JPWO2006033282A1 - THIN FILM TRANSISTOR AND THIN FILM TRANSISTOR ELEMENT SHEET, AND METHOD FOR PRODUCING THIN FILM TRANSISTOR AND THIN FILM TRANSISTOR ELEMENT SHEET - Google Patents

Abstract

Provided a high-performance, inexpensive thin film transistor and thin film transistor element sheet and a thin film transistor element sheet, and an electric circuit having those thin film transistors without performance variation, and a complicated, expensive, low-productivity vacuum system, etc. Providing a simple and efficient manufacturing method without using photolithography. Forming an insulating region having electrode material repellent properties on a support using an electrostatic suction ink jet apparatus having a nozzle inner diameter of 30 μm or less in a thin film transistor having at least a gate electrode, a semiconductor layer, a source electrode, and a drain electrode; Next, a flowable electrode material is supplied to the insulating region, and the flowable electrode material is divided at the insulating region, whereby the source electrode and the drain electrode are formed. A thin film transistor manufactured.

Description

  The present invention relates to a thin film transistor and a thin film transistor element sheet.

  With the widespread use of information terminals, there is an increasing need for flat panel displays as computer displays. In addition, with the progress of computerization, the information provided by paper media has increased the opportunity to be provided electronically, and as a mobile display medium that is thin, light and easy to carry, electronic paper or digital The need for paper is also increasing.

  In general, in a flat display device, a display medium is formed using an element utilizing liquid crystal, organic EL, electrophoresis, or the like. In such a display medium, a technique using an active drive element formed of a thin film transistor (TFT) as an image drive element has become mainstream in order to ensure uniformity of screen brightness, screen rewrite speed, and the like.

  Here, the TFT element is usually formed on a glass substrate, mainly a semiconductor thin film such as a-Si (amorphous silicon) or p-Si (polysilicon), or a metal thin film such as a source, drain, or gate electrode on the substrate. Manufactured by sequentially forming. The production of flat panel displays using TFTs usually requires high-precision photolithographic processes in addition to vacuum equipment such as CVD and sputtering and thin film forming processes that require high-temperature processing processes. The load is very large. Furthermore, along with the recent needs for larger display screens, their costs have become enormous.

  In recent years, research and development of organic TFT elements using organic semiconductor materials has been actively promoted as a technique to compensate for the disadvantages of conventional TFT elements (see Patent Document 1, Non-Patent Document 1, etc.). Since this organic TFT element can be manufactured by a low-temperature process, it is said that a light and hard-to-break resin substrate can be used, and further, a flexible display using a resin film as a support can be realized (non-patent) Reference 2). Further, by using an organic semiconductor material that can be manufactured by a wet process such as printing or coating under atmospheric pressure, a display with excellent productivity and a very low cost can be realized.

  In addition, an organic TFT technology using an ink jet for electrode formation has been disclosed (see, for example, Patent Document 2), and a process that does not use a vacuum system is possible, but in the channel region between the source and drain electrodes. A polyimide film is used.

These require a complicated process and are likely to increase the manufacturing cost, and the channel formation accuracy is poor and the channel length cannot be shortened. Since liquid materials are individually formed for the formation of the SD (source / drain) electrodes, they are easily short-circuited, and there is a problem that no element is formed when short-circuited.
Japanese Patent Laid-Open No. 10-190001 International Publication No. 01/47043 Pamphlet Advanced Material 2002 2002 No. 2 page 99 (Review) SID'02 Digest p57

  An object of the present invention is to provide a thin film transistor and a thin film transistor element sheet having high performance and low performance with no variation in performance, a short channel length, and an electric circuit having the thin film transistor, and making them complicated and expensive. Another object of the present invention is to provide a simple and efficient manufacturing method without using a low productivity vacuum system or photolithography.

  The inventor forms an insulating region with a material having electrode material repulsion by using an electrostatic suction type ink jet device having a nozzle inner diameter of 30 μm or less, and a source electrode formed so as to straddle the insulating region, Focusing on the fact that the width of the insulating region, which is the channel length of the TFT, can be accurately regulated by separating the drain electrode (also referred to as the SD electrode), and further, the static region that discharges extremely fine droplets to the insulating region is noted. The present invention was conceived to form with the capacity and discharge amount (drawing density) of the droplets of the electrosuction ink jet apparatus.

