JP2010030064A - Method for manufacturing functional flexible film and electronic device manufactured by using the same - Google Patents

Abstract

The present invention provides a method for producing a functional flexible film that has a high performance and a high functionality while being capable of increasing the area at a low cost. Moreover, the electronic device manufactured using the said method is provided.
In a method for producing a functional flexible film, a glass transition temperature (Tg) is 200 ° C. or higher between a region where the temperature is highest during a production process and a resin region which is a substrate, and a thermal conductivity. A method for producing a functional flexible film, comprising providing a heat-resistant low thermal conductive layer having a thickness of 0.25 W / m · K or less.
[Selection] Figure 7

Description

  The present invention relates to a method for producing a functional flexible film and an electronic device produced using the method. More specifically, the present invention relates to a method for producing a functional flexible film including an oxide semiconductor obtained by providing a precursor layer including a precursor of a metal oxide semiconductor on a substrate and oxidizing the precursor layer. The present invention relates to an electronic device such as a thin film transistor element using a conductive film.

  With the recent progress of miniaturization, miniaturization, thinning, high functionality, etc. of electronic devices and electronic devices, flexible films are used as base materials without using rigid base materials or substrates such as glass epoxy resins and ceramics. Alternatively, development of a functional film used as a substrate is desired.

  On the other hand, a metal oxide semiconductor film is used as a semiconductor device such as a transistor, a light emitting element, or a solar cell. As a method for manufacturing the metal oxide semiconductor film, a metal film formed on a substrate is oxidized to form a metal. A technique for converting to an oxide semiconductor film is known. For example, an attempt is made to oxidize a metal film such as Cu, Zn, or Al formed on a substrate by thermal oxidation or plasma oxidation to convert it into a metal oxide semiconductor film (see, for example, Patent Document 1). Also known is a method of forming an amorphous oxide by decomposing and oxidizing (heating, decomposition reaction) an organic metal (see, for example, Patent Documents 2 and 3). In these methods, thermal oxidation or plasma oxidation is used for oxidation of the precursor.

  In addition, a method of forming an amorphous oxide semiconductor by thermal oxidation using an organic metal or metal chloride as a precursor is also known (see, for example, Non-Patent Documents 1, 2, and 3).

  However, when a normal thermal oxidation method is used, processing is performed at a very high temperature range of 300 ° C. or higher, so that energy efficiency is low and a relatively long processing time is required, and the substrate temperature during processing However, since it rises to the same temperature as the processing temperature, there is a problem that it is difficult to apply to a resin substrate that is light and flexible. In the case of plasma oxidation, since processing is performed in a very reactive plasma space, in the manufacturing process of thin film transistors and the like, electrodes and insulating films are deteriorated, and mobility and off current (dark current) are deteriorated. There are problems such as.

Patent Documents 4 and 5 disclose techniques for improving characteristics by using local heating by electromagnetic waves without causing other adverse effects. However, there is a problem that it is difficult to increase the area and the device cost is increased.
JP-A-8-264794 JP 2003-179242 A JP 2005-223231 A JP 2003-46068 A JP 2003-264187 A December 2006 issue of chemical industry “Synthesis and application of oxide semiconductor thin films by sol-gel method” by Yutaka Oya Electrochemical and Solid-State Letters, 10 (5) H135-H138 (2007) Advanced Materials 19, 183-187 (2007)

  The present invention has been made in view of the above problems, and its solution is to provide a method for producing a functional flexible film capable of increasing the area at low cost while having high performance and high functionality. It is. Moreover, it is providing the electronic device manufactured using the said method.

  The above-mentioned problem according to the present invention is solved by the following means.

  1. In the method for producing a functional flexible film, the glass transition temperature (Tg) is 200 ° C. or more and the thermal conductivity is 0.25 W between the region that becomes the highest temperature during the production process and the resin region that becomes the substrate. The manufacturing method of a functional flexible film characterized by providing the heat resistant low heat conductive layer which is below / m * K.

  2. 2. The method for producing a functional flexible film as described in 1 above, wherein the heat-resistant low thermal conductive layer has a thickness of 1 to 100 μm.

  3. 3. The method for producing a functional flexible film as described in 1 or 2 above, wherein a region having the highest temperature is heated by a local heating method during the production process.

  4). 4. The method for producing a functional flexible film as described in 3 above, wherein the local heating method is a heating method using microwaves.

  5. 5. The microwave absorber-containing layer adjacent to the heat-resistant low thermal conductive layer is provided, and the microwave absorber-containing layer is heated by irradiating with microwaves to perform local heating. A method for producing a functional flexible film.

  6). 6. The functional flexible according to 5 above, wherein the microwave absorber-containing layer contains an oxide of at least one metal of indium (In), tin (Sn), and zinc (Zn). A method for producing a film.

  7). At least a substrate, a heat resistant low thermal conductive layer, and a heat conversion material-containing layer (hereinafter referred to as “functional layer precursor”) or a functional layer precursor pattern layer are provided, and the functional layer precursor or the functional layer precursor pattern is heated. Any one of the above 1 to 3, wherein a pattern having a desired pattern shape is locally heated by contacting or approaching the pattern of the functional layer precursor from the surface having the functional layer precursor on the side opposite to the substrate A method for producing the functional flexible film according to claim 1.

  8). The method for producing a functional flexible film according to any one of 1 to 7, wherein the pre-heat-resistant low thermal conductive layer contains a polyimide resin.

  9. The method for producing a functional flexible film according to any one of 1 to 8, wherein the substrate is a light-transmitting resin film and has a glass transition temperature (Tg) of 200 ° C or lower.

  10. An electronic device manufactured by the method for manufacturing a functional flexible film according to any one of 1 to 8 above.

  11. 11. The electronic device as described in 10 above, wherein the electronic device is a transistor element.

  By the above-mentioned means of the present invention, it is possible to provide a method for producing a functional flexible film capable of increasing the area at low cost while having high performance and high functionality. Moreover, the electronic device manufactured using the said method can be provided.

  In the present invention, by inserting a heat-resistant low thermal conductive layer between the local heating source and the resin substrate, the precursor layer can be thermally converted without being exposed to the high temperature of the local heating unit.

  In addition, due to the heat insulating effect of the heat-resistant low thermal conductive layer, it is possible to irradiate electromagnetic waves (microwaves) for a long time even on a non-heat-resistant substrate. By combining the local heating method and the structure of the present invention, it is possible to use a low-heat-resistant general-purpose resin film that is inexpensive as a substrate, and to produce a functional flexible film capable of high performance, low cost and large area Is possible.

  In the method for producing a functional flexible film of the present invention, the glass transition temperature (Tg) is 200 ° C. or more between the region that is the highest temperature during the production process and the resin region that is the substrate, and the thermal conductivity is high. It is characterized by providing a heat resistant low thermal conductive layer of 0.25 W / m · K or less. This feature is a technical feature common to the inventions according to claims 1 to 11.

  As an embodiment of the present invention, the thickness of the heat-resistant low thermal conductive layer is preferably in the range of 1 to 100 μm from the viewpoint of manifesting the effects of the present invention. Moreover, it is preferable that it is an aspect which heats the area | region used as the highest temperature by the local heating system during the said manufacturing process. In this case, the local heating method is preferably a heating method using microwaves.

  Furthermore, it is preferable that a microwave absorber-containing layer adjacent to the heat-resistant low thermal conductive layer is provided, and the microwave absorber-containing layer is heated to emit heat to perform local heating. In this case, it is preferable that the microwave absorber-containing layer contains an oxide of at least one metal selected from indium (In), tin (Sn), and zinc (Zn). As used herein, the “highest temperature region” refers to a region that generates heat due to absorption of electromagnetic waves (for example, microwaves) as in the microwave absorber-containing layer.

  As an embodiment of the present invention, at least a substrate, a heat-resistant low thermal conductive layer, and a heat conversion material-containing layer (hereinafter referred to as “functional layer precursor”) or a functional layer precursor pattern layer are provided, and the functional layer precursor is provided. The body or the functional layer precursor pattern is heated locally by bringing the pattern having a desired pattern shape into contact with or in proximity to the pattern of the functional layer precursor from the surface on the side opposite to the substrate. It is also preferable that it is an aspect.

  Here, the heat conversion material-containing layer (hereinafter also referred to as “functional layer precursor”) is a layer containing a “heat conversion material” that becomes a functional material by heat conversion, and functions by the heat conversion. The precursor used as a layer is said. The “functional layer precursor pattern layer” refers to a layer obtained by patterning a solution containing a functional layer precursor using a known printing method such as ink jet or gravure printing. In addition, the “patterned object” is a material that can be heated to a high temperature such as a metal so that a desired pattern shape is convex, and only the pattern part that has been processed into the heated convex is in contact with a plane. This includes those that have been processed into a flat surface (such as a thermal stamp). Further, it includes a material that scans a laser beam or the like and consequently imparts energy of a pattern shape to the precursor film, and refers to all that impart patterned oxidation conversion energy to the precursor film. The “pattern” means a geometric pattern represented by a circuit pattern and an electrode pattern.

  In this invention, it is preferable that the said heat resistant low heat conductive layer contains a polyimide resin. Moreover, it is preferable that the said board | substrate is an optically transparent resin film, and it is an aspect whose glass transition temperature (Tg) is 200 degrees C or less.

  The method for producing a functional flexible film of the present invention can be applied to the production of various electronic devices. In particular, it can be suitably used for manufacturing a thin film transistor element.

  Hereinafter, the present invention, its components, and the best mode and mode for carrying out the present invention will be described in detail.

(Heat resistant low thermal conductive layer)
The heat-resistant low thermal conductive layer according to the present invention refers to a layer that functions as a heat-resistant and heat-insulating layer that is provided between the region that becomes the highest temperature and the resin region that becomes the substrate during the manufacturing process of the functional flexible film.

  The heat-resistant low thermal conductive layer is characterized in that the glass transition temperature (Tg) is 200 ° C. or higher and the thermal conductivity is 0.25 W / m · K or lower from the viewpoint of the effects of the present invention. .

  In addition, in this application, the glass transition temperature of a heat-resistant low heat conductive layer means what was measured on temperature increase rate 20 degree-C / min conditions by DSC method.

  Further, from the same viewpoint as described above, the layer thickness of the heat resistant low thermal conductive layer is preferably in the range of 1 to 100 μm.

  As the heat resistant low thermal conductive material used for the heat resistant low thermal conductive layer, various known materials, in particular, resins can be used as long as the above requirements are satisfied. For example, an acrylic resin, a polyimide resin, a polyamide resin, a polyamideimide resin, a polyetherimide resin, a polyethersulfone resin, a polysulfone resin, or the like can be used alone or in combination. From the viewpoint of heat resistance, insulation reliability, and adhesiveness, a polyimide resin is preferably used.

  Here, the “polyimide resin” refers to a resin having a cyclic structure such as an imide ring, or a resin precursor that forms an imide ring or other cyclic structure by heating or an appropriate catalyst. The polyimide resin can be polymerized from tetracarboxylic dianhydride and diamine.

  Examples of the tetracarboxylic dianhydride preferably used in the present invention include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-. Biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7- Naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,3 ″, 4,4 ″- Paraterphenyl tetracarboxylic dianhydride, 3,3 ″, 4,4 ″ -metaterphenyl tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2, 7,8-Phenanthre Tetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltrifluoropropanetetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic acid Anhydride, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,3,3', 4'-diphenylsulfonetetracarboxylic dianhydride, , 3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2, 3,5-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-bicyclohexene tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,3, And 3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-C] furan-1,3-dione. These may be used alone or in combination of two or more.

  Examples of the diamine preferably used in the present invention include p-phenylenediamine, m-phenylenediamine, 2,5-diaminotoluene, 2,4-diaminotoluene, 3,5-diaminobenzoic acid, 2,6-diaminobenzoic acid, 2-methoxy-1,4-phenylenediamine, 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, 3,3'-diaminobenzanilide, 3,3'-dimethyl-4,4'- Diaminobenzanilide, benzidine, 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 3,3'-dimethylmethoxybenzidine, 2,4-diaminopyridine, 2,6-diaminopyridine, 1,5-diamino Naphthalene, 2,7-diaminofluorene, 1,3-diaminocyclohexane, 1,4-diaminocyclohex 4,4'-methylenebis (cyclohexylamine), 3,3'-methylenebis (cyclohexylamine), 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3 '-Dimethyldicyclohexyl, p-aminobenzylamine, m-aminobenzylamine, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminoben Phenone, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2 , 2-bis [4- (3-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] methane, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- ( 4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 9,9-bis (4-aminopheny And fluorene and 9,9-bis (3-aminophenyl) fluorene. These may be used alone or in combination of two or more.

