TWI623590B - Organic thin film transistor - Google Patents

Organic thin film transistor Download PDF

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TWI623590B
TWI623590B TW104142887A TW104142887A TWI623590B TW I623590 B TWI623590 B TW I623590B TW 104142887 A TW104142887 A TW 104142887A TW 104142887 A TW104142887 A TW 104142887A TW I623590 B TWI623590 B TW I623590B
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TW201631041A (en
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竹谷純一
熊澤和久
岩佐淳司
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日本曹達股份有限公司
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
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    • C—CHEMISTRY; METALLURGY
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    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
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    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/20—Organic diodes
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    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/468—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics
    • H10K10/474—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics the gate dielectric comprising a multilayered structure
    • H10K10/476—Insulated gate field-effect transistors [IGFETs] characterised by the gate dielectrics the gate dielectric comprising a multilayered structure comprising at least one organic layer and at least one inorganic layer
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors

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Abstract

提供一種有機薄膜電晶體，其具備由含有a)下述式(I)(式中，R表示碳原子直接鍵結於Si之有機基，X表示羥基或水解性基；n表示1或2，n為2時，各R可相同亦可不同，(4-n)為2以上時，各X可相同，亦可不同)所表示之有機矽化合物之縮合物、及b)電磁輻射硬化性化合物之硬化物的有機無機複合薄膜所構成之絕緣層作為閘極絕緣膜。 Provided is an organic thin film transistor comprising a) the following formula (I) (wherein R represents an organic group in which a carbon atom is directly bonded to Si, X represents a hydroxyl group or a hydrolyzable group; n represents 1 or 2, When n is 2, each R may be the same or different. When (4-n) is 2 or more, each X may be the same or different.) Condensates of organosilicon compounds represented by b) and electromagnetic radiation hardening compounds The insulating layer composed of the hardened organic-inorganic composite film serves as the gate insulating film.

RnSiX4-n (I) R n SiX 4-n (I)

Description

有機薄膜電晶體 Organic thin film transistor

本發明係關於一種有機薄膜電晶體。 The invention relates to an organic thin film transistor.

本申請案基於在2015年1月14日在日本提出申請之特願2015-005413號主張優先權，將其內容援用至本文中。 This application claims priority based on Japanese Patent Application No. 2015-005413 filed in Japan on January 14, 2015, and the contents thereof are incorporated herein.

作為具有低臨界電壓及驅動電壓且與有機活性層之電荷遷移率高之有機絕緣體，已知如下有機無機絕緣體形成組成物，其含有(i)有機-無機混合物質、(ii)一種以上有機金屬化合物及/或一種以上有機高分子、及(iii)使上述(i)及上述(ii)之成分溶解之溶劑(參照專利文獻1)。已知有機-無機混合物質為有機矽烷化合物或使用酸或鹼觸媒及水使有機矽烷化合物於有機溶劑內水解反應及縮合反應而獲得之聚合物，有機金屬化合物為正丁醇鈦(IV)等鈦化合物。 As an organic insulator having a low threshold voltage and a driving voltage and having a high charge mobility with an organic active layer, an organic-inorganic insulator-forming composition is known which contains (i) an organic-inorganic mixed substance, and (ii) one or more organic metals. A compound and / or one or more organic polymers, and (iii) a solvent in which the components (i) and (ii) are dissolved (see Patent Document 1). It is known that the organic-inorganic compound is an organic silane compound or a polymer obtained by using an acid or an alkali catalyst and water to hydrolyze and condense the organic silane compound in an organic solvent. The organic metal compound is titanium (IV) n-butoxide. And other titanium compounds.

又，作為有機溶劑與單體之溶解性優異，且具有高介電常數之新穎有機絕緣體組成物，已知有如下有機絕緣體組成物，其含有i)下述式1所表示之有機/無機金屬混合物質、ii)單體及/或有機高分子、及iii)使上述成分i)及ii)溶解之溶劑。已知下述式(1)所表示之化合物係使用酸或鹼 觸媒及水使有機矽烷化合物及有機金屬化合物於有機溶劑中進行水解反應或聚縮合反應而獲得(參照專利文獻2)。 In addition, as a novel organic insulator composition having excellent solubility in organic solvents and monomers and having a high dielectric constant, the following organic insulator composition is known, which contains i) an organic / inorganic metal represented by the following formula 1 A mixed substance, ii) a monomer and / or an organic polymer, and iii) a solvent in which the above components i) and ii) are dissolved. It is known that the compound represented by the following formula (1) uses an acid or a base The catalyst and water are obtained by subjecting an organosilane compound and an organometallic compound to a hydrolysis reaction or a polycondensation reaction in an organic solvent (see Patent Document 2).

上述式中，M為金屬原子，R1、R2及R3分別獨立為碳數2~5之(甲基)丙烯醯基、(甲基)丙烯醯氧基或經環氧基取代之碳數1~10之烷基、乙烯基等，R4、R5及R6分別獨立為氫原子、碳數1~10之烷基等。 In the above formula, M is a metal atom, and R 1 , R 2 and R 3 are each independently a (meth) acrylfluorenyl group having a carbon number of 2 to 5, a (meth) acrylfluorenyl group, or an epoxy-substituted carbon. An alkyl group, a vinyl group, etc. having 1 to 10, R 4 , R 5, and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbons, and the like.

[專利文獻1]日本專利特開2005-120371號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2005-120371

[專利文獻2]日本專利特開2006-70029號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2006-70029

然而，即便使用如上述之有機絕緣體組成物而設置絕緣層，於維持與有機半導體層之接著性，且具有實用之載子遷移率之方面，仍有改良之餘地。 However, even if an insulating layer is provided using the organic insulator composition as described above, there is still room for improvement in terms of maintaining the adhesiveness with the organic semiconductor layer and having a practical carrier mobility.

本發明之目的在於提供一種維持與有機半導體層之接著性，且具有實用之載子遷移率之有機薄膜電晶體。 An object of the present invention is to provide an organic thin film transistor that maintains the adhesion with an organic semiconductor layer and has a practical carrier mobility.

本發明人為了解決上述課題而進行努力研究，結果發現，藉由在積層有特定絕緣層之基板上設置有機半導體層，可解決上述課題，從而完成本發明。 The present inventors conducted diligent research in order to solve the above-mentioned problems, and as a result, they found that the above-mentioned problems can be solved by providing an organic semiconductor layer on a substrate laminated with a specific insulating layer, thereby completing the present invention.

即，本發明包含以下態樣。 That is, the present invention includes the following aspects.

(1)一種有機薄膜電晶體，其具備由含有下述a)及b)之有機無機複合薄膜所構成之閘極絕緣層，a)式(I)所表示之有機矽化合物之縮合物、及b)電磁輻射硬化性化合物之硬化物。 (1) An organic thin film transistor comprising a gate insulating layer composed of an organic-inorganic composite film containing the following a) and b), a) a condensate of an organic silicon compound represented by formula (I), and b) Hardened products of electromagnetic radiation curable compounds.

RnSiX4-n (I) R n SiX 4-n (I)

(式中，R表示碳原子直接鍵結於Si之有機基，X表示羥基或水解性基；n表示1或2，n為2時，各R可相同亦可不同，(4-n)為2以上時，各X可相同，亦可不同) (In the formula, R represents an organic group in which a carbon atom is directly bonded to Si, X represents a hydroxyl group or a hydrolyzable group; n represents 1 or 2, and when n is 2, each R may be the same or different, and (4-n) is When 2 or more, each X may be the same or different)

(2)如上述(1)記載之有機薄膜電晶體，其中上述式(I)所表示之有機矽化合物係由有機矽化合物Si1與有機矽化合物Si2所構成，其中該有機矽化合物Si1藉由Fedors之推算法求出之R之溶解度參數SP1較藉由Fedors之推算法求出之電磁輻射硬化性化合物之溶解度參數SP2小1.6以上，該有機矽化合物Si2之上述溶解度參數SP1較上述溶解度參數SP2小未達1.6或與上述溶解度參數SP2相等或較上述溶解度參數SP2大， (2) The organic thin film transistor according to the above (1), wherein the organic silicon compound represented by the above formula (I) is composed of an organic silicon compound Si1 and an organic silicon compound Si2, and the organic silicon compound Si1 is obtained through Fedors. The solubility parameter SP1 of R obtained by the inferred algorithm is smaller than the solubility parameter SP2 of the electromagnetic radiation hardening compound obtained by the inferred algorithm of Fedors by 1.6 or more. Less than 1.6 or equal to the above solubility parameter SP2 or greater than the above solubility parameter SP2,

上述有機矽化合物Si1與上述有機矽化合物Si2之莫耳比Si1：Si2為5：5~10：0。 The molar ratio Si1: Si2 of the organic silicon compound Si1 and the organic silicon compound Si2 is 5: 5-10: 0.

(3)如上述(1)記載之有機薄膜電晶體，其中上述式(I)所表示之 有機矽化合物係由式(I-1)所表示之化合物、式(I-2)所表示之化合物、及若存在則為該等之水解縮合物所構成， R1 nSiX4-n．．．(I-1) (3) The organic thin film transistor according to the above (1), wherein the organic silicon compound represented by the formula (I) is a compound represented by the formula (I-1) or a compound represented by the formula (I-2) And, if present, it is composed of these hydrolyzed condensates, R 1 n SiX 4-n . ． ． (I-1)

(式中，n表示1或2，n為2時，R1相互可相同亦可不同，R1為有機基，R1中之1個以上表示含乙烯基之烴基；X表示羥基或水解性基，相互可相同，亦可不同) (In the formula, n represents 1 or 2, and when n is 2, R 1 may be the same as or different from each other, R 1 is an organic group, and one or more of R 1 represents a vinyl-containing hydrocarbon group; X represents a hydroxyl group or hydrolyzability Base, can be the same or different from each other)

R2 nSiX4-n．．．(I-2) R 2 n SiX 4-n . ． ． (I-2)

(式中，n表示1或2，n為2時，R2可相同亦可不同，R2表示碳原子直接鍵結於式中之Si之含乙烯基之烴基以外之有機基；X表示羥基或水解性基，相互可相同，亦可不同)， {[式(I-1)之化合物]+[若存在的話，水解縮合物中之源自式(I-1)之化合物之單元]}/{[式(I-1)之化合物]+[式(I-2)之化合物]+[若存在的話，水解縮合物中之源自式(I-1)之化合物之單元]+[若存在的話，水解縮合物中之源自式(I-2)之化合物之單元]}×100=30~100莫耳%，且 {[式(I-2)之化合物]+[若存在的話，水解縮合物中之源自式(I-2)之化合物之單元]}/{[式(I-1)之化合物]+[式(I-2)之化合物]+[若存在的話，水解縮合物中之源自式(I-1)之化合物之單元]+[若存在的話，水解縮合物中之源自式(I-2)之化合物之單元]}×100=0~70莫耳%。 (In the formula, n represents 1 or 2. When n is 2, R 2 may be the same or different. R 2 represents an organic group other than a vinyl-containing hydrocarbon group in which Si is directly bonded to carbon in the formula; X represents a hydroxyl group. Or hydrolyzable groups, which may be the same or different from each other), [[Compound of formula (I-1)] + [If present, a unit derived from a compound of formula (I-1) in a hydrolyzed condensate]} / {[Compound of formula (I-1)] + [Compound of formula (I-2)] + [If present, hydrolyzed condensate-derived unit of compound of formula (I-1)] + [if If present, the unit derived from the compound of formula (I-2) in the hydrolysis condensate]} × 100 = 30 ~ 100 mole%, and {[compound of formula (I-2)] + [if present, Unit of compound of formula (I-2) derived from hydrolyzed condensate]} / {[compound of formula (I-1)] + [compound of formula (I-2)] + [if present, hydrolytic condensation The unit derived from the compound of the formula (I-1)] + [if present, the unit derived from the compound of the formula (I-2) in the hydrolyzed condensate]} × 100 = 0 to 70 mole% .

(4)一種顯示裝置，其具備上述(1)至(3)中任一項記 載之有機薄膜電晶體。 (4) A display device including any one of the items (1) to (3) Organic thin film transistor.

(5)一種感測器，其具備上述(1)至(3)中任一項記載之有機薄膜電晶體。 (5) A sensor including the organic thin film transistor described in any one of (1) to (3) above.

(6)一種電子標籤，其具有上述(1)至(3)中任一項記載之有機薄膜電晶體。 (6) An electronic tag having the organic thin film transistor according to any one of (1) to (3) above.

本發明之有機薄膜電晶體維持與有機半導體層之接著性，且顯示出實用之載子遷移率。 The organic thin film transistor of the present invention maintains adhesiveness with an organic semiconductor layer, and shows a practical carrier mobility.

圖1A係表示實施例1之有機薄膜電晶體中，施加有作為飽和區域之VD=-30V之源極/汲極電壓時之ID-VG之電晶體特性的圖。 FIG. 1A is a graph showing transistor characteristics of I D -V G when a source / drain voltage of V D = -30 V is applied as a saturation region in the organic thin film transistor of Example 1. FIG.

圖1B係表示實施例1之有機薄膜電晶體之傳達特性之圖。 FIG. 1B is a diagram showing transmission characteristics of the organic thin film transistor of Example 1. FIG.

圖2A係表示實施例1之有機薄膜電晶體之相對於閘極電壓之飽和區域之載子遷移率(場效遷移率)的圖。 FIG. 2A is a graph showing the carrier mobility (field-effect mobility) of the organic thin film transistor of Example 1 with respect to the saturation region of the gate voltage.

圖2B係表示相對於閘極電壓之於線形區域之載子遷移率(有效遷移率)的圖。 FIG. 2B is a graph showing the carrier mobility (effective mobility) of the linear region with respect to the gate voltage.

