic% or less.

The semiconductor element in the present invention includes an electrode and the semiconductor film described above connected to the electrode.

In the semiconductor element of the present invention, it is preferable that the film thickness of the semiconductor film is 1 nm to 1000 nm.

The semiconductor element in the present invention is preferably a transistor element.

The mobility of the semiconductor element in the present invention is preferably 0.001 cm ² / Vs or more and 10 cm ² / Vs or less.

The present invention is a dispersion liquid containing metal oxide particles, an organic compound, and a solvent, and the content of the metal oxide particles is 0.1% by mass or more and 60% by mass or less with respect to 100% by mass of the entire dispersion liquid. The content of the compound is 0.1% by mass or more and 20% by mass or less, the content of the aforementioned solvent is 20% by mass or more and 99.98% by mass or less. The O1s spectrum of the dispersion in the XPS measurement after drying of the dispersion is a metal oxide of O ^2- ion. The ratio (S2 / S1) of the peak area S1 to the peak area S2 of O ² -ion which is anoxic is 0.25 or more and 0.60 or less.

In addition, the present invention is a dispersion liquid containing indium oxide particles, an organic compound, and a solvent, and the content of the indium oxide particles is 0.01% by mass or more and 60% by mass or less with respect to 100% by mass of the entire dispersion liquid. The content is 0.01% by mass or more and 20% by mass or less, the content of the aforementioned solvent is 20% by mass or more and 99.98% by mass or less, and the O1s spectrum of the dispersion in the XPS measurement after drying is present in a peak area S1 of 528eV to 530eV and The ratio of the peak area S2 (S2 / S1) from 530eV to 533eV is 0.25 or more and 0.60 or less.

In addition, the present invention is a dispersion liquid containing zinc oxide particles, an organic compound, and a solvent, and the content of the zinc oxide particles is 0.1% by mass or more and 60% by mass or less with respect to 100% by mass of the entire dispersion liquid. The content is 0.1% by mass or more and 20% by mass or less, the content of the aforementioned solvent is 20% by mass or more and 99.98% by mass or less. The O1s spectrum of the O1s spectrum in the XPS measurement after the dispersion is dried is the peak area S1 of zinc ^2- O ² ions. The ratio (S2 / S1) to the peak area S2 of O ² -ion which is anoxic is 0.25 or more and 0.60 or less.

Semiconductor film according to the present invention, and using the semiconductor film Semiconductor devices can be manufactured in non-vacuum systems and low-temperature processes and exhibit high mobility.

By using the dispersion liquid of the present invention, a semiconductor film can be formed in a non-vacuum-based process and a low-temperature process.

100, 200, 300, 400‧‧‧ semiconductor devices

110, 210, 310‧‧‧ substrate

120, 220, 320, 420‧‧‧ Gate electrode

130, 230, 330, 430‧‧‧ insulator layers

140, 240, 340, 440‧‧‧ source electrodes

150, 250, 350, 450‧‧‧ Drain electrodes

160, 260, 360, 460‧‧‧ semiconductor layer

The cross-sectional view of FIG. 1 schematically shows an example of a semiconductor element in this embodiment.

The cross-sectional view of FIG. 2 schematically shows an example of a semiconductor element in this embodiment.

The cross-sectional view of FIG. 3 schematically shows an example of a semiconductor element in this embodiment.

The cross-sectional view of FIG. 4 schematically shows an example of a semiconductor element in this embodiment.

The cross-sectional view of FIG. 5 shows the sequence of steps in the method of manufacturing a semiconductor device in this embodiment.

Hereinafter, one embodiment of the present invention (hereinafter referred to as "embodiment") will be described in detail.

(Semiconductor film)

The semiconductor film of this embodiment will be described in detail. The semiconductor film of this embodiment is configured by including metal oxide particles and an organic compound.

The semiconductor film may be composed only of metal oxide particles and organic The film composed of the composite may be a film composed of metal oxide particles, organic compounds, and other components. The other component may be any one or more of a solvent, an adhesive component, or an inorganic component.

The semiconductor film (also referred to as a composite body) in this embodiment has the following characteristics.

(1) The content of the metal oxide is 55 mass% or more and 95 mass% or less with respect to 100 mass% of the entire semiconductor film.

(2) The content of the organic compound is 5 mass% or more and 45 mass% or less with respect to 100 mass% of the entire semiconductor film.

(3) The ratio (S2 / S1) of the peak area S1 of O ² ions belonging to metal oxides to the peak area S ² of O ² ions belonging to oxygen deficiency in the measurement of the O1s spectrum of the semiconductor film by XPS is 0.25 or more 0.60 or less.

First, materials, physical properties, and the like of metal oxide particles and organic compounds will be described.

<Metal oxide particles>

Metal oxide particles refer to particles composed of at least one metal and oxygen.

Examples of the metal oxide particles include alumina, bismuth oxide, cerium oxide, cobalt oxide, oxide, magnesium oxide, silicon oxide, yttrium oxide, zirconia, iron oxide, spinel (MgAl ₂ O ₄ ), BaTiO ₃ , FeTiO ₃ , cuprous oxide, copper oxide, iron oxide, zinc oxide, silver oxide, titanium oxide (for example, titanium oxide (IV) including rutile and anatase crystalline), aluminum doped Zinc oxide (AZO), gallium-doped zinc oxide (GZO), indium tin oxide (ITO), tin oxide, fluorine-doped tin oxide (FTO), antimony-doped tin oxide, indium oxide, indium / gallium / Zinc oxide, nickel oxide, vanadium oxide, strontium titanate, CuAlO ₂ , CuGaO ₂ , SrCu ₂ O ₂ , LaCuOS, LaCuOSe, CuInO ₂ , ZnRh ₂ O ₄ , 12CaO. 7Al ₂ O ₃ (Cl ₂ A ₇ ), Ga ₂ O ₃ , SrCuO, etc., or similar metal oxides.

From the viewpoint of transparency and carrier mobility, the metal oxide particles are preferably zinc oxide, indium oxide, indium / gallium / zinc oxide, and especially indium oxide. Further, from the viewpoint of low cost, titanium oxide (for example, titanium oxide (IV) having a crystal type of rutile and anatase) or zinc oxide, aluminum-doped zinc oxide (AZO), Gallium-doped zinc oxide (GZO). These metal oxides used for the metal oxide particles may be used in combination of two or more.

In the X-ray diffraction spectrum of the metal oxide particles, the half-width of the main peak is a scale representing the crystallinity of the metal oxide. When performing X-ray diffraction measurement of metal oxide particles, the half-width can be measured from the main peak. From the viewpoint of the carrier mobility in the metal oxide particles, the half-width obtained by X-ray diffraction indicating the crystallinity of the metal oxide is preferably 5.0 ° or less, more preferably 3.0 ° or less, and even more preferably 2.0 ° or less, preferably 1.0 ° or less. In addition, if the crystallinity of the metal oxide particles is too high, the film-forming property will be deteriorated. Therefore, the half width is preferably 0.004 ° or more, more preferably 0.01 ° or more, still more preferably 0.1 ° or more, and most preferably 0.2 °. the above.

The representative production method of metal oxide particles proposes the following method: adding alkali such as ammonia and sodium hydroxide to metal ions such as aqueous metal chloride solution and neutralizing and sinking to generate metal hydroxide or metal carbonate, in the atmospheric environment Or the reducing environment is heated at a temperature higher than 500 ° C (Calcined) and crystallized.

In addition, the method for producing metal oxide particles is, for example, a sol-gel method. The sol-gel method is a method in which a metal alkoxide is hydrolyzed and polycondensed under acidic or alkaline conditions to produce a sol, and the sol is dried and gelled. Method. Other production methods include, for example, a method of directly heating a metal to vaporize it and burning it in the air, or a method of thermally decomposing metal sulfuric acid or metal nitric acid.

In addition, other production methods can be used by pulverizing a metal oxide produced by a sputtering method or the like. The pulverization method may be dry pulverization or wet pulverization, or both methods may be used. For the dry pulverization, a hammer crusher or the like can be used. In the wet pulverization, a ball mill, a planetary ball mill, a bead mill, and a homogenizer can be used. The solvents used in the wet pulverization include the following.

That is, examples of the solvent include water, pentane, hexane, heptane, octane, nonane, decane, 2-methylhexane, decalin, tetralin, methanol, ethanol, n-propanol, 2-propanol, n-butanol, tertiary butanol, ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol Alcohol monobutyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, ethylene glycol mono 2-ethylhexyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol Ketones such as n-butyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, glycerol acetone, methyl ethyl ketone, benzene, xylene, toluene, phenol, aniline, diphenyl ether and other aromatics, dimethyl Alkylidene, dimethylformamide, acetonitrile, methyl acetate, tetrahydrofuran, butyl lactate, N-methylpyrrolidone, and the like. These may be used in combination.

The surface of the metal oxide particles may be modified with an organic functional group. By modifying the surface with an organic functional group, the dispersibility in an organic solvent can be improved, and a uniform film can be produced. Examples of the modification method of the organic functional group include cyanoethylation.

The average particle diameter of the metal oxide particles is measured using a transmission electron microscope or a scanning electron microscope.

The average particle diameter of the metal oxide particles is preferably 1 nm to 500 nm. From the viewpoint of reducing the contact resistance, the average particle diameter of the metal oxide particles is preferably 1 nm or more, more preferably 3 nm or more, still more preferably 5 nm or more, and most preferably 10 nm or more. From the viewpoint of film-forming properties, the average particle diameter of the metal oxide particles is preferably 500 nm or less, more preferably 300 nm or less, still more preferably 100 nm or less, and most preferably 50 nm or less.

The metal oxide particles used in the present embodiment preferably have a relative standard deviation σ of the particle size distribution of 0.1 nm to 5.0 nm. From the viewpoint of reducing resistance, the relative standard deviation σ is more preferably 3.0 nm or less, still more preferably 2.0 nm or less, and most preferably 1.0 nm or less.

Among the metal oxide particles, indium oxide is explained. Examples of usable shapes of indium oxide include a spherical shape, an irregular shape, a flat plate shape, a hexagonal plate shape, a rod shape, and a tube shape.

Usable types of indium oxide include indium (III) oxide nanopowder, <100nm particle size (TEM), indium (III) oxide 99.9% trace metals basis, indium (III) oxide 99.998% trace metals basis, 99.99% trace metals basis, indium (III) oxide 99.5 + CAS13143-2, molar mass 277.64g / mol., 99.5+ (EMD Millipore) (above manufactured by sigmaaldrich), indium oxide / 99.9%, Indium (III) oxide 99.999% -In PURATREM, indium oxide 99.99% metals basis (above manufactured by Wako Pure Chemical Industries), and Indium Oxide Nano particles (manufactured by SkySpring Nanomaterials Inc), indium oxide (SP) Company system), etc., but not limited to them.