  In the present invention, it is preferable to use a siloxane diamine as exemplified below in combination with the diamine. By using a siloxane diamine in combination, the adhesion between the heat-resistant low thermal conductive layer and the substrate and / or precursor layer can be further improved. The content of the siloxane-based diamine is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, still more preferably 1 mol% or more, preferably 80 mol% or less, based on the total diamine component. More preferably, it is 60 mol% or less, More preferably, it is 50 mol% or less. By containing the siloxane-based diamine in the above range, high adhesive strength can be obtained, and the glass transition temperature of the polyimide resin becomes a preferable range.

  Specific examples of the siloxane diamine include 1,1,3,3-tetramethyl-1,3-bis (4-aminophenyl) disiloxane, 1,1,3,3-tetraphenoxy-1,3-bis. (4-aminoethyl) disiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis (4-aminophenyl) trisiloxane, 1,1,3,3-tetraphenyl-1, 3-bis (2-aminoethyl) disiloxane, 1,1,3,3-tetraphenyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,5,5-tetraphenyl-3, 3-dimethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, , 1,5,5-Tetraf Nyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) trisiloxane, 1,1,3,3-tetramethyl-1,3-bis (2-aminoethyl) disiloxane, 1,1 , 3,3-tetramethyl-1,3-bis (3-aminopropyl) disiloxane, 1,1,3,3-tetramethyl-1,3-bis (4-aminobutyl) disiloxane, 1,3 -Dimethyl-1,3-dimethoxy-1,3-bis (4-aminobutyl) disiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (2-aminoethyl) ) Trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (4-aminobutyl) trisiloxane, 1,1,5,5-tetramethyl-3,3- Dimethoxy-1,5-bis (5-aminopen L) Trisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexaethyl-1,5 -Bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane and the like. The siloxane diamine may be used alone or in combination of two or more.

  The heat-resistant low thermal conductive layer according to the present invention may be converted to polyimide by applying a polyamic acid composition, which is a precursor of a polyimide resin, to the substrate and then heat-treating it, or an organic solvent-soluble polyimide. The resin composition may be applied and laminated on the substrate.

  In this invention, the synthesis | combination of the polyamic acid resin composition which is a polyimide resin composition or a polyimide resin precursor can be performed by a well-known method. For example, it can synthesize | combine by selectively combining tetracarboxylic dianhydride and diamine, stirring at 0-80 degreeC in a solvent for 1 to 100 hours, and making it react. It is preferable to synthesize with a molar ratio of excess acid or excess diamine so that the viscosity characteristics of the resin composition and the adhesive properties of the resulting film with a metal layer become desired characteristics. In order to seal the end of the polymer chain, dicarboxylic acid such as benzoic acid, phthalic anhydride, tetrachlorophthalic anhydride, aniline or its anhydride, and monoamine are charged simultaneously with tetracarboxylic dianhydride and diamine. Alternatively, tetracarboxylic dianhydride and diamine may be reacted and added after polymerization to react.

  Examples of the solvent for polyamic acid synthesis include amide polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, β-propiolactone, γ-butyrolactone, Lactone polar solvents such as γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, and others, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, ethyl cellosolve acetate, methyl carbitol, ethyl carbitol And tall, diethylene glycol dimethyl ether (diglyme), and ethyl lactate. These may be used alone or in combination of two or more. As a density | concentration of a polyamic acid, 5-60 mass% is preferable normally, More preferably, it is 10-40 mass%.

  When obtaining a polyimide resin composition, the polyamic acid resin solution synthesize | combined above is raised to the temperature of 120-300 degreeC, is stirred for 1 to 100 hours, and converts into a polyimide. Also, at room temperature to 200 ° C., an imidation catalyst such as acetic anhydride, trifluoroacetic anhydride, p-hydroxyphenylacetic acid, pyridine, picoline, imidazole, quinoline, triethylamine or the like is added alone or in combination of two or more, and polyimide Can also be converted.

  In the present invention, the imidation catalyst may be added to the polyamic acid resin solution, applied to the substrate, then converted to polyimide simultaneously with the drying of the solvent, and a heat resistant low thermal conductive layer may be laminated.

  In the present invention, the heat-resistant low thermal conductive layer may contain other resins and fillers as long as the effects of the present invention are not impaired. Examples of other resins include acrylic resins, acrylonitrile resins, and butadiene resins. Examples thereof include heat-resistant polymer resins such as resins, urethane resins, polyester resins, polyamide resins, polyamideimide resins, epoxy resins, and phenol resins. Examples of the filler include organic or inorganic fine particles, fillers, and the like. Specific examples of the fine particles and filler include silica, alumina, titanium oxide, quartz powder, magnesium carbonate, potassium carbonate, barium sulfate, mica and talc.

(Microwave absorber-containing layer)
In the present invention, it is preferable to provide a microwave absorber-containing layer adjacent to the heat-resistant low thermal conductive layer, and to heat the microwave absorber-containing layer by irradiating the microwave to perform local heating.

  The microwave absorber contained in the microwave absorber-containing layer is, for example, a metal oxide and preferably a conductor. Note that it seems that the microwaves are absorbed by Me-O bonds in the metal oxide (the metal itself is not absorbed).

  In the present invention, the metal oxide preferably contains at least one oxide of at least one of indium (In), tin (Sn), and zinc (Zn) because of its high conductivity. In addition, since it has higher microwave absorption capability, it is preferable to include at least In, Sn, and particularly Sn oxide. Hereinafter, this point will be monitored and explained in more detail.

  In the present invention, as a microwave absorber, that is, a substance having microwave absorption ability, one is a metal oxide fine particle, and indium oxide, tin oxide, zinc oxide, IZO, ITO, etc. are preferable, and at least It is preferable that an oxide of In or Sn is included.

  In the ITO film obtained by doping tin with indium oxide, the In: Sn atomic number ratio of the obtained ITO film is preferably adjusted to be in the range of 100: 0.5 to 100: 10. The atomic ratio of In: Sn can be determined by XPS measurement.

In addition, a transparent conductive film (referred to as FTO film) obtained by doping tin oxide with fluorine (Sn: F atomic ratio in the range of 100: 0.01 to 100: 50), In ₂ O ₃ —ZnO-based amorphous A conductive film (In: Zn atomic ratio in the range of 100: 50 to 100: 5) or the like can be used. The atomic ratio can be determined by XPS measurement.

The formation of a conductive thin film made of metal oxide material fine particles having microwave absorption ability can be achieved by using vacuum deposition, sputtering, etc., metal alkoxides such as indium and tin, and organometallic compounds such as alkyl metals. It is also preferable to use the plasma CVD method. It can also be produced by a coating method such as a sol-gel method using a metal alkoxide such as indium or tin, and an ITO film having excellent electrical conductivity in the order of 10 ⁻⁴ Ω · cm can be obtained. An electrode pattern can be obtained in combination with an appropriate patterning method.

  The substance having the ability to absorb microwaves may be a conductive IZO or ITO thin film formed by vapor deposition, sputtering, plasma CVD, or the like as described above. May be an electrode precursor material that is a dispersion of metal oxide fine particles containing metal, and in this case, it becomes conductive by baking after film formation. Thus, after forming an electrode precursor area with this, this is baked to obtain an electrode material. Firing is preferably performed by microwave irradiation.

  As a dispersion of metal oxide fine particles containing at least an oxide of In and Sn, ITO fine particles are particularly preferable because they are very fine and highly dispersed. Since the Sn oxide has a high microwave absorption capability and the electrode pattern portion containing the Sn oxide first has a high temperature, when it contains an electrode material precursor, the vicinity of the electrode pattern portion also becomes high, which is preferable.

  These metal oxide fine particles are obtained, for example, from a gel-like material obtained by heating a solution having a adjusted pH, by a method such as heating or low-temperature sintering. The coating material (ink) dispersed in an appropriate solvent is a finely dispersed fine particle which does not cause clogging due to aggregation or the like even when used for coating or ink jet or printing.

Such particles preferably have a particle size in the range of 5 to 50 nm. These are commercially available and can also be obtained directly from the market. Examples thereof include NanoTek Slurry ITO, SnO _{2 and the} like manufactured by CI Kasei Co., Ltd.

  When these fine particle dispersions are used as an electrode material precursor, an electrode material such as ITO can be easily patterned by a coating method such as an ink jet method, and the surface temperature of the thin film is 200 to 600 ° C., regardless of the sputtering method or the like. Due to the relatively low temperature heat treatment or sintering, fine particles are crystallized to obtain a highly conductive thin film.

  Examples of the electrode material precursor include at least In, Sn, and Zn atom-containing compounds, and examples thereof include metal salts, metal halide compounds, and organometallic compounds containing these metal atoms.

  As metal salts containing at least In, Sn, and Zn, nitrates, acetates, and the like can be suitably used, and as halogen metal compounds, chlorides, iodides, bromides, and the like can be suitably used.

  Among the electrode material precursors described above, preferred are indium, tin, zinc nitrates, halides, and alkoxides. Specific examples include indium nitrate, tin nitrate, zinc nitrate, indium chloride, tin chloride (divalent), tin chloride (tetravalent), zinc chloride, tri-i-propoxyindium, diethoxyzinc, bis (dipivaloylme Tanato) zinc, tetraethoxytin, tetra-i-propoxytin and the like.

  These electrode material precursors, such as indium nitrate and tin nitrate, are formed on the substrate according to the electrode pattern to form an electrode material precursor area, and in the same manner, an insulating film precursor area serving as an insulating layer is formed thereon. By forming and irradiating this with microwaves, the oxide partially formed in these electrode material precursors acts as a heating element. In addition, heat can be applied to adjacent insulating film precursor areas, which can be converted into insulating films.

  In the present invention, for example, when ITO fine particles, which are conductors, are used, Sn oxide has a higher microwave absorption capacity than In oxide and Zn oxide. It becomes hot. After forming a pattern of such a substance having microwave absorption ability, for example, a functional precursor (for example, a semiconductor precursor) layer (area) is formed on the pattern, and microwave irradiation is performed. Not only the electrode pattern portion to be formed but also the vicinity thereof becomes a high temperature, and for example, formation from a heat conversion material to a functional material (for example, a semiconductor) can be simultaneously advanced by ITO.

  In addition, if an electrode material precursor layer is formed in accordance with the electrode pattern, a layer containing a heat conversion material is formed, and microwave irradiation is performed, both the electrode and the functional material layer are formed simultaneously.

  An electrode is preferably used as an area containing a substance having a microwave absorbing ability or a substance having a microwave absorbing ability.

  For example, a thin film transistor element is preferable as an electronic device in which a substance having a microwave absorbing ability or an area including a substance having a microwave absorbing ability is applied to an electrode.

  Using microwave-absorbing substances or areas containing microwave-absorbing substances as electrodes, forming multiple functional layer areas such as insulating films, semiconductors, and protective films, and having microwave absorption ability by microwave irradiation Since the functional precursor layer area can be heated at the same time by using the electrode and the electrode precursor area as a heat source to form a plurality of functional layers at the same time, a thin film transistor element is preferable.

  For example, at least two functional precursor layer areas of an electrode containing a substance having microwave absorption ability or a substance having microwave absorption ability, and an insulating film precursor area, a semiconductor precursor area, and a protective film precursor area are provided. After the formation, microwaves are irradiated and the functional precursor layer area is simultaneously heated to simultaneously form a plurality of functional layers.

  In addition, the electrode is formed of a material having a microwave absorbing ability or an electrode precursor containing a substance having a microwave absorbing ability, and the insulating film precursor area, the semiconductor precursor area, the protective film precursor area, etc. After forming at least one functional precursor area, microwaves may be irradiated to heat the electrode precursor area itself and the functional layer precursor area to form both the electrode and the functional layer.