The above object of the present invention is achieved by the invention described in the following claims.
(Structure 1) In a thin film transistor having at least a gate electrode, a semiconductor layer, a source electrode, and a drain electrode on a support, an insulating region having an electrode material repellent property by an electrostatic suction ink jet apparatus having a nozzle inner diameter of 30 μm or less. Forming and then supplying a fluid electrode material to the insulating region, and dividing the fluid electrode material at the insulating region, thereby forming each of the source electrode and the drain electrode. Thin film transistor manufactured through the process.
(Structure 2) The thin film transistor according to structure 1, wherein the insulating region contains silicon rubber.
(Configuration 3) The thin film transistor according to Configuration 1 or 2, wherein the insulating region is formed by a step of supplying an insulating region forming material to the receiving layer.
(Configuration 4) The thin film transistor according to any one of configurations 1 to 3, wherein the source electrode and the drain electrode are formed by a step of supplying the fluid electrode material to a receiving layer.
(Structure 5) The thin film transistor according to any one of structures 1 to 4, wherein the insulating region is formed on the semiconductor layer by the step of forming the insulating region on the semiconductor layer.
(Structure 6) The thin film transistor according to any one of structures 1 to 5, wherein an intermediate layer is provided between the insulating region and the semiconductor layer.
(Structure 7) The thin film transistor according to any one of structures 1 to 6, wherein the semiconductor layer includes an organic semiconductor material.
(Structure 8) In the method for manufacturing a thin film transistor according to any one of Structures 1 to 7, a step of forming an insulating region having electrode material repulsion by the electrostatic attraction type inkjet device, and the insulating region A method for manufacturing a thin film transistor, which includes a step of forming each of a source electrode and a drain electrode by dividing a fluid electrode material supplied to the substrate by the insulating region.
(Structure 9) The method for manufacturing a thin film transistor according to Structure 8, wherein the insulating region contains silicon rubber, and the fluid electrode material is supplied to the insulating region by the electrostatic suction ink jet apparatus.
(Structure 10) The method for manufacturing a thin film transistor according to Structure 9, wherein the fluid electrode material supplied from the electrostatic suction ink jet apparatus includes a solvent or a dispersion medium containing 50% by mass or more of water.
(Configuration 11) A plurality of thin film transistor elements each having a channel region including a gate electrode, a gate insulating layer, and a semiconductor layer, a source electrode, and a drain electrode are connected to each other through a gate bus line and a source bus line. In the method of manufacturing a thin film transistor element sheet, a step of forming an insulating region having electrode material repellent property on the channel region or the support by the electrostatic suction ink jet apparatus directly or via another layer Then, the flowable electrode material is supplied directly on the channel region or on the support or through another layer, and the flowable electrode material is divided by the insulating region, so that at least the source electrode and A method for manufacturing a thin film transistor element sheet including a step of forming the drain electrode.
(Structure 12) The method for manufacturing a thin film transistor element sheet according to Structure 11, wherein the channel region intersects the gate bus line.
(Structure 13) The method for producing a thin film transistor element sheet according to Structure 11 or 12, wherein the support is a resin substrate.
(Structure 14) The drain electrode forms a pixel electrode, or the drain electrode is connected to the pixel electrode, and the pixel electrode and the source bus line are separated by the insulating region. The manufacturing method of the thin-film transistor element sheet | seat of any one of the structures 11-13.
(Structure 15) The method for producing a thin film transistor element sheet according to any one of structures 11 to 14, wherein the fluid electrode material is supplied by the electrostatic suction ink jet apparatus.
(Structure 16) The method for producing a thin film transistor element sheet according to any one of structures 11 to 15, wherein the semiconductor layer contains an organic semiconductor material.
(Structure 17) The thin film transistor element sheet according to any one of structures 11 to 16, further comprising a step of supplying a fluid electrode material to the entire surface of the sheet after forming the insulating region having electrode material repulsion. Manufacturing method.
(Structure 18) The manufacturing method of the thin-film transistor element sheet | seat of any one of the structures 11-17 manufactured while conveying the said support body.
(Configuration 19) A thin film transistor element sheet manufactured by the manufacturing method according to any one of configurations 11 to 18.

It is an example of a layer structure example of a bottom-gate thin film transistor. It is an example of a layer structure example of a top-gate thin film transistor. It is sectional drawing of the member which concerns on the recording head which has a nozzle, and a recording head. It is explanatory drawing which shows the relationship between the discharge operation of ink, and the voltage applied to ink. 6A and 6B illustrate a method for manufacturing a thin film transistor of the present invention. It is a schematic diagram which shows an example which forms an insulating area | region on an organic-semiconductor layer with the electrostatic attraction-type inkjet apparatus of this invention. It is a schematic diagram which shows an example which forms a source / drain electrode by the inkjet method. It is a schematic diagram which shows another example which forms a source / drain electrode by the inkjet method. It is explanatory drawing of the one aspect | mode of the manufacturing process of the thin-film transistor element of the thin-film transistor element sheet | seat of this invention by the inkjet method. It is an equivalent circuit diagram showing one mode of a thin film transistor element sheet in which a plurality of thin film transistor elements of the present invention are arranged. It is a schematic diagram which shows the one aspect | mode of the organic thin-film transistor which forms one pixel of the thin-film transistor element sheet | seat of this invention. It is explanatory drawing of the 1st aspect which forms an insulating area | region in the shape of a line on an element sheet | seat. It is explanatory drawing of the 2nd aspect which forms an insulating area | region in the shape of a line on an element sheet | seat. It is explanatory drawing of the 3rd aspect which forms an insulating area | region in the shape of a line on an element sheet | seat. It is explanatory drawing of the 4th aspect which forms an insulating area | region in the shape of a line on an element sheet | seat. It is a structural diagram of a thin film transistor element.

  Hereinafter, an embodiment of an organic thin film transistor which is an embodiment of the thin film transistor of the present invention will be described with reference to the drawings.

  The organic thin film transistor of the present invention is roughly classified into a bottom gate type and a top gate type. In the bottom gate type, a gate electrode is provided on a support directly or via another layer such as an undercoat layer, and then a source electrode and a drain connected by an organic semiconductor layer via a gate insulating layer It has a layer structure consisting of electrodes. The top gate type has a layer structure in which a source electrode and a drain electrode in contact with an organic semiconductor layer are provided on a support, and a gate electrode is provided thereon via a gate insulating layer.

  A specific layer structure of the organic thin film transistor of the present invention will be described with reference to FIGS. 1 (a) to 1 (c) and FIG.

  FIG. 1 illustrates an example of a layer structure of a bottom-gate thin film transistor.

  FIGS. 1A to 1C are examples of bottom gate type layer structures. In FIG. 1A, a gate electrode 2 is provided on a support 1, and a gate insulating layer 2a is provided on the gate electrode 2. FIG. On the gate insulating layer 2a, an organic semiconductor layer 3 and an insulating region 6 having electrode material repellent property (hereinafter also simply referred to as an insulating region 6) are provided, and a source electrode 5 and a drain are formed on both sides of the insulating region 6. Each electrode 4 is provided.

  Although not shown in the drawing, an undercoat layer is provided between the support 1 and the gate electrode 2, and anodization is performed before the gate insulating layer 2 a is provided on the gate electrode 2. An anodic oxide film is formed on the gate electrode 2.

  FIG. 1B shows another example of the bottom gate type layer structure. A receiving layer 7 (for example, an ink receiving layer) is provided on the organic semiconductor layer 3. In the receiving layer 7, an insulating region 6 having electrode material repellent properties and a source electrode on both sides of the insulating region 6 are provided. Except that 5 and the drain electrode 4 are provided, the configuration is the same as that shown in FIG.

  FIG. 1C shows another example of a bottom gate type layer structure. FIG. 1A shows that an organic semiconductor protective layer (also referred to as an intermediate layer) 3a is provided between the organic semiconductor layer 3 and the insulating region 6 having electrode material repulsion. It is the same configuration as the configuration. Here, the organic semiconductor protective layer 3a is provided in order to reduce the chemical and physical influence on the organic semiconductor layer from the material (not shown) forming the insulating region 6.

  FIG. 2 illustrates an example of a layer structure of a top-gate thin film transistor.