The representative production method of indium oxide particles proposes the following method: adding an alkali such as ammonia and sodium hydroxide to indium ions such as an indium chloride aqueous solution and neutralizing and sinking to generate indium hydroxide in the atmospheric environment or reducing environment It is then heat-treated (fired) at a high temperature of 500 ° C or higher to crystallize it. In addition, other production methods propose the following method: To prevent sintering during heating, additives such as cetyltrimethylammonium bromide are added.

The crystal form of indium oxide is cubic or bixbyite, which can be identified by X-ray diffraction measurement.

Describe zinc oxide in metal oxide particles. Examples of the shape that can be used for zinc oxide include a spherical shape, an irregular shape, a flat plate shape, a hexagonal plate shape, a rod shape, and a tube shape.

The types of zinc oxide particles that can be used include zinc oxide I, zinc oxide II, zinc oxide III, and hexagonal plate-shaped zinc oxide XZ series (Specification name: XZ-100F-LP, XZ-300-LP, XZ -1000F-LP, XZ-2000-LP, XZ-3000-LP), plate-shaped concentrated spherical zinc oxide CANDY ZINC series (specification name: CANDY ZINC 1000), large particle zinc oxide LPZINC series (specification name: LPZINC- 30S, LPZINC-30SR, LPZINC-20, LPZINC-2), Ultrafine Zinc Oxide FINEX Series (Specification Name: FINEX-50, FINEX-30, SF-20), Ultrafine Zinc Oxide Dispersion DIF Series (Specification Name: DIF-3ST2, DIF-5W, DIF-AW4, DIF-3W4, DIF-5CS), high-purity zinc oxide HPZ series (specification name: HPZ-06) (the above is manufactured by Hori Chemical Industry Co., Ltd.), zinc oxide type I, zinc oxide type II, zinc oxide type III, ZINCOX SUPER F series (specification Name: F-1, F-2), 23-K, PAZET, zinc oxide for varistor, pharmacopoeia zinc oxide, special No. 1 zinc oxide, zinc oxide for EF, PZ, fired zinc oxide, active zinc oxide ( The following are manufactured by HakusuiTech), FZO-50 (made by Ishihara Industries, Ltd.), MZ-300, MZY-303S, MZ-306X, MZ-500, MZY-505S, MZY-510M3S, MZ-506X, MZ-510HPSX (The above is made by TAYCA), zinc oxide dispersion (product number: 721077, 721093, 721107, 721085, 633844, above is made by sigmaaldrich), zinc oxide nanoparticle, <100nm particle size, zinc oxide nano particles, 40wt% in ethanol, <130nm particle size, zinc oxide nano particles, <110nm particle size, 40wt% in butyl acetate (the above is made by sigmaaldrich), zinc oxide 0.02μm, zinc oxide nanoparticle 20nm, zinc oxide-5μm, 99.9%, oxidation Zinc 99.999% -Zn PURATREM, zinc oxide 99.999% metal basis (the above is made by Wako Pure Chemical Industries, Ltd.), etc. .

A typical method for producing zinc oxide particles is to heat metallic zinc to vaporize and burn it in air, or to thermally decompose zinc sulfate or zinc nitrate. In addition, other manufacturing methods also use a method in which alkaline zinc carbonate is sunk and fired from an aqueous zinc chloride solution.

In particular, the method of heating metallic zinc to vaporize it and burning it in the air (commonly referred to as the French method) is a point in which zinc oxide particles have very high crystallinity and can reduce impurities very much, which is preferable.

<Organic compound>

The organic compound used in this embodiment exists between the particles of the metal oxide particles and on the surface of the metal oxide particles, and thereby it is expected that the adhesion between the particles or the adhesion between the particles and the substrate can be improved.

From the viewpoint of preventing carrier recombination and high mobility, the specific dielectric constant of the organic compound is preferably 5 or more and 100 or less, more preferably 7 or more and 70 or less, still more preferably 8 or more and 50 or less, and most preferably 10 Above 30 and below. As described above, the organic compound has a function as a dielectric.

Moreover, the organic compound can improve the film-forming property by being present around the metal oxide particles.

Examples of the organic compound include polyvinylidene chloride, acrylic resin, cellulose acetate, aniline resin, ABS resin, hard rubber, vinyl chloride resin, acrylonitrile resin, aniline formaldehyde resin, amino alkyl resin, and uramic acid. Ethyl ester, AS resin, epoxy resin, vinyl butyral resin, silicone resin, vinyl acetate resin, styrene butadiene rubber, silicone rubber, cellulose acetate, styrene resin, dextrin, Nylon, soft vinyl butyral resin, fluorine resin, furfural resin, polyamide, polyester resin, polycarbonate resin, phenol resin, furan resin, polyacetal resin, melamine resin, urea resin, polysulfide Ether polymers, polyethylene, etc. In addition, acetone, methanol, isobutanol, ethanol, aniline, isobutyl methyl ketone, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, cresol glycol, diallyl phthalate Ester, dextrin, pyranyl alcohol, phenol, bakelite varnish, formalin, thioglycerol, chloroamidine, succinic acid, nitrile succinate, nitrocellulose, ethyl cellulose, hydroxyethyl cellulose, starch, hydroxyl Propyl starch, poly Triglucose, glycidol polytriglucose, polyvinyl alcohol, sucrose, sorbitol, cyano-containing organic compounds, etc.

Here, the cyano group-containing organic compound refers to a compound containing one or more cyano groups. The cyano-containing organic compound is more preferably a cyanoethyl-containing organic compound. Specific examples of the cyano-containing organic compound include cyanoethyl polyglucose, cyanoethyl polyvinyl alcohol, cyanoethyl sucrose (cyanoethyl sucrose), cyanoethyl cellulose, and cyanoethyl Hydroxyethyl cellulose, cyanoethyl starch, cyanoethyl hydroxypropyl starch, cyanoethyl glycidyl polytriglucose, cyanoethyl sorbitol, and the like.

Specific examples of the fluorine-based resin are polymers having C ₂ F _4-n H _n (n is 0 to 3) as a skeleton. Specifically, for example, polyvinyl fluoride, polyvinylidene fluoride, and polytetrafluoroethylene may be mentioned. Fluorinated ethylene, etc. These may be copolymerized, or the above-mentioned fluorine-based resin may be copolymerized with other resins. Moreover, a part of hydrogen in the aforementioned chemical formula may be replaced with chlorine. Examples include polychlorotrifluoroethylene.

Specific examples of the fluorine-based resin include a fluorine-based ion exchange resin. Specific examples include a fluoroethylene compound represented by the general formula CF ₂ = CF-O (CF ₂ CF _X ) _n O- (CF ₂ ) _m -W, and a fluorinated compound represented by the general formula CF ₂ = CFZ. An olefin composed of at least two copolymers. Here, X is F or a perfluoroalkyl group having 1 to 3 carbon atoms, n is an integer of 0 to 3, m is an integer of 1 to 5, Z is H, Cl, F, or all of 1 to 3 carbons Fluoroalkyl. W is any one of the groups shown by COOH, SO ₃ H, SO ₂ F, SO ₂ Cl, SO ₂ Br, COF, COCl, COBr, CO ₂ CH ₃ , and CO ₂ C ₂ H ₅ .

In particular, in the case of an organic compound, if the organic compound contains a highly polar atom or a functional group, the dielectric constant is large, which is preferable. The dipole moment of the polarity index can be estimated by the sum of the bonding moments. The organic compound having a relative dielectric constant of 2 or more is preferably a compound having a substituent having a bond moment of 1.4D (D = 3.33564 × 10 ^-30 Cm) or more. Substituents with a bond moment of 1.4D or more include OH, CF, CCl, C = O, N = O, CN, and the like. Examples of the organic compound having a specific permittivity of two or more of these substituents include fluorine-based resins, glycerol, thioglycerin, and cyano-containing organic compounds. From the viewpoint of mobility, a fluorine-based resin or a cyano-containing organic compound is preferred. Especially, a cyano group-containing organic compound is preferable, and a cyanoethyl group-containing organic compound is more preferable.

From the viewpoint of functioning as a binder for metal oxide particles, the organic compound in the semiconductor film may be an organic compound having a molecular weight of 600 or more.

In addition, the present inventors found that the content of the above-mentioned characteristic points (1) and (2), and that when the metal oxide particles and the organic compound are mixed to make a semiconductor film, the O1s spectrum of the semiconductor film in the XPS measurement belongs to metal oxidation. When the ratio (S2 / S1) of the peak area S1 of the O ^2- ion of the substance to the peak area S2 of the O ^2- ion that is anoxic is controlled to be 0.25 or more and 0.60 or less, the semiconductor characteristics are significantly improved (the above-mentioned characteristic point (3) ). This range can control, for example, the annealing temperature or time of the oxide semiconductor particles before the semiconductor film is formed. When the annealing temperature is increased and the annealing time is increased, the ratio (S2 / S1) becomes smaller. In addition, by performing a firing treatment in the presence of ozone, the ratio (S2 / S1) can be controlled to be smaller.

On the other hand, the ratio (S2 / S1) can be increased by the interaction caused by the addition of organic compounds, and as a result, the ratio (S2 / S1) can be controlled to be 0.25 or more and 0.60 or less.

That is, the semiconductor film in this embodiment is used for a semiconductor element using an oxide semiconductor as described later, but in order to improve semiconductor characteristics, it is necessary to appropriately control the oxygen defect of the semiconductor element. Therefore, the inventors worked hard to review, and found the following: In order to properly control the oxygen defects of the semiconductor element, the O1s spectrum of the semiconductor film in the XPS measurement, the peak area S1 of the O ^2- ion belonging to the metal oxide and the oxygen deficiency The ratio (S2 / S1) of the peak area S2 of O ² -ions is 0.25 or more and 0.60 or less, which is very important.

This ratio (S2 / S1) is based on the interaction between metal oxide particles and organic compounds. The peak area S1 is composed of oxygen inside the semiconductor film, and the peak area S2 is formed by the lack of oxygen in the semiconductor film and oxygen on the surface of the semiconductor film. And organic compounds. Therefore, by adjusting the ratio (S2 / S1) of the peak area S1 to the peak area S2, the oxygen deficiency can be appropriately controlled.

In this embodiment, from the viewpoint of carrier mobility of semiconductor characteristics, the ratio (S2 / S1) of the peak area S1 to the peak area S2 of the O1s spectrum of the semiconductor film in the XPS measurement is preferably 0.25 or more, more preferably It is 0.30 or more, more preferably 0.31 or more, and most preferably 0.32 or more. Similarly, from the viewpoint of semiconductor characteristics, in particular, from the viewpoint of reducing the off current of the transistor element, the ratio (S2 / S1) is preferably 0.60 or less, more preferably 0.50 or less, and even more preferably 0.40 or less, preferably 0.35 or less.

Moreover, the semiconductor film formed by mixing metal oxide particles and an organic compound can improve the flexibility of the semiconductor film. The increase in flexibility is also important for the interaction between metal oxide particles and organic compounds.