  Accordingly, in the present invention, a layer (area) is formed on a substrate with a substance having microwave absorption ability, and a layer (area) containing a functional material precursor is formed thereon, and then microwaves are irradiated to the layer (area). As a result, the layer (area) formed of the substance having the ability to absorb microwaves generates heat, and the generated heat causes the functional material precursor in the vicinity of the layer (area) containing the substance having the ability to absorb microwaves. It can be said that this is a method for manufacturing a thin film element (thin film device) in which a layer (area) containing is heated to convert a functional material precursor into a functional material (thin film).

(Microwave irradiation)
In this invention, it is preferable to heat the area | region where it becomes the highest temperature by a local heating system during the manufacturing process of a functional flexible film. Moreover, it is preferable that the said local heating system is a heating system using a microwave.

  That is, after forming a layer (thin film) containing a source and drain electrode pattern having a microwave absorption capability and a metal that is a metal oxide semiconductor precursor, a microwave (frequency 0.3) is applied to the layer (thin film). The electrode pattern and the adjacent metal oxide semiconductor precursor are heated by causing the electrode pattern thin film itself having microwave absorption ability to generate heat from the inside by irradiating with ~ 50 GHz), and the electrode pattern and the metal oxide semiconductor are heated. Manufacturing.

  When heating a thin film containing a metal oxide semiconductor precursor together with a pattern of an electrode precursor having microwave absorption ability, it is possible to irradiate microwaves in the presence of oxygen in a short time. It is preferable in promoting the body oxidation reaction.

  In addition, in microwave irradiation, heat may be transferred to the base material due to heat conduction. Especially in the case of a base material with low heat resistance such as a resin substrate, the output of microwave, irradiation time, and further irradiation. By controlling the number of times, the substrate temperature is preferably 50 ° C. to 200 ° C. and the surface temperature of the thin film containing the precursor is preferably 200 ° C. to 600 ° C. The surface temperature of the thin film, the temperature of the substrate, etc. can be measured with a surface thermometer using a thermocouple.

  In addition, the thin film containing the metal oxide semiconductor precursor is cleaned by a dry cleaning process such as oxygen plasma or UV ozone cleaning after the formation and before the microwave irradiation. It is also preferable that organic substances other than the metal component are excluded by decomposing and washing the causative organic substances.

  In general, the microwave refers to an electromagnetic wave having a frequency of 0.3 to 50 GHz, and is used in 0.8 MHz and 1.5 GHz band, 2 GHz band, amateur radio, aircraft radar, etc. used in mobile communication. 1.2 GHz band, 2.4 GHz band used in microwave ovens, local radio, VICS, 3 GHz band used for ship radar, etc., and 5.6 GHz used for other ETC communications are all in the microwave category. Electromagnetic waves.

  In the field of ceramics, it is already known to use such microwaves for sintering. When a material containing magnetism is irradiated with microwaves, heat can be generated in accordance with the size of the loss portion of the complex permeability of the substance, and the temperature can be increased uniformly and in a short time. On the other hand, it is well known that when a metal is irradiated with microwaves, free electrons start to move at a high frequency, so that arc discharge occurs and heating cannot be performed.

  Based on such a background, the inventors, in addition to the electrode material precursor having a microwave absorption ability, simultaneously and uniformly in a short time and at a high temperature, a precursor of a metal oxide semiconductor. It was found that they can be simultaneously converted into an electrode material and a metal oxide semiconductor, respectively. Unlike the field of ceramics, since metal oxide semiconductor precursors such as metal ion-containing solutions have little magnetism, loss components related to electron and / or dipole motion such as Joule loss and / or dielectric loss. However, it is not clear why such a phenomenon occurs in a thin film that is simply coated / dried with a metal ion-containing solution.

  The thin film including the thin film electrode pattern and the metal oxide precursor is not necessarily formed by coating. However, in the present invention, forming these by coating includes forming an electrode by coating, and forming a semiconductor by coating. The production efficiency can be improved in the manufacture of the thin film transistor because it can be reduced to about 1. This is preferable.

(Heat conversion material-containing layer: functional layer precursor)
The “heat conversion material-containing layer (hereinafter also referred to as“ functional layer precursor ”)” according to the present invention is a layer containing a “heat conversion material” that becomes a functional material by heat conversion, and is formed by the heat conversion. It refers to a precursor that becomes a functional layer.

  The heat conversion material means a material as a precursor that is converted into various functional materials (layers) in an electronic device by heat. Specifically, for example, a semiconductor material precursor, an insulating material precursor, An electrode material precursor or the like, which is a functional material precursor that is converted into a semiconductor, an insulating material, an electrode, or the like by heat. The heat conversion material includes not only a material that reacts by heat but also a material that exhibits a so-called annealing effect.

  In this invention, as a suitable heat conversion material, the case where a heat conversion material is a semiconductor precursor material is mentioned as a 1st aspect, for example. In addition, the second aspect includes a case where the heat conversion material is an insulating film precursor material, and the third aspect includes a case where the heat conversion material is a protective film precursor material, Further, there may be mentioned a case where the heat conversion material is an electrode precursor material. Hereinafter, detailed description will be made sequentially.

  As a first aspect, a substrate having a microwave absorbing ability or an electrode pattern (area) containing a substance having a microwave absorbing ability is formed on a substrate, and a semiconductor precursor material area (as a heat conversion material) is formed thereon. After forming a thin film, the electrode and the semiconductor layer can be formed simultaneously by irradiating the film with microwaves.

  The said 1st aspect is demonstrated using figures. FIG. 1 shows, for example, a cross-sectional view in which a gate electrode 4 made of an ITO thin film is formed on a glass substrate 6 and a gate insulating film 5 is further formed thereon (FIG. 1 (1)). On the glass substrate, for example, an ITO thin film is formed by sputtering and then patterned to form an electrode pattern, and then an insulating layer made of silicon oxide is similarly formed by sputtering or plasma CVD. Here, the conductive ITO has microwave absorption ability.

Next, a metal ion-containing thin film that is a semiconductor precursor material, for example, In (NO ₃ ) ₃ , Zn (NO ₃ ) ₂ , Ga (NO ₃ ) ₃ (composition ratio mass 1 :) on the gate insulating film 5. 1: 1) A solution obtained by dissolving each in a mixed solvent of water / ethanol = 8/2 (mass ratio) is ejected by an ink jet apparatus to form an area of the semiconductor precursor material. This is dehydrated and dried to form, for example, a semiconductor precursor material area (thin film) 1 ′ having an average film thickness of 100 nm (FIG. 1 (2)).

  In this way, when a thin film containing a metal oxide semiconductor precursor material is formed on the channel region (area) on the gate electrode and then irradiated with microwaves, it is made of ITO having microwave absorption ability. Since the electrode pattern absorbs this, Joule heat is generated inside the electrode pattern, and the Joule heat heats the vicinity thereof by heat transfer. Therefore, the metal oxide semiconductor precursor material film 1 ′ is formed in the presence of oxygen. It undergoes thermal oxidation and is converted into a metal oxide semiconductor layer 1 (FIG. 1 (3)).

  Oxygen is required to produce a metal oxide semiconductor from a metal oxide semiconductor precursor material, and thermal oxidation takes place by performing microwave irradiation in the presence of air (oxygen), resulting in metal oxide The semiconductor precursor material thin film is converted into a semiconductor film.

  When using a substrate having low heat resistance such as a resin substrate, the substrate temperature is 50 ° C. to 200 ° C. by controlling the microwave output, the irradiation time, and the number of irradiations. It is preferable to perform the treatment so that the surface temperature is 200 to 600 ° C.

  Next, if the source electrode 2 and the drain electrode 3 are formed by, for example, gold vapor deposition, the thin film transistor element 14 is obtained (FIG. 1 (4)).

  Further, as a semiconductor layer, for example, an organic semiconductor precursor material, for example, a bicycloporphyrin compound as described in JP-A-2003-304014 is used to produce a semiconductor precursor layer, thereby generating heat due to microwave absorption of the ITO electrode. Similarly, it can be converted into an organic semiconductor layer by thermal decomposition, so that an organic thin film transistor can be formed efficiently.

  ITO thin film is a substance with microwave absorption ability. However, when an electrode made of a normal metal material is used, it does not absorb microwave, so a substance with microwave absorption ability such as ITO is formed on the electrode. Thus, the electrode can be used as a heat source. In addition, it is also possible to form an electrode pattern using the electrode precursor material described later, and convert this into an electrode material by a substance having a microwave absorbing ability such as ITO formed thereon. .

  Conversely, on the ITO thin film, which is a metal oxide conductor, electrode material precursors, for example, metal nanoparticles (dispersions) described in JP-A-3-34211, JP-A-11-80647, etc. It is also possible to apply electrodes to calcinate the electrodes by heat generation of ITO.

  The above is an example in which a semiconductor layer is formed as a functional layer by heat generation by microwave irradiation from an electrode pattern having a microwave absorption capability. For example, as in the second aspect, an insulating layer precursor is used as a conversion material. It is possible to convert and form this into an insulating layer using a material (described later).

  An example of this second aspect is shown in FIG. The figure shows that a gate electrode 4 made of ITO and an insulating film precursor area 5 ′ are formed on a glass substrate 6 in accordance with an insulating film pattern. ITO is formed on a glass substrate by sputtering, for example. The pattern of the gate electrode 4 is obtained by using a mask and patterning with a photoresist.

  As the insulating film precursor material, for example, when a silicon oxide film is formed, a metal compound material such as tetraethoxysilane, disilazane, polysilazane, and the like can be used. For example, tetraethoxysilane (TEOS) is made of the above ITO. A thin insulating film precursor material area 5 'is formed on the gate electrode pattern (FIG. 2 (1)).

  Examples of the insulating film precursor material include a precursor that forms a metal oxide film having a high relative dielectric constant, such as silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, and vanadium oxide. Of these, silicon oxide, aluminum oxide, tantalum oxide, and titanium oxide are preferable. Metal nitrides such as silicon nitride and aluminum nitride can also be suitably used.

  As a precursor for forming these, for example, a so-called sol-gel film is preferable, and a metal of the above-described metal oxide, for example, a metal alkoxide such as silicon, a metal halide, or the like, which is called a sol-gel method, is an arbitrary organic solvent. Or the method of apply | coating and drying the liquid hydrolyzed and polycondensed with the acid catalyst etc. in water is used. According to this method, a spray coating method, a spin coating method, a blade coating method, a dip coating method, a casting method, a roll coating method, a bar coating method, a coating method such as a die coating method, a printing or ink jet patterning method, etc. The wet process can be used depending on the material.

  When an organic compound film is used as the insulating film precursor material, for example, a material that forms an insulating organic film by polycondensation with heat, for example, a precursor material that forms an insulating film by polycondensation such as curable polyimide In addition, a photo-curing resin of a photo radical polymerization system, a photo cation polymerization system, or a copolymer containing an acrylonitrile component, a polyvinyl phenol containing a cross-linking agent, a polyvinyl alcohol, a novolac resin, etc. are formed by coating, These can be converted into insulating films. For example, as a curable polyimide, Kyocera Chemical Co., Ltd. CT4112,4200,4150 etc. can be obtained.

  The thickness of these insulating films is generally 50 nm to 3 μm, preferably 100 nm to 1 μm.

  After the formation of the insulating film precursor material area 5 ′, electromagnetic waves, preferably microwaves are then irradiated. By the microwave irradiation, the gate electrode material (ITO) having a microwave absorbing ability absorbs this. Microwave absorption concentrates on a substance with high micro-absorption capacity. As a result, in the electrode material precursor pattern, the substance first generates Joule heat and is heated from inside the thin film, and this Joule heat is transferred to the vicinity. As a result, the adjacent insulating film precursor material area 'is heated, and the insulating film precursor material area is converted into the gate insulating film 5 (FIG. 2 (2)).

TEOS, which is a precursor of SiO ₂ film, which is a typical insulating film material, has almost no microwave absorption ability, but an SiO ₂ bond is formed around (in the vicinity of) the gate electrode portion having microwave absorption ability to oxidize. By forming an insulating film, an electrode and an oxide insulating film can be formed at the same time (FIG. 2 (3)).