圖3係表示實施例1之有機薄膜電晶體之輸出特性的圖。 FIG. 3 is a graph showing output characteristics of the organic thin film transistor of Example 1. FIG.

圖4A係表示實施例2之有機薄膜電晶體中，施加有作為飽和區域之VD=-30V之源極/汲極電壓時之ID-VG之電晶體特性的圖。 4A is a graph showing the transistor characteristics of I D -V G when a source / drain voltage of V D = -30 V is applied as a saturation region in the organic thin film transistor of Example 2.

圖4B係表示實施例2之有機薄膜電晶體之傳達特性的圖。 FIG. 4B is a diagram showing transmission characteristics of the organic thin film transistor of Example 2. FIG.

圖5A係表示實施例2之有機薄膜電晶體之相對於閘極電壓之飽和區域 之載子遷移率(場效遷移率)的圖。 FIG. 5A shows the saturation region of the organic thin film transistor with respect to the gate voltage of Example 2 A graph of carrier mobility (field-effect mobility).

圖5B(b)係表示相對於閘極電壓之於線形區域之載子遷移率(有效遷移率)的圖。 FIG. 5B (b) is a graph showing the carrier mobility (effective mobility) of the linear region with respect to the gate voltage.

圖6係表示實施例2之有機薄膜電晶體之輸出特性的圖。 FIG. 6 is a graph showing output characteristics of the organic thin film transistor of Example 2. FIG.

<有機薄膜電晶體> <Organic thin film transistor>

本發明之有機薄膜電晶體較佳為於基板上具備有機半導體層、與該有機半導體層接觸之源極電極及汲極電極、以及相對於上述有機半導體層隔著絕緣層而設置之閘極電極。 The organic thin film transistor of the present invention preferably includes an organic semiconductor layer on a substrate, a source electrode and a drain electrode in contact with the organic semiconductor layer, and a gate electrode provided through the insulating layer with respect to the organic semiconductor layer. .

[基板] [Substrate]

作為基板，可列舉樹脂基板。作為樹脂基板，可例示由聚對酞酸乙二酯(PET)、聚萘二甲酸乙二酯(PEN)、聚醚碸(PES)、聚醚醯亞胺、聚醚醚酮、聚苯硫、聚芳酯、聚醯亞胺、聚碳酸酯(PC)、三乙酸纖維素(TAC)、醋酸丙酸纖維素(CAP)等所構成之基板，其中較佳為由聚萘二甲酸乙二酯(PEN)、聚醯亞胺(PI)所構成之基板。基板之形狀可為膜狀、片狀、板狀等任意形狀，尤佳為膜狀。 Examples of the substrate include a resin substrate. Examples of the resin substrate include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether fluorene (PES), polyether fluorene imine, polyether ether ketone, and polyphenylene sulfide. , Polyarylate, polyimide, polycarbonate (PC), cellulose triacetate (TAC), cellulose acetate propionate (CAP) and other substrates, of which polyethylene naphthalate is preferred Ester (PEN), polyimide (PI) substrate. The shape of the substrate may be any shape such as a film shape, a sheet shape, and a plate shape, and a film shape is particularly preferred.

基板可為由未延伸膜所構成者，亦可為由延伸膜所構成者。又，可為單層膜，亦可為使兩層以上藉由層壓、塗佈等手段積層而成之積層膜。 The substrate may be composed of an unstretched film, or may be composed of an stretched film. Further, it may be a single-layer film or a laminated film in which two or more layers are laminated by means of lamination, coating, or the like.

基板之厚度並無特別限制，較佳為1~1000μm，更佳為3~500μm。 The thickness of the substrate is not particularly limited, but is preferably 1 to 1000 μm, and more preferably 3 to 500 μm.

[閘極電極、源極電極、汲極電極] [Gate electrode, source electrode, drain electrode]

形成源極電極、汲極電極及閘極電極之材料只要為導電性材料，則無特別限定，可使用鉑、金、銀、鎳、鉻、銅、鐵、錫、含銻鉛、鉭、銦、鈀、碲、錸、銥、鋁、釕、鍺、鉬、鎢、氧化錫-銻、氧化銦-錫(ITO)、摻氟氧化鋅、鋅、碳、石墨、玻璃石墨、銀漿及碳漿、鋰、鈹、鈉、鎂、鉀、鈣、鈧、鈦、錳、鋯、鎵、鈮、鈉、鈉-鉀合金、鎂、鋰、鋁、鎂/銅混合物、鎂/銀混合物、鎂/鋁混合物、鎂/銦混合物、鋁/氧化鋁混合物、鋰/鋁混合物等，尤佳為鉑、金、銀、銅、鋁、銦、ITO、碳、鉻/金/鉻之積層體。或者亦可適宜地使用利用摻雜等而提高導電率之公知之導電性聚合物例如導電性聚苯胺、導電性聚吡咯、導電性聚噻吩、聚伸乙二氧基噻吩與聚苯乙烯磺酸之錯合物等。其中，較佳為於與有機半導體層之接觸面電阻小者。 The material forming the source electrode, the drain electrode, and the gate electrode is not particularly limited as long as it is a conductive material, and platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony-containing lead, tantalum, and indium can be used. , Palladium, tellurium, osmium, iridium, aluminum, ruthenium, germanium, molybdenum, tungsten, tin oxide-antimony, indium oxide-tin (ITO), fluorine-doped zinc oxide, zinc, carbon, graphite, glass graphite, silver paste, and carbon Paste, lithium, beryllium, sodium, magnesium, potassium, calcium, hafnium, titanium, manganese, zirconium, gallium, niobium, sodium, sodium-potassium alloy, magnesium, lithium, aluminum, magnesium / copper mixture, magnesium / silver mixture, magnesium / Aluminum mixtures, magnesium / indium mixtures, aluminum / alumina mixtures, lithium / aluminum mixtures, etc., particularly preferably platinum, gold, silver, copper, aluminum, indium, ITO, carbon, chromium / gold / chromium laminates. Alternatively, well-known conductive polymers such as conductive polyaniline, conductive polypyrrole, conductive polythiophene, polyethylene dioxythiophene, and polystyrene sulfonic acid can be suitably used by doping to increase the conductivity. Complex. Among them, those having a low contact resistance with the organic semiconductor layer are preferred.

作為電極之形成方法，可列舉：使用公知之照相石印法或舉離法(lift-off method)使利用蒸鍍或濺鍍等方法以上述作為原料而形成之導電性薄膜形成為電極之方法；使用藉由熱轉印、噴墨等所形成之抗蝕劑於鋁或銅等金屬箔上進行蝕刻之方法。又，可藉由直接噴墨使導電性聚合物之溶液或分散液、導電性微粒子分散液圖案化，亦可藉由平版印刷或雷射剝蝕等而由塗佈膜所形成。進而，亦可使用利用凸版、凹版、平版、網版印刷等印刷法使含有導電性聚合物或導電性微粒子之墨水(ink)、導電性糊等進行圖案化之方法。 Examples of the method for forming the electrode include a method of forming a conductive thin film formed by using the above-mentioned method as a raw material as an electrode using a known photolithography method or lift-off method; A method of etching a metal foil such as aluminum or copper by using a resist formed by thermal transfer, inkjet, or the like is used. In addition, the solution or dispersion of the conductive polymer and the dispersion of the conductive fine particles may be patterned by direct inkjet, or may be formed from a coating film by lithography, laser ablation, or the like. Further, a method of patterning an ink (conductive ink) containing conductive polymer or conductive fine particles, conductive paste, or the like by a printing method such as letterpress, gravure, lithography, or screen printing can also be used.

作為使用於此種電極之金屬微粒子分散液之製造方法，可列舉：氣相蒸發法、濺鍍法、金屬蒸汽合成法等物理生成法，或膠體法、共 沈澱法等於液相中將金屬離子還原而生成金屬微粒子之化學生成法，較佳為藉由日本專利特開平11-76800號公報、日本專利特開平11-80647號公報、日本專利特開平11-319538號公報、日本專利特開2000-239853號公報等所揭示之膠體法、日本專利特開2001-254185號公報、日本專利特開2001-53028號公報、日本專利特開2001-35255號公報、日本專利特開2000-124157號公報、日本專利特開2000-123634號公報等所記載之氣相蒸發法所製造之金屬微粒子分散物。藉由使用該等金屬微粒子分散物而形成層後，將溶劑乾燥，進而於100~300℃、較佳為150~200℃之範圍內熱處理，使金屬微粒子熱熔合，藉此形成電極。 Examples of the method for producing the metal fine particle dispersion used for such an electrode include a physical production method such as a vapor phase evaporation method, a sputtering method, and a metal vapor synthesis method, or a colloid method and a co-polymer method. The precipitation method is equivalent to a chemical generation method in which metal ions are reduced in a liquid phase to generate metal fine particles. Preferably, the method is prepared by Japanese Patent Laid-Open No. 11-76800, Japanese Patent Laid-Open No. 11-80647, and Japanese Patent Laid-Open No. 11- Colloidal method disclosed in JP 319538, JP 2000-239853, JP JP 2001-254185, JP 2001-53028, JP 2001-35255, Dispersions of metal fine particles produced by a vapor phase evaporation method described in Japanese Patent Laid-Open No. 2000-124157, Japanese Patent Laid-Open No. 2000-123634, and the like. After forming a layer by using these metal fine particle dispersions, the solvent is dried and further heat-treated at a temperature in the range of 100 to 300 ° C, preferably 150 to 200 ° C, so that the metal fine particles are thermally fused to form an electrode.

[絕緣層] [Insulation]

絕緣層係由作為閘極絕緣膜之(A)有機無機複合薄膜所構成。 The insulating layer is composed of (A) an organic-inorganic composite thin film as a gate insulating film.

構成絕緣層之有機無機複合薄膜至少含有a)有機矽化合物之縮合物、及b)電磁輻射硬化性化合物之硬化物。 The organic-inorganic composite thin film constituting the insulating layer contains at least a) a condensate of an organic silicon compound, and b) a cured product of an electromagnetic radiation-curable compound.

《a)有機矽化合物之縮合物》 "A) Condensate of organosilicon compound"

使用於本發明之有機矽化合物由以下式(I)表示。 The organosilicon compound used in the present invention is represented by the following formula (I).

RnSiX4-n (I) R n SiX 4-n (I)

式中，R表示碳原子直接鍵結於Si之有機基，X表示羥基或水解性基。n表示1或2，n為2時，各R可相同亦可不同，(4-n)為2以上時，各X可相同，亦可不同。 In the formula, R represents an organic group in which a carbon atom is directly bonded to Si, and X represents a hydroxyl group or a hydrolyzable group. n represents 1 or 2; when n is 2, each R may be the same or different; when (4-n) is 2 or more, each X may be the same or different.

此處，作為R所表示之「碳原子直接鍵結於Si之有機基」， 可列舉亦可經取代之烴基。 Here, as the "organic group in which carbon atom is directly bonded to Si" represented by R, Examples include hydrocarbon groups which may be substituted.

作為上述「亦可經取代之烴基」之烴基，較佳為碳數1~30之烴基，例如可列舉：烷基、環烷基、環烷基烷基、烯基、環烯基、炔基、芳基、芳基烷基、芳基烯基等。 As the hydrocarbon group of the "optionally substituted hydrocarbon group", a hydrocarbon group having 1 to 30 carbon atoms is preferred, and examples thereof include an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, an alkenyl group, a cycloalkenyl group, and an alkynyl group. , Aryl, arylalkyl, arylalkenyl and the like.

又，上述「烴基」亦可具有氧原子、氮原子、或矽原子。 The "hydrocarbon group" may have an oxygen atom, a nitrogen atom, or a silicon atom.

作為烷基，較佳為碳數1~10之直鏈或支鏈之烷基，例如可列舉：甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、正戊基、異戊基、新戊基、正己基、異己基、正庚基、正辛基、正壬基、異壬基、正癸基等。進而，作為碳數超過10之長鏈之烷基，可列舉：月桂基、十三基、肉豆蔻基、十五基、棕櫚基、十七基、硬脂基(stearyl group)等。 The alkyl group is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tertiary. Butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-nonyl, isononyl, n-decyl and the like. Furthermore, examples of the long-chain alkyl group having more than 10 carbon atoms include lauryl, tridecyl, myristyl, pentadecyl, palmityl, heptadecyl, and stearyl group.

作為環烷基，較佳為碳數3~8之環烷基，例如可列舉環丙基、環丁基、環戊基、環己基、環庚基、環辛基等。 The cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

作為環烷基烷基，較佳為碳數4~20之環烷基烷基，例如可列舉環丙基甲基、環丁基甲基、環戊基甲基、環己基甲基、環庚基乙基、環辛基乙基、環癸基甲基、環十四基甲基、環十八基甲基等。 The cycloalkylalkyl group is preferably a cycloalkylalkyl group having 4 to 20 carbon atoms, and examples thereof include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, and cycloheptylethyl. Group, cyclooctylethyl, cyclodecylmethyl, cyclotetradecylmethyl, cyclooctadecylmethyl and the like.