In addition, by mixing the metal oxide particles and the organic compound, it has the effect of increasing the conduction channel of the carrier. If the semiconductor film is formed only with metal oxide particles, that is, the semiconductor film is formed with 100% of the metal oxide, a large number of places where the metal oxide particles are not connected to each other are generated. Therefore, by mixing the metal oxide particles and the organic compound, it is suspected that the contact between the metal oxide particles is increased. In addition, it is estimated that the carrier can pass through the inside of the semiconductor film by adding an organic compound at intervals of several nm even if the metal oxide particles are not closely connected to each other. Moreover, if there are too many metal oxide particles in the semiconductor film, there is a problem that the film-forming property of the substrate is reduced.

In addition, by compounding the metal oxide particles with the organic compound, it is possible to block the surrounding oxygen (that is, the air existing in the interstices between the particles). As a result, it is possible to reduce the carrier which is deactivated by oxygen, and therefore it is possible to increase the carrier density or the mobility.

When the content of the metal oxide particles in the semiconductor film containing the metal oxide particles and the organic compound is 100% by mass of the entire semiconductor film, from the viewpoint of semiconductor characteristics, it is preferably 55% by mass or more, and more preferably 65% by mass. % Or more, more preferably 80% by mass, and most preferably 90% by mass. From the same viewpoint, the content of the metal oxide particles is preferably 95% by mass or less, more preferably 94% by mass or less, still more preferably 93% by mass or less, and most preferably 92% by mass or less.

When the content of the metal oxide particles in the semiconductor film containing the metal oxide particles and the organic compound is 100% by mass of the entire semiconductor film, from the viewpoint of semiconductor characteristics, it is preferably 15% by volume or more, more preferably 21% by volume. It is more than 36% by volume, more preferably 36% by volume, and most preferably 56% by volume. From the same viewpoint, the content of the metal oxide particles is preferably 73% by volume or less, more preferably 69% by volume or less, still more preferably 65% by volume or less, and most preferably 62% by volume or less.

From the viewpoint of flexibility, the content of the organic compound in the semiconductor film is preferably 5 mass% or more, more preferably 6 mass% or more, still more preferably 7 mass%, and most preferably 8 mass%. . From the same viewpoint, the content of the organic compound is preferably 45% by mass or less, more preferably 35% by mass or less, still more preferably 20% by mass or less, and still more preferably 10% by mass or less.

From the same viewpoint, it is preferably 27 vol% or more, more preferably 31 vol% or more, still more preferably 35 vol%, and most preferably 38 vol%. From the same viewpoint, the content of the organic compound is preferably 85% by volume or less, more preferably 79% by volume or less, still more preferably 64% by volume or less, and still more preferably 44% by volume or less.

When the relative elemental concentration of impurities in the XPS measurement of the semiconductor film was controlled to be 1.0 atomic% or less, it was found that the off-state current and hysteresis characteristics of the semiconductor film, especially when used as a transistor, were significantly improved. From the same viewpoint, the relative elemental concentration of impurities is more preferably 0.8 atomic% or less, more preferably 0.5 atomic% or less, and particularly preferably 0.1 atomic% or less. Examples of the impurity element include, but are not limited to, Na, Cl, and Ca.

In order to reduce the amount of impurities, the metal oxide particles can be washed and used. The washing method includes wet washing and dry washing, and can be used in appropriate combination.

The wet cleaning includes three steps of impregnating the metal oxide particles in the cleaning solution, transferring impurities from the metal oxide particles to the cleaning solution, and recovering the metal oxide particles. In the step of impregnating the metal oxide particles in the cleaning solution, the cleaning solution is not particularly limited, and ultrapure water, an aqueous citric acid solution, and an aqueous sodium hydrogen carbonate solution can be used alone or in combination. Moreover, you may use a commercially available surfactant as a washing | cleaning liquid.

In the step of transferring impurities from the metal oxide particles to the cleaning solution, manual stirring or an ultrasonic washing machine can be used. In particular, the ultrasonic cleaning machine uses physical effects such as ultrasonic cavitation, vibration acceleration, and direct flow to transfer more impurities to the cleaning solution. In addition, the ultrasonic wave can promote the chemical reaction of the cleaning solution and transfer more impurities to the cleaning solution.

The step of recovering metal oxide particles is to separate the cleaning solution and particles containing impurities by membrane distillation and centrifugation to recover metal oxides with a large solid content. By repeating the above three steps, the impurities of the metal oxide particles can be further reduced.

Dry cleaning includes UV-ozone cleaning and oxygen plasma treatment. Dry cleaning can reduce the strong chemical adsorption of molecules and elements on the surface of metal oxides that are difficult to wash off in wet cleaning.

(Semiconductor element)

In this embodiment, the structure of the semiconductor element includes an electrode and the semiconductor film formed by being connected to the electrode.

Examples of the semiconductor device include a diode, a transistor, a thin film transistor, a memory, a photodiode, a light-emitting diode, a light-emitting transistor, and a sensor.

Transistors and thin-film transistors (hereinafter collectively referred to as transistor elements) can be used in various display devices such as active matrix drive displays, liquid crystal displays, dispersive liquid crystal displays, electrophoretic displays, electrochromic displays, organic light-emitting displays, and electronic paper. And particle display elements.

The transistor device can be used in such a display device as a transistor for switching a pixel, a signal driver circuit element, a memory circuit element, a signal processing circuit element, and the like.

The switching crystal system for a display device or a display element (hereinafter collectively referred to as a display device) is arranged at each pixel of the display device and switches the display state of each pixel. Such an active driving element does not require patterning of the conductive substrate on the opposite side, and therefore, compared with a passive driving type display device that does not have a transistor to switch the pixel display state, the circuit configuration can simplify pixel wiring. Usually, one to several switching transistors are arranged per pixel. Such a display device has a structure in which a two-dimensional data line and a gate line are formed on a substrate surface, and the data line and the gate line are respectively connected to a gate, a source, and a drain of a transistor. In addition, the data line and the gate line may be divided, or a current supply line and a signal line may be added.

In addition, in addition to pixel wiring and transistors, each pixel in the display device may be provided with a capacitor in parallel, and a function of recording a signal may be provided. In addition, a driver for data lines and gate lines may be mounted on a substrate on which a display device is formed. Circuit, pixel signal memory circuit, pulse generator, signal divider, controller, etc.

When the semiconductor element is a thin film transistor, the element structure may include, for example, a substrate / gate / insulator layer (dielectric layer) / source electrode and a drain electrode / semiconductor layer structure (bottom contact structure); / Source electrode and drain electrode / insulator layer (dielectric layer) / gate electrode structure (top gate structure); and substrate / gate electrode / insulator layer (dielectric layer) / semiconductor layer / source Structure (top contact structure) of the electrode and the drain electrode. The insulator layer (dielectric layer) is a gate insulating film, and is made of, for example, an organic compound film having a specific permittivity of 3 to 150. Further, a plurality of source electrodes, drain electrodes, and gate electrodes may be provided separately. Moreover, a plurality of semiconductor layers may be provided in the same plane, or may be stacked and provided.

In order to use the element for displaying an image, the mobility of the semiconductor element (for example, the mobility of the above-mentioned thin film transistor) is preferably 0.001 cm ² / Vs or more, more preferably 0.01 cm ² / Vs or more, and still more preferably 0.1 cm ² / Vs or more, preferably 1 cm ² / Vs or more. From the same viewpoint, it is preferably 10 cm ² / Vs or less, more preferably 8 cm ² / Vs or more, still more preferably 6 cm ² / Vs or more, and most preferably 4 cm ² / Vs or more.

In addition to a thin-film transistor, any of a MOS (metal-oxide (insulator layer) -semiconductor) type transistor and a bipolar transistor may be used as the configuration of the transistor element. The element structure of the bipolar transistor may include, for example, a structure of an n-type semiconductor layer / p-type semiconductor layer / n-type semiconductor layer, and a structure of a p-type semiconductor layer / n-type semiconductor layer / p-type semiconductor layer, and may be The semiconductor layer is connected to an electrode. Next, on the p-type semiconductor layer or the n-type semiconductor layer At least one of them uses a semiconductor film containing metal oxide particles and an organic compound according to this embodiment.

When the semiconductor element is a diode, the element structure may be, for example, an electrode / n-type semiconductor layer / p-type semiconductor layer / electrode structure. Next, a semiconductor film containing metal oxide particles and an organic compound according to this embodiment is used for the p-type semiconductor layer or the n-type semiconductor layer.

A semiconductor film containing metal oxide particles and an organic compound is in contact with the electrode, and at least a part of the joint surface between the semiconductor film and the electrode may be a Schottky junction and / or a tunnel junction. Examples of such a junction structure include an electrode / Schottky junction (tunnel junction) / semiconductor layer / electrode structure, an electrode / semiconductor layer / tunnel junction / semiconductor layer / electrode structure, and an electrode / Schottky junction (tunnel junction). ) / Semiconductor layer / tunnel junction / semiconductor layer / electrode structure.

These Schottky junctions and tunnel junctions can not only be used to adjust diode characteristics or tunnel junction elements. By using magnetic materials and photo-responsive materials for the Schottky junction and the tunnel junction, high-performance semiconductor devices can be manufactured.

In addition, in the semiconductor film containing metal oxide particles and organic compounds in this embodiment, only a Schottky junction and / or a tunnel junction can be applied, whereby a diode can be formed. A semiconductor element having such a junction structure can be fabricated with a simple structure to form a diode or a transistor, so it is preferable. Furthermore, a plurality of semiconductor elements having such a bonding structure may be bonded to form various elements such as an inverter, an oscillator, a memory circuit, and a sensor.

The semiconductor element of this embodiment can also be used as Calculating and memory elements in electronic devices such as IC cards, smart cards, or electronic tags. At this time, these can be either contact type or non-contact type, and they can be applied smoothly.

These IC cards, smart cards, and electronic tags are composed of a memory, a pulse generator, a signal divider, a controller, and a capacitor, and may further include an antenna and a battery.

In addition, the semiconductor device of this embodiment can be used as a sensor, and can be applied to various sensors such as a gas sensor, a biosensor, a blood sensor, an immune sensor, an artificial omentum, and a taste sensor. Tester.

Next, a specific example of a semiconductor element using the semiconductor film of this embodiment will be described.

The cross-sectional view of FIG. 1 is an example of a configuration example of a semiconductor element 100 according to this embodiment. As shown in FIG. 1, the semiconductor element 100 is a thin-film transistor having a bottom-contact structure, and includes a substrate 110, a gate electrode 120 formed on the substrate 110, an insulator layer 130 formed on the substrate 110 and covering the gate electrode 120, and a source. The electrode 140, the drain electrode 150, and the semiconductor layer 160. The source electrode 140 is formed on the substrate 110 and covers one end of the gate electrode 120 through the insulator layer 130. The drain electrode 150 is formed on the substrate 110 and covers the other end of the gate electrode 120 through the insulator layer 130. The semiconductor layer 160 is formed on the gate 120 through the insulator layer 130 and is exposed from the insulator layer 130 to the source electrode 140 and the drain electrode 150 exposed between the source 140 and the drain 150 (ie, the gap). On the top.