  In the case of an insulating film such as TiN made of a metal having an absorptivity as an oxide insulating film (for example, Ti), TiN is formed in the air, and at the same time, the sintering of the film proceeds due to heat generation. Become.

  Oxygen is required for the production of these insulating films, and thermal oxidation occurs by performing microwave irradiation in the presence of air (oxygen), thereby forming a highly insulating film (dielectric film).

  When the resin substrate is used, since the heat resistance is low, the substrate temperature is 50 ° C. to 200 ° C. and the surface temperature of the thin film containing the precursor is 200 to 200 ° C. by controlling the microwave output, the irradiation time, and the number of irradiations. It is preferable to treat it at 600 ° C.

  After the formation of the insulating layer, a thin film transistor element can be obtained in the same manner by performing semiconductor layer formation and source and drain electrode formation by a known method in the same process as in FIG. 1 (FIGS. 2 (3) to (5)). .

  In addition, after the formation of the insulating film precursor material area 5 ′, a metal oxide semiconductor precursor area is further formed, and after drying, microwave irradiation is performed, thereby generating heat associated with microwave absorption by the ITO electrode. By using the metal oxide semiconductor precursor area together with the insulating film precursor material area, the metal oxide semiconductor precursor area can be thermally oxidized at the same time to be converted into an insulating layer and a semiconductor layer, respectively.

  In the present invention, the heat conversion of the area where the shortest distance between the substance having the microwave absorbing ability or the area (heat source area) containing the substance having the microwave absorbing ability and the substrate of the electronic device absorbs the microwave and generates heat. The boundary between the functional precursor layer (area) side to be processed and the longest distance determined between all the boundaries of the functional layer precursor area to be heat-converted (if there are multiple functional layer precursor areas, the boundary between them) In the meantime, it is preferably 1/200 to 10 times.

  This is illustrated in FIG. FIG. 3 shows that a functional layer precursor layer thin film 1 ′ to be converted into a semiconductor layer is formed on the substrate 6 through the intermediate layer 8 via the intermediate layer 8.

  The gate electrode is a substance having a microwave absorbing ability or an area (heat source area) containing a substance having a microwave absorbing ability, and the shortest distance between the heat source area and the substrate is herein referred to as the gate electrode and the substrate. The layer thickness l of the formed intermediate layer corresponds. Of the layer thicknesses, the shortest distance of the layer thickness under the gate electrode is taken.

  In addition, the longest distance determined between the boundary of the functional layer precursor area where heat conversion is performed in the area that generates heat by absorbing microwaves and the entire boundary of the functional layer precursor area that is subjected to heat conversion is the circumference of the heat generation area The longest distance between the boundary surface of the functional layer precursor area side where the interface is heated and converted and the interface of the functional layer precursor area. This is the longest distance when any position on the functional layer precursor area side interface is connected from an arbitrary position on the functional layer precursor area side where heat conversion is performed at the heat generation area interface in FIG. It hits. It is determined by looking at the entire interface of the area where each layer precursor is formed.

  In addition, the longest distance (D) determined between the boundary surface of the functional precursor layer (area) side where heat conversion is performed in the area that generates heat by absorbing microwaves and the boundary of the functional precursor layer (area) subjected to heat conversion In order to understand this concept, another example is shown in FIG.

  In FIG. 3B, if an area that absorbs microwaves and generates heat is a source electrode 2 or a drain electrode 3, a boundary on the functional layer precursor area side where the microwaves absorb and generate heat is converted. The longest distance determined between the entire boundary of the surface and the functional layer (semiconductor layer) precursor area formed in the channel region between the source electrode 2 and the drain electrode 3 is represented by D here.

  D represents the longest distance from a material that absorbs microwaves and generates heat to a conversion material area that is converted into a functional layer by the generated heat, and an electrode material composed of a substance that absorbs microwaves is Since the film thickness of the electrode is in the range of 30 to 500 nm, when the conversion material area is far from the heat generating material, the heat conversion of the conversion material is not sufficient.

  In other words, if an area (heat source area) containing a substance having microwave absorption ability is, for example, a gate electrode, the heat conversion material is sufficiently converted into a functional material by propagation of heat generated by absorption of microwaves by the gate electrode. In order to prevent damage to the substrate (especially a plastic substrate), for D indicating the distance from the heat source to the heat-converted, for example, insulator precursor layer or semiconductor precursor layer area, The shortest distance l from the gate electrode to the substrate (in many cases, the thickness of the undercoat layer or the like formed on the resin support on which the gate electrode is formed) is 1/200 to 10 times. preferable.

  For example, even if there is a heat conversion material layer between the area (heat source area) containing a substance having microwave absorption ability and the substrate (support) or on the opposite side of the substrate, the microwave absorption ability The distance between the area containing the substance (heat source area) and the substrate, and the distance between the area containing the substance with microwave absorption ability (heat source area) and the heat conversion material layer is converted by the heat conversion material layer by heat. The measurement is performed after the functional layer is formed.

  When in this range, the heat conversion material is sufficiently converted into a functional material in the vicinity of an area including a substance having a microwave absorbing ability as a heat source, and the influence of heat on the substrate is small. When the ratio is less than 1/200, there is a concern about damage to the substrate, and on the other hand, the conversion of the heat conversion material into the functional material becomes insufficient. On the other hand, when the ratio exceeds 10 times, the performance of the element is still insufficient, and on the other hand, problems such as cracks begin to become apparent and advantages such as flexibility as a thin film material may be lost.

  Therefore, in the case where the above relationship is satisfied, in the case where a protective film is formed over a transistor element, the present invention can also be applied to the formation of a protective film. For example, as a third aspect, a protective film can be formed by microwave irradiation using a protective film precursor material as a heat conversion material. In forming these protective films, the same material as the insulating film precursor material described above is used.

  In the present invention, a substance having microwave absorption ability can be used as a material that can be converted into an electrode material by itself as a heat source that absorbs microwaves and generates Joule heat even if it is an electrode material precursor. .

  That is, it is possible to convert the electrode itself and the adjacent functional layer into, for example, an insulating layer or a semiconductor layer by heat generated by the microwave from the formed electrode precursor area.

  As in FIG. 1, the electrode precursor area can be formed by a material having a microwave absorption ability, for example, ITO fine particles, according to the pattern of the gate electrode 4. For example, a dispersion of ITO particles in an organic solvent such as water or alcohol is formed on a substrate like a gate electrode pattern by coating (inkjet method) and dried to form an electrode precursor area. Here, coating means not only so-called coating, but also a wet process in which a coating solution, ink, and the like in a broad sense such as an inkjet method and a printing method are applied.

  A dispersion in which ITO particles are dispersed in an organic solvent such as water or alcohol can be drawn on a substrate by a coating (inkjet) method or the like using this as a paint.

For example, a metal ion-containing thin film, for example, In (NO ₃ ) ₃ , Zn (NO), as the metal oxide semiconductor material precursor on the electrode material precursor area formed according to the electrode pattern using ITO fine particles. ₃ ) ₂ , Ga (NO ₃ ) ₃ (1: 1: 1 by composition ratio) were dissolved in water / ethanol = 8/2 (mass ratio) mixed solvent and discharged by an inkjet apparatus. After the film is formed, dried, and irradiated with microwaves, Joule heat is generated inside the electrode pattern of the thin film, so the electrode material precursor area is heated from the inside, and the electrode material precursor is baked to the electrode. Further, the metal oxide semiconductor precursor area is also converted into a metal oxide semiconductor layer by thermal oxidation in the presence of oxygen by Joule heat transfer.

  Electrode materials or precursor materials having microwave absorption ability are heated uniformly from the inside because electrons vibrate and generate Joule heat when irradiated with electromagnetic waves such as microwaves. On the other hand, substrates such as glass and resin hardly absorb heat in the microwave region, and therefore the substrate itself hardly generates heat. Therefore, when a plastic substrate is used, an electronic device such as a thin film transistor element can be manufactured without causing thermal deformation or deterioration of the substrate or the like by providing a heat generating layer while maintaining a predetermined distance or more as described above.

  As is common in microwave heating such as microwaves, microwave absorption concentrates on strongly absorbing substances and can be heated up to 500-600 ° C. in a very short time. The substrate itself on which the device is formed is hardly affected by heating by microwaves, and can only raise the temperature of a substance having microwave absorption capability in a short time. For example, when this is used as an electrode in a transistor element, the electrode itself Also, because the adjacent metal oxide semiconductor precursor material area, eg, a thin film, can be instantaneously heated, it can be quickly converted to a semiconductor. Further, the heating temperature and the heating time can be controlled by the output of the microwave to be irradiated and the irradiation time, and can be adjusted according to the precursor material and the substrate material.

  In addition, when a metal oxide having a microwave absorbing ability is used as an electrode material precursor, a layer made of metal fine particles is further combined as an electrode material (metal does not absorb microwaves), for example, from ITO fine particles and metal fine particles. An electrode material precursor area is formed according to an electrode pattern to form an electrode precursor layer, or a material layer having these microwave absorption capabilities is formed on an electrode material precursor layer formed from, for example, metal fine particles. A method may be employed in which a precursor layer is formed, and microwaves are irradiated to the precursor layer to form an electrode material.

  As described above, the mode in which the material having the ability to absorb microwaves is applied to the gate electrode to convert the heat conversion material in the functional layer into the functional material has been described. For example, in a thin film transistor, the source electrode, the drain electrode, etc. A thin film transistor element can also be formed by converting a heat conversion material into a functional material by applying a substance having microwave absorption ability. These aspects will be specifically described in Examples.

<Semiconductor precursor material>
In the present invention, a metal oxide semiconductor precursor or an organic semiconductor precursor material can also be used as the semiconductor precursor material that is a heat conversion material.

  Examples of the metal oxide semiconductor precursor include a metal atom-containing compound, and examples of the metal atom-containing compound include metal salts, metal halide compounds, and organic metal compounds containing a metal atom.

  Metals of metal salts, halogen metal compounds, and organometallic compounds include Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Mo, Cd, In, Ir, Sn, Sb, Cs, Ba, La, Hf, Ta, W, Tl, Pb, Bi, Ce, Pr Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and the like.

  Among these metal salts, it is preferable to contain any metal ion of indium, tin, and zinc, and they may be used in combination.

  Moreover, it is preferable that a gallium or aluminum is included as another metal.

  As metal salts, nitrates, acetates and the like can be suitably used, and as halogen metal compounds, chlorides, iodides, bromides and the like can be suitably used.

  Examples of the organometallic compound include those represented by the following general formula (I).

Formula (I) R ¹ _x MR ² _y R ³ _z
In the formula, M is a metal, R ¹ is an alkyl group, R ² is an alkoxy group, R ³ is a β-diketone complex group, a β-ketocarboxylic acid ester complex group, a β-ketocarboxylic acid complex group, and a ketooxy group (ketooxy complex group). X + y + z = m, x = 0 to m, or x = 0 to m−1, and y = 0 to m, z = 0. ~ M, each of which is 0 or a positive integer. Examples of the alkyl group for R ¹ include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkoxy group for R ² include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a 3,3,3-trifluoropropoxy group. Further, a hydrogen atom in the alkyl group may be substituted with a fluorine atom. Examples of the group selected from a β-diketone complex group, a β-ketocarboxylic acid ester complex group, a β-ketocarboxylic acid complex group, and a ketooxy group (ketooxy complex group) of R ³ include, for example, 2,4 -Pentanedione (also called acetylacetone or acetoacetone), 1,1,1,5,5,5-hexamethyl-2,4-pentanedione, 2,2,6,6-tetramethyl-3,5-heptanedione , 1,1,1-trifluoro-2,4-pentanedione, and the β-ketocarboxylic acid ester complex group includes, for example, acetoacetic acid methyl ester, acetoacetic acid ethyl ester, acetoacetic acid propyl ester, trimethylacetate Examples thereof include ethyl acetate, methyl trifluoroacetoacetate and the like, and examples of β-ketocarboxylic acid include Examples thereof include acetoacetic acid and trimethylacetoacetic acid, and examples of ketooxy include acetooxy group (or acetoxy group), propionyloxy group, butyryloxy group, acryloyloxy group, and methacryloyloxy group. These groups preferably have 18 or less carbon atoms. Further, it may be linear or branched, or a hydrogen atom may be a fluorine atom. Among organometallic compounds, those having at least one oxygen in the molecule are preferable. As such, an organometallic compound containing at least one alkoxy group of R ² , a β-diketone complex group, a β-ketocarboxylic acid ester complex group, a β-ketocarboxylic acid complex group and a ketooxy group (ketooxy group) of R ³ Most preferred are metal compounds having at least one group selected from (complex groups). Among the metal salts, nitrate is preferable. Nitrate is easily available as a high-purity product and has high solubility in water, which is preferable as a medium for use. Examples of nitrates include indium nitrate, tin nitrate, zinc nitrate, and gallium nitrate.