作為烯基，較佳為碳數2~10之直鏈或支鏈之烯基，其意指於任意一處以上具有碳-碳雙鍵之碳數2~10之直鏈或支鏈之烯基，例如可列舉：乙烯基、1-丙烯-1-基、2-丙烯-1-基、1-丙烯-2-基、1-丁烯-1-基、2-丁烯-1-基、3-丁烯-1-基、1-丁烯-2-基、3-丁烯-2-基、1-戊烯-1-基、4-戊烯-1-基、1-戊烯-2-基、4-戊烯-2-基、3-甲基-1-丁烯-1-基、1-己烯-1-基、5-己烯-1-基、1-庚烯-1-基、6-庚烯-1-基、1-辛烯-1-基、7-辛烯-1 -基、1,3-丁二烯-1-基等。 As the alkenyl group, a straight or branched alkenyl group having 2 to 10 carbon atoms is preferred, which means a straight or branched chain alkenyl group having 2 to 10 carbon atoms having a carbon-carbon double bond at any one or more places. Examples include vinyl, 1-propen-1-yl, 2-propen-1-yl, 1-propen-2-yl, 1-butene-1-yl, 2-butene-1-yl , 3-butene-1-yl, 1-butene-2-yl, 3-butene-2-yl, 1-pentene-1-yl, 4-pentene-1-yl, 1-pentene 2-yl, 4-penten-2-yl, 3-methyl-1-buten-1-yl, 1-hexen-1-yl, 5-hexen-1-yl, 1-heptene -1-yl, 6-hepten-1-yl, 1-octen-1-yl, 7-octene-1 -Yl, 1,3-butadien-1-yl, and the like.

作為環烯基，較佳為碳數3~8之環烯基，其意指於任意一處以上具有碳-碳雙鍵且具有環狀部分之碳數3~8之烯基，例如可列舉：1-環戊烯-1-基、2-環戊烯-1-基、1-環己烯-1-基、2-環己烯-1-基、3-環己烯-1-基等。 The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 8 carbon atoms, which means an alkenyl group having a carbon-carbon double bond and having a cyclic portion having 3 to 8 carbon atoms at any one or more places, and examples thereof include : 1-cyclopenten-1-yl, 2-cyclopenten-1-yl, 1-cyclohexen-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl Wait.

作為炔基，較佳為碳數2~10之炔基，例如可列舉乙炔基、1-丙炔-1-基、2-丙炔-1-基、1-丁炔-1-基、3-丁炔-1-基、1-戊炔-1-基、4-戊炔-1-基、1-己炔-1-基、5-己炔-1-基、1-庚炔-1-基、1-辛炔-1-基、7-辛炔-1-基等。 The alkynyl group is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include ethynyl, 1-propyn-1-yl, 2-propyn-1-yl, 1-butyn-1-yl, and 3 -Butyn-1-yl, 1-pentyn-1-yl, 4-pentyn-1-yl, 1-hexyn-1-yl, 5-hexyn-1-yl, 1-heptyne-1 -Yl, 1-octyn-1-yl, 7-octyn-1-yl, and the like.

作為環烷基烷基，較佳為碳數3~10之環烷基與碳數1~10之烷基鍵結而成之基，例如可列舉：環丙基甲基、環丙基丙基、環丁基甲基、環戊基甲基、環戊基乙基、環己基乙基、環庚基甲基等。 The cycloalkylalkyl group is preferably a group in which a cycloalkyl group having 3 to 10 carbon atoms and an alkyl group having 1 to 10 carbon atoms are bonded, and examples thereof include cyclopropylmethyl, cyclopropylpropyl , Cyclobutylmethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylethyl, cycloheptylmethyl, and the like.

作為芳基，意指單環或多環之芳基，於多環芳基之情形時，除完全不飽和以外，亦包含部分飽和之基，具體而言，可例示苯基、萘基、薁基、茚基、二氫茚基、四氫萘基等，較佳為碳數6~10之芳基。 As an aryl group, it means a monocyclic or polycyclic aryl group. In the case of a polycyclic aryl group, in addition to being completely unsaturated, it also includes a partially saturated group. Specifically, phenyl, naphthyl, and fluorene may be exemplified. Group, indenyl, dihydroindenyl, tetrahydronaphthyl and the like, and preferably an aryl group having 6 to 10 carbon atoms.

作為芳基烷基，較佳為碳數6~10之芳基與碳數1~10之烷基鍵結而成之基，例如可列舉：苄基、苯乙基、3-苯基-正丙基、4-苯基-正丁基、5-苯基-正戊基、8-苯基-正辛基、萘基甲基等。 The arylalkyl group is preferably a group in which an aryl group having 6 to 10 carbon atoms is bonded to an alkyl group having 1 to 10 carbon atoms, and examples thereof include benzyl, phenethyl, and 3-phenyl-n- Propyl, 4-phenyl-n-butyl, 5-phenyl-n-pentyl, 8-phenyl-n-octyl, naphthylmethyl, and the like.

作為芳基烯基，較佳為碳數6~10之芳基與碳數2~10之烯基鍵結而成之基，例如可列舉：苯乙烯基、3-苯基-1-丙烯-1-基、3-苯基-2-丙烯-1-基、4-苯基-1-丁烯-1-基、4-苯基-3-丁烯-1-基、5-苯基-1-戊烯-1-基、5-苯基-4-戊烯-1一基、8-苯基 -1-辛烯-1-基、8-苯基-7-辛烯-1-基、萘基乙烯基等。 As the arylalkenyl group, an aryl group having 6 to 10 carbon atoms and an alkenyl group having 2 to 10 carbon atoms are preferably bonded, and examples thereof include styryl and 3-phenyl-1-propene- 1-yl, 3-phenyl-2-propen-1-yl, 4-phenyl-1-buten-1-yl, 4-phenyl-3-buten-1-yl, 5-phenyl- 1-pentene-1-yl, 5-phenyl-4-pentene-1 monoyl, 8-phenyl -1-octen-1-yl, 8-phenyl-7-octen-1-yl, naphthyl vinyl, and the like.

作為「具有氧原子之烴基」，可列舉：烷氧基烷基、環氧烷基、環氧丙氧基烷基等具有環氧乙烷環(環氧基)之基、丙烯醯氧基甲基、甲基丙烯醯氧基甲基等。 Examples of the "hydrocarbon group having an oxygen atom" include a group having an ethylene oxide ring (epoxy group) such as an alkoxyalkyl group, an alkylene oxide group, and a propylene oxide alkyl group, and acryloxymethyl group. Group, methacryloxymethyl and the like.

此處，作為烷氧基烷基，較佳為碳數1~6之烷氧基與碳數1~6之烷基鍵結而成之基，例如可列舉：甲氧基甲基、2-甲氧基乙基、3-乙氧基-正丙基等。 Here, the alkoxyalkyl group is preferably a group in which an alkoxy group having 1 to 6 carbon atoms is bonded to an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methoxymethyl group and a 2-methyl group. Methoxyethyl, 3-ethoxy-n-propyl and the like.

作為環氧烷基，較佳為碳數3~10之直鏈或支鏈之環氧烷基，例如可列舉：環氧丙基、環氧丙基甲基、2-環氧丙基乙基、3-環氧丙基丙基、4-環氧丙基丁基、3,4-環氧丁基、4,5-環氧戊基、5,6-環氧己基等直鏈狀之含有環氧基之烷基；β-甲基環氧丙基、β-乙基環氧丙基、β-丙基環氧丙基、2-環氧丙基丙基、2-環氧丙基丁基、3-環氧丙基丁基、2-甲基-3-環氧丙基丙基、3-甲基-2-環氧丙基丙基、3-甲基-3,4-環氧丁基、3-乙基-3,4-環氧丁基、4-甲基-4,5-環氧戊基、5-甲基-5,6-環氧己基等分枝狀之含有環氧基之烷基等。 As the alkylene oxide group, a linear or branched alkylene oxide group having 3 to 10 carbon atoms is preferred, and examples thereof include epoxypropyl group, epoxypropylmethyl group, and 2-epoxypropylethyl group. , 3-epoxypropylpropyl, 4-epoxypropylbutyl, 3,4-epoxybutyl, 4,5-epoxypentyl, 5,6-epoxyhexyl, etc. Epoxy-based alkyl groups; β-methylglycidyl, β-ethylglycidyl, β-propylglycidyl, 2-glycidylpropyl, 2-glycidylbutyl Group, 3-glycidylbutyl, 2-methyl-3-glycidylpropyl, 3-methyl-2-glycidylpropyl, 3-methyl-3,4-epoxy Butyl, 3-ethyl-3,4-epoxybutyl, 4-methyl-4,5-epoxypentyl, 5-methyl-5,6-epoxyhexyl and other branched rings Oxyalkyl and the like.

作為環氧丙氧基烷基，可列舉環氧丙氧基甲基、環氧丙氧基丙基等。 Examples of the glycidoxyalkyl group include glycidoxymethyl and glycidoxypropyl.

作為「具有氮原子之烴基」，較佳為具有-NR'2(式中，R'表示氫原子、烷基或芳基，各R'相互可相同，亦可不同)之基、或具有-N=CR"2(式中，R"表示氫原子、烷基或芳基，各R"相互可相同，亦可不同)之基，作為烷基，可列舉與上述相同者，作為芳基，可列舉苯基、萘基、蒽-1-基、菲-1-基等。 As the "hydrocarbon group having a nitrogen atom", a group having -NR ' 2 (wherein R' represents a hydrogen atom, an alkyl group, or an aryl group, and each R 'may be the same as or different from each other) or- N = CR " 2 (wherein R" represents a hydrogen atom, an alkyl group, or an aryl group, and each R "may be the same as or different from each other. Examples of the alkyl group include the same ones as the above, and aryl groups, Examples include phenyl, naphthyl, anthracen-1-yl, and phenanthrene-1-yl.

例如，作為具有-NR'2之基，可列舉：-CH2NH2基、-CH2(CH2)2NH2基、-CH2NHCH3基等。作為具有-N=CR"2之基，可列舉：-CH2N=CHCH3基、-C2N=C(CH3)2基、-CH2CH2N=CHCH3基、-CH2N=CHPh基、-CH2N=C(Ph)CH3基等。 Examples of the group having -NR ' 2 include a -CH 2 NH 2 group, a -CH 2 (CH 2 ) 2 NH 2 group, a -CH 2 NHCH 3 group, and the like. Examples of the group having -N = CR " 2 include: -CH 2 N = CHCH 3 group, -C 2 N = C (CH 3 ) 2 group, -CH 2 CH 2 N = CHCH 3 group, -CH 2 N = CHPh group, -CH 2 N = C (Ph) CH 3 group, and the like.

作為上述「亦可經取代」之取代基，例如可列舉：鹵素原子、烷基、烯基、芳基、甲基丙烯醯氧基等。作為烷基、烯基、芳基，可例示與R中相同者。 Examples of the "optionally substituted" substituent include a halogen atom, an alkyl group, an alkenyl group, an aryl group, and a methacryloxy group. Examples of the alkyl group, the alkenyl group and the aryl group are the same as those of R.

上述中，就有機無機複合薄膜之表面之無機化之觀點而言，乙烯基、具有環氧乙烷環之基、具有-NR'2之基、或具有-N=CR"2之基為較佳之基。 Among the above, from the viewpoint of the inorganicization of the surface of the organic-inorganic composite film, a vinyl group, a group having an ethylene oxide ring, a group having -NR ' 2 or a group having -N = CR " 2 Jiazhiji.

又，式(I)中，n表示1或2，尤佳為n=1者。於n為2時，各R可相同，亦可不同。又，該等可使用單獨1種，或將2種以上組合使用。 In formula (I), n represents 1 or 2, and particularly preferably n = 1. When n is 2, each R may be the same or different. These can be used alone or in combination of two or more.

式(I)中，X表示羥基或水解性基。於式(I)之(4-n)為2以上時，各X可相同，亦可不同。所謂水解性基，意指例如可於無觸媒、過量水之共存下，藉由在25℃~100℃進行加熱，被水解而生成矽烷醇基之基、或可形成矽氧烷縮合物之基，具體而言，可列舉：烷氧基、醯氧基、鹵基原子、異氰酸基、未經取代或經取代之胺基等，較佳為碳數1~4之烷氧基或碳數1~6之醯氧基。 In formula (I), X represents a hydroxyl group or a hydrolyzable group. When (4-n) in the formula (I) is 2 or more, each X may be the same or different. The hydrolyzable group means, for example, a group that can be hydrolyzed to form a silanol group by heating at 25 ° C to 100 ° C in the coexistence of a catalyst-free and excess water, or a siloxane condensate Specific examples include alkoxy, fluorenyloxy, halo, isocyanate, unsubstituted or substituted amine groups, etc., preferably alkoxy having 1 to 4 carbon atoms or A fluorenyl group having 1 to 6 carbon atoms.

作為碳數1~4之烷氧基，可列舉：甲氧基、乙氧基、正丙氧基、異丙氧基、正丁氧基、異丁氧基、第三丁氧基等，作為碳數1~6之醯氧基(其中，碳數不包括羰基之碳)，可列舉乙醯氧基、苄醯氧基等。作 為鹵素原子，可列舉：氟原子、氯原子、溴原子、碘原子等。 Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a third butoxy group. Examples of the fluorenyloxy group having 1 to 6 carbon atoms (wherein the carbon number does not include the carbon of a carbonyl group) include ethynyloxy and benzylfluorenyloxy. Make Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

再者，(A)有機無機複合薄膜所含之有機矽化合物之縮合物意指該等有機矽化合物之縮合物及/或有機矽化合物之縮合物之進一步之縮合物。 Furthermore, (A) the condensate of the organic silicon compound contained in the organic-inorganic composite film means a further condensate of the condensate of the organic silicon compound and / or the condensate of the organic silicon compound.

有機矽化合物之縮合物之摻合比率相對於(A)有機無機複合薄膜總體之固形物成分，較佳為2~98質量%，更佳為5~50質量%，進而較佳為5~30質量%。 The blending ratio of the condensate of the organic silicon compound is preferably 2 to 98% by mass, more preferably 5 to 50% by mass, and still more preferably 5 to 30% relative to the solid content of the overall organic-inorganic composite film. quality%.

作為本發明中所使用之有機矽化合物之較佳態樣，具體而言，可例示下述a-1)、a-2)、及a-3)之混合物。 As a preferable aspect of the organosilicon compound used in the present invention, specifically, a mixture of the following a-1), a-2), and a-3) can be exemplified.

a-1)式(I-1)所表示之化合物。 a-1) A compound represented by formula (I-1).