Examples of the material of the substrate 110 include glass and resin. also, Examples of the materials of the gate electrode 120, the source electrode 140, and the drain electrode 150 include metals, conductive ceramic materials, carbon, and conductive organic materials. From the viewpoint of good bonding and adhesion with metal oxides or silicon, the materials of the gate electrode 120, the source electrode 140, and the drain electrode 150 are more preferably gold, silver, aluminum, copper, Indium tin oxide (ITO), or indium gallium alloy. The semiconductor layer 160 is a bulk layer of a thin film transistor (that is, a layer formed with a channel), and is formed by a semiconductor film containing metal oxide particles and an organic compound in this embodiment.

The cross-sectional view of FIG. 2 schematically shows an example of the semiconductor device 200 according to this embodiment. As shown in FIG. 2, the semiconductor element 200 is a thin-film transistor having a top gate structure, and has a substrate 210, a source 240 and a drain 250 formed on the substrate 210, and a source 210 and a source 240 formed on the substrate 210. The semiconductor layer 260 of the drain 250, the insulator layer 230 formed on the semiconductor layer 260, and the gate electrode 220 formed on the insulator layer 230. As shown in FIG. 2, the source electrode 240 and the drain electrode 250 are arranged separately from each other. The semiconductor layer 260 is formed from the substrate 210 exposed between the source electrode 240 and the drain electrode 250 (ie, the gap) to the source electrode 240 and the drain electrode 250. The semiconductor layer 260 is formed by a semiconductor film containing metal oxide particles and an organic compound in this embodiment. The gate electrode 220 is formed on the semiconductor layer 260 through the insulator layer 230. The gate electrode 220, the source electrode 240, and the drain electrode 250 are partially opposed to each other through the insulator layer 230 and the semiconductor layer 260.

The cross-sectional view of FIG. 3 schematically shows an example of the semiconductor device 300 according to this embodiment. As shown in FIG. 3, the semiconductor device 300 The thin film transistor having a top contact structure includes a substrate 310, a gate electrode 320 formed on the substrate 310, an insulator layer 330 formed on the substrate 310 and covering the gate electrode 320, a semiconductor layer 360 formed on the insulator layer 330, And a source electrode 340 and a drain electrode 350. The semiconductor layer 360 is formed by a semiconductor film containing metal oxide particles and an organic compound in this embodiment. The source electrode 340 is formed on the substrate 310 and covers one end of the semiconductor layer 360. The drain electrode 350 is also formed on the substrate 310 and covers the other end portion of the semiconductor layer 360. The source electrode 340 and the drain electrode 350 are separated from each other. The gate electrode 320, the source electrode 340, and the drain electrode 350 are partially opposed to each other through the insulator layer 330 and the semiconductor layer 360, and are disposed.

The cross-sectional view of FIG. 4 schematically shows an example of a semiconductor element in this embodiment. The semiconductor element 400 shown in FIG. 4 is a thin film transistor that also serves as the bottom contact structure of the substrate 110 and the gate electrode 120 in FIG. 1. The semiconductor device 400 includes a gate electrode 420, an insulator layer 430, a source electrode 440, a drain electrode 450, and a semiconductor layer 460 that also serve as a substrate. The semiconductor layer 460 is formed on the gate electrode 420 through the insulator layer 430 and is exposed from the insulator layer 430 to the source electrode 440 and the drain electrode exposed between the source electrode 440 and the drain electrode 450 (ie, the gap). It is formed on the electrode 250.

Examples of the material of the gate electrode 420 that also has a substrate include p-type silicon and n-type silicon.

Although not shown, the semiconductor element of this embodiment can be provided with a semiconductor layer between a source electrode and a drain electrode, and can be formed to These three layers of transistors are laminated in the film thickness direction. At this time, the gate electrode may be disposed in the semiconductor layer or near the source electrode (drain electrode).

Next, the materials of the layers of the semiconductor elements 100, 200, 300, and 400 will be described. Examples of the material of the substrates 110, 210, and 310 include glass and resin. The materials of the gate electrodes 120, 220, 320, the source electrodes 140, 240, 340, 440, and the drain electrodes 150, 250, 350, 450 include metals, conductive ceramic materials, carbon, and conductivity. Organic materials, etc. From the standpoint of good adhesion to metal oxides or silicon, to obtain adhesion, the gate electrodes 120, 220, 320, source electrodes 140, 240, 340, 440, and drain electrodes 150, 250, 350, 450 Each of the materials is preferably gold, silver, aluminum, copper, ITO, or an indium gallium alloy. In addition, the semiconductor layers 160, 260, 360, and 460 are bulk layers of thin film transistors, as described above, and are formed of a semiconductor film containing metal oxide particles and an organic compound. The metal oxide particles and organic compounds have already been described, so refer to this description. In addition, regarding each of the semiconductor elements 100, 200, 300, and 400 in FIGS. 1 to 4, although the expression of a “semiconductor layer” is used, the “semiconductor layer” is formed by a “semiconductor film”. No special difference.

From the viewpoint of electrical characteristics, the layer thickness (film thickness) of the semiconductor layers 160, 260, 360, and 460 (semiconductor film) is preferably 0.001 μm (1 nm) or more, more preferably 0.01 μm or more, and more preferably It is 0.02 μm or more, and more preferably 0.05 μm or more. From the same viewpoint, the layer thickness of the semiconductor layers 160, 260, 360, and 460 (semiconductor film) is preferably 1 μm (1000 nm) or less, more preferably 0.4 μm or less, and still more preferably 0.2 μm or less. It is 0.1 μm or less.

(Manufacturing method of semiconductor element)

The method for manufacturing the semiconductor device may include, for example, a method in which a semiconductor layer is formed by coating a dispersion liquid (described later) for forming a semiconductor layer in a predetermined pattern on an electrode or a predetermined region on an insulator layer that is patterned in advance. Moreover, as another manufacturing method of a semiconductor element, the following methods are mentioned: after forming a semiconductor film on a board | substrate, patterning this semiconductor film and forming a semiconductor layer, and forming an electrode and an insulator layer further. The patterning method of the semiconductor film at this time can adopt, for example, the following methods: forming a pattern using a method such as screen printing, gravure printing, offset printing, inkjet printing, and spraying.

In this embodiment, a semiconductor element can be formed on a substrate such as glass or resin. In addition, since the semiconductor film can be formed by a simple method such as solution printing and coating, a large number of semiconductor elements can be easily formed at a time on a large area. Therefore, a semiconductor element and a device using the semiconductor element (the aforementioned display element, calculation element, memory element, etc.) can be manufactured at low cost. Further, the production of a semiconductor element using a semiconductor film is also effective for reducing the thickness and weight of a device using the semiconductor element.

Next, a method for manufacturing the semiconductor elements 100, 200, 300, and 400 shown in FIGS. 1 to 4 will be described using drawings.

5A to 5C are cross-sectional views showing a method of manufacturing the semiconductor device 100 according to this embodiment in the order of steps. As shown in FIG. 5A, a gate electrode 120 is first formed on a substrate 110.

Next, as shown in FIG. 5B, the insulator layer 130 is applied. Cover the upper and side surfaces of the gate electrode 120. Next, as shown in FIG. 5C, a source electrode 140 and a drain electrode 150 are formed from the substrate 110 to the insulator layer 130, respectively. Thereafter, a semiconductor layer 160 is formed, and a gap between the source electrode 140 and the drain electrode 150 is buried by the semiconductor layer 160. This completes the semiconductor device 100 shown in FIG. 1.

The semiconductor device 200 shown in FIG. 2 can be manufactured in the following steps. That is, a source electrode 240 and a drain electrode 250 are formed on the substrate 210. Next, a semiconductor layer 260 is formed on the substrate 210 and is covered between the source electrode 240 and the drain electrode 250, and on the source electrode 240 and the drain electrode 250. An insulator layer 230 is formed on the semiconductor layer 260. Thereafter, a gate electrode 220 is formed on the insulator layer 230. This completes the semiconductor device 200 shown in FIG. 2.

The semiconductor device 300 shown in FIG. 3 can be manufactured in the following steps. That is, the gate electrode 320 is formed on the substrate 310. Next, an insulator layer 330 is formed on the substrate 310 and covers the top and side surfaces of the gate electrode 320. A semiconductor layer 360 is then formed on the insulator layer 330. Thereafter, a source electrode 340 and a drain electrode 350 are formed from the substrate 310 to the semiconductor layer 360. Thereby, the semiconductor device 300 shown in FIG. 3 is completed.

The semiconductor device 400 shown in FIG. 4 can be manufactured by the following steps. That is, an insulator layer 430 is formed on the gate electrode 420 having a substrate and covers the upper surface of the gate electrode 420 having a substrate. Next, a source electrode 440 and a drain electrode 450 are formed on the insulator layer 430. Thereafter, the insulator layer 430 exposed between the source electrode 440 and the drain electrode 450 (ie, the gap) to the source 440 and the drain 450 forms a half. Conductor layer 460. This completes the semiconductor device 400 shown in FIG. 4.

The gate electrodes, source electrodes and drain electrodes of the semiconductor elements (such as thin-film transistors), the insulator layer, and the semiconductor layer can be formed by printing, coating, or other methods. Therefore, it is not necessary to manufacture a semiconductor element under vacuum, but it can be performed under normal pressure.

Examples of the materials of the gate electrode, source electrode, and drain electrode (hereinafter referred to as electrode materials) include metals, conductive ceramic materials, carbon, and conductive organic materials. From the viewpoint of good bonding or adhesion with metal oxides or silicon, the electrode material is more preferably gold, silver, aluminum, copper, indium tin oxide (ITO), or indium gallium alloy.

In addition, in order to form the gate electrode, the source electrode, and the drain electrode by methods such as printing and coating, the electrode material must be liquid. Therefore, the liquid electrode material can be used as the electrode material directly, but the non-liquid electrode material must be dispersed in the liquid and used. Examples of dispersing non-liquid electrode materials in a liquid include powders such as gold, silver, copper, indium tin oxide (ITO), osmium, palladium, nickel, cobalt, iron, and aluminum in a liquid. The conductive paste is more preferably gold, aluminum, copper, or indium tin oxide (ITO). Indium-gallium is a liquid alloy at room temperature, so it can be printed directly and the liquid can be fixed with a sealing material or the like.

Alternatively, as for the electrode material, if the precursor is liquid or is easily solvable, the precursor may be used. Examples of such electrode materials include organic metal complexes such as gold, silver, nickel, and indium, and solutions of inorganic metal complexes.

In addition, the material of the insulator layer is preferably a high dielectric constant. Insulating ceramic materials, organic compounds, polymers, and the like can be used. However, the material of the insulator layer must be liquid like the electrode material, so solutions, dispersions, and precursors of these materials can be used. For example, an alcoholate, an acetamidoacetone complex, or these solutions are coated or printed to form a thin film, and the thin film is converted into an oxide or a sulfide with radiant energy such as heat and light to form an insulator layer. In addition, as the material of the insulator layer, polymers such as polyvinylidene fluoride, polyacrylonitrile, polyester, and liquid crystal polymer, or polar organic compounds are preferably used. In addition, the material of the insulator layer can also be used for those organic compounds in which a high dielectric material such as a ceramic material is dispersed.