  Of the above metal oxide semiconductor precursors, metal nitrates, metal halides, and alkoxides are preferable. Specific examples include indium nitrate, zinc nitrate, gallium nitrate, tin nitrate, aluminum nitrate, indium chloride, zinc chloride, tin chloride (divalent), tin chloride (tetravalent), gallium chloride, aluminum chloride, tri-i-. Examples include propoxyindium, diethoxyzinc, bis (dipivaloylmethanato) zinc, tetraethoxytin, tetra-i-propoxytin, tri-i-propoxygallium, and tri-i-propoxyaluminum.

<Film formation method and patterning method of metal oxide semiconductor precursor thin film>
In order to form a thin film containing a metal as a precursor of these metal oxide semiconductors, a known film formation method, vacuum deposition method, molecular beam epitaxial growth method, ion cluster beam method, low energy ion beam method, ion A plating method, a CVD method, a sputtering method, an atmospheric pressure plasma method, and the like can be used. In the present invention, a solution in which a metal salt, a halide, an organometallic compound, or the like is dissolved in an appropriate solvent is used on the substrate. The continuous coating is preferable because it can greatly improve the productivity. Also from this point, it is more preferable from the viewpoint of solubility to use a chloride, nitrate, acetate, metal alkoxide or the like as the metal compound.

  The solvent is not particularly limited as long as it dissolves the metal compound to be used in addition to water, but water, alcohols such as ethanol, propanol, and ethylene glycol, ethers such as tetrahydrofuran and dioxane, acetic acid, and the like. Esters such as methyl and ethyl acetate, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, glycol ethers such as diethylene glycol monomethyl ether, acetonitrile, and aromatic hydrocarbon solvents such as xylene and toluene, o-dichlorobenzene , Aromatic solvents such as nitrobenzene and m-cresol, aliphatic hydrocarbon solvents such as hexane, cyclohexane and tridecane, α-terpineol, and halogenated alkyl solvents such as chloroform and 1,2-dichloroethane N- methylpyrrolidone, can be preferably used carbon disulfide and the like.

  When a metal halide and / or metal alkoxide is used, a solvent having a relatively high polarity is preferable. Among them, water having a boiling point of 100 ° C. or less, alcohols such as ethanol and propanol, acetonitrile, or a mixture thereof is dried. Since the temperature can be lowered, it is possible to coat the resin substrate, which is more preferable.

  Addition of metal alkoxide and various ligands such as alkanolamines, α-hydroxy ketones, β-diketones and other chelating ligands in the solvent stabilizes the metal alkoxide and the solubility of the carboxylate. It is preferable to add it in a range that does not cause adverse effects.

  As a method for forming a thin film by applying a liquid containing a semiconductor precursor material on a substrate, a spin coating method, a spray coating method, a blade coating method, a dip coating method, a casting method, a bar coating method, a die coating method, or the like is applied. Methods, and printing methods such as letterpress, intaglio, lithographic, screen printing, and ink jet, and the like, and a method by coating in a broad sense, and a method of patterning by this. Alternatively, the coating film may be patterned by photolithography, laser ablation, or the like. Among these, the ink jet method, spray coating method, etc. which can apply | coat a thin film are preferable.

  In the case of film formation, a thin film of a metal oxide precursor is formed by volatilizing the solvent at about 150 ° C. after coating. In addition, when dropping the solution, it is preferable to heat the substrate itself to about 150 ° C. because two processes of coating and drying can be performed simultaneously.

<Composition ratio of metal>
As a preferred metal composition ratio, when In is 1, Zn _y Sn _1-y (where y is a positive number from 0 to ₁ ) is 0.2 to 5, preferably 0.5 to 2. . Furthermore, when In is set to 1, the composition ratio of Ga is 0.2 to 5, preferably 0.5 to 2.

  Moreover, the film thickness of the thin film containing the metal used as a precursor is 1-200 nm, More preferably, it is 5-100 nm.

<Amorphous oxide>
As the metal oxide semiconductor to be formed, any state of single crystal, polycrystal, and amorphous can be used, but an amorphous thin film is preferably used.

The electron carrier concentration of an amorphous oxide, which is a metal oxide according to the present invention, formed from a metal compound material that is a precursor of a metal oxide semiconductor only needs to be less than 10 ¹⁸ / cm ³ . The electron carrier concentration is a value when measured at room temperature. The room temperature is, for example, 25 ° C., specifically, a certain temperature appropriately selected from the range of about 0 ° C. to 40 ° C. Note that the electron carrier concentration of the amorphous oxide according to the present invention does not need to satisfy less than 10 ¹⁸ / cm ³ in the entire range of 0 ° C. to 40 ° C. For example, a carrier electron density of less than 10 ¹⁸ / cm ³ may be realized at 25 ° C. Further, when the electron carrier concentration is further reduced to 10 ¹⁷ / cm ³ or less, more preferably 10 ¹⁶ / cm ³ or less, a normally-off TFT can be obtained with a high yield.

  The electron carrier concentration can be measured by Hall effect measurement.

  The film thickness of the semiconductor that is a metal oxide is not particularly limited, but the characteristics of the obtained transistor are often greatly influenced by the film thickness of the semiconductor film, and the film thickness varies depending on the semiconductor. Generally, 1 μm or less, particularly 10 to 300 nm is preferable.

In the present invention, the precursor material, composition ratio, production conditions, and the like are controlled so that, for example, the electron carrier concentration is 10 ¹² / cm ³ or more and less than 10 ¹⁸ / cm ³ . More preferably, it is in the range of 10 ¹³ / cm ³ or more and 10 ¹⁷ / cm ³ or less, and more preferably 10 ¹⁵ / cm ³ or more and 10 ¹⁶ / cm ³ or less.

  Examples of the organic semiconductor precursor material include bicyclo compounds (bicycloporphyrin compounds) having a cyclic structure as described in JP-A-2003-304014. A film formed of these compounds undergoes a deethylation reaction by heating, whereby a film such as tetrabenzoporphyrin having high planarity can be obtained, and a highly efficient organic semiconductor layer is formed. By using these bicycloporphyrin compounds or metal complexes thereof as the semiconductor precursor, an organic semiconductor layer having high planarity can be formed by heat generated by microwave absorption of the ITO electrode.

  Specific examples of these bicycloporphyrin compounds are described in the above-mentioned organic Japanese Patent Application Laid-Open No. 2003-304014, paragraphs (0022) to (0025), and these compounds and metal complexes such as copper are used. be able to. Specific examples are given below.

  These bicyclo compounds can also be dissolved and applied in a solvent as required. Particularly useful are those in which the molecules converted by the deethyleneation reaction are hardly soluble in the solvent. Coating methods include casting methods, spin coating methods, spray coating methods, blade coating methods, dip coating methods, bar coating methods, die coating methods, and printing methods such as relief printing, intaglio printing, lithographic printing, screen printing, and inkjet printing. A method by coating in a broad sense such as a method can be used. Moreover, the method of patterning by this is mentioned. Alternatively, the coating film may be patterned by photolithography, laser ablation, or the like.

  According to the present invention, electrodes and the like can be formed by a coating process (wet process) including a printing method and an ink jet method, and the semiconductor layer is also formed by applying a semiconductor material precursor. Since it can be formed by a method, it is possible to improve the production efficiency in the manufacture of thin film transistors by, for example, forming an electrode by coating and a semiconductor forming step by coating.

(Other semiconductor layers)
In the present invention, when an insulating layer is formed using an electrode or an insulating layer precursor material as a heat conversion material, the semiconductor layer may be formed by a known method.

  For example, it is not necessary to use the method of the present invention in which a semiconductor layer is formed by using a substance having microwave absorption ability as an electrode by using microwave irradiation, and using the metal oxide semiconductor precursor material described above as a semiconductor precursor. After the body area is formed, the body area can be formed by, for example, thermal oxidation, plasma oxidation, or thermal oxidation by irradiation with ultraviolet rays in the presence of oxygen.

  For example, when plasma oxidation is used, the atmospheric pressure plasma method is preferable, and in the plasma oxidation, a substrate on which a thin film containing a precursor is formed is heated in a range of 150 ° C. to 300 ° C. An inert gas such as nitrogen gas is used as a discharge gas, and a reaction gas (a gas containing oxygen) is introduced into the discharge space together with this, a high frequency electric field is applied, the discharge gas is excited, plasma is generated, and the reaction gas To generate oxygen plasma and expose it to the surface of the substrate to oxidize the semiconductor precursor material. Under atmospheric pressure represents a pressure of 20 to 110 kPa, preferably 93 to 104 kPa.

  When an oxygen plasma is generated using a gas containing oxygen as a reactive gas by the atmospheric pressure plasma method, the gas to be used varies depending on the type of thin film, but basically a discharge gas (inert gas) and an oxidizing gas. It is a mixed gas. When performing plasma oxidation, it is preferable to contain 0.01-10 volume% of oxygen gas with respect to mixed gas as oxidizing gas. Although it is more preferable that it is 0.1-10 volume%, More preferably, it is 0.1-5 volume%.

  Examples of the inert gas include Group 18 elements of the periodic table, specifically helium, neon, argon, krypton, xenon, radon, nitrogen gas, and the like, but helium, argon, and nitrogen gas are preferably used. It is done.

  The plasma method under atmospheric pressure is described in JP-A-11-61406, JP-A-11-133205, JP-A-2000-121804, JP-A-2000-147209, JP-A-2000-185362, WO2006 / 129461, and the like. Yes.

(Other organic semiconductor layers)
In the present invention, an organic semiconductor thin film (layer) can be used as a semiconductor layer.

  As the organic semiconductor material, various condensed polycyclic aromatic compounds and conjugated compounds described later can be applied.

  Examples of the condensed polycyclic aromatic compound as the organic semiconductor material include anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, obalene, circumanthracene, bisanthene. , Zestrene, heptazelene, pyranthrene, violanthene, isoviolanthene, sacobiphenyl, phthalocyanine, porphyrin, and derivatives thereof.

  Examples of the conjugated compound include polythiophene and its oligomer, polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polythienylene vinylene and its oligomer, polyacetylene, polydiacetylene, tetrathiafulvalene compound, quinone And compounds, cyano compounds such as tetracyanoquinodimethane, fullerenes and derivatives or mixtures thereof.

  In particular, among polythiophene and oligomers thereof, thiophene hexamer α-seccithiophene α, ω-dihexyl-α-sexualthiophene, α, ω-dihexyl-α-kinkethiophene, α, ω-bis (3- Butoxypropyl) -α-secthiothiophene and oligomers such as the following compounds can be preferably used.

  Furthermore, metal phthalocyanines such as copper phthalocyanine and fluorine-substituted copper phthalocyanine described in JP-A No. 11-251601, naphthalene 1,4,5,8-tetracarboxylic acid diimide, N, N′-bis (4-trifluoromethyl) Benzyl) naphthalene 1,4,5,8-tetracarboxylic acid diimide, N, N'-bis (1H, 1H-perfluorooctyl), N, N'-bis (1H, 1H-perfluorobutyl) and N, N '-Dioctylnaphthalene 1,4,5,8-tetracarboxylic acid diimide derivatives, naphthalene 2,3,6,7 tetracarboxylic acid diimides and other naphthalene tetracarboxylic acid diimides, and anthracene 2,3,6,7-tetra Condensed ring tet such as anthracene tetracarboxylic acid diimides such as carboxylic acid diimide Carboxylic acid diimides, C60, C70, C76, C78, C84 etc. fullerenes, carbon nanotubes such as SWNT, merocyanine dyes, etc. dyes such hemicyanine dyes and the like.