  FIG. 2 shows an example of a top gate type layer structure, in which an insulating region 6 having electrode material repellent property is provided on a support 1, and a source electrode 5 and a drain electrode 4 are provided on both sides of the insulating region 6, respectively. Next, the organic semiconductor layer 3 is provided so as to be connected to the source electrode 5 and the drain electrode 4, and the gate insulating layer 2 a and the gate electrode 2 are provided on the organic semiconductor layer 3.

  In the following, the electrode material is repelled by an ink jet apparatus (electrostatic suction type liquid ejecting apparatus) having at least a gate electrode, a semiconductor layer, a source electrode, and a drain electrode on a support, and having an inner diameter of a nozzle of 1 to 20 μm. Forming a conductive insulating region, and then supplying a fluid electrode material to the insulating region, and the fluid electrode material is divided at the insulating region, whereby the source electrode and the drain electrode A structure of each layer of a thin film transistor that is manufactured through a process of forming each will be described with reference to FIG.

  The electrostatic suction type liquid ejecting apparatus described above can also continuously eject an ink flow having a diameter substantially the same as the diameter perpendicular to the ejection direction of 1 to 400 fl droplets per droplet. Hereinafter, such an electrostatic suction type liquid discharge device having a two-pattern discharge function is also referred to as an electrostatic suction type ink jet device. In addition, this electrostatic suction type ink jet device has a smaller nozzle diameter than a normal ink jet device, can effectively use the local electric field concentration effect, secures fine droplets, and provides high-precision printing. Is possible.

  Further, in the following description, a configuration for ejecting ink as droplets will be described in order to make the explanation easy to understand. However, by using the continuous ejection function, approximately the same diameter and the same amount of ink per unit area are applied to the droplets. It is also possible to form an insulating region having electrode material repellent properties by continuous ejection.

  Compared to intermittent droplet discharge, for example, this continuous discharge has less irregularities in the shape of the edge of the ink landed when a straight line is formed, and is preferable because the width of the insulating region that is the channel length of the TFT can be regulated with high accuracy. It is.

<< Insulating region with electrode material repulsion >>
An insulating region 6 having electrode material repellent properties containing silicon rubber according to the present invention will be described.

  In the present invention, an insulating region having electrode material repulsion is a region (also referred to as a layer) having a performance of repelling an electrode material that becomes an electrode (specifically, a source electrode or a drain electrode). In the case where the thin film transistor is a bottom gate type, the insulating region is formed and formed on the (organic) semiconductor layer by the step of forming the insulating region on the semiconductor layer. Then, patterning is performed directly on the support or on another layer (such as an undercoat layer).

  In the present invention, any means can be used as a means for patterning as long as it can be patterned, but from the viewpoint of minimizing the influence on the organic semiconductor layer described later, A wet process such as printing is preferable, and an inkjet method is particularly preferable among them.

  As the ink jet method, a known ink jet such as a piezo method can be used, but from the viewpoint of drawing a fine pattern, an electrostatic suction type ink jet device that discharges extremely fine droplets is particularly preferable.

  Here, when the insulating region 6 is formed by the electrostatic suction type ink jet device, it is preferable to provide a receiving layer described later from the viewpoint of adjusting the formation region by ink ejection to an appropriate size. The droplets are absorbed and held in the receiving layer, and then dried or cured, whereby the spread of the droplets can be suppressed.

  That is, the insulating region having the electrode material repellent property is formed by supplying the insulating region forming material to the (ink) receiving layer.

(Receptive layer)
As the receiving layer to be the insulating region 6, a void type receiving layer, which will be described later and is used for a conventionally known ink jet recording medium, is preferably used.

  As the insulating region 6 (layer) having the electrode material repellent property, any insulating region 6 (layer) may be used as long as it has a performance of repelling the electrode material.

  A forming material such as a so-called waterless flat ink repellent layer may be used, or a silane coupling agent, a titanate coupling agent, a silicon polymer adhesive, or the like may be used. In addition, when an electrode material using a solvent containing water as a main component is used, an oleophilic material such as a phenol resin or an epoxy resin may be used.

  More preferably, silicon rubber or the like is used.

  The silicon rubber (layer) which is the receiving layer and the insulating region 6 having electrode material repellent properties can be appropriately selected from known ones as described in JP-A-7-164773. Two types, a condensation crosslinking type for curing a silicone rubber composition by a condensation reaction and an addition crosslinking type for curing a silicone rubber composition by an addition reaction, described in Japanese Laid-Open Patent Publication No. 10-244773 are preferably used.

  Examples of the condensation-crosslinking type silicon rubber include those containing, as essential components, a linear organopolysiloxane having hydroxyl groups at both ends and a reactive silane compound that crosslinks with the organopolysiloxane to form a silicon rubber layer.

  Condensation-crosslinking type silicon rubber is used to increase the reaction efficiency of the condensation-crosslinking reaction between the organopolysiloxane having a hydroxyl group at both ends and a reactive silane compound in order to improve the reaction efficiency of organic carboxylic acid, titanate, stannate, aluminum organic ether. In addition, a condensation catalyst such as a platinum-based catalyst can be mixed as appropriate to perform a condensation reaction and cure.

  The organopolysiloxane having hydroxyl groups at both ends, the reactive silane compound and the condensation catalyst in the silicone rubber are mixed in an amount of 80 to 98 mass by weight of the organopolysiloxane having hydroxyl groups at both ends with respect to the solid content of the total silicone rubber. %, Preferably 85-98% by mass, the reactive silane compound is usually 2-20% by mass, preferably 2-15% by mass, more preferably 2-7% by mass, and the condensation catalyst is 0.05-5% by mass. Preferably, it is 0.1-3 mass%, More preferably, it is 0.1-1 mass%.

  In addition, in order to increase the ink repellency of the silicone rubber (layer), polysiloxane other than the polyorganosiloxane having hydroxyl groups at both ends is added to the silicone rubber of the condensation crosslinking type with respect to the total solid content of the silicon rubber. 15 mass%, Preferably 3-12 mass% can be contained. Examples of the polysiloxane include Mw 10,000 to 1,000,000 polydimethylsiloxane having both ends trimethylsilylated.

  On the other hand, addition-crosslinking type silicone rubber is composed of organopolysiloxane having at least two aliphatic unsaturated groups in one molecule and crosslinked with the organopolysiloxane to form a silicon rubber layer. Examples thereof include an organopolysiloxane having at least two bonds as an essential component.