As the substrates 110, 210, and 310, glass substrates, PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PC (polycarbonate), PP (polypropylene), and poly Ether, polyimide, cycloolefin polymer, acrylic resin, fluorine resin, melamine resin, phenol resin and other plastic substrates, aluminum substrates, stainless steel (SUS) substrates, substrates made of clay, paper substrates, etc. Of all the substrates. From the viewpoints of light weight, flexibility, and low cost, PET (polyethylene terephthalate), PC (polycarbonate), PP (polypropylene), and PEN (polyethylene naphthalate) are preferred. Diester), polyether fluorene, polyfluorene imine, cycloolefin polymer, acrylic resin, fluorine resin, melamine resin, phenol resin and other plastic substrates or paper substrates.

Furthermore, if a plurality of printing devices and / or coating devices arranged in series in the order of manufacturing steps are used, the coating liquid for forming a semiconductor layer can be continuously printed and / or coated on a continuous substrate (or sheet). Thereby, an electrode, a dielectric layer, and a semiconductor layer can be continuously formed on a substrate (or sheet) to manufacture a semiconductor element.

For example, when manufacturing a thin film transistor having a substrate / gate electrode / insulator layer (dielectric layer) / source electrode and a drain electrode / semiconductor layer structure (bottom contact structure), a strip substrate is sequentially passed through. A gate electrode printing device, an insulator layer printing device, a source electrode and a drain electrode printing device, and a semiconductor layer printing device arranged in series according to their manufacturing steps. The strip substrate is, for example, the above-mentioned sheet. Thereby, the aforementioned constituent elements of the thin-film transistor are continuously formed on the substrate, and the thin-film transistor is efficiently manufactured.

Such a continuous method for manufacturing a thin film transistor has the advantages of less equipment load, shorter steps, and greatly reduced the number of operators, and low cost. In addition, a large number of thin-film transistors can be easily formed at once on a large-area substrate, so that a large-area display device can be manufactured at low cost.

For the printing method and coating method, known methods such as screen printing, gravure printing, offset printing, inkjet printing, spraying, and doctor blade coating can be used. In the plural printing apparatuses and / or coating apparatuses, the same printing method and coating method may be used, and different printing methods and coating methods may be used for each constituent element.

The formation of the semiconductor film in this embodiment is performed by applying and printing on a substrate or the like using a dispersion liquid described below, and then drying it if necessary.

(Dispersions)

Since the dispersion liquid of the present invention is coated on a substrate, it can be called a coating liquid. The dispersion liquid of the present invention contains metal oxide particles, an organic compound, and a solvent. It may also contain a dispersant. Examples of the solvent system include water, pentane, and hexane. Alkane, heptane, octane, nonane, decane, 2-methylhexane, decalin, tetralin, methanol, ethanol, n-propanol, 2-propanol, n-butanol, third butanol , Terpineol, ethylene glycol, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol Alcohol diethyl ether, diethylene glycol dibutyl ether, ethylene glycol mono 2-ethylhexyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, dipropylene glycol methyl Ethers, ketones such as tripropylene glycol methyl ether, glycerol acetone, methyl ethyl ketone, aromatics such as benzene, xylene, toluene, phenol, aniline, diphenyl ether, dimethyl sulfene, dimethyl formamidine Amine, acetonitrile, methyl acetate, tetrahydrofuran, butyl lactate, N-methylpyrrolidone and the like.

In particular, in terms of improving the dispersibility of the metal oxide particles, a solvent with a high polarity is preferred. The highly polar solvent is a solvent having a polarity parameter of 4 or more, more preferably 5 or more, still more preferably 6 or more, and still more preferably 7 or more.

Specific examples of preferred solvents include terpineol, dimethylmethylene, dimethylformamide, and N-methylpyrrolidone. These may be used in combination.

The metal oxide particles and organic compounds in the dispersion have been described in the above (semiconductor film). Therefore, reference can be made to these descriptions.

Examples of the dispersant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. Specific examples of the anionic surfactant include fatty acid sodium, monoalkyl sulfate, alkylbenzenesulfonate, and monoalkyl phosphate. Examples of the cationic surfactant include an alkyltrimethylammonium salt, a dialkyldimethylammonium salt, and an alkylbenzylmethylammonium salt. Examples of the amphoteric surfactant include alkyldimethylamine oxide, Alkyl carboxybetaine. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, fatty acid sorbitan ester, alkyl polyglycoside, fatty acid triethanolamine, and alkyl monoglyceryl ether. Further, other dispersants include "Disperbyk-102", "Disperbyk-111", "Disperbyk-142", "Disperbyk-145", "Disperbyk-110", "Disperbyk-180", "Disperbyk-" 2013 "," Byk-9076 "," ANTI-TERRA-U "," Plysurf M208F "and" Plysurf DBS "manufactured by Daiichi Kogyo. Examples include Triton X-45, Triton X-100, Triton X, Triton A-20, Triton X-15, Triton X-114, Triton X-405, Tween # 20, Tween # 40, Tween # 60, Tween # 80, Tween # 85, Pluronic F-68, Pluronic F-127, Span 20, Span 40, Span 60, Span 80, Span 83, Span 85, AGC SEIMI CHEMICAL manufactured "surflon S-211", "surflon S -221 "," surflon S-231 "," surflon S-232 "," surflon S-233 "," surflon S-242 "," surflon S-243 "," surflon S-611 ", 3M" Novec "FC-4430", "Novec FC-4432", "Megafac F-444" and "Megafac F-558" manufactured by DIC.

From the viewpoint of improving the dispersibility of the metal oxide particles to the solvent, a phosphate polyester-based dispersant, an alkylammonium salt-based dispersant, an alkanolamine salt-based dispersant, and a copolymer system having pigment affinity As a dispersing agent, specifically, it is preferable to use "Disperbyk-111", "Disperbyk-145", "Disperbyk-180", and "Disperbyk-2013" manufactured by BYK.

From the viewpoint of improving the affinity between the metal oxide particles and the organic compound, a phosphate polyester-based dispersant and a pigment-based copolymer-based dispersant are preferred. Specifically, BYK Corporation is preferably used. "Disperbyk-111", "Disperbyk-2013". The interaction between the metal oxide particles and the organic compound in a solvent can be confirmed by infrared absorption spectroscopy. It can also be confirmed by Raman spectrometry and ultraviolet-visible spectrometry. These dispersants can be used alone or in combination.

From the viewpoint of dispersion stability, the addition amount of the dispersant is preferably 0.1% by mass or more and 20% by mass relative to the entire dispersion, more preferably 0.2% by mass or more and 10% by mass or less, and still more preferably 0.3% by mass % To 5% by mass, most preferably 0.5% to 5% by mass.

The dispersion liquid can be produced by using a ball mill, a planetary ball mill, a bead mill, a homogenizer, and the like. Further, a dispersant and the like can be appropriately added.

The concentration of the dispersion liquid is preferably 0.1 mass% or more and 60 mass% or less, more preferably 1 mass% or more and 55 mass% or less, and still more preferably 10 mass% with respect to 100 mass% of the entire dispersion. % To 50% by mass, preferably 20% to 48% by mass.

The content of the organic compound is preferably from 0.1% by mass to 20% by mass, more preferably from 1% by mass to 15% by mass, still more preferably from 2% by mass to 10% by mass, and most preferably from 2.5% by mass or more. 5 mass% or less.

The content of the solvent is preferably 20% by mass or more and 99.98% by mass or less, more preferably 30% by mass or more and 90% by mass or less, still more preferably 30% by mass or more and 80% by mass or less, and most preferably 40% by mass or more and 70% by mass. Mass% or less. The average particle diameter of the metal oxide particles is preferably 1 nm to 500 nm. From the viewpoint of reducing contact resistance, metal oxidation The average particle diameter of the particles is preferably 1 nm or more, more preferably 3 nm or more, and still more preferably 5 nm or more. From the viewpoint of film-forming properties, the average particle diameter of the metal oxide particles is more preferably 200 nm or less, still more preferably 100 nm or less, and most preferably 50 nm or less.

In addition, in the dispersion liquid of this embodiment, when the dispersion liquid is dried and subjected to XPS measurement, from the viewpoint of the carrier mobility of the semiconductor characteristics, the O1s spectrum in the XPS measurement exists in the peak area S1 and the existence of 528eV to 530eV. The ratio (S2 / S1) of the peak area S2 from 530eV to 533eV is preferably 0.25 or more, more preferably 0.30 or more, still more preferably 0.31 or more, and most preferably 0.32 or more. Also, from the viewpoint of semiconductor characteristics, especially from the viewpoint of reducing the off current of the transistor element, the ratio (S2 / S1) is preferably 0.60 or less, more preferably 0.50 or less, and still more preferably 0.40 or less. , And even more preferably 0.35 or less.

(Manufacturing steps of semiconductor film)

The method for manufacturing a semiconductor film in this embodiment includes the following steps: a coating step of applying a dispersion liquid containing metal oxide particles, organic compounds, and a solvent to a substrate to obtain a coating film; and applying the coating film at a temperature of 20 ° C. to 300 ° C. The drying step is performed at the following drying temperature, and at least a part of the solvent is removed from the coating film.

When forming a semiconductor film by a printing method or a coating method, it is preferable to perform the coating step and the drying step to form a semiconductor film.

In addition, the step of preparing the dispersion liquid used in the coating step (that is, the preparation step of the dispersion liquid) can be performed on the same production line as the coating step. It can also be carried out on a production line or other manufacturing plant different from the coating step. The dispersion can be purchased from other companies. In addition, in this embodiment, a printing system is applied, and a dispersion liquid (coating liquid) may be referred to as a printing liquid, and a coating step may be referred to as a printing step. The dispersion preparation step, coating step, and drying step will be described below.

(1) Dispersion preparation steps

The dispersion preparation step is a step of preparing a dispersion from metal oxide particles, an organic compound, and a solvent. The solvent is preferably an organic solvent for dissolving or dispersing metal oxide particles and organic compounds. A metal oxide particle, an organic compound, and a solvent are mixed to obtain a dispersion liquid for forming a semiconductor film.

The metal oxide particles can be annealed and used before being mixed with an organic compound in a solvent. The annealing environment can be annealed in oxygen, in an inert gas such as nitrogen, or in a mixed gas of nitrogen and oxygen such as air. From the viewpoint of controlling oxygen defects, the annealing temperature is preferably 300 ° C or higher, more preferably 400 ° C or higher, and most preferably 600 ° C or higher. From the same viewpoint, the temperature is preferably 2000 ° C. or lower, more preferably 1500 ° C. or lower, and most preferably 1200 ° C. or lower.