R1 nSiX4-n．．．(I-i) R 1 n SiX 4-n . ． ． (Ii)

式中，n表示1或2，n為2時，R1可相同亦可不同，R1為有機基，R1中之1個以上表示含乙烯基之烴基。X表示羥基或水解性基，相互可相同，亦可不同。此處，作為有機基、水解性基，較佳可例示式(I)所記載者。作為含乙烯基之烴基，可例示：乙烯基、烯丙基、3-丁烯基、4-己烯基等烯基(較佳為C2-C8烯基)等。 In the formula, n represents 1 or 2, and when n is 2, R 1 may be the same or different, R 1 is an organic group, and one or more of R 1 represents a vinyl-containing hydrocarbon group. X represents a hydroxyl group or a hydrolyzable group, and may be the same as or different from each other. Here, as the organic group and the hydrolyzable group, those described in Formula (I) are preferably exemplified. Examples of the vinyl-containing hydrocarbon group include an alkenyl group (preferably a C2-C8 alkenyl group) such as a vinyl group, an allyl group, a 3-butenyl group, and a 4-hexenyl group.

a-2)式(I-2)所表示之化合物。 a-2) A compound represented by the formula (I-2).

R2 nSiX4-n．．．(I-2) R 2 n SiX 4-n . ． ． (I-2)

式中，n表示1或2，n為2時，R2可相同亦可不同，R2表 示碳原子直接鍵結於式中之Si之含乙烯基之烴基以外之有機基。X表示羥基或水解性基，相互可相同，亦可不同。此處，作為含乙烯基之烴基以外之有機基，可例示自式(I)所記載者中除去烯基或芳基烯基等含乙烯基之有機基者。作為水解性基，可例示式(I)所記載者。 In the formula, n represents 1 or 2, and when n is 2, R 2 may be the same or different, and R 2 represents an organic group other than the vinyl-containing hydrocarbon group of the carbon atom directly bonded to Si in the formula. X represents a hydroxyl group or a hydrolyzable group, and may be the same as or different from each other. Here, examples of the organic group other than the vinyl-containing hydrocarbon group include those in which a vinyl-containing organic group such as an alkenyl group or an arylalkenyl group is removed from those described in formula (I). Examples of the hydrolyzable group include those described in formula (I).

a-3)若存在的話，該等之水解縮合物。 a-3) If present, such hydrolyzed condensates.

式(I-2)所表示之化合物及將其作為單元而含有之水解縮合物亦可未必存在。所謂水解縮合物係化合物彼此水解縮合而形成有矽氧烷鍵結之二聚物等，可為僅式(I-1)或式(I-2)之化合物進行水解縮合而成者，亦可為式(I-1)之化合物及式(I-2)之化合物進行水解縮合而成者，亦可為該等2種以上混合存在。 The compound represented by formula (I-2) and the hydrolyzed condensate contained as a unit may not necessarily exist. The hydrolyzed condensate-based compounds are hydrolyzed and condensed to form a dimer having a siloxane bond, or the like, and may be obtained by hydrolyzing and condensing only the compound of the formula (I-1) or the formula (I-2). It is obtained by hydrolyzing and condensing the compound of the formula (I-1) and the compound of the formula (I-2), and may also exist in a mixture of two or more of these.

{[式(I-1)之化合物]+[若存在的話，水解縮合物中之源自式(I-1)之化合物之單元]}/{[式(I-1)之化合物]+[式(I-2)之化合物]+[若存在的話，水解縮合物中之源自式(I-1)之化合物之單元]+[若存在的話，水解縮合物中之源自式(I-2)之化合物之單元]}×100較佳為30~100莫耳%，更佳為30~95莫耳%。 {[Compound of Formula (I-1)] + [If present, hydrolyzed condensate-derived unit of compound of Formula (I-1)]} / {[Compound of Formula (I-1)] + [ Compound of formula (I-2)] + [If present, unit derived from compound of formula (I-1) in hydrolyzed condensate] + [If present, derived from formula (I- 2) The unit of the compound]} × 100 is preferably 30 to 100 mole%, more preferably 30 to 95 mole%.

另一方面，{[式(I-2)之化合物]+[若存在的話，水解縮合物中之源自式(I-2)之化合物之單元]}/{[式(I-1)之化合物]+[式(I-2)之化合物]+[若存在的話，水解縮合物中之源自式(I-1)之化合物之單元]+[若存在的話，水解縮合物中之源自式(I-2)之化合物之單元]}×100較佳為0~70莫耳%，更佳為5~70莫耳%。 On the other hand, {[compound of formula (I-2)] + [if present, hydrolyzed condensate-derived unit of compound of formula (I-2)]} / {[of formula (I-1) Compound] + [compound of formula (I-2)] + [if present, unit derived from compound of formula (I-1) in hydrolyzed condensate] + [if present, derived from hydrolyzed condensate The unit of the compound of formula (I-2)]} 100 is preferably 0 to 70 mole%, more preferably 5 to 70 mole%.

又，水解縮合物之平均粒徑較佳為2nm~100nm，更佳為5nm~30nm。若平均粒徑大於100nm，則膜白濁，溶液變得不穩定，而變得容易凝膠化。 若平均粒徑小於2nm，則有對塗膜性產生影響之情形。 The average particle diameter of the hydrolyzed condensate is preferably 2 nm to 100 nm, and more preferably 5 nm to 30 nm. When the average particle diameter is larger than 100 nm, the film becomes cloudy, the solution becomes unstable, and gelation becomes easy. If the average particle diameter is less than 2 nm, the film properties may be affected.

該等可單獨使用1種，或者亦可將2種以上組合使用。 These can be used individually by 1 type or in combination of 2 or more types.

於將有機矽化合物組合使用之情形時，例如，可較佳地例示乙烯基三甲氧基矽烷與3-甲基丙烯醯氧基丙基三甲氧基矽烷之組合、乙烯基三甲氧基矽烷與3-環氧丙氧基丙基三甲氧基矽烷之組合。 In the case of using an organosilicon compound in combination, for example, a combination of vinyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane and 3 -A combination of glycidoxypropyltrimethoxysilane.

又，作為式(I-1)所表示之有機矽化合物，R1之碳數為3以下之有機矽化合物摻合30莫耳%以上，更佳為50~100莫耳%，更佳為R1之碳數為4以上之有機矽化合物摻合70莫耳%以下，更佳為0~50莫耳%。 In addition, as the organosilicon compound represented by the formula (I-1), an organosilicon compound having a carbon number of 3 or less of R 1 is blended with 30 mol% or more, more preferably 50 to 100 mol%, and even more preferably R the carbon number of 1 or more of the organic silicon compound 4 blend 70 mole% or less, more preferably 0 to 50 mole%.

作為本發明中所使用之有機矽化合物之另一較佳態樣，具體而言，由藉由Fedors之推算法求出之上述R之溶解度參數SP1較藉由Fedors之推算法求出之電磁輻射硬化性化合物之溶解度參數SP2小1.6以上，較佳為小1.6~8.5，進而更佳為小1.6~7.2之有機矽化合物Si1及上述溶解度參數SP1較上述溶解度參數SP2小未達1.6或與上述溶解度參數SP2相等或較上述溶解度參數SP2大之有機矽化合物Si2所構成，上述有機矽化合物Si1與上述有機矽化合物Si2之莫耳比Si1：Si2為5：5~10：0，更佳為9：1~10：0。 As another preferable aspect of the organosilicon compound used in the present invention, specifically, the solubility parameter SP1 of the above-mentioned R obtained by the inferred algorithm of Fedors is more than the electromagnetic radiation obtained by the inferred algorithm of Fedors. The solubility parameter SP2 of the hardening compound is less than 1.6, preferably 1.6 to 8.5, and even more preferably 1.6 to 7.2. The organosilicon compound Si1 and the solubility parameter SP1 are less than 1.6 or less than the solubility parameter SP2. The parameter SP2 is composed of an organosilicon compound Si2 which is equal to or larger than the above-mentioned solubility parameter SP2. The molar ratio Si1: Si2 of the organosilicon compound Si1 and the organosilicon compound Si2 is 5: 5-10: 0, and more preferably 9: 1 ~ 10: 0.

有機矽化合物根據所使用之電磁輻射硬化性化合物之種類而異。有機矽化合物及電磁輻射硬化性化合物之溶解度參數(SP值)可基於Fedors之推算法進行計算，因此可基於預先計算出之SP值，決定有機矽化合物與電磁輻射硬化性化合物之組合。 The organosilicon compound varies depending on the type of the electromagnetic radiation-curable compound used. The solubility parameters (SP values) of organosilicon compounds and electromagnetic radiation-hardening compounds can be calculated based on Fedors' inferred algorithm. Therefore, the combination of organosilicon compounds and electromagnetic radiation-hardening compounds can be determined based on the SP value calculated in advance.

上述式(I)中，於n為2且R不同之情形時，將數值較大者之SP值設為上述SP1，而決定與電磁輻射硬化性化合物之組合。 In the above formula (I), when n is 2 and R is different, the SP value of the larger value is set to the above-mentioned SP1, and the combination with the electromagnetic radiation-curable compound is determined.

將可用於本發明之有機矽化合物之一例與SP值一起列示於以下之第1表。再者，化合物No.1~No.15相當於上述式(I-1)之化合物。 An example of the organosilicon compound that can be used in the present invention is shown in Table 1 below along with the SP value. Compounds No. 1 to No. 15 correspond to the compound of the formula (I-1).

《b)電磁輻射硬化性化合物之硬化物》 `` B) Hardened product of electromagnetic radiation hardening compound ''

使用於本發明之所謂電磁輻射硬化性化合物係具有於視需要添加之聚合起始劑之存在下藉由電磁輻射之照射而引起聚合反應之官能基的化合物或樹脂，作為所使用之電磁輻射，可使用紫外線、X射線、放射線、離子化放射線、電離性放射線(α、β、γ射線、中子射線、電子束)，較佳為 包含350nm以下之波長之光。 The so-called electromagnetic radiation-curable compound used in the present invention is a compound or resin having a functional group that causes a polymerization reaction by irradiation of electromagnetic radiation in the presence of a polymerization initiator added as needed, as the electromagnetic radiation used, Ultraviolet rays, X-rays, radiation, ionizing radiation, ionizing radiation (α, β, γ rays, neutron rays, electron beams) can be used, preferably Contains light with a wavelength below 350nm.

電磁輻射之照射例如可使用超高壓水銀燈、高壓水銀燈、低壓水銀燈、金屬鹵素燈、準分子燈、碳弧燈、氙弧燈等公知裝置而進行，作為所照射之光源，較佳為包含150~350nm之範圍之任意波長之光之光源，更佳為包含250~310nm之範圍之任意波長之光之光源。 Irradiation of electromagnetic radiation can be performed using known devices such as ultra-high-pressure mercury lamps, high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, excimer lamps, carbon arc lamps, xenon arc lamps, etc., and preferably contains 150 ~ A light source of light of any wavelength in the range of 350 nm is more preferably a light source of light of any wavelength in the range of 250 to 310 nm.

又，作為為了使有機無機複合薄膜形成用組成物充分地硬化而照射之光之照射光量，例如可列舉0.1~100J/cm2左右，若考慮膜硬化效率(照射能量與膜硬化程度之關係)，則較佳為1~10J/cm2左右，更佳為1~5J/cm2左右。 In addition, as the amount of light to be irradiated in order to sufficiently harden the composition for forming an organic-inorganic composite thin film, for example, about 0.1 to 100 J / cm 2 may be mentioned. If the film curing efficiency is considered (the relationship between the irradiation energy and the degree of film curing) , It is preferably about 1 to 10 J / cm 2 , and more preferably about 1 to 5 J / cm 2 .

作為電磁輻射硬化性化合物，可例示(甲基)丙烯酸酯系化合物、環氧系化合物、除丙烯酸酯系化合物以外之乙烯基化合物等。官能基之數量只要為1個以上，則無特別限定。將可使用於本發明之電磁輻射硬化性化合物之一例與SP值一起列示於以下之第2表。 Examples of the electromagnetic radiation-curable compound include (meth) acrylate compounds, epoxy compounds, vinyl compounds other than acrylate compounds, and the like. The number of functional groups is not particularly limited as long as it is one or more. An example of the electromagnetic radiation-curable compound that can be used in the present invention is shown in Table 2 below along with the SP value.

又，除上述化合物以外，作為上述丙烯酸酯系化合物，可使用聚胺酯(甲基)丙烯酸酯(polyurethane(meth)acrylate)、聚酯(甲基)丙烯酸酯、環氧聚(甲基)丙烯酸酯、聚醯胺(甲基)丙烯酸酯、聚丁二烯(甲基)丙烯酸酯、聚苯乙烯基(甲基)丙烯酸酯、聚碳酸酯二丙烯酸酯等。該等化合物之SP值亦取決於所含有之官能基之種類，為9~11之範圍內。 In addition to the above-mentioned compounds, as the acrylate-based compound, polyurethane (meth) acrylate, polyester (meth) acrylate, epoxy poly (meth) acrylate, Polyamide (meth) acrylate, polybutadiene (meth) acrylate, polystyrene-based (meth) acrylate, polycarbonate diacrylate, and the like. The SP value of these compounds also depends on the type of functional group contained, and is in the range of 9-11.

環氧聚(甲基)丙烯酸酯例如可藉由低分子量之雙酚型環氧樹脂或酚醛清漆環氧樹脂之環氧乙烷環與丙烯酸之酯化反應而獲得。 The epoxy poly (meth) acrylate can be obtained, for example, by an esterification reaction of an ethylene oxide ring of a low molecular weight bisphenol type epoxy resin or novolac epoxy resin with acrylic acid.