  Among these π-conjugated materials, at least one selected from the group consisting of condensed polycyclic aromatic compounds such as pentacene, fullerenes, condensed ring tetracarboxylic acid diimides, and metal phthalocyanines is preferable.

  Other organic semiconductor materials include tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenetetrathiafulvalene (BEDTTTTF) -perchloric acid complex, BEDTTTTF-iodine complex, TCNQ-iodine complex. Organic molecular complexes such as can also be used. Furthermore, (sigma) conjugated polymers, such as polysilane and polygermane, and organic-inorganic hybrid material as described in Unexamined-Japanese-Patent No. 2000-260999 can also be used.

  As the organic semiconductor material, a compound represented by the following general formula (OSC1) is preferable.

In the formula, R _{1 to} R ₆ represent a hydrogen atom or a substituent, Z ₁ or Z ₂ represents a substituted or unsubstituted aromatic hydrocarbon ring, or a substituted or unsubstituted aromatic heterocyclic ring, and n1 or n2 Represents an integer of 0 to 3.

In the general formula (OSC1), examples of the substituent represented by each of R _{1 to} R ₆ include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a pentyl group, and a tert-pentyl group). Group, hexyl group, octyl group, tert-octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group (for example, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (for example, vinyl group, for example) Allyl group, 1-propenyl group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group, isopropenyl group, etc.), alkynyl group (for example, ethynyl group, propargyl group, etc.), aromatic hydrocarbon group (Also called aromatic carbocyclic group, aryl group, etc., for example, phenyl group, p-chlorophenyl group, Cytyl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group, etc.), aromatic heterocyclic group (also called heteroaryl group, For example, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzoimidazolyl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl group, 1,2,3- Triazol-1-yl group, etc.), oxazolyl group, benzoxazolyl group, thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group, benzothienyl group, dibenzothienyl group , Indolyl group, carbazoli Group, carbolinyl group, diazacarbazolyl group (in which one of carbon atoms constituting the carboline ring of the carbolinyl group is replaced by a nitrogen atom), quinoxalinyl group, pyridazinyl group, triazinyl group, quinazolinyl group, phthalazinyl group Etc.), heterocyclic groups (for example, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy groups (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, Dodecyloxy group etc.), cycloalkoxy group (eg cyclopentyloxy group, cyclohexyloxy group etc.), aryloxy group (eg phenoxy group, naphthyloxy group etc.), alkylthio group (eg methylthio group, ethylthio group, propylthio group) , Pentyl Thio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyl Oxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, Aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylamino Sulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, Octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group, naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group) Group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonyl) Nylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group ( For example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylamino Carbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), ureido group (for example, methylureido) Group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, Butylsulfinyl group, cyclohexylsulfinyl group, 2-ethylhexylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl) Group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group (phenylsulfonyl group, naphthyl) Sulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, naphthylamino) Group, 2-pyridylamino group, etc.), halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), fluorinated hydrocarbon group (eg, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophenyl) Group), cyano group, nitro group, hydroxy group, mercapto group, silyl group (for example, trimethylsilyl group, triisopropylsilyl group, triphenylsilyl group, phenyldiethylsilyl group, etc.), and the like.

  These substituents may be further substituted with the above substituents. In addition, a plurality of these substituents may be bonded to each other to form a ring.

In the general formula (OSC1), the aromatic hydrocarbon group or aromatic heterocyclic group represented by Z ₁ or Z ₂ is an aromatic carbonization described as a substituent represented by each of R _{1 to} R ₆ above. It is synonymous with a hydrogen group and an aromatic heterocyclic group, respectively.

  Furthermore, a compound represented by the following general formula (OSC2) is preferable.

(Wherein R ₇ or R ₈ represents a hydrogen atom or a substituent, Z ₁ or Z ₂ represents a substituted or unsubstituted aromatic hydrocarbon ring, or a substituted or unsubstituted aromatic heterocyclic ring, and n1 or n2 represents an integer of 0 to 3.)
In the general formula (OSC2), the substituent represented by R ₇ or R ₈ has the same meaning as the substituents represented by R _{1 to} R ₆ in the general formula (OSC1). Moreover, the aromatic hydrocarbon group and aromatic heterocyclic group represented by Z ₁ or Z ₂ are the aromatic hydrocarbon groups and aromatics described as the substituents represented by R _{1 to} R ₆ , respectively. Each has the same meaning as a heterocyclic group.

In the general formula (OSC2), the substituents R ₇ -and R _8- are preferably represented by the general formula (SG1).

(Wherein R _{9 to} R ₁₁ represent a substituent, and X represents silicon (Si), germanium (Ge), or tin (Sn)).
In the general formula (SG1), the substituent represented by R _{9 to} R ₁₁ has the same meaning as the substituent represented by R _{1 to} R ₃ in the general formula (1).

  Specific examples of the compound represented by the general formula (OSC2) are shown below, but are not limited thereto.

  Examples of organic semiconductor materials include J. Org. Am. Chem. Soc. 2006, 128, 12604, J. Am. Am. Chem. Soc. The compounds described in 2007, 129, 2224, Liquid Crystals 2003, 30, 603-610 can be used.

  In the present invention, for example, a material having a functional group such as acrylic acid, acetamide, dimethylamino group, cyano group, carboxyl group, nitro group, benzoquinone derivative, tetracyanoethylene and tetracyanoquino Materials that accept electrons, such as dimethane and their derivatives, materials having functional groups such as amino, triphenyl, alkyl, hydroxyl, alkoxy, and phenyl, phenylenediamine, etc. Including substituted amines, anthracene, benzoanthracene, substituted benzoanthracenes, pyrene, substituted pyrene, carbazole and derivatives thereof, tetrathiafulvalene and derivatives thereof, and the like materials that serve as donors of electrons, So-called doping treatment It may be.

  The doping means introducing an electron-donating molecule (acceptor) or an electron-donating molecule (donor) into the thin film as a dopant. Therefore, the doped thin film is a thin film containing the condensed polycyclic aromatic compound and the dopant. A well-known thing can be employ | adopted as a dopant used for this invention.

  As a method of forming these organic semiconductor layers, it can be formed by a known method, for example, vacuum deposition, MBE (Molecular Beam Epitaxy), ion cluster beam method, low energy ion beam method, ion plating method, Sputtering method, CVD (Chemical Vapor Deposition), laser deposition, electron beam deposition, electrodeposition, casting from solution, spin coating, dip coating, bar coating method, die coating method, spray coating method, LB method, etc. Examples include screen printing, ink jet printing, blade coating, and the like.

  Among these, the spin coating method, blade coating method, dip coating method, roll coating method, bar coating method, die coating method and the like that can form a thin film easily and precisely using an organic semiconductor solution are preferred in terms of productivity. . In particular, when the organic semiconductor layer is formed by the pattern forming method according to the present invention, it is preferable to apply and apply the organic semiconductor solution to the patterned substrate surface.

  The organic solvent used in preparing the organic semiconductor solution is preferably an aromatic hydrocarbon, an aromatic halogenated hydrocarbon, an aliphatic hydrocarbon or an aliphatic halogenated hydrocarbon, an aromatic hydrocarbon, an aromatic halogenated More preferred are hydrocarbons or aliphatic hydrocarbons.

  Examples of the aromatic hydrocarbon organic solvent include toluene, xylene, mesitylene, and methylnaphthalene, but the present invention is not limited thereto.

  Aliphatic hydrocarbons include octane, 4-methylheptane, 2-methylheptane, 3-methylheptane, 2,2-dimethylhexane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethyl. Although hexanecyclohexane, cyclopentane, methylcyclohexane, etc. can be mentioned, this invention is not limited to these.

  Examples of the organic solvent for the aliphatic halogenated hydrocarbon include chloroform, bromoform, dichloromethane, dichloroethane, trichloroethane, difluoroethane, fluorochloroethane, chloropropane, dichloropropane, chloropentane, and chlorohexane. It is not limited to these.

  These organic solvents used in the present invention may be used alone or in combination of two or more. The organic solvent preferably has a boiling point of 50 ° C to 250 ° C.

  In addition, as described in Advanced Material 1999 No. 6, p. 480 to 483, a precursor such as pentacene is soluble in a solvent, a target organic material formed by heat treatment of a precursor film formed by coating A thin film may be formed.

  The film thickness of these organic semiconductor layers is not particularly limited, but the characteristics of the obtained transistor are often greatly influenced by the film thickness of the organic semiconductor layer, and the film thickness varies depending on the organic semiconductor. Generally, 1 μm or less, particularly 10 to 300 nm is preferable.

  Furthermore, according to the organic semiconductor device of the present invention, at least one of the gate electrode and the source / drain electrode is formed by the method of manufacturing an organic semiconductor device of the present invention, so that a low-resistance electrode requires a high temperature. Instead, it can be formed without causing deterioration of the characteristics of the organic semiconductor layer material layer.

  In the case of forming an organic semiconductor layer, prior to the formation of the organic semiconductor layer, a surface treatment made of an organic material is applied to the region where the organic semiconductor layer is formed on the surface of the substrate made of, for example, a metal oxide such as an undercoat. Is preferred. As the surface treatment made of an organic substance, one that is physically adsorbed on the substrate surface, a surfactant, or the like can be used. It is particularly preferable to form a monomolecular film by physical adsorption or chemical adsorption on the substrate surface on which an organic semiconductor layer is formed, for example, an insulating film or the like. Of these, surface treatment with a silane coupling agent is preferred. A silane coupling agent forms a monomolecular film by bonding with an oxide surface serving as an insulating layer by a chemical reaction.

In particular, silane coupling agents such as octyltrichlorosilane, octadecyltrichlorosilane, phenyltrichlorosilane, octyltriethoxysilane, silazanes such as hexamethyldisilazane,
The following compounds are also preferable silane coupling agents.

  A surface treatment with a titanium coupling agent such as octyltrichlorotitanium or octyltriisopropoxytitanium is also preferable.

(substrate)
Various materials can be used as the support material constituting the substrate. For example, ceramic substrates such as glass, quartz, aluminum oxide, sapphire, silicon nitride, silicon carbide, silicon, germanium, gallium arsenide, gallium phosphide. In addition, a semiconductor substrate such as gallium nitrogen, paper, and non-woven fabric can be used. In the present invention, the support is preferably made of a resin, for example, a plastic film sheet can be used. Examples of plastic films include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), and cellulose. Examples include films made of triacetate (TAC), cellulose acetate propionate (CAP), and the like. By using a plastic film, the weight can be reduced as compared with the case of using a glass substrate, the portability can be improved, and the resistance to impact can be improved.

  In the present invention, it is preferable to use a film that is a light-transmitting resin film and has a glass transition temperature (Tg) of 200 ° C. or lower as the substrate. From this viewpoint, a film containing polyethylene naphthalate (PEN) is preferable. Here, “light transmissivity” means that the light transmittance at a wavelength in the visible light range (380 to 780 nm) is 80% or more.

(Electronic device)
The manufacturing method of the functional flexible film of this invention can be used suitably in preparation of various electronic devices. In particular, it can be suitably used in the production of a thin film transistor element.

  Hereinafter, each component other than the above-described component in the case of manufacturing a thin film transistor will be described.

(electrode)
In the present invention, as a conductive material used for electrodes such as a source electrode, a drain electrode, and a gate electrode constituting a TFT element, an electrode material having a microwave absorbing ability manufactured by the above method, for example, a metal oxide In addition to the conductive material, other electrode materials can be used. For example, after the gate electrode and the gate insulating layer are formed by the microwave irradiation according to the method of the present invention according to the first embodiment, the source and drain electrodes may not necessarily be the same method.

  Even when an electrode material having microwave absorption capability is used for the source and drain electrodes and the semiconductor precursor material is a semiconductor layer, there is no limitation on the electrode material of the gate electrode, for example.