When the dispersion liquid for forming a semiconductor film contains a cyano group-containing organic compound as an organic compound, the content of the cyano group-containing organic compound is preferably 100% by mass or more, and more preferably 0.1% by mass or more and 20% by mass or less, more preferably It is 1 mass% or more and 15 mass% or less, more preferably 2 mass% or more and 10 mass% or less, and most preferably 2.5 mass% or more and 5 mass% or less.

The content of the metal oxide contained in the dispersion liquid for forming a semiconductor film is preferably 0.1% by mass or more and 60% by mass or less based on the concentration of the dispersion liquid relative to 100% by mass of the entire dispersion liquid. , More preferably 1% by mass to 55% by mass, still more preferably 10% by mass to 50% by mass, and most preferably 20% by mass to 48% by mass.

(2) Coating step

The coating step is a step of applying a dispersion liquid to a substrate to obtain a coating film. For example, when a thin film transistor having a substrate / gate / insulator layer (dielectric layer) / source electrode and drain electrode / semiconductor layer structure (bottom contact structure) is manufactured, the coating step is to apply a coating liquid to And a step of obtaining a coating film on the substrate of the source electrode and the drain electrode.

(3) drying step

The drying step is a step of drying the coating film to remove all or part of the organic solvent from the coating film. This drying step is a low temperature process different from the conventional high temperature sintering. The so-called low-temperature process refers to a temperature range of 20 ° C to 300 ° C in this embodiment. This area temperature becomes a usable resin substrate, which is a very important temperature range in industrial processes. The temperature range of the drying step is preferably 20 ° C to 300 ° C, more preferably 20 ° C to 200 ° C, and still more preferably 20 ° C to 150 ° C. If it is 150 ° C or lower, an inexpensive general-purpose resin substrate such as a PET film and a PC film can be used, so it is optimal.

According to the embodiment described above, the metal oxide particles and the organic compound are mixed to form a semiconductor film containing the metal oxide particles and the organic compound. There are many conductive channels of the carrier in this semiconductor film, which further inhibits carrier capture and recombination. The semiconductor film can block peripheral oxygen. As a result, the flow of the carrier is increased and the moving speed of the carrier is also accelerated. This makes it possible to provide a semiconductor device that has a high mobility and is stable in the air (that is, it does not easily undergo chemical changes and is not easily deteriorated even when in contact with air).

In addition, the semiconductor film system containing metal oxide particles and organic compounds does not require a vacuum system process, and can be formed at a low cost and a low temperature process. For example, a coating method or a printing method can be formed by a non-vacuum system process. This can reduce the manufacturing cost of the semiconductor device.

As described above, according to this embodiment, it is possible to provide a semiconductor device which can be manufactured by a non-vacuum system process and exhibits a higher mobility.

[Example]

Hereinafter, the present invention will be described in more detail through specific examples.

<Evaluation method>

Hereinafter, unless otherwise specified, the evaluation is performed under the conditions of 25 ° C. and 45% humidity.

(1) average particle size

The average particle size is measured using a field radial scanning electron microscope SU-8820 (Manufactured by Hitachi, Ltd.). After cutting around the observation position of a semiconductor film formed on a substrate, an ion polishing apparatus E-3500Plus (manufactured by Hitachi, Ltd.) was used to cool and irradiate an argon ion beam while cooling and perform a cross-section processing. The cross section of the semiconductor film was observed, and a total of 10 particle diameters were measured, and the average value was used as the average particle diameter.

(2) XPS measurement

The XPS measurement is carried out at a measurement temperature of 23 ° C. by X-ray photoelectric spectrometry. Specifically, it was covered with a metal mask (2 mmφ) and measured using the following measurement conditions using X-ray photoelectric spectrometry (using a device: VersaProbeII manufactured by ULVAC-PHI Co., Ltd.).

Excitation source: monoAl Kα 25W × 15kV.

Analysis size: about 200 μmφ.

Pass Energy

Survey scan: 117.4eV.

Narrow scan: 23.5eV.

The peak separation is to perform background correction on the 1s spectrum of oxygen, and then separate it into peaks of In-O bonds appearing at 528eV to 530eV, and peaks of OH groups appearing at 530eV to 533eV to obtain the respective peak areas. Peak separation is performed using a curve fitting method obtained by a non-linear least square method of a Gaussian mixture function. At this time, the upper limits of the obtained values of the full width at half maximum of the three peaks are 2.0 eV, respectively.

The relative elemental concentration of Na on the surface of the sample is calculated from the area using the Survey scan result to calculate the proportion of the whole.合 实施 例 Each embodiment The sample impurities of Comparative Examples are shown in Tables 1, 2, and 3.

(3) Film thickness

The layer thickness of the semiconductor film was measured by a stepped portion of the film measured by a stylus section drawing system (Dektak XTL, manufactured by Bruker Co., Ltd.).

(4) Mobility of semiconductor film

The mobility was measured using a parameter analyzer (manufactured by Keithley, 4200-SCS). The measurement parameters are not particularly limited, but unless otherwise specified, the source voltage is 0V, the drain voltage is 80V, and the gate voltage is scanned from -60V to 100V every 1V under vacuum conditions, and further measured to 60V. The change in the drain current is calculated from the field-effect mobility formula.

<Substrate with electrode>

The device structure is not particularly limited, but unless otherwise specified, it is attached to an n-type silicon wafer (resistivity from 0.001 to 0.0015 Ω · cm) with a thermally oxidized film of 200 nm, and Ti is adhered with a thickness of 2 nm. Layer, and deposited thereon Au with a film thickness of 22 nm to form a source electrode and a drain electrode. The size of the source electrode and the drain electrode is 200 μm × 500 μm, the channel length is 50 μm, and the channel width is 500 μm.

Substrates with electrodes are immersed in Semico Clean 56, ultra-pure water, acetone, and 2-propanol before use. After being treated with an ultrasonic cleaner for 5 minutes, they are cleaned and modified by a desktop ultraviolet light. PL21-200 (manufactured by SEN Special Light Co., Ltd.) was subjected to UV ozone treatment for 10 minutes.

[Example 1]

For the metal oxide particles, indium (III) oxide nanopowder <100nm particle size (TEM), 99.9% trace metals basis (manufactured by sigmaaldrich), and 5.0 g of indium oxide particles using a high-temperature furnace SSTR-11K (manufactured by ISUZU) Annealing was performed in the air at 600 ° C for 1 hour.

3.33 g of indium oxide particles and 1.67 g of cyanoethyl sucrose (manufactured by Shin-Etsu Chemical Co., Ltd.), 5.00 g of dimethylarsinide, and 5.0 g of spherical zirconia with a diameter of 0.3 mm were placed in a container, and a planet was used. Type ball mill device P-6 (manufactured by Fritsch), and processed at 600 rpm for 30 minutes to prepare a coating liquid (dispersion liquid) containing cyanoethylsucrose and indium oxide particles.

The coating solution was formed on a substrate with an electrode using a spin coater MS-B1000 (manufactured by MIKASA Co., Ltd.) at 2000 rpm for 30 seconds, and dried on a hot plate at 120 ° C. for 10 minutes to form a coating material. A semiconductor film (composite) of indium oxide and an organic compound, and a semiconductor element is obtained. At this time, the spherical zirconia system with a diameter of 0.3 mm moved out of the system without remaining in the semiconductor film.

[Example 2]

In addition to changing the indium oxide particles to 3.75 g and cyanoethyl sucrose Except for 1.25 g, the rest was obtained in the same manner as in Example 1.

[Example 3]

For the metal oxide particles, indium (III) oxide nanopowder <100nm particle size (TEM), 99.9% trace metals basis (manufactured by sigmaaldrich) were used. In order to wash the indium oxide particles, a 10-fold amount of a 1 mol / L sodium bicarbonate aqueous solution was added to the indium oxide particles and thoroughly stirred, and the operation of sedimentation with a centrifugal separator was repeated 5 times, and then a 10-fold amount of ultrapure water was added and thoroughly stirred. , Repeat 5 times to settle the centrifuge. Thereafter, it was heated on a 150 ° C. hot plate for 2 hours to obtain indium oxide particles.

Thereafter, 5.0 g of indium oxide particles were placed in a firing dish and installed in a tubular furnace connected to a table-type ultraviolet cleaning and reforming device PL21-200 (manufactured by SEN Special Light Co., Ltd.), and circulated at 2.0 L / min In the state of ozone, it was treated at 300 ° C for 1 hour.

4.00 g of indium oxide particles and 1.00 g of cyanoethyl sucrose (manufactured by Shin-Etsu Chemical Co., Ltd.), 5.00 g of dimethylsulfene, and 5.0 g of spherical zirconia having a diameter of 0.3 mm were put into a container and used after the above treatment. The planetary ball mill device P-6 (manufactured by Fritsch) was processed at 600 rpm for 30 minutes to prepare a coating liquid (dispersion liquid) containing cyanoethylsucrose and indium oxide particles.

The above-mentioned coating solution was formed into a film under the same conditions as in Example 1 to thereby obtain a semiconductor element.

[Example 4]

5.0 g of indium oxide particles were placed in a firing dish and installed in a tubular furnace connected to a UV ozone cleaner. The indium oxide was replaced with 300 ° C for 1 hour under a state of flowing ozone at 2.0 L / min. A semiconductor device was obtained in the same manner as in Example 3 except that 5.0 g of the particles were annealed in air at 600 ° C. for 1 hour using a high-temperature furnace SSTR-11K (manufactured by ISUZU).

[Example 5]

A semiconductor device was obtained in the same manner as in Example 3 except that the indium oxide particles were changed to 4.55 g and the cyanoethyl sucrose was changed to 0.45 g.

[Example 6]

A semiconductor device was obtained in the same manner as in Example 5 except that the indium oxide particles were not cleaned.

[Example 7]

Cyanoethylsucrose (manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed with 2-methoxyethanol to prepare a 20% by mass solution. This solution was printed on an electrode-attached substrate using an inkjet printer DMP-2831 (manufactured by Fujifilm) so that the film thickness after drying became about 400 nm.

Use of indium (III) oxide for metal oxide particles nanopowder <100nm particle size (TEM), 99.9% trace metals basis (manufactured by sigmaaldrich). In order to wash the indium oxide particles, a 10-fold amount of a 1 mol / L sodium bicarbonate aqueous solution was added to the indium oxide particles and thoroughly stirred, and the operation of sedimentation with a centrifugal separator was repeated 5 times. Then, 10-fold amount of ultrapure water was added and sufficiently Stir and repeat the operation to settle by centrifugal separator 5 times. Then, it heated on the 150 degreeC hotplate for 2 hours, and obtained the particle.

Thereafter, 5.0 g of indium oxide particles were annealed in air at 600 ° C. for one hour using a high-temperature furnace SSTR-11K (manufactured by ISUZU).

The semiconductor element was obtained by placing the washed and annealed indium oxide particles on a substrate with an electrode printed with cyanoethyl sucrose, pressing it with a spatula and drying on a hot plate at 120 ° C for 10 minutes. The semiconductor element includes a semiconductor film composed of a composite of indium oxide and an organic compound.