關於聚酯(甲基)丙烯酸酯，例如藉由如下方式獲得，即，將藉由多元羧 酸與多元醇之縮合而獲得之於兩末端具有羥基之聚酯低聚物之羥基利用丙烯酸進行酯化。或者，將藉由多元羧酸與烯化氧(alkylene oxide)加成而獲得之低聚物之末端之羥基利用丙烯酸進行酯化，藉此獲得。 The polyester (meth) acrylate is obtained, for example, by a polycarboxylic acid The hydroxyl groups of the polyester oligomer having hydroxyl groups at both ends obtained by the condensation of an acid and a polyol are esterified with acrylic acid. Alternatively, the terminal hydroxyl group of the oligomer obtained by the addition of a polycarboxylic acid and an alkylene oxide is obtained by esterifying an acrylic acid with acrylic acid.

胺酯(甲基)丙烯酸酯係使多元醇與二異氰酸酯進行反應而獲得之異氰酸酯化合物、與具有羥基之丙烯酸酯單體之反應生成物，作為多元醇，可列舉聚酯多元醇、聚醚多元醇、聚碳酸酯二醇。 The urethane (meth) acrylate is an isocyanate compound obtained by reacting a polyol with a diisocyanate, and a reaction product with an acrylate monomer having a hydroxyl group. Examples of the polyol include polyester polyols and polyether polyols. Alcohol, polycarbonate diol.

作為本發明所使用之胺酯(甲基)丙烯酸酯之市售品，例如可列舉：荒川化學工業股份有限公司製造之商品名：BEAMSET(註冊商標)102、502H、505A-6、510、550B、551B、575、575CB、EM-90、EM92；聖諾普科(San Nopco)股份有限公司製造之商品名：Photomer(註冊商標)6008、6210；新中村化學工業股份有限公司製造之商品名：NK Oligo U-2PPA、U-4HA、U-6HA、H-15HA、UA-32PA、U-324A、U-4H、U-6H；東亞合成股份有限公司製造之商品名：ARONIX(註冊商標)M-1100、M-1200、M-1210、M-1310、M-1600、M-1960；共榮社化學股份有限公司製造之商品名：AH-600、AT606、UA-306H；日本化藥股份有限公司製造之商品名：Kayarad(註冊商標)UX-2201、UX-2301、UX-3204、UX-3301、UX-4101、UX-6101、UX-7101；日本合成化學工業股份有限公司製造之商品名：紫光(註冊商標)UV-1700B、UV-3000B、UV-6100B、UV-6300B、UV-7000、UV-7600B、UV-2010B；根上工業股份有限公司製造之商品名：Art resin(註冊商標)UN-1255、UN-5200、HDP-4T、HMP-2、UN-901T、UN-3320HA、UN-3320HB、UN-3320HC、UN-3320HS、H-61、HDP-M20；Daicel-UCB股份有限公司製造之商品 名：Ebecryl(註冊商標)I6700、204、205、220、254、1259、1290K、1748、2002、2220、4833、4842、4866、5129、6602、8301等。 As a commercially available product of the amine ester (meth) acrylate used in the present invention, for example, a trade name manufactured by Arakawa Chemical Industry Co., Ltd .: BEAMSET (registered trademark) 102, 502H, 505A-6, 510, 550B , 551B, 575, 575CB, EM-90, EM92; Trade names made by San Nopco Co., Ltd .: Photomer (registered trademark) 6008, 6210; Trade names made by Shin Nakamura Chemical Industry Co., Ltd .: NK Oligo U-2PPA, U-4HA, U-6HA, H-15HA, UA-32PA, U-324A, U-4H, U-6H; Trade name manufactured by East Asia Synthesis Co., Ltd .: ARONIX (registered trademark) M -1100, M-1200, M-1210, M-1310, M-1600, M-1960; trade names manufactured by Kyoeisha Chemical Co., Ltd .: AH-600, AT606, UA-306H; Nippon Kayaku Co., Ltd. Product names manufactured by the company: Kayarad (registered trademark) UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101; product names manufactured by Japan Synthetic Chemical Industry Co., Ltd. : Ziguang (registered trademark) UV-1700B, UV-3000B, UV-6100B, UV-6300B, UV-7000, UV-7600B, UV-2010B; Genshang Industrial Co., Ltd. Product names manufactured by the company: Art resin (registered trademark) UN-1255, UN-5200, HDP-4T, HMP-2, UN-901T, UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS, H- 61. HDP-M20; Products manufactured by Daicel-UCB Co., Ltd. Name: Ebecryl (registered trademark) I6700, 204, 205, 220, 254, 1259, 1290K, 1748, 2002, 2220, 4833, 4842, 4866, 5129, 6602, 8301, etc.

該等中，較佳為聚酯(甲基)丙烯酸酯、聚胺酯(甲基)丙烯酸酯、環氧聚(甲基)丙烯酸酯，更佳為聚胺酯(甲基)丙烯酸酯。 Among these, polyester (meth) acrylate, polyurethane (meth) acrylate, and epoxy poly (meth) acrylate are preferred, and polyurethane (meth) acrylate is more preferred.

關於分子量，只要能夠溶解至有機無機複合薄膜形成用組成物中，則無限度，作為質量平均分子量，較佳為500~50,000，更佳為1,000~10,000。 The molecular weight is infinite as long as it can be dissolved in the composition for forming an organic-inorganic composite thin film. The mass average molecular weight is preferably 500 to 50,000, and more preferably 1,000 to 10,000.

關於上述有機無機複合薄膜中之上述電磁輻射硬化性化合物之硬化物之摻合量，相對於上述有機無機複合薄膜總體之固形物成分(有機矽化合物之縮合物、電磁輻射硬化性化合物之硬化物及視需要摻合之其他成分之總質量)，較佳為2~98質量%，更佳為50~95質量%，進而較佳為70~95質量%。 The blending amount of the hardened material of the electromagnetic radiation-curable compound in the organic-inorganic composite film is relative to the solid content of the entire organic-inorganic composite film (condensate of organic silicon compound, hardened material of electromagnetic radiation-curable compound) And the total mass of other ingredients blended as needed), preferably 2 to 98% by mass, more preferably 50 to 95% by mass, and even more preferably 70 to 95% by mass.

於本發明中，可混合聚合起始劑，作為此種起始劑，可列舉藉由照射電磁輻射而產生陽離子種之化合物及藉由照射電磁輻射而產生活性自由基種之化合物等公知之起始劑。 In the present invention, a polymerization initiator may be mixed, and examples of such initiators include compounds that generate cationic species by irradiating electromagnetic radiation and compounds that generate active radical species by irradiating electromagnetic radiation. Starting agent.

<(A)有機無機複合薄膜之製造法> <(A) Manufacturing method of organic-inorganic composite film>

[有機無機複合薄膜形成用溶液之製備] [Preparation of solution for forming organic-inorganic composite film]

關於本發明之(A)有機無機複合薄膜之形成用溶液，除有機矽化合物、電磁輻射硬化性化合物以外，適當混合具有聚合起始劑、矽烷醇縮合觸媒能力等之金屬化合物、水及/或溶劑等而製備。 Regarding the solution for forming the (A) organic-inorganic composite thin film of the present invention, in addition to an organic silicon compound and an electromagnetic radiation hardening compound, a metal compound having a polymerization initiator, a silanol condensation catalyst ability, water, and / Or solvent.

再者，作為用作矽烷醇縮合觸媒之金屬化合物，具體而言，可例示：金屬烷氧化物、金屬螯合化合物、有機酸金屬鹽或該等之水解縮合物等，更具體而言，可例示：四異丙氧基鈦(tetraisopropoxy titanium)、二異丙氧基 雙乙醯丙酮酸鈦、或其水解縮合物等。 Further, as the metal compound used as the silanol condensation catalyst, specifically, a metal alkoxide, a metal chelate compound, a metal salt of an organic acid, or a hydrolyzed condensate thereof can be exemplified, and more specifically, Examples: tetraisopropoxy titanium, diisopropoxy titanium Titanium diacetam pyruvate, or a hydrolyzed condensate thereof.

製備方法並無特別限制，具體而言，可例示如下製備方法：將金屬螯合化合物等金屬化合物混合至溶劑中，添加特定量之水，進行(部分)水解，繼而添加有機矽化合物(部分)進行水解，另一方面，將熱或電磁輻射硬化性化合物溶解至溶劑，視需要添加聚合起始劑或硬化劑，然後將兩溶液混合等。該等四成分亦可同時混合，又，關於有機矽化合物與金屬化合物之混合方法，可列舉於將有機矽化合物與金屬化合物混合後，添加水進行(部分)水解之方法、或將使有機矽化合物及金屬化合物分別(部分)水解者混合之方法。未必需要添加水或溶劑，但較佳預先添加水製成(部分)水解物。作為特定量之水之量，亦取決於金屬化合物之種類，例如於金屬化合物為具有2個以上羥基或者水解性基之金屬化合物之情形時，相對於金屬化合物1莫耳，較佳使用0.5莫耳以上之水，更佳使用0.5~2莫耳之水。又，於金屬化合物為金屬螯合化合物或有機酸金屬鹽之情形時，相對於金屬螯合化合物或有機酸金屬鹽1莫耳，較佳使用5~100莫耳之水，更佳使用5~20莫耳之水。 The preparation method is not particularly limited. Specifically, the preparation method can be exemplified by mixing a metal compound such as a metal chelate compound into a solvent, adding a specific amount of water, performing (partial) hydrolysis, and then adding an organic silicon compound (part). Hydrolysis is performed. On the other hand, a heat or electromagnetic radiation-curable compound is dissolved in a solvent, a polymerization initiator or a hardening agent is added as necessary, and the two solutions are then mixed. These four components can also be mixed at the same time. Regarding the mixing method of the organosilicon compound and the metal compound, a method of mixing the organosilicon compound and the metal compound and adding water for (partial) hydrolysis can be cited, or the organosilicon A method in which compounds and metal compounds are separately (partially) hydrolyzed. It is not necessary to add water or a solvent, but it is preferable to add water in advance to make a (partial) hydrolysate. The specific amount of water also depends on the type of metal compound. For example, when the metal compound is a metal compound having two or more hydroxyl groups or hydrolyzable groups, it is preferable to use 0.5 mol relative to 1 mol of the metal compound. For water above ear, it is better to use 0.5 ~ 2 mole water. In addition, when the metal compound is a metal chelate compound or a metal salt of an organic acid, it is preferable to use 5 to 100 mols of water, more preferably 5 to 100 mols of water relative to the metal chelate compound or the metal salt of an organic acid. 20 moles of water.

作為a)有機矽化合物之縮合物，亦可使用利用公知之矽烷醇縮合觸媒將有機矽化合物(部分)水解而成者。 As a) condensate of an organosilicon compound, the organosilicon compound (partially) hydrolyzed by a well-known silanol condensation catalyst can also be used.

作為有機無機複合薄膜形成用組成物，除上述各成分以外，較佳含有水及/或溶劑等。 The composition for forming an organic-inorganic composite thin film preferably contains water and / or a solvent and the like in addition to the above components.

作為所使用之溶劑，並無特別限制，例如可列舉：苯、甲苯、二甲苯等芳香族烴類；己烷、辛烷等脂肪族烴類；環己烷、環戊烷等脂環族烴類；丙酮、甲基乙基酮、甲基異丁基酮、環己酮等酮類；四氫呋喃、二烷等 醚類；乙酸乙酯、乙酸丁酯等酯類；N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等醯胺類；二甲基亞碸等亞碸類；甲醇、乙醇等醇類；乙二醇單甲醚、乙二醇單甲醚乙酸酯等多元醇衍生物類等。該等溶劑可單獨使用1種，或者組合2種以上使用。 The solvent to be used is not particularly limited, and examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane and octane; and alicyclic hydrocarbons such as cyclohexane and cyclopentane. Ketones; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; tetrahydrofuran, two Ethers such as alkane; Esters such as ethyl acetate and butyl acetate; Amines such as N, N-dimethylformamide, N, N-dimethylacetamide; and other fluorenes such as dimethylene Alcohols such as methanol and ethanol; polyol derivatives such as ethylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate. These solvents can be used singly or in combination of two or more kinds.

作為矽烷醇縮合觸媒，除上述金屬化合物以外，可列舉酸、鹼等。 Examples of the silanol condensation catalyst include, in addition to the above metal compounds, acids, bases, and the like.

作為酸，可列舉有機酸、無機酸，具體而言，例如作為有機酸，可列舉：乙酸、甲酸、草酸、碳酸、酞酸、三氟乙酸、對甲苯磺酸、甲磺酸等，作為無機酸，可列舉：鹽酸、硝酸、硼酸、氟硼酸等。 Examples of the acid include organic acids and inorganic acids. Specifically, examples of the organic acid include acetic acid, formic acid, oxalic acid, carbonic acid, phthalic acid, trifluoroacetic acid, p-toluenesulfonic acid, and methanesulfonic acid. Examples of the acid include hydrochloric acid, nitric acid, boric acid, and fluoboric acid.

此處，具體而言，藉由光照射產生酸之光酸產生劑亦包括六氟磷酸二苯基錪鎓、六氟磷酸三苯基鏻等。 Here, specifically, a photoacid generator that generates an acid by light irradiation also includes diphenylphosphonium hexafluorophosphate, triphenylphosphonium hexafluorophosphate, and the like.

作為鹼，可列舉：四甲基胍、四甲基胍基丙基三甲氧基矽烷等強鹼類；有機胺類、有機胺之羧酸中和鹽、四級銨鹽等。 Examples of the base include strong bases such as tetramethylguanidine and tetramethylguanidinopropyltrimethoxysilane; organic amines, carboxylic acid neutralization salts of organic amines, and quaternary ammonium salts.