  The structure of the organopolysiloxane having at least two aliphatic unsaturated groups in one molecule may be any of a chain, a ring, and a branch, but a chain is preferable. Examples of aliphatic unsaturated groups include vinyl, allyl, butenyl, pentenyl, hexenyl and other alkenyl groups; cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl and other cycloalkenyl groups; ethynyl group And alkynyl groups such as propynyl group, butynyl group, pentynyl group and hexynyl group. Among these, an alkenyl group having an unsaturated bond at the terminal is preferable from the viewpoint of reactivity, and a vinyl group is particularly preferable. Further, the remaining substituents other than the aliphatic unsaturated group are preferably methyl groups in order to obtain good ink repellency.

  Mw of the organopolysiloxane having at least two aliphatic unsaturated groups in one molecule is usually 500 to 500,000, preferably 1,000 to 3,000,000.

  The structure of the organopolysiloxane having at least two Si—H bonds in one molecule may be any of a chain, a ring, and a branch, but a chain is preferable. The Si—H bond may be either at the end or in the middle of the siloxane skeleton, and the proportion of hydrogen atoms to the total number of substituents is usually 1 to 60%, preferably 2 to 50%. The remaining substituents other than hydrogen atoms are preferably methyl groups in order to obtain good ink repellency. The Mw of the organopolysiloxane having at least two Si-H bonds in one molecule is usually 300 to 300,000, preferably 500 to 200,000. If Mw is extremely high, sensitivity and image reproducibility are liable to be lowered.

  An addition reaction catalyst is usually used for addition reaction of an organopolysiloxane having at least two aliphatic unsaturated groups in one molecule and an organopolysiloxane having at least two Si-H bonds in one molecule. The addition reaction catalyst can be arbitrarily selected from known catalysts, but platinum-based catalysts are preferred, and one or a mixture of two or more selected from platinum group metals and platinum group compounds are used.

  Examples of the platinum group metal include platinum alone (eg, platinum black), palladium alone (eg, palladium black), and rhodium alone. Examples of platinum group compounds include chloroplatinic acid, platinum-olefin complexes, platinum-alcohol complexes, platinum-ketone complexes, platinum and vinylsiloxane complexes, tetrakis (triphenylphosphine) platinum, tetrakis (triphenylphosphine) palladium, and the like. Is exemplified. Among these, those obtained by dissolving chloroplatinic acid or a platinum-olefin complex in an alcohol solvent, a ketone solvent, an ether solvent, a hydrocarbon solvent, or the like are particularly preferable.

  The blending ratio of each composition forming the above-mentioned silicon rubber (layer) is such that the organopolysiloxane having at least two aliphatic unsaturated groups in one molecule is 80 to 98 with respect to the total solid content of the silicon rubber. % By mass, preferably 85 to 98% by mass, and 2 to 20% by mass, preferably 2 to 15% by mass of organopolysiloxane having at least two Si—H bonds in one molecule. However, it is 0.00001-10 mass%, Preferably it is 0.0001-5 mass%.

  In addition to the above-described composition, the addition-crosslinking type silicon rubber used in the present invention has the general formula (VII) described in JP-A-10-244773 for the purpose of further increasing the film strength of the silicon rubber (layer). An amino-based organosilicon compound having a hydrolyzable group represented by the formula can be added.

  The amino-based organosilicon compound is 0 to 10% by mass, preferably 0 to 5% by mass, based on the total solid content of the silicon rubber.

  In addition, a curing retarder can be added to the addition-crosslinking type silicone rubber for the purpose of preventing rapid curing of the silicon composition when the silicone rubber (layer) is applied. The curing retarder can be arbitrarily selected from generally known acetylenic alcohols, maleic acid esters, silylated products of acetylenic alcohols, silylated products of maleic acid, triallyl isocyanurate, vinyl siloxane and the like.

  Although the addition amount of this hardening retarder changes with desired hardening speeds, it is 0.0001-1.0 mass part normally with respect to the total solid of a silicone rubber.

  The film thickness of the silicon rubber (layer) used in the present invention is 0.1 to 10 μm, preferably 0.2 to 5 μm, and more preferably 0.3 to 2 μm.

  The silicon rubber composition can be dissolved in an appropriate solvent to form a solution, applied (patterned), and then dried to form a silicon rubber layer.

  Coating solvents include n-hexane, cyclohexane, petroleum ether, aliphatic hydrocarbon solvent Exxon Chemical Co., Ltd .: Isopar E, H, G and these solvents and ketones such as methyl ethyl ketone and cyclohexanone, butyl acetate, acetic acid Esters such as amyl and ethyl propionate, hydrocarbons and halogenated hydrocarbons such as toluene, xylene, monochlorobenzene, carbon tetrachloride, trichloroethylene and trichloroethane, ethers such as methyl cellosolve, ethyl cellosolve and tetrahydrofuran, and propylene A mixed solvent with glycol monomethyl ether acetate, bentoxone, dimethylformamide, or the like can be used.

  In addition, a super water-repellent material as shown in SCIENCE magazine, 299, 1377 can be used.

  The insulating region 6 according to the present invention preferably has a light transmittance of 10% or less, more preferably 1% or less. Thereby, the deterioration of the characteristic by the light of the organic-semiconductor layer 3 can be suppressed.

  Here, the light transmittance refers to an average transmittance in a wavelength region in which photo-generated carriers can be generated in the organic semiconductor layer 3. In general, it is preferable to have the ability to shield light from 350 to 750 nm.

  In addition, since this technique is intended to suppress light reaching the organic semiconductor layer 3 in order to suppress deterioration of the organic semiconductor layer due to light, not only does the insulating region 6 reduce light transmittance, The light transmittance may be 10% or less in other layers (all layers in the case of a multilayer) such as the intermediate layer 3a and the receiving layer 7 that can be formed on the organic semiconductor layer. More preferably.

  In order to reduce the light transmittance of the layer, a method of incorporating a color material such as a pigment or a dye or an ultraviolet absorber into the layer can be used.

<Method for forming insulating region>
If the conventional ink jet device having a capacity per droplet of several pl to several tens of pl is used to form the insulating region 6 having repellent properties of the electrode material, the dot diameter of the ink droplet that lands on the recording medium (For example, in the case of 20 pl, the dot diameter is 60 μm), which is unsuitable for forming an insulating region of a thin film transistor that requires a channel length (insulating region width) of 10 μm or less, for example. there were.