[Example 8]

A semiconductor device was obtained in the same manner as in Example 7 except that the cleaning process of the indium oxide particles was not performed.

[Example 9]

The indium oxide particles were synthesized by the following method. 99.99% of indium chloride and 8.00 g (manufactured by Transmetal) were dissolved in 160 ml of dehydrated ethanol. After adding dehydrated triethylamine (manufactured by sigmaaldrich) and stirring for 1 hour, the solid content was recovered by filtration. Wash with 50ml of dehydrated ethanol and decompress at 40 ° C Dry for 12 hours. The recovered solid content was 1.59 g, and the yield was 22%. In a 100 ml flask, 0.36 g of cetyltrimethylammonium bromide (manufactured by sigmaaldrich) was dissolved in 20 ml of dehydrated ethanol. 0.62 g of the solid content was added, and 60 ml of ultrapure water was further added. Ammonium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto so that the pH became 10. This was homogenized in the air at 100 W / cm, 2.20 kHz, and 1.5 hours, and then the solid content was recovered by filtration. It was washed with 100 ml of ultrapure water, and solid content was recovered by filtration. Repeat 5 times of washing with ultrapure water. The entire recovered solid content was calcined in a high-temperature furnace SSTR-11K (manufactured by ISUZU) at 350 ° C for 1 hour, thereby obtaining 0.34 g of yellow indium oxide particles.

XRD measurement was performed on Ultima-IV (manufactured by Rigaku) of the indium oxide particles thus synthesized, and it was identified as indium oxide, and the crystallite diameter was 13.0 nm.

Thereafter, 0.50 g of indium oxide particles were annealed in the air at 400 ° C. for 1 hour using a high-temperature furnace SSTR-11K (manufactured by ISUZU).

Cyanoethylsucrose (manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed with 2-methoxyethanol to prepare a 20% by mass solution. This solution was printed on an electrode-attached substrate using an inkjet printer DMP-2831 (manufactured by Fujifilm) so that the film thickness after drying became about 400 nm.

The washed and annealed indium oxide particles were placed on a substrate with electrodes printed with cyanoethyl sucrose, pressed with a spatula, and dried on a hot plate at 120 ° C for 10 minutes, thereby obtaining a semiconductor device. The semiconductor element is provided with a composite body composed of indium oxide and an organic compound Of semiconductor film.

[Example 10]

A semiconductor device was obtained in the same manner as in Example 8 except that the annealing treatment of the indium oxide particles was not performed.

[Example 11]

A semiconductor device was obtained in the same manner as in Example 8 except that cyanoethyl polyvinyl alcohol (manufactured by Shin-Etsu Chemical Co., Ltd.) was used in place of cyanoethyl sucrose.

[Example 12]

A semiconductor device was obtained in the same manner as in Example 8 except that cyanoethyl polytriglucose (manufactured by Shin-Etsu Chemical Co., Ltd.) was used in place of cyanoethyl sucrose.

[Example 13]

A semiconductor device was obtained in the same manner as in Example 8 except that glycerin (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of cyanoethyl sucrose.

[Example 14]

Except that polyvinyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd., average polymerization degree: about 1500 to 1800) was used instead of cyanoethyl sucrose, and 2-methoxyethanol was replaced with water, the rest were obtained in the same manner as in Example 8. Semiconductor element.

[Example 15]

Cyanoethylsucrose (manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed with 2-methoxyethanol to prepare a 10% by mass solution. This solution was printed on an electrode-attached substrate using an inkjet printer DMP-2831 (manufactured by Fujifilm) so that the film thickness became about 200 nm after drying.

In the metal oxide particle system, indium (III) oxide nanopowder <100 nm particle size (TEM), 99.9% trace metals basis> (manufactured by sigmaaldrich) was used.

Thereafter, 5.0 g of the indium oxide particles were annealed in the air at 600 ° C. for 1 hour using a high-temperature furnace SSTR-11K (manufactured by ISUZU).

The washed and annealed indium oxide particles were placed on a substrate with electrodes printed with cyanoethyl sucrose, pressed with a spatula, and dried on a hot plate at 120 ° C for 10 minutes, thereby obtaining a semiconductor device. The semiconductor element includes a semiconductor film composed of a composite of indium oxide and an organic compound.

[Example 16]

A semiconductor device was obtained in the same manner as in Example 1 except that zinc oxide nano particles <100 nm particle size (manufactured by Sigma Aldrich) were used instead of the indium oxide particles.

[Example 17]

A semiconductor device was obtained in the same manner as in Example 6, except that zinc oxide nano particles <100 nm particle size (manufactured by Sigma Aldrich) were used instead of the indium oxide particles.

[Example 18]

A semiconductor device was obtained in the same manner as in Example 8 except that zinc oxide nano particles <100 nm particle size (manufactured by Sigma Aldrich) were used instead of the indium oxide particles.

[Example 19]

A semiconductor device was obtained in the same manner as in Example 10 except that zinc oxide nano particles <100 nm particle size (manufactured by Sigma Aldrich) were used instead of the indium oxide particles.

[Example 20]

As the metal oxide particle system, zinc oxide HPZ-06 (manufactured by Sakai Chemical Co., Ltd.) was used. 5.0 g of zinc oxide particles were placed in a firing dish and installed in a tubular furnace connected to a table-type ultraviolet cleaning and reforming device PL21-200 (manufactured by SEN Special Light Co., Ltd.). In the state, the treatment was performed at 300 ° C for 1 hour.

Cyanoethyl sucrose (manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed with dimethylsulfene to prepare a 20% by mass solution. This solution was printed on an electrode-attached substrate using an inkjet printer DMP-2831 (manufactured by Fujifilm) so that the film thickness after drying became about 400 nm.

The washed and annealed zinc oxide particles were placed on a printed substrate with electrodes of cyanoethyl sucrose, pressed with a spatula, and dried on a hot plate at 120 ° C for 10 minutes, thereby obtaining a semiconductor device. Half of this conductor element is provided with a semiconductor film composed of a composite of indium oxide and an organic compound.

[Example 21]

As the metal oxide particle system, zinc oxide HPZ-06 (manufactured by Sakai Chemical Co., Ltd.) was used. 5.0 g of zinc oxide particles were placed in a firing dish and installed in a tubular furnace connected to a desktop UV cleaning and reforming device PL21-200 (manufactured by SEN Special Lighting Co., Ltd.) in a state where ozone was flowing at 2.0 L / min. Then, it processed at 300 degreeC for 1 hour.

4.35 g of zinc oxide particles and 0.65 g of cyanoethyl sucrose (manufactured by Shin-Etsu Chemical Co., Ltd.), 1.7 g of dimethyl sulfene, and 5.8 g of spherical zirconia having a diameter of 0.3 mm were placed in a container using a planetary system. A ball mill device P-6 (manufactured by Fritsch) was processed at 600 rpm for 30 minutes to prepare a coating liquid (dispersion liquid) containing cyanoethylsucrose and zinc oxide particles.

The coating solution was formed on a substrate with an electrode using a spin coater MS-B1000 (manufactured by MIKASA Co., Ltd.) at 2000 rpm for 30 seconds, and dried on a hot plate at 120 ° C for 10 minutes, thereby forming a coating containing oxidation. A semiconductor film (composite) of zinc and an organic compound to obtain a semiconductor element. At this time, the spherical zirconia system with a diameter of 0.3 mm moved outside the system and did not remain in the semiconductor film.

[Example 22]

As the metal oxide particle system, zinc oxide HPZ-06 (manufactured by Sakai Chemical Co., Ltd.) was used. 5.0 g of zinc oxide particles were placed in a firing dish, set inside a desktop UV cleaning and reforming device PL21-200 (manufactured by SEN Special Light Co., Ltd.), and treated with ozone at room temperature for 20 minutes.

Cyanoethyl sucrose (manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed with dimethylsulfene to prepare a 20% by mass solution. This solution was printed on an electrode-attached substrate using an inkjet printer DMP-2831 (manufactured by Fujifilm) so that the film thickness after drying became about 400 nm.

The washed and annealed zinc oxide particles were placed on a printed substrate with electrodes of cyanoethyl sucrose, pressed with a spatula, and dried on a hot plate at 120 ° C for 10 minutes, thereby obtaining a semiconductor element. It is equipped with a semiconductor film composed of a composite of indium oxide and an organic compound.

[Example 23]

As the metal oxide particle system, zinc oxide HPZ-06 (manufactured by Sakai Chemical Co., Ltd.) was used. 5.0 g of zinc oxide particles were placed in a firing dish, and placed inside a desktop UV cleaning and reforming device PL21-200 (manufactured by SEN Special Light Co., Ltd.), and treated with ozone at room temperature for 20 minutes.

4.675 g of zinc oxide particles and 0.325 g of cyanoethyl sucrose (manufactured by Shin-Etsu Chemical Co., Ltd.), 11.7 g of dimethyl fluorene, and 5.8 g of spherical zirconia having a diameter of 0.3 mm were placed in a container using a planetary system. A ball mill device P-6 (manufactured by Fritsch) was processed at 600 rpm for 30 minutes to prepare a coating liquid (dispersion liquid) containing cyanoethylsucrose and zinc oxide particles.

The coating solution was formed on a substrate with an electrode using a spin coater MS-B1000 (manufactured by MIKASA Co., Ltd.) at 2000 rpm for 30 seconds, and dried on a hot plate at 120 ° C for 10 minutes, thereby forming a coating containing oxidation. A semiconductor film (composite) of zinc and an organic compound to obtain a semiconductor element. At this time, the spherical zirconia system with a diameter of 0.3 mm moved outside the system and did not remain in the semiconductor film.

[Comparative Example 1]

Cyanoethylsucrose (manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed with 2-methoxyethanol to prepare a 20% by mass solution. This solution was formed on a substrate with electrodes using a spin coater MS-B1000 (manufactured by MIKASA Co., Ltd.) at 2000 rpm for 30 seconds, and dried on a hot plate at 120 ° C for 10 minutes to obtain a cyano group. Ethyl sucrose membrane.

[Comparative Example 2]

A semiconductor device was obtained in the same manner as in Example 1 except that the indium oxide particles were changed to 2.50 g and the cyanoethyl sucrose was changed to 2.50 g.

[Comparative Example 3]

In the metal oxide particle system, indium oxide nano particles (Nanopowder), 99.99%, 20-70 nm (manufactured by Sky Springs Nanomaterials) were used, and 5.0 g of indium oxide particles were used in a high-temperature furnace SSTR-11K (manufactured by ISUZU) in the air. 1 hour retreat at 600 ° C Fire treatment.

4.00 g of indium oxide particles and 1.00 g of cyanoethyl sucrose (manufactured by Shin-Etsu Chemical Co., Ltd.), 5.00 g of dimethyl sulfene, and 5.0 g of spherical zirconia with a diameter of 0.3 mm were placed in a container in a planetary manner. The ball mill device P-6 (manufactured by Fritsch) was processed at 600 rpm for 30 minutes to prepare a coating liquid (dispersion liquid) containing cyanoethylsucrose and indium oxide particles.