  Other electrode materials are only required to have conductivity at a level that can be used as an electrode, and are not particularly limited. Platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, Palladium, tellurium, rhenium, iridium, aluminum, ruthenium, germanium, molybdenum, tungsten, tin oxide / antimony, indium tin oxide (ITO), fluorine-doped zinc oxide, zinc, carbon, graphite, glassy carbon, silver paste and carbon paste , Lithium, beryllium, sodium, magnesium, potassium, calcium, scandium, titanium, manganese, zirconium, gallium, niobium, sodium, sodium-potassium alloy, magnesium, lithium, aluminum, magnesium / copper mixture, Magnesium / silver mixture, a magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide mixture, a lithium / aluminum mixture, or the like is used.

  Moreover, as a conductive material, a conductive polymer, metal fine particles, or the like can be suitably used. As the dispersion containing metal fine particles, for example, a known conductive paste may be used, but a dispersion containing metal fine particles having a particle diameter of 1 nm to 50 nm, preferably 1 nm to 10 nm is preferable. In order to form an electrode from metal fine particles, the above-described method can be used in the same manner, and the metal described above can be used as the material of the metal fine particles.

  In addition, as described above, these electrode materials can be used as an electrode material having a microwave absorption ability by combining the substance having the microwave absorption ability.

(Method for forming electrodes, etc.)
As a method for forming these electrodes, a conductive thin film formed using a method such as vapor deposition or sputtering using the above as a raw material, a method for forming an electrode using a known photolithographic method or a lift-off method, aluminum, copper or the like There is a method in which a resist is formed on a metal foil by thermal transfer, ink jet or the like and etched. Alternatively, a conductive polymer solution or dispersion, a dispersion containing metal fine particles, or the like may be directly patterned by an ink jet method, or may be formed from a coating film by lithography or laser ablation. Further, a method of patterning a conductive ink or conductive paste containing a conductive polymer or metal fine particles by a printing method such as relief printing, intaglio printing, planographic printing, or screen printing can also be used.

  As a method for forming an electrode such as a source, drain, or gate electrode, a gate, or a source bus line without patterning a metal thin film using a photosensitive resin such as etching or lift-off, a method by an electroless plating method is used. Are known.

  Regarding the method of forming an electrode by electroless plating, as described in Japanese Patent Application Laid-Open No. 2004-158805, a liquid containing a plating catalyst that causes electroless plating by acting with a plating agent on a portion where an electrode is provided After patterning, for example, by a printing method (including inkjet printing), a plating agent is brought into contact with a portion where an electrode is provided. If it does so, electroless plating will be performed to the said part by the contact of the said catalyst and a plating agent, and an electrode pattern will be formed.

  The application of the electroless plating catalyst and the plating agent may be reversed, and the pattern formation may be performed either. However, a method of forming a plating catalyst pattern and applying the plating agent to this is preferable.

  As the printing method, for example, screen printing, planographic printing, letterpress printing, intaglio printing, printing by ink jet printing, or the like is used.

(Gate insulation film)
When the oxide insulating film is not formed by the method of the present invention, various insulating films can be used as the gate insulating film of the thin film transistor. In particular, an inorganic oxide film having a high relative dielectric constant is preferable. Inorganic oxides include silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, barium zirconate titanate, lead zirconate titanate, lead lanthanum titanate, strontium titanate, Examples thereof include barium titanate, barium magnesium fluoride, bismuth titanate, strontium bismuth titanate, strontium bismuth tantalate, bismuth tantalate niobate, and yttrium trioxide. Of these, silicon oxide, aluminum oxide, tantalum oxide, and titanium oxide are preferable. Inorganic nitrides such as silicon nitride and aluminum nitride can also be suitably used.

  Examples of the method for forming the film include a vacuum process, a molecular beam epitaxial growth method, an ion cluster beam method, a low energy ion beam method, an ion plating method, a CVD method, a sputtering method, an atmospheric pressure plasma method, and a spray process. Examples include wet processes such as coating methods, spin coating methods, blade coating methods, dip coating methods, casting methods, roll coating methods, bar coating methods, die coating methods, and other methods such as printing and ink jet patterning. Can be used depending on the material.

  The wet process is a method of applying and drying a liquid in which fine particles of inorganic oxide are dispersed in an arbitrary organic solvent or water using a dispersion aid such as a surfactant as required, or an oxide precursor, for example, A so-called sol-gel method in which a solution of an alkoxide body is applied and dried is used.

  Of these, the atmospheric pressure plasma method described above is preferable.

  It is also preferable that the gate insulating film (layer) is composed of an anodized film or the anodized film and an insulating film. The anodized film is preferably sealed. The anodized film is formed by anodizing a metal that can be anodized by a known method.

  Examples of the metal that can be anodized include aluminum and tantalum, and the anodizing method is not particularly limited, and a known method can be used.

  Examples of organic compound films include polyimides, polyamides, polyesters, polyacrylates, photo-radical polymerization-type, photo-cation polymerization-type photo-curing resins, copolymers containing acrylonitrile components, polyvinyl phenol, polyvinyl alcohol, novolac resins, etc. Can also be used.

  An inorganic oxide film and an organic oxide film can be laminated and used together. The thickness of these insulating films is generally 50 nm to 3 μm, preferably 100 nm to 1 μm.

[Protective layer]
It is also possible to provide a protective layer on the organic thin film transistor element as the electronic device according to the present invention. Examples of the protective layer include inorganic oxides or inorganic nitrides, metal thin films such as aluminum, polymer films with low gas permeability, and laminates thereof. By having such a protective layer, durability of organic thin film transistors can be mentioned. Improves. As a method for forming these protective layers, the same method as the method for forming the gate insulating film described above can be used. Further, the protective layer may be provided by a method such as simply laminating a film in which various inorganic oxides are laminated on the polymer film.

(Thin film transistor device configuration)
FIG. 4 is a diagram showing a typical configuration of a thin film transistor element. In FIG. 4A, a source electrode 2 and a drain electrode 3 are formed on a support 6, and a semiconductor layer 1 is formed between both electrodes using this as a base material (substrate), and an insulating layer 5 is formed thereon. Then, a gate electrode 4 is formed thereon to form a field effect thin film transistor. FIG. 4B shows the semiconductor layer 1 formed between the electrodes in FIG. 4A so as to cover the entire surface of the electrode and the support using a coating method or the like. In FIG. 4C, the semiconductor layer 1 is first formed on the support 6 and then the source electrode 2, the drain electrode 3, the insulating layer 5, and the gate electrode 4 are formed.

  In FIG. 4D, the gate electrode 4 and the insulating layer 5 are formed on the support 6, the source electrode 2 and the drain electrode 3 are formed thereon, and the semiconductor layer 1 is formed between the electrodes. In addition, the configuration shown in FIGS. 4E and 4F can be adopted.

  Among the above, the present invention can be applied to the process of simultaneously forming the gate electrode and the insulating layer, the semiconductor layer, the source and drain electrodes, and the semiconductor layer in FIG. Although not shown here, it can also be used in the process of forming a protective layer or the like.

  In the present invention, the transistor element preferably has a bottom gate structure (FIGS. 4D to 4F). In the case of this structure, it is preferable to use a substance that absorbs microwaves in the gate electrode, since this can be used as a heat source and a plurality of layers such as a (gate) insulating layer and a semiconductor layer can be simultaneously converted from a heat conversion material to a functional layer.

  Further, the bottom contact type in which the source / drain electrode is in front of the organic semiconductor layer as viewed from the gate electrode (FIGS. 4C and 4E, etc.) is preferable. Since the formation of the insulating layer and the like can be separated from the formation of the semiconductor layer, it is preferable that the conversion to the electrode material and the insulating layer is different from the conversion condition to the semiconductor layer because the respective conversions can be performed sufficiently.

  In the case of the top gate structure (FIGS. 4A to 4C), the gate electrode has a structure far from the substrate, and when the substrate is a plastic substrate, from the viewpoint of thermal deformation and alteration of the substrate. preferable.

  FIG. 5 is a schematic equivalent circuit diagram of an example of a thin film transistor sheet 10 which is an electronic device in which a plurality of thin film transistor elements are arranged.

  The thin film transistor sheet 10 has a large number of thin film transistor elements 14 arranged in a matrix. Reference numeral 11 denotes a gate bus line of the gate electrode of each thin film transistor element 14, and reference numeral 12 denotes a source bus line of the source electrode of each thin film transistor element 14. An output element 16 is connected to the drain electrode of each thin film transistor element 14, and the output element 16 is, for example, a liquid crystal or an electrophoretic element, and constitutes a pixel in the display device. In the illustrated example, a liquid crystal is shown as an output element 16 by an equivalent circuit composed of a resistor and a capacitor. 15 is a storage capacitor, 17 is a vertical drive circuit, and 18 is a horizontal drive circuit.

  The method of the present invention can be used for producing such a thin film transistor sheet in which TFT elements are two-dimensionally arranged on a support.

  Moreover, the manufacturing method of the electronic device of this invention is applicable to any electronic device, for example, it can apply to an organic electroluminescent element etc.

  The organic EL element has a configuration in which an organic layer that emits light is laminated and sandwiched between two electrodes on a substrate, and at least one of the electrodes is a transparent electrode for extracting light.

  For example, an organic electroluminescence element is most simply composed of an anode / a light emitting layer / a cathode, but usually the organic layer functions as a hole transport layer, a light emitting layer, an electron transport layer, etc. in order to increase luminous efficiency. It consists of a laminated structure of various functional layers separated.

  The organic layer and each thin film have a film thickness ranging from 1 nm to several μm. In addition to the above, the electron blocking layer, the hole blocking layer, the buffer layer, and other necessary layers are arranged in a predetermined layer order. They are stacked so that carriers such as holes and electrons injected from both electrodes can move smoothly.

  In each of these organic layers constituting the organic EL device, the organic light emitting material contained in the light emitting layer includes aromatic heterocyclic compounds such as carbazole, carboline, diazacarbazole, triarylamine derivatives, stilbene derivatives, polyarylenes. , Aromatic condensed polycyclic compounds, aromatic heterocondensed ring compounds, metal complex compounds, etc., and single oligo compounds or composite oligo compounds thereof, but the present invention is not limited thereto, and widely known Materials can be used.

  In the light emitting layer (film forming material), preferably about 0.1 to 20% by mass of a dopant may be included in the light emitting material. Examples of the dopant include known fluorescent dyes such as perylene derivatives and pyrene derivatives, and in the case of phosphorescent light emitting layers, for example, tris (2-phenylpyridine) iridium, bis (2-phenylpyridine) (acetylacetonate). A complex compound such as an orthometalated iridium complex represented by iridium, bis (2,4-difluorophenylpyridine) (picolinato) iridium, and the like is similarly contained in an amount of about 0.1 to 20% by mass. The thickness of the light emitting layer ranges from 1 nm to several hundred nm.

  Examples of materials used in the hole injection / transport layer include phthalocyanine derivatives, heterocyclic azoles, aromatic tertiary amines, polyvinyl carbazole, polyethylene dioxythiophene / polystyrene sulfonic acid (PEDOT: PSS), and the like. Polymer materials such as conductive polymers are also used for the light emitting layer, for example, carbazole-based light emitting materials such as 4,4′-dicarbazolylbiphenyl, 1,3-dicarbazolylbenzene, (di ) Low molecular light emitting materials represented by pyrene-based light emitting materials such as azacarbazoles, 1,3,5-tripyrenylbenzene, polymer light emitting materials represented by polyphenylene vinylenes, polyfluorenes, polyvinyl carbazoles, etc. Etc.

  Examples of the electron injection / transport layer material include metal complex compounds such as 8-hydroxyquinolinate lithium and bis (8-hydroxyquinolinate) zinc, and nitrogen-containing five-membered ring derivatives listed below. That is, oxazole, thiazole, oxadiazole, thiadiazole or triazole derivatives are preferred. Specifically, 2,5-bis (1-phenyl) -1,3,4-oxazole, 2,5-bis (1-phenyl) -1,3,4-thiazole, 2,5-bis (1 -Phenyl) -1,3,4-oxadiazole, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) 1,3,4-oxadiazole, 2,5-bis ( 1-naphthyl) -1,3,4-oxadiazole, 1,4-bis [2- (5-phenyloxadiazolyl)] benzene, 1,4-bis [2- (5-phenyloxadiazolyl) -4-tert-butylbenzene], 2- (4'-tert-butylphenyl) -5- (4 "-biphenyl) -1,3,4-thiadiazole, 2,5-bis (1-naphthyl) -1 , 3,4-thiadiazole, 1,4-bis [2- (5-phenyl) Asiazolyl)] benzene, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1,3,4-triazole, 2,5-bis (1-naphthyl) -1,3,4 -Triazole, 1,4-bis [2- (5-phenyltriazolyl)] benzene and the like.