  Hereinafter, an ink jet system for forming the insulating region 6 having the electrode material repellent property of the present invention will be described.

  The ink jet device that forms the insulating region 6 having the electrode material repellent property enables the formation of a channel length (for example, 3 μm) necessary for the insulating region. Therefore, the dot diameter attached to the organic semiconductor layer 3 is equal to the channel length. An electrostatic suction type ink jet apparatus according to the present invention capable of ejecting droplets having an extremely fine diameter that is equal to or smaller than that is used.

  Hereinafter, an object (an organic semiconductor layer in the present invention) to which inkjet droplets adhere is also simply referred to as a substrate.

An inkjet apparatus capable of ejecting droplets of extremely fine diameters that form an insulating region 6 having electrode material repellent properties has an electrostatic suction capacity of 1 to 400 fl, preferably 1 to 100 fl per ejected droplet. A type inkjet apparatus is suitable and will be described in detail below. (Configuration of recording head and members related to recording head)
Hereinafter, the recording head 20 and the member related to the recording head 20 of the electrostatic attraction type ink jet apparatus capable of discharging droplets of extremely fine diameters used for forming the insulating region of the thin film transistor of the present invention will be described with reference to FIGS. This will be explained based on.

  FIG. 3 is a cross-sectional view of a recording head having nozzles and members related to the recording head, and FIG. 4 is an explanatory diagram showing the relationship between the ink ejection operation and the voltage applied to the ink.

  FIG. 4A shows a state where no discharge is performed, and FIG. 4B shows a discharge state.

  In FIG. 3, the recording head 20 is provided with an ultrafine nozzle 21 that discharges ink droplets of chargeable ink from its tip.

  A counter electrode 23 is provided below the nozzle 21 of the recording head 20 so as to oppose the nozzle 21, and the counter electrode 23 has a counter surface that opposes the tip of the nozzle 21, and ink droplets are formed on the counter surface. The thin film transistor K receiving the landing is supported.

  In addition, the recording head 20 includes an ink supply unit that supplies ink to the flow path (nozzle flow path) 22 in the nozzle 21, and an ejection voltage application unit 25 that applies a discharge voltage to the ink in the nozzle 21. It is connected.

  A part of the nozzle 21 and the ink supply unit and a part of the discharge voltage applying unit 25 are integrally formed by a nozzle plate 26.

  The recording head 20 is a scanning recording head that can be scanned in a direction (front and back direction in the figure) orthogonal to the transport direction (left and right direction in the figure) of the thin film transistor K by a driving mechanism (not shown). Insulating discharge liquid (hereinafter referred to as ink) is supplied from an ink tank (not shown) of the ink supply means, and the recording head 20 discharges from the nozzle 21 as ink droplets.

(nozzle)
The nozzle 21 is integrally formed with a lower surface layer 26c of the nozzle plate 26 described later, and is erected vertically from the flat plate surface of the nozzle plate 26. Further, the nozzle 21 is formed with a flow path 22 penetrating from the tip portion along the center line.

The nozzle 21 is formed with an ultrafine diameter. Specifically, the inner diameter d at the tip A of the nozzle 21 is 30 μm or less. As an example of specific dimensions of each part, the nozzle inner diameter d is 1 μm, the external diameter d ₁ at the tip of the nozzle 21 is 2 μm, the root diameter d ₂ of the nozzle 21 is 5 μm, and the height h of the nozzle 21 is 100 μm. The shape is formed in a truncated cone shape that is close to a conical shape. The entire nozzle 21 is formed of an insulating resin material together with the lower surface layer 26 c of the nozzle plate 26.

In addition, each dimension of a nozzle is not limited to the said example. In particular, the nozzle inner diameter d is a range in which an ejection voltage that enables ejection of ink droplets by the effect of electric field concentration, which will be described later, is less than 1000 V. For example, the nozzle when the electrostatic force exceeds the surface tension Since the upper limit of the inner diameter is approximately 30 μm, the upper limit value of the nozzle inner diameter is preferably 30 μm. In particular, 15 μm is more preferable. In particular, in order to more effectively use the local electric field concentration effect, the inner diameter of the nozzle is preferably in the range of 0.01 to 8 μm. Moreover, it is preferable that the capacity | capacitance per droplet of the discharge droplet from the said nozzle is 1-400 fl (10 < ^-15 > l).

(Ink supply means)
The ink supply means is provided at a position inside the nozzle plate 26 and at the base of the nozzle 21 and also supplies ink to the ink chamber 24 from an external ink tank (not shown). An ink supply path 27 is provided, and a supply pump (not shown) that is connected to the ink supply path 27 and applies an ink supply pressure to the ink chamber 24 is provided.

  Ink is stored in the external ink tank, and the supply pump supplies ink to the tip of the nozzle 21 and maintains the supply pressure in a range that does not spill from the tip (FIG. 4). (See (A)).

(Discharge voltage application means)
A bias power source 30 for constantly applying a DC bias voltage to a discharge electrode 28 for applying a discharge voltage provided inside the nozzle plate 26 and at a boundary position between the ink chamber 24 and the flow path 22 in the nozzle; An ejection voltage applying means 25 having an ejection voltage power supply 29 for applying a pulse voltage, which is a potential required for ejection, superimposed on a bias voltage is connected to 28.

  The discharge electrode 28 is in direct contact with the ink inside the ink chamber 24 to charge the ink and apply a discharge voltage.

  The bias voltage from the bias power source 30 is applied in a voltage range in which ink is not ejected, so that the width of the voltage to be applied during ejection is reduced in advance, thereby improving the responsiveness during ejection. ing.

  The ejection voltage power supply 29 applies the pulse voltage superimposed on the bias voltage only when ejecting ink. At this time, the value of the pulse voltage is set so that the superimposed voltage V satisfies the following equation.

However, γ: ink surface tension, ε ₀ : vacuum dielectric constant, r: nozzle radius, k: proportional constant (1.5 <k <8.5) depending on the nozzle shape.

  As an example, the bias voltage is applied at DC 300 [V] and the pulse voltage is marked at 100 [V]. In this case, the superimposed voltage at the time of discharge is 400 [V].