作為本發明之有機無機複合薄膜形成用溶液中之固形物成分，較佳為1~98質量%，更佳為10~60質量%，進而較佳為15~45質量%。 As a solid component in the solution for forming an organic-inorganic composite film of the present invention, it is preferably 1 to 98% by mass, more preferably 10 to 60% by mass, and even more preferably 15 to 45% by mass.

[(A)有機無機複合薄膜之製造] [(A) Manufacture of organic-inorganic composite film]

(A)有機無機複合薄膜可藉由經過將上述有機無機複合薄膜形成用溶液塗佈於樹脂基板上，進行乾燥及/或加熱之步驟；實施電漿處理或者UV臭氧處理之步驟而製造。 (A) The organic-inorganic composite film can be produced by applying the above-mentioned solution for forming an organic-inorganic composite film on a resin substrate, drying and / or heating, and performing a plasma treatment or UV ozone treatment.

關於(A)有機無機複合薄膜，較佳為藉由ESCA分析所測定之距表面10nm之深度之碳原子濃度較距表面100nm之深度之碳原子濃 度少20%以上之膜。 Regarding (A) the organic-inorganic composite film, it is preferable that the carbon atom concentration at a depth of 10 nm from the surface as measured by ESCA analysis is higher than the carbon atom concentration at a depth of 100 nm from the surface. 20% less film.

此處，所謂「碳原子濃度」，意指於將(總金屬原子+氧原子+碳原子)設為100%時之碳原子之莫耳濃度。其他元素之濃度亦相同。 Here, the "carbon atom concentration" means the molar concentration of carbon atoms when (total metal atom + oxygen atom + carbon atom) is set to 100%. The concentrations of other elements are also the same.

作為有機無機複合薄膜形成用溶液之塗佈方法，可使用公知之塗佈方法，例如可列舉浸漬法、噴霧法、棒式塗佈法、輥塗法、旋轉塗佈法、簾塗佈法、凹版印刷法、絲網印刷法、噴墨法等。又，作為所形成之膜厚，並無特別限制，例如為0.1~20μm左右。 As a method for applying the solution for forming an organic-inorganic composite film, a known coating method can be used, and examples thereof include a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, Gravure printing method, screen printing method, inkjet method, and the like. The thickness of the formed film is not particularly limited, and is, for example, about 0.1 to 20 μm.

作為塗佈有機無機複合薄膜形成用溶液所形成之膜之乾燥、加熱處理，例如較佳於40~200℃進行0.5~120分鐘左右，更佳於60~160℃進行1~60分鐘左右，進而較佳於60~120℃進行1~60分鐘左右。 The drying and heating treatment of the film formed by applying the solution for forming an organic-inorganic composite thin film is preferably performed at 40 to 200 ° C for about 0.5 to 120 minutes, more preferably 60 to 160 ° C for about 1 to 60 minutes, and further It is preferably performed at 60 to 120 ° C for about 1 to 60 minutes.

絕緣層由上述構成所構成作為閘極絕緣膜。因此，於有機薄膜電晶體中，絕緣層與有機半導體層之親和性提高，變得可抑制漏電流。有機薄膜電晶體具有實用之載子遷移率。 The insulating layer is composed of the above-mentioned structure as a gate insulating film. Therefore, in the organic thin film transistor, the affinity between the insulating layer and the organic semiconductor layer is improved, and leakage current can be suppressed. Organic thin film transistors have practical carrier mobility.

[有機半導體層] [Organic semiconductor layer]

作為構成有機薄膜電晶體之有機半導體層之材料，可使用π共軛系材料，例如可使用聚吡咯、聚(N-取代吡咯)、聚(3-取代吡咯)、聚(3,4-二取代吡咯)等聚吡咯類；聚噻吩、聚(3-取代噻吩)、聚(3,4-二取代噻吩)、聚苯并噻吩等聚噻吩類、聚異苯并噻吩等聚異苯并噻吩類、聚伸噻吩乙炔等聚伸噻吩乙炔類；聚(對苯乙炔)等聚(對苯乙炔)類、聚苯胺、聚(N-取代苯胺)、聚(3-取代苯胺)、聚(2,3-取代苯胺)等聚苯胺類、聚乙炔等聚乙炔類；聚二乙炔等聚二乙炔類、聚薁等聚薁類、聚芘等聚芘類、聚咔唑、聚(N-取代咔唑)等聚咔唑類、聚硒吩等聚硒吩類；聚呋喃、聚苯并呋喃等聚呋喃 類；聚(對苯)等聚(對苯)類；聚吲哚等聚吲哚類、聚嗒等聚嗒類；稠四苯、稠五苯、稠六苯、稠七苯、二苯并稠五苯、四苯并稠五苯、芘、二苯并芘、、苝、蔻、特銳烯(terrylene)、卵苯、誇特銳烯(quaterrylene)、循環蒽(circumanthracene)等多并苯類；將多并苯類之碳之一部分取代為N、S、O等原子、羰基等官能基之衍生物(三苯并二、三苯并二噻、稠六苯-6,15-醌等)；聚乙烯基咔唑、聚苯硫、聚乙烯硫(polyvinylene sulfide)等聚合物；日本專利特開平11-195790號公報所記載之多環縮合體等。 As the material of the organic semiconductor layer constituting the organic thin film transistor, a π-conjugated material can be used. For example, polypyrrole, poly (N-substituted pyrrole), poly (3-substituted pyrrole), poly (3,4-di Polypyrroles such as substituted pyrrole); polythiophene, poly (3-substituted thiophene), poly (3,4-disubstituted thiophene), polythiophene such as polybenzothiophene, polyisobenzothiophene such as polyisobenzothiophene And poly (p-phenylene acetylene) and other poly (p-phenylene acetylene), polyaniline, poly (N-substituted aniline), poly (3-substituted aniline), poly (2 , 3-substituted aniline) and other polyanilines, polyacetylene and other polyacetylenes; polydiacetylene and other polydiacetylenes, polyfluorene and other polyfluorenes, polyfluorene and other polyfluorenes, polycarbazole, and poly (N-substituted Polycarbazoles such as carbazole), polyselenols such as polyselenophene; polyfurans such as polyfuran and polybenzofuran; poly (p-phenylene) such as poly (p-phenylene); polyindoles such as polyindole Class Wait Class; thick tetrabenzene, thick pentabenzene, thick hexabenzene, thick heptabenzene, dibenzo thick pentabenzene, tetrabenzo thick pentabenzene, pyrene, dibenzofluorene, Polyacenes such as sulfonium, hydrazone, terrylene, ovene, quaterrylene, circumanthracene, etc .; part of the carbons of the polyacenes are replaced by N, S, O Derivatives of functional groups such as isoatoms and carbonyls (tribenzobis Tribenzodithia , Polyhexaphenyl-6,15-quinone, etc.); polymers such as polyvinyl carbazole, polyphenylene sulfide, and polyvinyl sulfide; polycyclic condensates described in Japanese Patent Laid-Open No. 11-195790 Wait.

又，亦可較佳地使用與該等聚合物具有相同重複單元之例如作為噻吩六聚物之α-六噻吩α,ω-二己基-α-六噻吩、α,ω-二己基-α-五噻吩(quinquetliophene)、α,ω-雙(3-丁氧基丙基)-α-六噻吩、苯乙烯苯(styrylbenzene)衍生物等低聚物。 In addition, α-hexathiophene α, ω-dihexyl-α-hexathiophene, α, ω-dihexyl-α- Oligomers such as quinquetliophene, α, ω-bis (3-butoxypropyl) -α-hexathiophene, and styrylbenzene derivatives.

進而，可列舉：銅酞青或日本專利特開平11-251601號公報所記載之氟取代銅酞青等金屬酞青類；萘1,4,5,8-四羧酸二醯亞胺、N,N'-雙(4-三氟甲基苄基)萘1,4,5,8-四羧酸二醯亞胺、以及N,N'-雙(1H,1H-全氟辛基)、N,N'-雙(1H,1H-全氟丁基)及N,N'-二辛基萘1,4,5,8-四羧酸二醯亞胺衍生物、萘2,3,6,7四羧酸二醯亞胺等萘四羧酸二醯亞胺類、及蒽2,3,6,7-四羧酸二醯亞胺等蒽四羧酸二醯亞胺類等縮合環四羧酸二醯亞胺類；C60、C70、C76、C78、C84等富勒烯類；SWNT等奈米碳管、部花青素色素類、半花青素(hemicyanine)色素類等色素等。 Further examples include metal phthalocyanines such as copper phthalocyanine or fluorine-substituted copper phthalocyanine described in Japanese Patent Application Laid-Open No. 11-251601; naphthalene 1,4,5,8-tetracarboxylic acid diamidine, N , N'-bis (4-trifluoromethylbenzyl) naphthalene 1,4,5,8-tetracarboxylic acid diamidoimine, and N, N'-bis (1H, 1H-perfluorooctyl), N, N'-bis (1H, 1H-perfluorobutyl) and N, N'-dioctylnaphthalene 1,4,5,8-tetracarboxylic acid diamidoimine derivative, naphthalene 2,3,6 Condensed rings such as naphthalenetetracarboxylic acid difluorene, such as 1,7 tetracarboxylic acid diamimine, and anthracene tetracarboxylic acid difluorene, such as anthracene 2,3,6,7-tetracarboxylic acid Dicarboxylic acid dihydrazones; C60, C70, C76, C78, C84 and other fullerenes; Nano carbon tubes such as SWNT, methocyanin pigments, hemicyanine pigments, etc. .

該等π共軛系材料之中，較佳為選自由將噻吩、伸乙烯基、伸噻吩乙炔、苯乙炔、對伸苯基、該等之取代體或該等之2種以上作為重複單元，且該重複單元之數量n為4~10之低聚物或者該重複單元之數量n 為20以上之聚合物、稠五苯等縮合多環芳香族化合物、富勒烯類、縮合環四羧酸二醯亞胺類、金屬酞青所組成之群中之至少1種。 Among these π conjugated materials, it is preferred that the π-conjugated material is selected from the group consisting of thiophene, vinylidene, thiopheneacetylene, phenylacetylene, p-phenylene, a substituent thereof, or two or more of these. And the number of repeating units n is 4 to 10 oligomers or the number of repeating units n It is at least one selected from the group consisting of polymers of 20 or more, condensed polycyclic aromatic compounds such as pentacene, fullerenes, condensed cyclotetracarboxylic acid diamidoimides, and metal phthalocyanines.

又，作為其他有機半導體材料，亦可使用四硫富瓦烯(TTF)-四氰基苯醌二甲烷(TCNQ)錯合物、雙伸乙基四硫富瓦烯(BEDTTTF)-過氯酸錯合物、BEDTTTF-碘錯合物、TCNQ-碘錯合物等有機分子錯合物。進而，亦可使用聚矽烷、聚鍺烷等σ共軛系聚合物或日本專利特開2000-260999號公報所記載之有機-無機混成材料。 In addition, as other organic semiconductor materials, tetrathiafulvalene (TTF) -tetracyanobenzoquinone dimethane (TCNQ) complex, bis-ethyltetrathiafulvalene (BEDTTTF) -perchloric acid can also be used. Organic molecular complexes such as complexes, BEDTTTF-iodine complexes, TCNQ-iodine complexes. Furthermore, a σ-conjugated polymer such as polysilane or polygermane or an organic-inorganic hybrid material described in Japanese Patent Laid-Open No. 2000-260999 can also be used.

作為有機半導體層之製作法，可列舉：真空蒸鍍法、分子束磊晶生長法、離子團束法、低能量離子束法、離子鍍敷法、CVD法、濺鍍法、電漿聚合法、電解聚合法、化學聚合法、噴塗法、旋轉塗佈法、刮刀塗佈法、浸漬法、澆鑄法、輥塗法、棒式塗佈法、模塗佈(die coat)法、或LB法等，可根據材料使用。然而，該等中，就生產性之方面而言，較佳為可使用有機半導體之溶液簡單且精密地形成薄膜之旋轉塗佈法、刮刀塗佈法、浸漬塗佈法、輥塗法、棒式塗佈法、模塗佈法、或澆鑄法等。進而，就控制構成有機半導體層之分子化合物之配向性之方面而言，較佳為作為特殊之澆鑄法之間隙澆鑄法、或邊緣澆鑄法。 Examples of the production method of the organic semiconductor layer include a vacuum evaporation method, 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, and a plasma polymerization method. , Electrolytic polymerization method, chemical polymerization method, spraying method, spin coating method, doctor blade coating method, dipping method, casting method, roll coating method, rod coating method, die coat method, or LB method Etc. can be used depending on the material. However, among these, in terms of productivity, a spin coating method, a blade coating method, a dip coating method, a roll coating method, and a rod that can easily and precisely form a thin film using a solution of an organic semiconductor are preferred. The coating method, the die coating method, or the casting method. Furthermore, in terms of controlling the orientation of the molecular compounds constituting the organic semiconductor layer, a gap casting method or an edge casting method, which is a special casting method, is preferred.

再者，亦可如Advanced Material雜誌1999年第6號、p480~483所記載般，對於稠五苯等前驅物可溶於溶劑者，對藉由塗佈形成之前驅物之膜進行熱處理，而形成目標有機材料之薄膜。 In addition, as described in Advanced Material Magazine No. 6, 1999, p480 to 483, the precursors such as thick pentabenzene can be dissolved in the solvent, and the film of the precursors formed by coating can be heat treated, and Form a thin film of the target organic material.

作為有機半導體層之膜厚，並無特別限制，所獲得之元件之特性大多會受到由有機半導體所構成之活性層之膜厚較大之影響，其膜厚根據有機半導體而異，較佳為1μm以下，尤佳為10~300nm。 The film thickness of the organic semiconductor layer is not particularly limited, and the characteristics of the obtained elements are mostly affected by the film thickness of the active layer composed of the organic semiconductor. The film thickness varies depending on the organic semiconductor, and is preferably 1 μm or less, particularly preferably 10 to 300 nm.