  These organic materials preferably have a crosslinkable group such as a vinyl group. Since a material having a crosslinkable group is crosslinked by heat or light, it is easy to apply and forms a network polymer by crosslinking so that the layer is preferably insolubilized when applied and laminated thereon.

  That is, a precursor layer is formed as a precursor of the organic material layer by coating, and this can be similarly made into each functional layer by proceeding with crosslinking by microwave heating with an electrode material having microwave absorption ability.

  The film thickness of the organic EL element and each organic layer is required to be about 0.05 to 0.3 μm, and preferably about 0.1 to 0.2 μm.

  The organic layer (organic EL functional layers) may be formed by any means such as vapor deposition and coating, but coating and printing are preferred. Coating is performed by spin coating, transfer coating, and extrusion coating. Etc. can be used. In consideration of material use efficiency, a method capable of applying a pattern such as transfer coating and extrusion coating is preferable, and transfer coating is particularly preferable.

  Moreover, screen printing, offset printing, inkjet printing, etc. can be used for printing. As the display element, a thin film, a small element size, and high-precision high-definition printing such as offset printing and inkjet printing are preferable in consideration of overlapping RGB patterns.

  Each organic material has its own solubility characteristics (solubility parameters, ionization potential, polarity), and there are limitations on the solvents that can be dissolved. In this case, since the solubility is different from each other, the concentration cannot be generally determined. However, depending on the organic EL material to be formed into a film, a solvent suitable for the above conditions can be used. For example, halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, dibutyl ether, tetrahydrofuran, dioxane, anisole, etc. Ether solvents, methanol, alcohol solvents such as ethanol, isopropanol, butanol, cyclohexanol, 2-methoxyethanol, ethylene glycol, and glycerin, and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene Medium, paraffinic solvents such as hexane, octane, decane and tetralin, ester solvents such as ethyl acetate, butyl acetate and amyl acetate, amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone Solvent, ketone solvent such as acetone, methyl ethyl ketone, cyclohexanone and isophorone, amine solvent such as pyridine, quinoline and aniline, nitrile solvent such as acetonitrile and valeronitrile, sulfur solvent such as thiophene and carbon disulfide .

  In addition, the solvent which can be used is not restricted to these, You may mix and use 2 or more types of these as a solvent.

  Among these, preferable examples of the organic EL material are different depending on each functional layer material. However, as a good solvent, for example, an aromatic solvent, a halogen solvent, an ether solvent, and the like are preferable. Aromatic solvents and ether solvents. Examples of the poor solvent include alcohol solvents, ketone solvents, paraffin solvents, and the like. Among them, alcohol solvents and paraffin solvents are used.

  Of the two electrodes, those having a work function larger than 4 eV are suitable as the conductive material used for the anode for injecting holes, such as silver, gold, platinum, palladium and their alloys, oxidation Metal oxides such as tin, indium oxide and ITO, and organic conductive resins such as polythiophene and polypyrrole are used. It is preferable that it is translucent, and ITO is preferable as a transparent electrode. As a method for forming the ITO transparent electrode, mask vapor deposition or photolithography patterning can be used, but is not limited thereto.

  As the conductive material used as the cathode, those having a work function smaller than 4 eV are suitable, such as magnesium and aluminum. Typical examples of the alloy include magnesium / silver and lithium / aluminum. The formation method can be mask vapor deposition, photolithography patterning, plating, printing, or the like, but is not limited thereto.

  According to the present invention, even in an electronic device such as an organic EL element having such a configuration, microwave irradiation is used for each functional layer precursor layer using, for example, an electrode having microwave absorption capability or an electrode precursor material. Thus, it can be converted into a functional layer.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto (see FIGS. 6 and 7).

Example 1 Heat resistance of substrate film <Preparation of substrate>
A heat-resistant adhesive Kapton film = polyimide (PI) film (thickness 30 μm) is bonded to a 180 μm-thick annealed polyethylene naphthalate (PEN) substrate film 1 to form a base film 2 and a similar PEN A base film 3 was prepared by depositing 500 nm of SiO ₂ on the film by the CVD method.

<Production of ITO film>
An ITO film having a thickness of 110 nm was formed on each of a PEN substrate bonded with a PI film, a PEN substrate not bonded, and a PEN substrate bonded with SiO ₂ by a conventional sputtering method. The surface resistance at that time was 30Ω / □ (see FIG. 6).

<Microwave heating test>
As shown in FIG. 6, a Si wafer (thickness 0.5 mm) is sandwiched between them, cooled to 0 ° C. with a cooling medium from the surface (back surface) opposite to the ITO film, and alumina as a main component from above. did.

  The micro was covered with a non-absorbing heat insulating material, irradiated with 2.45 GHz microwave at an output of 500 W, heated to 300 ° C., and held at 300 ° C. for 30 minutes while controlling the output.

  For microwave irradiation, a μ-Reactor manufactured by Shikoku Instruments Co., Ltd. was used. In addition, the temperature measured the surface temperature of the base material with the thermocouple.

<Evaluation of film>
The degree of deformation of the film after microwave heating was visually evaluated according to the following criteria.
○: No damage such as deformation, cracking, or scorching can be confirmed on the base film.
(Triangle | delta): Although the base film has caused the dimensional change etc., the crack and the burning have not generate | occur | produced and the original pattern is hold | maintained.
X: Significant damage such as dimensional change, cracks, and scorching is confirmed.

<Evaluation results>
Base film 1: x (The film is greatly deformed and carbonized, and the original pattern is not retained.)
Base film 2: ○
Base film 3: x (The film is greatly deformed and carbonized, and the original pattern is not retained.)
Example 2 Production of Transistor <Production of Gate Insulating Film>
A coating type SiO ₂ precursor (Aquamica NN110-20) made of polysilazane is spin-coated on the ITO upper surface of the base film 2 of Example 1 to a dry film thickness of 300 nm and dried at 100 ° C. to obtain a gate insulating film precursor. A base film 4 with a body was produced (see FIG. 6).

<Fabrication of semiconductor layer>
Indium nitrate, gallium nitrate, and zinc nitrate are adjusted so that the metal ratio is 1: 1: 1, and dissolved in a solution of water / ethanol = 9/1 so that the total metal concentration becomes 10% by mass, and further dissolved. Then, a defoaming treatment (ultrasonic wave 10 minutes) was performed to prepare a semiconductor precursor coating solution.

The SiO ₂ surface of the substrate 4 was subjected to UV irradiation treatment at 70 ° C. for 10 minutes under an oxygen flow rate of 500 ml / min using a dry cleaner UV-1 manufactured by Samco.

A semiconductor precursor dot pattern was coated on the surface of SiO _{2 of} the base material using a piezo ink jet head having a discharge amount of 4 pl at a base material temperature of 100 ° C.

  The dot diameter after printing was 60 to 70 μm.

The substrate was baked at 300 ° C. for 30 minutes by microwave heating in the same manner as in Example 1 to convert the semiconductor precursor layer into a semiconductor active layer and the SiO ₂ precursor layer into SiO ₂ .

  Even after this treatment, no significant damage was observed on the substrate.

<Production of source electrode and drain electrode>
On this semiconductor layer, source and drain electrodes were formed by vapor deposition of Au so that L / W = 20 μm / 50 μm.

  Thus, a bottom-gate / top-contact transistor using ITO as the gate electrode and Au as the source and drain electrodes was fabricated (see FIG. 7).

<Evaluation of device performance>
When this device was evaluated under the conditions of a gate bias of −40 to 40 V and a voltage between SD of 30 V, it showed a saturation mobility of 2 cm ² / Vs, an On / Off ratio of 5.5 digits, and a high-performance and flexible field effect transistor. Functioned as.

Example 3
In the dot pattern precursor film used in Example 2, the same dot pattern as the precursor pattern heated to 300 ° C. was used to accurately overlap the precursor pattern with an aluminum pattern product, The convex pattern part was made to contact the precursor part. After maintaining for 30 minutes, the pattern was slowly removed, and a transistor element was produced in the same manner as in Example 2. As a result, the mobility was 3.0 cm ² / Vs, the On / Off ratio was 5.5 digits, and high performance. And it functioned as a flexible field effect transistor (see FIG. 8).

Schematic sectional view showing a mode in which the heat conversion material is converted into a semiconductor layer by irradiating microwaves with the electrode pattern (area) as a heat source Schematic cross-sectional view that converts the heat conversion material above into an insulating layer by irradiating microwaves with the electrode pattern (area) as a heat source The figure which shows the relationship between the distance of a heat source area and a board | substrate, and the distance of a heat source area and the functional layer precursor area | region which is heat-converted. The figure which shows the typical structure of a film transistor element Schematic equivalent circuit diagram of an example of a thin film transistor sheet 10 which is an electronic device in which a plurality of thin film transistor elements are arranged Cross-sectional view of functional flexible film and electronic device (Examples 1 and 2) Cross-sectional view of functional flexible film and electronic device (Example 2) Schematic sectional view showing a production process of a functional flexible film (Example 3)

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Semiconductor layer 2 Source electrode 3 Drain electrode 4 Gate electrode 5 Gate insulating layer 6 Substrate 10 Thin film transistor sheet 11 Gate bus line 12 Source bus line 14 Thin film transistor element 15 Storage capacitor 16 Output element 17 Vertical drive circuit 18 Horizontal drive circuit 20 Resin substrate 21 Heat resistant low thermal conductive layer 22 Microwave absorber containing layer (heat source)
23 Doped Si Wafer with Thermal Oxide Film 24 Cooling Medium 25 Gate Insulating Film 26 Semiconductor Precursor Layer 27 Heating Pattern Object (In Case of Convex Pattern)

Claims (11)

In the method for producing a functional flexible film, the glass transition temperature (Tg) is 200 ° C. or more and the thermal conductivity is 0.25 W between the region that becomes the highest temperature during the production process and the resin region that becomes the substrate. The manufacturing method of a functional flexible film characterized by providing the heat resistant low heat conductive layer which is below / m * K. The method for producing a functional flexible film according to claim 1, wherein the heat-resistant low thermal conductive layer has a thickness of 1 to 100 μm. The method for producing a functional flexible film according to claim 1 or 2, wherein a region having the highest temperature is heated by a local heating method during the production process. The method for producing a functional flexible film according to claim 3, wherein the local heating method is a heating method using a microwave. The microwave absorber containing layer adjacent to the heat-resistant low thermal conductive layer is provided, and the microwave absorber containing layer is heated by irradiating the microwave to perform local heating. Of producing a functional flexible film. The functionality according to claim 5, wherein the microwave absorber-containing layer contains an oxide of at least one metal selected from indium (In), tin (Sn), and zinc (Zn). A method for producing a flexible film. At least a substrate, a heat resistant low thermal conductive layer, and a heat conversion material-containing layer (hereinafter referred to as “functional layer precursor”) or a functional layer precursor pattern layer are provided, and the functional layer precursor or the functional layer precursor pattern is heated. The patterned product having a desired pattern shape is locally heated from the surface having the functional layer precursor on the side opposite to the substrate in contact with or in proximity to the pattern of the functional layer precursor. The manufacturing method of the functional flexible film as described in any one. The method for producing a functional flexible film according to any one of claims 1 to 7, wherein the pre-heat resistant low thermal conductive layer contains a polyimide resin. The method for producing a functional flexible film according to any one of claims 1 to 8, wherein the substrate is a light-transmitting resin film and has a glass transition temperature (Tg) of 200 ° C or lower. . An electronic device manufactured by the method for manufacturing a functional flexible film according to claim 1. The electronic device according to claim 10, wherein the electronic device is a transistor element.

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