(Nozzle plate)
The nozzle plate 26 includes a base layer 26a positioned in the uppermost layer in FIG. 3, a flow path layer 26b forming an ink supply path positioned therebelow, and a lower surface layer formed further below the flow path layer 26b. 26c, and the discharge electrode 28 described above is interposed between the flow path layer 26b and the upper surface layer 26c.

  The base layer 26a is formed of a silicon substrate or a highly insulating resin or ceramic, forms a soluble resin layer on the base layer 26a, and removes only a portion that follows the pattern of the supply path 27 and the ink chamber 24, An insulating resin layer is formed on the removed portion.

  This insulating resin layer becomes the flow path layer 26b. Then, the discharge electrode 28 is formed on the lower surface of the insulating resin layer by plating with a conductive material (for example, NiP), and an insulating resist resin layer is further formed thereunder. Since the resist resin layer becomes the lower surface layer 26 c, the resin layer is formed with a thickness in consideration of the height of the nozzle 21.

  Then, this insulating resist resin layer is exposed by an electron beam method or a femtosecond laser to form a nozzle shape. The nozzle internal flow path 22 is also formed by laser processing. Then, the dissolvable resin layer according to the pattern of the supply path 27 and the ink chamber 24 is removed, and the supply path 27 and the ink chamber 24 are opened to complete the nozzle plate.

(Counter electrode)
The counter electrode 23 has a counter surface perpendicular to the nozzle 21 as described above, and supports the thin film transistor K along the counter surface. As an example, the distance L from the tip of the nozzle 21 to the opposing surface of the opposing electrode 23 is set to 100 [μm]. Since the counter electrode 23 is grounded, the ground potential is always maintained. Therefore, when a pulse voltage is applied, an ink droplet ejected by an electrostatic force generated by an electric field generated between the tip A of the nozzle 21 and the opposing surface is guided to the opposing electrode 23 side.

  Since the recording head 20 can eject ink droplets in a state where the electric field strength is increased by concentration of the electric field at the tip A of the nozzle 21, the ink droplets can be ejected without being guided by the counter electrode 23. Although possible, it is desirable that induction by electrostatic force is performed between the nozzle 21 and the counter electrode 23. In addition, the charge of the charged ink droplet can be released by grounding the counter electrode 23.

(ink)
The ink preferably does not contain particles having a diameter of 0.3 μm or more.

  More specifically, the ink has a viscosity of 0.1 to 1000 mPa · s (preferably 1 to 100 mPa · s) and a surface tension of 20 to 70 mN / m (preferably 25 to 50 mN / m). Some inks are applicable. When the viscosity of the ink is less than 0.1 mPa · s or greater than 1000 mPa · s, the ink ejection from the nozzle 21 becomes unstable. Further, when the surface tension of the ink is less than 20 mN / m, the ink droplets ejected from the nozzle 21 are likely to bleed into the substrate K. When the surface tension of the ink is greater than 70 mN / m, each pixel of the substrate K cannot be completely filled with the ink droplets ejected from the nozzle 21.

(Discharge operation of minute ink droplets by recording head)
The operation of the recording head 20 will be described with reference to FIGS.

  In FIG. 4, the horizontal axis represents time T, and the vertical axis represents the superimposed voltage V generated by the ejection voltage power supply 29 and the bias power supply 30.

  Ink is supplied to the nozzle flow path 22 by the supply pump of the ink supply means, and a bias voltage is applied to the ink via the discharge electrode 28 by the bias power supply 30.

  In such a state, the ink is charged and a meniscus that is recessed in the tip end portion A of the nozzle 21 is formed (FIG. 4A).

  When a pulse voltage is applied by the discharge voltage power supply 29, the electric field is concentrated at the tip of the nozzle 21, and the ink is guided to the tip of the nozzle 21 by the electrostatic force due to the concentrated electric field, and protrudes to the outside. In addition, an electric field is concentrated on the apex of the convex meniscus, and finally, a minute ink droplet is ejected toward the counter electrode 23 against the surface tension of the ink (FIG. 4B).

  In this case, an ink droplet having a droplet amount of 1 to 400 fl per droplet is ejected from the nozzle 21.

  Since the electrostatic suction type ink jet apparatus having the recording head 20 described above has a small diameter, the discharge flow rate per unit time can be easily controlled by the low nozzle conductance, and the pulse Ink ejection using sufficiently small ink droplets (ink droplets having a droplet amount of 1 to 400 fl per droplet) is realized without narrowing the width.

  Furthermore, since the ejected ink droplets are charged, the vapor pressure is reduced even for very small ink droplets and the evaporation is suppressed, so the loss of ink droplet mass is reduced and the flight is stabilized. In addition, the ink droplet landing accuracy is prevented from being lowered.

  In addition, as described above, the amount of ink droplets ejected from the nozzle 21 can be set to 1 to 400 fl as described above, and the ink ejected from the nozzle 21 and landed on the thin film transistor K Since the droplet adhesion amount can be suppressed to 0.2 to 5.6 ml / m 2, each dot diameter of the ink droplet adhered to the thin film transistor K can be greatly reduced. Accordingly, the insulating region width (channel length) required to be 10 μm or less, which has been a problem in the past, can be reduced, such as ink bleeding, poor drying of the ink itself, and variations in the insulating region width (channel length). Detrimental effects can be suppressed, and as a result, a high-definition insulating region with a plurality of ultrafine dots can be formed on the organic semiconductor layer.

  In the above embodiment, in order to obtain the electrowetting effect on the nozzle 21, an electrode is provided on the outer periphery of the nozzle 21, or an electrode is provided on the inner surface of the nozzle internal flow path 22, and the insulating film is coated thereon. May be.

  By applying a voltage to this electrode, the wettability of the inner surface of the nozzle flow path 22 can be increased by the electrowetting effect for the ink to which the voltage is applied by the ejection electrode 28, and the inside of the nozzle can be increased. Ink supply to the flow path 22 can be performed smoothly, and it is possible to discharge well and improve the responsiveness of discharge.

  In the above embodiment, the ejection voltage application means 25 constantly applies a bias voltage and ejects ink droplets using a pulse voltage as a trigger. However, an alternating current or continuous rectangular wave is always applied with an amplitude required for ejection. Moreover, it is good also as a structure which discharges by switching the high and low of the frequency.