[摻雜劑層] [Dopant layer]

本發明之有機薄膜電晶體較佳於源極電極及汲極電極與有機半導體層之間具備摻雜劑層。作為摻雜劑層，例如亦可含有具有丙烯酸、乙醯胺、二甲基胺基、氰基、羧基、硝基等官能基之材料、或如苯并醌衍生物、四氰乙烯及四氰基苯醌二甲烷或該等之衍生物等般成為接受電子之受體之材料、或例如具有胺基、三苯基、烷基、羥基、烷氧基、苯基等官能基之材料、如苯二胺等取代胺類、蒽、苯并蒽、取代苯并蒽類、芘、取代芘、咔唑及其衍生物、四硫富瓦烯及其衍生物等般成為作為電子之供予體之施體般之材料，實施所謂摻雜處理。 The organic thin film transistor of the present invention is preferably provided with a dopant layer between the source electrode and the drain electrode and the organic semiconductor layer. The dopant layer may contain, for example, a material having a functional group such as acrylic acid, acetamide, dimethylamine group, cyano group, carboxyl group, or nitro group, or a benzoquinone derivative, tetracyanoethylene, and tetracyano Materials such as benzoquinone dimethane or derivatives thereof, which are electron acceptors, or materials having functional groups such as amine, triphenyl, alkyl, hydroxyl, alkoxy, and phenyl groups, such as Substituted amines such as phenylenediamine, anthracene, benzoanthracene, substituted benzoanthracene, fluorene, substituted fluorene, carbazole and its derivatives, tetrathiafulvalene and its derivatives, etc. have generally become electron donors The donor-like material is subjected to a so-called doping treatment.

所謂上述摻雜處理，意指將電子授予性分子(受體)或電子供予性分子(施體)作為摻雜劑而導入至該有機半導體層。因此，實施有摻雜之有機半導體層係含有上述縮合多環芳香族化合物及摻雜劑之薄膜。作為使用於本發明之摻雜劑，可採用公知者。 The above-mentioned doping treatment means that an electron-donating molecule (acceptor) or an electron-donating molecule (donor) is introduced into the organic semiconductor layer as a dopant. Therefore, the doped organic semiconductor layer is a thin film containing the above-mentioned condensed polycyclic aromatic compound and a dopant. As the dopant used in the present invention, a known one can be used.

作為摻雜劑層所使用之材料，進而可列舉三氯化鐵、TCNQ、F4TCNQ(四氟四氰基苯醌二甲烷)、富勒烯及其衍生物等，較佳為F4TCNQ。 Examples of the material used for the dopant layer include ferric chloride, TCNQ, F4TCNQ (tetrafluorotetracyanobenzoquinone dimethane), fullerene and derivatives thereof, and F4TCNQ is preferred.

[自組化單分子膜] [Self-organized monomolecular film]

又，為了於絕緣層與有機半導體層之間提高有機半導體層之電荷遷移率，較佳具備有自組化單分子膜(SAM)。又，藉由具備SAM，亦可進行閾值電壓之控制。作為用以形成SAM之成分，具體而言，可例示：十八基三氯矽烷、十八基三甲氧基矽烷、癸基三氯矽烷、癸基三甲氧基矽烷、β-苯乙基三氯矽烷、β-苯乙基三甲氧基矽烷(β-PTS)、三氯甲基矽氮烷、或烷烴磷酸、烷烴膦酸、烷烴磺酸、烷烴羧酸等。 In addition, in order to improve the charge mobility of the organic semiconductor layer between the insulating layer and the organic semiconductor layer, it is preferable to include a self-assembled monomolecular film (SAM). Moreover, by including SAM, control of the threshold voltage can also be performed. Specific examples of the component for forming the SAM include octadecyltrichlorosilane, octadecyltrimethoxysilane, decyltrichlorosilane, decyltrimethoxysilane, and β-phenethyltrichloro. Silane, β-phenethyltrimethoxysilane (β-PTS), trichloromethylsilazane, or alkane phosphoric acid, alkane phosphonic acid, alkane sulfonic acid, alkane carboxylic acid, and the like.

本發明之有機薄膜電晶體可組入至各種電子裝置而使用。例如，可在液晶顯示裝置、有機EL顯示裝置、電子紙等各種顯示裝置中用作主動驅動之驅動元件，可用作在各種感測器中使用之電晶體元件，又，可在電子標籤(IC標籤)中與電容器一併構成記憶體作為元件使用。 The organic thin film transistor of the present invention can be incorporated into various electronic devices and used. For example, it can be used as a driving element for active driving in various display devices such as liquid crystal display devices, organic EL display devices, and electronic paper. It can be used as a transistor element used in various sensors, and it can also be used in electronic tags ( IC tag) and a capacitor together with a capacitor are used as components.

[實施例] [Example]

以下，基於實施例更具體地說明本發明，但本發明不受該等實施例之任何限定。 Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

[製造例1](有機無機複合薄膜形成用溶液之製備) [Manufacturing Example 1] (Preparation of a solution for forming an organic-inorganic composite film)

將二異丙氧基雙乙醯丙酮酸鈦(日本曹達股份有限公司製造，T-50，氧化鈦換算固形物成分量：16.5重量%)30.3g溶解至Solmix(註冊商標)AP-7(Japan Alcohol Trading股份有限公司製造)58.4g後，一面攪拌一面緩慢滴加離子交換水11.3g(相對於鈦為10倍莫耳)，使其水解。1天後過濾溶液，而獲得黃色透明之氧化鈦換算濃度5重量%之氧化鈦奈米分散液[A-1]。氧化鈦之平均粒徑為4.1nm且為單分散性。 30.3 g of titanium diisopropoxybisacetamidine pyruvate (manufactured by Soda Co., Ltd., T-50, titanium oxide equivalent solid content: 16.5% by weight) was dissolved in Solmix (registered trademark) AP-7 (Japan 58.4 g of Alcohol Trading Co., Ltd., 11.3 g of ion-exchanged water (10 times mole relative to titanium) was slowly added dropwise while stirring, and hydrolyzed. After 1 day, the solution was filtered to obtain a yellow transparent titanium oxide nano-dispersion solution [A-1] having a concentration of 5 wt% in terms of titanium oxide. The titanium oxide has an average particle diameter of 4.1 nm and is monodisperse.

作為有機矽化合物，使用將乙烯基三甲氧基矽烷(信越化學工業股份有限公司製造、KBM-1003)(SP值：7.00)及3-甲基丙烯醯氧基丙基三甲氧基矽烷(信越化學工業股份有限公司製造、KBM-503)(SP值：9.48)以7/3(=乙烯基三甲氧基矽烷/3-甲基丙烯醯氧基丙基三甲氧基矽烷)之莫耳比混合之液體[B-1]。 As the organosilicon compound, vinyltrimethoxysilane (manufactured by Shin-Etsu Chemical Industry Co., Ltd., KBM-1003) (SP value: 7.00) and 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) were used. Manufactured by Industrial Co., Ltd., KBM-503) (SP value: 9.48) mixed with a molar ratio of 7/3 (= vinyltrimethoxysilane / 3-methacryloxypropyltrimethoxysilane) Liquid [B-1].

以成為元素比(Ti/Si=1/9)之方式將上述[A-1]與[B-1]混合，製作攪拌了12小時之液體[C-1]。[C-1]之固形物成分為29.2重量%。 The above-mentioned [A-1] and [B-1] were mixed so as to become an element ratio (Ti / Si = 1/9) to prepare a liquid [C-1] which was stirred for 12 hours. The solid content of [C-1] was 29.2% by weight.

作為電磁輻射硬化性化合物，以使胺酯丙烯酸酯低聚物(日本合成化 學工業股份有限公司製造、紫光UV1700B)(SP值：10~11)成為40重量%之方式溶解至甲基異丁基酮(MIBK)。使作為光聚合起始劑之1-羥基-環己基苯基酮(和光純藥工業股份有限公司製造)以相對於胺酯丙烯酸酯低聚物之固形物成分成為4重量%之方式溶解於該溶液，而製作溶液[D-1]。 As an electromagnetic radiation hardening compound, amine acrylate oligomer (1) UV1700B (SP value: 10 ~ 11) manufactured by Xue Industrial Co., Ltd. is dissolved in methyl isobutyl ketone (MIBK) so that it becomes 40% by weight. 1-Hydroxy-cyclohexylphenyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.) as a photopolymerization initiator was dissolved in the solid content of the amine acrylate oligomer to 4 wt% Solution to make a solution [D-1].

以固形物成分之比率成為10重量%/90重量%=[C-1]/[D-1]之方式，將上述[C-1]液與[D-1]溶液混合，製作有機無機複合薄膜形成用溶液[E-1]。 The above-mentioned [C-1] solution and the [D-1] solution were mixed so that the ratio of the solid components became 10% by weight / 90% by weight = [C-1] / [D-1] to prepare an organic-inorganic composite Solution for film formation [E-1].

[實施例1] [Example 1]

使用聚萘二甲酸乙二酯膜(PEN膜)作為基板。於該PEN膜上，使用愛發科(ULVAC)公司製造之真空蒸鍍機「EX-400」(真空度：1.3×10-4Pa)，依序積層厚度3nm之鉻(Cr)層、厚度20nm之金(Au)層、及厚度5nm之鉻(Cr)層，而形成閘極電極。 As the substrate, a polyethylene naphthalate film (PEN film) was used. On this PEN film, a vacuum deposition machine "EX-400" (vacuum degree: 1.3 × 10 -4 Pa) manufactured by ULVAC was used to sequentially deposit a chromium (Cr) layer and a thickness of 3 nm in thickness. A 20 nm gold (Au) layer and a 5 nm thickness chromium (Cr) layer form a gate electrode.

繼而，利用稀釋液將製造例1中所製備之有機無機複合薄膜形成溶液[E-1]稀釋至4倍，使用旋轉塗佈機(2000rpm)將該稀釋後之液體以20秒塗佈於閘極電極上，進行乾燥(熱風乾燥、80℃、3分鐘)、紫外線照射(集光型高壓水銀燈、160W/cm、燈高9.8cm、累積照射量約500mJ/cm2)，而獲得膜厚650nm之絕緣層。 Next, the organic-inorganic composite film-forming solution [E-1] prepared in Production Example 1 was diluted to 4 times with a diluent, and the diluted liquid was applied to the gate with a spin coater (2000 rpm) for 20 seconds. The electrode was dried (hot air drying, 80 ° C, 3 minutes), and irradiated with ultraviolet rays (light-collecting high-pressure mercury lamp, 160 W / cm, lamp height 9.8 cm, and cumulative irradiation dose of about 500 mJ / cm 2 ) to obtain a film thickness of 650 nm. The insulation layer.

繼而，將於閘極電極上形成有絕緣層之PEN膜切出2.5×2.5cm2。 Then, a 2.5 × 2.5 cm 2 PEN film having an insulating layer formed on the gate electrode was cut out.

其次，依據本發明人等所開發出之塗佈法(邊緣澆鑄：Apple.Phys.Exp.2，111501(2009))，形成有機半導體層。即，於上述切出之PEN膜上放置有溶液保持用之矽基板之碎片(以下亦稱為「溶液保持構造」)。一面使基板傾斜，一面使有機半導體溶液(Pi-crystal公司製造，C10-DNBDT) 以75℃垂滴至溶液保持構造之邊緣。隨著溶劑之蒸發，結晶一面生長一面貼附於基板，以數分鐘結束結晶生長。於該狀態下，於減壓下以室溫放置1小時，進而於減壓下以100℃放置8小時，使結晶膜完全地乾燥(膜厚：10~100nm)。 Next, an organic semiconductor layer was formed according to a coating method (edge casting: Apple. Phys. Exp. 2, 111501 (2009)) developed by the present inventors. That is, pieces of a silicon substrate for solution holding (hereinafter also referred to as a "solution holding structure") are placed on the cut PEN film. The substrate is tilted while the organic semiconductor solution (C10-DNBDT manufactured by Pi-crystal Corporation) is tilted. Drop at 75 ° C to the edge of the solution holding structure. As the solvent evaporates, the crystal grows and attaches to the substrate while growing, ending the crystal growth in a few minutes. In this state, the crystal film was completely dried (film thickness: 10 to 100 nm) by being left at room temperature under reduced pressure for 1 hour and then at 100 ° C. for 8 hours under reduced pressure.

為了於該有機半導體層上製作源極-汲極電極，使用通道(L：100μm，W：2000μm)之陰影遮罩，形成由F4-TCNQ所構成之厚度1nm之摻雜劑層後，以40nm之厚度蒸鍍金，而製作底部閘極-頂部接點型之有機薄膜電晶體。 In order to fabricate a source-drain electrode on the organic semiconductor layer, a shadow mask of a channel (L: 100 μm, W: 2000 μm) was used to form a dopant layer made of F4-TCNQ with a thickness of 1 nm, followed by 40 nm Gold is vapor-deposited to form a bottom gate-top contact type organic thin film transistor.

針對所製作之有機薄膜電晶體，使用半導體參數分析儀(型號「keithley 4200」、凱斯雷儀器股份有限公司製造)測定了傳輸特性。 Regarding the produced organic thin film transistor, the transmission characteristics were measured using a semiconductor parameter analyzer (model "keithley 4200", manufactured by Keithley Instrument Co., Ltd.).

圖1A係表示實施例1之有機薄膜電晶體之飽和區域之結果，圖1B係表示實施例1之有機薄膜電晶體之線形區域之結果。 FIG. 1A shows the results of the saturated region of the organic thin film transistor of Example 1, and FIG. 1B shows the results of the linear region of the organic thin film transistor of Example 1. FIG.