A semiconductor element was obtained by forming the coating liquid under the same conditions as in Example 1.

[Comparative Example 4]

A semiconductor device was obtained in the same manner as in Comparative Example 3 except that indium (III) hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of indium oxide nano particles (Nanopowder), 99.99%, and 20-70 nm (manufactured by SkySprings Nanomaterials). .

[Comparative Example 5]

Indium oxide particles were synthesized in the following manner. 99.99% of indium chloride (manufactured by Transmetal) was dissolved in 160 ml of dehydrated ethanol. To this was added dehydrated triethylamine (manufactured by Sigma Aldrich), and after stirring for 1 hour, the solid content was recovered by filtration. It was washed with 50 ml of dehydrated ethanol and dried under reduced pressure at 40 ° C for 12 hours. The recovered solid content was 1.59 g, and the yield was 22%. In a 100 ml flask, 0.36 g of cetyltrimethylammonium bromide (manufactured by Sigma Aldrich) was dissolved in 20 ml of dehydrated ethanol. 0.62 g of the solid content was added, and 60 ml of ultrapure water was further added. Add it to pH 10 Ammonium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.). This was homogenized in the air at 100 W / cm, 2.20 kHz, and 1.5 hours, and then the solid content was recovered by filtration. It was washed with 100 ml of ultrapure water, and solid content was recovered by filtration. Repeat 5 times of washing with ultrapure water. The whole amount of the recovered solid content was calcined at 350 ° C. for 1 hour using a high-temperature furnace SSTR-11K (manufactured by Isuzu Corporation), thereby obtaining 0.34 g of yellow indium oxide particles.

The indium oxide particles obtained by the synthesis were subjected to XRD measurement by Ultima-IV (manufactured by Rigaku), and it was identified as indium oxide, and the crystallite diameter was 13.0 nm.

Thereafter, 0.50 g of indium oxide particles were annealed at 1000 ° C. for 1 hour in air using a high-temperature furnace SSTR-11K (manufactured by ISUZU).

Cyanoethylsucrose (manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed with 2-methoxyethanol to prepare a 20% by mass solution. This solution was printed on an electrode-attached substrate using an inkjet printer DMP-2831 (manufactured by Fujifilm Corporation) so that the film thickness after drying became about 400 nm.

The washed and annealed indium oxide particles were placed on a substrate with an electrode printed with cyanoethyl sucrose, pressed with a spatula, and dried on a hot plate at 120 ° C for 10 minutes, thereby obtaining a semiconductor element. The semiconductor element includes a semiconductor film composed of a composite of indium oxide and an organic compound.

[Comparative Example 6]

In addition to changing indium oxide particles to 4.85 g, cyanoethyl sucrose Other than 0.15 g, a semiconductor element was obtained in the same manner as in Example 1.

[Comparative Example 7]

In the metal oxide particle system, indium (III) oxide nano particles (100 nm particle size (TEM), 99.9% trace metals basis (manufactured by sigmaaldrich)) were used. The indium oxide was annealed at 600 ° C for 1 hour in a high temperature furnace SSTR-11K (manufactured by ISUZU).

The annealed indium oxide particles were loaded on a wafer with a gold electrode, pressed with a spatula, and dried on a hot plate at 120 ° C for 10 minutes, thereby obtaining an indium oxide particle block.

[Comparative Example 8]

A semiconductor device was obtained in the same manner as in Comparative Example 2 except that zinc oxide nano particles <100 nm particle size (manufactured by sigmaaldrich) were used instead of the indium oxide particles.

[Comparative Example 9]

A semiconductor device was obtained in the same manner as in Comparative Example 6 except that zinc oxide nano particles <100 nm particle size (manufactured by sigmaaldrich) were used instead of the indium oxide particles.

The evaluation results of the samples of Examples and Comparative Examples are shown in Tables 1, 2, and 3 below.

The film-forming property was observed on the surface of the semiconductor film with a microscope at a magnification of 50 times. A state where a semiconductor film was formed in an area of 80% or more was ○, and a state where a semiconductor film was formed in an area of less than 80% was ×.

The movement rate is ◎ for 0.1cm ² / Vs or more, ○ for 1.0E-3cm ² / Vs or more and less than 0.1cm ² / Vs is ○, and for those who are less than 1.0E-3cm ² / Vs and become transistors, △, not become Transistors are ×.

The cut-off current is ○ for 1.0E-10A, and × for 1.0E-10A or more. When the hysteresis is Id = 1.0nA, the difference between the return and return Vg is less than 10V, which is ○, and 10V or more is ×.

As shown in Tables 1, 2, and 3, in each of the examples, the film-forming properties and the mobility were good. In particular, it can be seen that the mobility of Examples 5, 6, 7, 8, and 18 is good. Further, it can be seen that the cut-off currents of Examples 5, 7, 9, 17, 18, 20, 21, and 22 were good. Furthermore, it can be seen that the hysteresis of Examples 7, 9, 17, 18, and 20 is good. On the other hand, in any of Comparative Example 1 and Comparative Example 2, each was an insulator, and a transistor element could not be produced. Moreover, in Comparative Example 1, the film-forming property was poor.

The present invention is not limited to the embodiments and examples described above. According to the knowledge of a person with ordinary knowledge in the technical field, the implementation form, each embodiment can be added with design changes, etc. The implementation form, each embodiment can be arbitrarily combined, and such implementation changes are also included in the present invention. Range.

(Industrial availability)

According to the present invention, it is possible to provide a semiconductor film which can be manufactured in a non-vacuum-based process and a low-temperature process and can exhibit higher mobility, a semiconductor element using the semiconductor film, and a dispersion liquid.

This application is based on Japanese Patent Application No. 2016-236699 filed on December 6, 2016 and Japanese Patent Application No. 2017-233319 filed on December 5, 2017. These contents are used in the present invention.

Claims (17)

A semiconductor film containing metal oxide particles and an organic compound, the content of the metal oxide is 55% by mass or more and 95% by mass or less, and the content of the organic compound is 5% by mass relative to 100% by mass of the entire semiconductor film. Above 45% by mass, the ratio of the peak area S1 of O ² ions belonging to metal oxides to the peak area S2 of O ² ions belonging to anoxic oxygen in the O1s spectrum of the aforementioned semiconductor film in XPS measurement (S2 / S1 ) Is 0.25 or more and 0.60 or less. For example, the semiconductor film described in the first item of the patent application range, wherein the organic compound is a dielectric and the relative permittivity is 5 or more and 100 or less. A semiconductor film containing indium oxide particles and an organic compound, the content of the indium oxide is 55% by mass or more and 95% by mass or less, and the content of the organic compound is 5% by mass or more relative to 100% by mass of the entire semiconductor film. Mass% or less, the ratio (S2 / S1) of the peak area S1 of the O1s spectrum of the semiconductor film existing in the 528eV to 530eV to the peak area S2 of the 530eV to 533eV in the XPS measurement is 0.25 or more and 0.60 or less. For example, the semiconductor film described in item 3 of the scope of patent application, wherein the organic compound is a dielectric, and the relative permittivity is 5 or more and 100 or less. A semiconductor film containing zinc oxide particles and an organic compound, and the content of the zinc oxide is 55% by mass or more and 95% by mass or less, and the content of the organic compound is 5% by mass or more relative to 100% by mass of the entire semiconductor film. mass% or less, the semiconductor film O1s spectrum in XPS measurement of the peak belonging to the area S1 of zinc oxide O ^2- ions belonging to the ratio of the O ^2- ions hypoxia peak area of S2 (S2 / S1) is 0.25 or more 0.60 or less. For example, the semiconductor film described in item 5 of the scope of patent application, wherein the aforementioned organic compound is a dielectric, and the relative permittivity is 5 or more and 100 or less. The semiconductor film according to any one of claims 1 to 6, wherein the aforementioned organic compound is a cyano-containing organic compound. The semiconductor film according to any one of claims 1 to 6 of the scope of application for a patent, wherein the relative element concentration of Na in the semiconductor film in the XPS measurement is 1.0 atomic% or less. The semiconductor film according to any one of the claims 1 to 6, wherein the organic compound is a cyano-containing organic compound, and the relative element concentration of Na in the semiconductor film in the XPS measurement is 1.0 atomic% or less. A semiconductor element includes: an electrode; and the aforementioned semiconductor film according to any one of claims 1 to 9 of an application patent range connected to the aforementioned electrode. The semiconductor device according to item 10 of the scope of patent application, wherein the thickness of the semiconductor film is 1 nm or more and 1000 nm or less. For example, the semiconductor device described in item 10 or 11 of the patent application scope is a transistor device. The semiconductor device according to item 10 or 11 of the scope of application for a patent, wherein the mobility is 0.001 cm ² / Vs or more and 10 cm ² / Vs or less. For example, the semiconductor device described in item 10 or 11 of the patent application scope is a transistor device and has a mobility of 0.001 cm ² / Vs or more and 10 cm ² / Vs or less. A dispersion liquid containing metal oxide particles, organic compounds, and a solvent, and the content of the metal oxide particles is 0.1% by mass or more and 60% by mass or less based on 100% by mass of the entire dispersion, and the content of the organic compound It is 0.1% by mass to 20% by mass, the content of the aforementioned solvent is 20% by mass to 99.98% by mass, and the O1s spectrum of the O1s spectrum in the XPS measurement of the dispersion after drying is a peak area S1 of O ² ions belonging to metal oxides. The ratio (S2 / S1) to the peak area S2 of O ² -ion which is anoxic is 0.25 or more and 0.60 or less. A dispersion liquid containing indium oxide particles, an organic compound, and a solvent, and the content of the indium oxide particles is 0.01% by mass or more and 60% by mass or less relative to 100% by mass of the entire dispersion, and the content of the organic compound is 0.01 The mass content is from 20% by mass to 20% by mass, the content of the aforementioned solvent is from 20% by mass to 99.98% by mass, and the O1s spectrum in the XPS measurement of the dispersion after drying is present at a peak area S1 of 528eV to 530eV and at 530eV to 533eV The ratio (S2 / S1) of the peak area S2 is 0.25 or more and 0.60 or less. A dispersion liquid containing zinc oxide particles, an organic compound, and a solvent, and the content of the zinc oxide particles is 0.1% by mass to 60% by mass based on 100% by mass of the entire dispersion, and the content of the organic compound is 0.1. The content of the solvent is 20 mass% or more and 20 mass% or less, and the content of the solvent is 20 mass% or more and 99.98 mass% or less. The O1s spectrum of the O1s spectrum in the XPS measurement after drying of the dispersion liquid is a peak area S1 of zinc ^2- O ² ions and The ratio (S2 / S1) of the peak area S2 of the O2 ^- ion of oxygen is 0.25 or more and 0.60 or less.