  Ink discharge is essential to eject ink droplets, and even if a discharge voltage is applied at a frequency that exceeds the rate at which the ink is charged, ejection is not performed, and if the frequency is changed so that the ink can be sufficiently charged. Discharging is performed. Therefore, when discharging is not performed, the discharge voltage is applied at a frequency higher than the dischargeable frequency, and control is performed to reduce the frequency to a frequency band that can be discharged only when discharging is performed, thereby controlling ink discharge. Is possible. In such a case, since the voltage applied to the ink itself does not change, it is possible to further improve the responsiveness and thereby improve the ink droplet landing accuracy.

<< Flowable electrode material: source electrode, drain electrode >>
(Method of forming source and drain electrodes)
In FIG. 1, in the manufacture of the thin film transistor of the present invention, the following fluid electrode material is supplied to the insulating region 6, and the supplied fluid electrode material is stretched left and right around the insulating region. The flowable electrode material is divided into left and right in the insulating region, thereby forming the source electrode 5 in one of the insulating regions and the drain electrode 4 in the other.

(Flowable electrode material)
The fluid electrode material according to the present invention specifically includes a solution containing the following conductive material,
Paste, ink, liquid dispersion. In addition to the conductive material, a precursor material that develops conductivity by a treatment such as heating or light irradiation may be used.

  In the fluid electrode material supplied from the electrostatic suction type ink jet device, the solvent or the dispersion medium contains 50% by mass or more of water.

(Conductive material)
The conductive material is not particularly limited as long as it has conductivity at a practical level as an electrode. Platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, palladium , Tellurium, rhenium, iridium, aluminum, ruthenium, germanium, molybdenum, tungsten, tin / antimony oxide, 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 Nesium / silver mixtures, magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide mixtures, lithium / aluminum mixtures, etc. are used, with platinum, gold, silver, copper, aluminum, indium, ITO and carbon being particularly preferred. .

  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.

  Platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, palladium, tellurium, rhenium, iridium, aluminum, ruthenium, germanium, molybdenum, tungsten, zinc, etc. Can be used.

  It is preferable to form an electrode using a dispersion in which fine particles made of these metals are dispersed in water or a dispersion medium that is an arbitrary organic solvent using a dispersion stabilizer mainly made of an organic material.

  As a method for producing such a dispersion of metal fine particles, metal ions are reduced in a liquid phase, such as a physical generation method such as gas evaporation method, sputtering method, and metal vapor synthesis method, colloid method, and coprecipitation method. Examples of the chemical production method for producing metal fine particles include those described in JP-A-11-76800, JP-A-11-80647, JP-A-11-319538, JP-A-2000-239853, and the like. Colloidal methods, gas evaporation methods described in JP-A Nos. 2001-254185, 2001-53028, 2001-35255, 2000-124157, 2000-123634, etc. This is a dispersion of produced metal fine particles.

  Further, as the source electrode and the drain electrode, it is also preferable to use a known conductive polymer whose conductivity has been improved by doping or the like, for example, conductive polyaniline, conductive polypyrrole, conductive polythiophene, polyethylenedioxythiophene and polystyrene. A sulfonic acid complex or the like is also preferably used. Thereby, the contact resistance between the source electrode, the drain electrode, and the organic semiconductor layer can be reduced.

<< Flowable electrode forming method: Method of forming source electrode, drain electrode, etc. >>
In the present invention, the patterning method for the source electrode, the drain electrode, and the like described above can be patterned by supplying a fluid electrode material to an insulating region having electrode material repulsion and dividing the source electrode and the drain electrode. Any material can be used.

  In the present invention, a fluid electrode material made of a solution or a dispersion containing a source electrode and a drain electrode forming material is supplied onto an insulating region having electrode material repellent property by an electrostatic suction ink jet method. The fluid electrode material is divided by the electrode material repellent property of the insulating region to obtain the source electrode and the drain electrode.

  Here, when the source electrode and the drain electrode are formed by discharging ink containing a fluid electrode material onto the insulating region by the electrostatic suction ink jet method, the electrode formation region by ink discharge is adjusted to an appropriate size. From the viewpoint, it is preferable to provide a receiving layer. As the receiving layer, a void-type receiving layer used in a conventionally known ink jet recording medium is preferably used.

  That is, the source electrode and the drain electrode are formed by supplying the fluid electrode material to the receiving layer.

  Next, the receiving layer will be described.

(Receptive layer)
Here, the receptor layer is preferably a void type, and the void type is a mixture of fine particles and a water-soluble binder applied.

  Examples of the fine particles that can be used in the receptor layer include inorganic fine particles and organic fine particles. In particular, inorganic fine particles are preferable because fine particles can be easily obtained. Examples of such inorganic fine particles include light calcium carbonate, heavy calcium carbonate, magnesium carbonate, kaolin, clay, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc hydroxide, zinc sulfide, zinc carbonate, White inorganic pigments such as hydrotalcite, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, alumina, colloidal alumina, pseudoboehmite, aluminum hydroxide, lithopone, zeolite, magnesium hydroxide, etc. Can be mentioned. The inorganic fine particles can be used as primary particles or in a state where secondary aggregated particles are formed.

  As the inorganic fine particles, alumina, pseudoboehmite, colloidal silica or fine particle silica synthesized by a gas phase method is preferable, and fine particle silica synthesized by a gas phase method is particularly preferable. The silica synthesized by this vapor phase method may have a surface modified with Al. The Al content of the vapor-phase process silica whose surface is modified with Al is preferably 0.05% to 5% by mass with respect to silica.

  The inorganic fine particles having any particle diameter can be used, but those having an average particle diameter of 1 μm or less are preferable, more preferably 0.2 μm or less, and particularly preferably 0.1 μm or less. It is.

  Here, the lower limit of the particle diameter is not particularly limited, but is preferably approximately 0.003 μm or more, and particularly preferably 0.005 μm or more, from the viewpoint of manufacturing inorganic fine particles.

  The average particle size of the inorganic fine particles is obtained as a simple average value (number average) by observing the cross section and surface of the porous layer with an electron microscope and determining the particle size of 100 arbitrary particles. Here, each particle size is expressed by a diameter assuming a circle equal to the projected area.

  The fine particles may remain as primary particles, or may be present in the porous film as secondary particles or higher-order aggregated particles, but the average particle size is determined by observation with an electron microscope. The particle size of the particles forming independent particles in the porous layer.