根據圖1A之結果，使用下述式(1)，算出實施例1之有機薄膜電晶體之飽和區域之載子遷移率及閾值電壓。 Based on the results of FIG. 1A, the carrier mobility and the threshold voltage of the saturation region of the organic thin film transistor of Example 1 were calculated using the following formula (1).

此處，ID為汲極電流，W為通道之寬度，L為通道之長度，μ為載子遷移率，COX為閘極絕緣膜之每單元面積之電容，VG為閘極電壓，VT為閾值電壓。 Here, I D is the drain current, W is the width of the channel, L is the length of the channel, μ is the carrier mobility, C OX is the capacitance per cell area of the gate insulating film, and V G is the gate voltage. V T is the threshold voltage.

汲極電壓(VD)設為-30V，使閘極電壓(VG)於20V~-30V變化，測定遷移率。於飽和區域，獲得了5.2cm2/Vs之載子遷移率。閾值電壓為 1.9V。 The drain voltage (V D ) was set to -30V, the gate voltage (V G ) was changed from 20V to -30V, and the mobility was measured. In the saturation region, a carrier mobility of 5.2 cm 2 / Vs was obtained. The threshold voltage is 1.9V.

根據圖1B之結果，使用下述式(2)，算出實施例1之有機薄膜電晶體之線形區域之載子遷移率及閾值電壓。 Based on the results of FIG. 1B, the carrier mobility and the threshold voltage of the linear region of the organic thin film transistor of Example 1 were calculated using the following formula (2).

汲極電壓(VD)設為-1V，使閘極電壓(VG)於20V~-30V變化，測定了遷移率。於線形區域，獲得了4.5cm2/Vs之載子遷移率。閾值電壓為-4.3V。 The drain voltage (V D ) was set to -1 V, and the gate voltage (V G ) was changed from 20 V to -30 V, and the mobility was measured. In the linear region, a carrier mobility of 4.5 cm 2 / Vs was obtained. The threshold voltage is -4.3V.

又，將載子遷移率相對於由上述式(1)及(2)所求出之閘極電壓之變化示於圖2A及圖2B。圖2A為實施例1之有機薄膜電晶體之飽和區域之載子遷移率(場效遷移率)，圖2B為實施例1之有機薄膜電晶體於線形區域之載子遷移率(有效遷移率)。由圖2A及圖2B確認，相對於閘極電壓，顯示出有實效之載子遷移率。 In addition, changes in the carrier mobility with respect to the gate voltages obtained from the above formulas (1) and (2) are shown in FIGS. 2A and 2B. FIG. 2A is the carrier mobility (field-effect mobility) of the saturated region of the organic thin-film transistor of Example 1, and FIG. 2B is the carrier mobility (effective mobility) of the organic thin-film transistor of Example 1 in a linear region . It is confirmed from FIG. 2A and FIG. 2B that the effective carrier mobility is shown with respect to the gate voltage.

又，圖3表示實施例1之有機薄膜電晶體之輸出特性。汲極電流(ID)與閘極電壓(VG)、汲極電流(ID)與汲極電壓(VD)均顯示出明確之相關關係，確認了實施例1之有機電晶體顯示出優異之特性。 FIG. 3 shows the output characteristics of the organic thin film transistor of Example 1. The drain current (I D ) and the gate voltage (V G ), the drain current (I D ) and the drain voltage (V D ) all showed a clear correlation, and it was confirmed that the organic transistor of Example 1 showed that Excellent characteristics.

[實施例2] [Example 2]

關於實施例2，就於在形成有閘極電極及絕緣層之PEN膜上形成有機半導體層之前，於絕緣層上形成β-苯乙基三氯矽烷(β-PTS)(信越化學製造之LP-1990)之自組化單分子膜之方面而言，與實施例1不同。關於自組化單分子膜，使用UV臭氧清洗裝置(SEN LIGHTS公司製造)對形 成有閘極電極及絕緣層之PEN膜進行10分鐘UV臭氧清洗，進而於β-苯乙基三氯矽烷中浸漬18小時，而形成於絕緣層上。 Regarding Example 2, β-phenethyltrichlorosilane (β-PTS) was formed on the insulating layer before the organic semiconductor layer was formed on the PEN film on which the gate electrode and the insulating layer were formed. -1990) is different from Example 1 in terms of the self-assembled monomolecular film. About self-assembled monomolecular film, a UV ozone cleaning device (manufactured by SEN LIGHTS) was used. The PEN film formed with the gate electrode and the insulating layer was subjected to UV ozone cleaning for 10 minutes, and then immersed in β-phenethyltrichlorosilane for 18 hours to form on the insulating layer.

於實施例2中，藉由與實施例1相同之方法測定傳輸特性。圖4A表示實施例2之有機薄膜電晶體之飽和區域之結果，圖4B表示實施例2之有機薄膜電晶體之線形區域之結果。 In Example 2, the transmission characteristics were measured by the same method as in Example 1. FIG. 4A shows the result of the saturated region of the organic thin film transistor of Example 2, and FIG. 4B shows the result of the linear region of the organic thin film transistor of Example 2.

根據圖4A之結果，算出飽和區域之載子遷移率及閾值電壓。與實施例1同樣地，汲極電壓(VD)設為-30V，使閘極電壓(VG)於20V~-30V變化，測定了遷移率。於飽和區域，獲得了4.5cm2/Vs之載子遷移率。閾值電壓為16V。 Based on the results of FIG. 4A, the carrier mobility and the threshold voltage in the saturation region are calculated. As in Example 1, the drain voltage (V D ) was set to -30 V, and the gate voltage (V G ) was changed from 20 V to -30 V, and the mobility was measured. In the saturated region, a carrier mobility of 4.5 cm 2 / Vs was obtained. The threshold voltage is 16V.

又，根據圖4B之結果，算出線形區域之載子遷移率及閾值電壓。與實施例1同樣地，汲極電壓(VD)設為-1V，使閘極電壓(VG)於20V~-30V變化，測定了遷移率。於線形區域，獲得了4.0cm2/Vs之載子遷移率。閾值電壓為29V。可確認藉由形成自組化單分子膜，可在不較大地改變載子遷移率之情況下控制閾值電壓。 The carrier mobility and the threshold voltage of the linear region were calculated based on the results of FIG. 4B. As in Example 1, the drain voltage (V D ) was set to -1 V, and the gate voltage (V G ) was changed from 20 V to -30 V, and the mobility was measured. In the linear region, a carrier mobility of 4.0 cm 2 / Vs was obtained. The threshold voltage is 29V. It was confirmed that by forming a self-assembled monomolecular film, the threshold voltage can be controlled without greatly changing the carrier mobility.

又，與實施例1同樣地，將載子遷移率相對於由上述式(1)及(2)求出之閘極電壓之變化示於圖5A及圖5B。圖5A為實施例2之有機薄膜電晶體之飽和區域之載子遷移率(場效遷移率)，實施例2之有機薄膜電晶體之圖5B為於線形區域之載子遷移率(有效遷移率)。 In addition, as in Example 1, the change in the carrier mobility with respect to the gate voltage obtained from the above-mentioned equations (1) and (2) is shown in Figs. 5A and 5B. FIG. 5A is the carrier mobility (field-effect mobility) of the saturated region of the organic thin film transistor of Example 2. FIG. 5B is the carrier mobility (effective mobility) of the organic thin film transistor of Example 2 in the linear region ).

又，圖6表示實施例2之有機薄膜電晶體之輸出特性。汲極電流(ID)及閘極電壓(VG)、汲極電流(ID)及汲極電壓(VD)均表示明確之相關關係，確認了實施例2之有機電晶體顯示出優異之特性。 6 shows output characteristics of the organic thin film transistor of Example 2. The drain current (I D ) and the gate voltage (V G ), the drain current (I D ), and the drain voltage (V D ) all show a clear correlation, and it was confirmed that the organic transistor of Example 2 showed excellent performance. Of characteristics.

[產業上之可利用性] [Industrial availability]

本發明之有機薄膜電晶體維持與有機半導體層之接著性，且顯示出實用之載子遷移率。 The organic thin film transistor of the present invention maintains adhesiveness with an organic semiconductor layer, and shows a practical carrier mobility.

Claims (6)

一種有機薄膜電晶體，於基板上具備有機半導體層、與該有機半導體層接觸之源極電極及汲極電極、以及相對於該有機半導體層隔著絕緣層而設置之閘極電極，該絕緣層係由作為閘極絕緣膜之有機無機複合薄膜構成，該有機無機複合薄膜含有下述a)、b)及矽烷醇縮合觸媒，a)式(I)所表示之有機矽化合物之縮合物，b)電磁輻射硬化性化合物之硬化物，RnSiX4-n (I)(式中，R表示碳原子直接鍵結於Si之有機基，X表示羥基或水解性基；n表示1或2，n為2時，各R可相同亦可不同，(4-n)為2以上時，各X可相同，亦可不同)，該式(I)所表示之有機矽化合物係由式(I-1)所表示之化合物、式(I-2)所表示之化合物及若存在則為該等之水解縮合物所構成，R1 nSiX4-n．．．(I-1)(式中，R1為有機基，R1中之1個以上表示含乙烯基之烴基；n與X表示與式(I)相同之意義)R2 nSiX4-n．．．(I-2)(式中，R2表示碳原子直接鍵結於式中之Si之含乙烯基之烴基以外之有機基；n與X表示與式(I)相同之意義){[式(I-1)之化合物]+[若存在的話，水解縮合物中之源自式(I-1)之化合物之單元]}/{[式(I-1)之化合物]+[式(I-2)之化合物]+[若存在的話，水解縮合物中之源自式(I-1)之化合物之單元]+[若存在的話，水解縮合物中之源自式(I-2)之化合物之單元]}×100=30~100莫耳%，且{[式(I-2)之化合物]+[若存在的話，水解縮合物中之源自式(I-2)之化合物之單元]}/{[式(I-1)之化合物]+[式(I-2)之化合物]+[若存在的話，水解縮合物中之源自式(I-1)之化合物之單元]+[若存在的話，水解縮合物中之源自式(I-2)之化合物之單元]}×100=0~70莫耳%。An organic thin film transistor includes an organic semiconductor layer on a substrate, a source electrode and a drain electrode in contact with the organic semiconductor layer, and a gate electrode provided through the insulating layer with respect to the organic semiconductor layer. The insulating layer It is composed of an organic-inorganic composite film as a gate insulating film, and the organic-inorganic composite film contains the following a), b) and a silanol condensation catalyst, a) a condensate of an organic silicon compound represented by formula (I), b) Hardened product of electromagnetic radiation hardening compound, R n SiX 4-n (I) (where R represents an organic group in which carbon atom is directly bonded to Si, X represents a hydroxyl group or a hydrolyzable group; n represents 1 or 2 When n is 2, each R may be the same or different, and (4-n) is 2 or more, each X may be the same or different.) The organosilicon compound represented by the formula (I) is represented by the formula (I The compound represented by -1), the compound represented by formula (I-2), and the hydrolyzed condensate thereof if present, R 1 n SiX 4-n . ． ． (I-1) (In the formula, R 1 is an organic group, and one or more of R 1 represents a vinyl-containing hydrocarbon group; n and X represent the same meaning as in formula (I)) R 2 n SiX 4-n . ． ． (I-2) (In the formula, R 2 represents an organic group other than the vinyl-containing hydrocarbon group of Si in the carbon atom directly bonded to the formula; n and X have the same meanings as the formula (I)) {[Formula ( Compound of I-1)] + [If present, hydrolyzed condensate-derived unit of compound of formula (I-1)]} / {[Compound of formula (I-1)] + [Formula (I- 2) Compound] + [If present, hydrolyzed condensate-derived unit of compound of formula (I-1)] + [If present, hydrolyzed condensate-derived compound of formula (I-2) Unit]} × 100 = 30 ~ 100 mole%, and {[compound of formula (I-2)] + [if present, unit of compound derived from formula (I-2) in hydrolyzed condensate] } / {[Compound of formula (I-1)] + [compound of formula (I-2)] + [if present, unit of hydrolyzed condensate derived from compound of formula (I-1)] + [ If present, the unit derived from the compound of formula (I-2) in the hydrolysis condensate]} × 100 = 0 to 70 mole%. 如申請專利範圍第1項之有機薄膜電晶體，其中，該矽烷醇縮合觸媒為四異丙氧基鈦(tetraisopropoxy titanium)、二異丙氧基雙乙醯丙酮酸鈦，或其水解縮合物。For example, the organic thin film transistor of the first scope of the patent application, wherein the silanol condensation catalyst is tetraisopropoxy titanium, diisopropoxy diacetamidine pyruvate, or a hydrolyzed condensate thereof. . 如申請專利範圍第1項之有機薄膜電晶體，其中，該有機矽化合物為乙烯基三甲氧基矽烷與3-甲基丙烯醯氧基丙基三甲氧基矽烷之組合，或乙烯基三甲氧基矽烷與3-環氧丙氧基丙基三甲氧基矽烷之組合。For example, the organic thin film transistor of the first patent application range, wherein the organic silicon compound is a combination of vinyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane, or vinyltrimethoxy A combination of silane and 3-glycidoxypropyltrimethoxysilane. 一種顯示裝置，其具備申請專利範圍第1至3項中任一項之有機薄膜電晶體。A display device includes an organic thin film transistor according to any one of claims 1 to 3. 一種感測器，其具備申請專利範圍第1至3項中任一項之有機薄膜電晶體。A sensor includes an organic thin film transistor according to any one of claims 1 to 3. 一種電子標籤，其具有申請專利範圍第1至3項中任一項之有機薄膜電晶體。An electronic tag has an organic thin film transistor according to any one of claims 1 to 3.
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