  The content of the fine particles in the water-soluble coating solution is preferably 5% by mass to 40% by mass, and particularly preferably 7% by mass to 30% by mass.

  There is no restriction | limiting in particular as a hydrophilic binder contained in a space | gap type receiving layer, A conventionally well-known hydrophilic binder can be used, For example, gelatin, polyvinylpyrrolidone, polyethylene oxide, polyacrylamide, polyvinyl alcohol etc. are used. Polyvinyl alcohol is particularly preferred.

  Polyvinyl alcohol has an interaction with inorganic fine particles, has a particularly high holding power with respect to the inorganic fine particles, and is a polymer having a relatively small hygroscopic humidity dependency. Examples of the polybilyl alcohol preferably used in the present invention include, in addition to ordinary polyvinyl alcohol obtained by hydrolysis of polyvinyl acetate, modified polyvinyl alcohol having a terminal cation modified, anion-modified polyvinyl alcohol having an anionic group, and the like. Polyvinyl alcohol is also included.

  As the polyvinyl alcohol obtained by hydrolysis of vinyl acetate, those having an average degree of polymerization of 300 or more are preferably used, and those having an average degree of polymerization of 1000 to 5000 are particularly preferably used. The saponification degree is preferably 70% to 100%, particularly preferably 80% to 99.5%.

  Examples of the cation-modified polyvinyl alcohol include a primary to tertiary amino group or a quaternary ammonium group as described in JP-A No. 61-10383 in the main chain or side chain of the polyvinyl alcohol. These are obtained by saponifying a copolymer of an ethylenically unsaturated monomer having a cationic group and vinyl acetate.

  Examples of the ethylenically unsaturated monomer having a cationic group include trimethyl- (2-acrylamido-2,2-dimethylethyl) ammonium chloride and trimethyl- (3-acrylamido-3,3-dimethylpropyl) ammonium chloride. N-vinylimidazole, N-vinyl-2-methylimidazole, N- (3-dimethylaminopropyl) methacrylamide, hydroxylethyltrimethylammonium chloride, trimethyl- (3-methacrylamidopropyl) ammonium chloride, N- (1, 1-dimethyl-3-dimethylaminopropyl) acrylamide and the like.

  The ratio of the cation-modified group-containing monomer in the cation-modified polyvinyl alcohol is 0.1 mol% to 10 mol%, preferably 0.2 mol% to 5 mol%, relative to vinyl acetate.

  Examples of the anion-modified polyvinyl alcohol include polyvinyl alcohols having an anionic group described in JP-A-1-206088, vinyls described in JP-A-61-237681, and JP-A-63-330779. Examples thereof include a copolymer of an alcohol and a vinyl compound having a water-soluble group, and a modified polyvinyl alcohol having a water-soluble group described in JP-A-7-285265.

  Nonionic modified polyvinyl alcohol is, for example, a polyvinyl alcohol derivative obtained by adding a polyalkylene oxide group described in JP-A No. 7-9758 to a part of vinyl alcohol, and described in JP-A No. 8-25795. And a block copolymer of a vinyl compound having a hydrophobic group and vinyl alcohol.

  Polyvinyl alcohol can also use 2 or more types together, such as a polymerization degree and a different kind of modification | denaturation. In particular, when polyvinyl alcohol having a degree of polymerization of 2000 or more is used, 0.05 wt% to 10 wt% of polyvinyl alcohol having a degree of polymerization of 1000 or less is preferably previously added to the inorganic fine particle dispersion with respect to the inorganic fine particles. It is preferable to add 0.1% by mass to 5% by mass and then add polyvinyl alcohol having a degree of polymerization of 2000 or more without significant thickening.

  The ratio of fine particles to the hydrophilic binder in the void-type receiving layer is such that the porosity of the porous layer is properly maintained and sufficient void volume is maintained, while excess hydrophilic binder swells during ink jet recording to block the voids. From the viewpoints of preventing this, maintaining the proper absorption rate of the conductive polymer, and preventing cracking of the porous layer, the mass ratio is preferably 2 to 20 times, more preferably 2.5. Times to 12 times, particularly preferably 3 times to 10 times.

<Semiconductor layer>
The semiconductor layer according to the present invention can include a conventionally known inorganic or organic semiconductor material such as amorphous silicon or polysilicon, but in the present invention, it is preferable to include an organic semiconductor material.

(Organic semiconductor materials)
As an organic semiconductor material used for the organic semiconductor layer 3 according to the present invention, a π-conjugated material is used. For example, polypyrrole, poly (N-substituted pyrrole), poly (3-substituted pyrrole), poly (3,4-diphenyl). Polypyrroles such as substituted pyrrole), polythiophenes such as polythiophene, poly (3-substituted thiophene), poly (3,4-disubstituted thiophene), polybenzothiophene, polyisothianaphthenes such as polyisothianaphthene, poly Polychenylene vinylenes such as chelenylene vinylene, poly (p-phenylene vinylenes) such as poly (p-phenylene vinylene), polyaniline, poly (N-substituted aniline), poly (3-substituted aniline), poly (2 , 3-substituted anilines) and the like, polyacetylenes such as polyacetylene, and polydiacetes Polydiacetylenes such as lenene, polyazulenes such as polyazulene, polypyrenes such as polypyrene, polycarbazoles such as polycarbazole and poly (N-substituted carbazole), polyselenophenes such as polyselenophene, polyfuran, polybenzofuran, etc. Polyfurans, poly (p-phenylene) s such as poly (p-phenylene), polyindoles such as polyindole, polypyridazines such as polypyridazine, naphthacene, pentacene, hexacene, heptacene, dibenzopentacene, tetrabenzopentacene , Pyrene, dibenzopyrene, chrysene, perylene, coronene, terylene, ovarene, quaterylene, circaanthracene, and other polyacenes, and some of the carbons of polyacenes are atoms such as N, S, O, carbon Derivatives such as triphenodioxazine, triphenodithiazine, hexacene-6,15-quinone, polymers such as polyvinylcarbazole, polyphenylene sulfide, and polyvinylene sulfide; The polycyclic condensates described in 1) can be used.

  Further, for example, α-sexual thiophene α, ω-dihexyl-α-sexual thiophene, α, ω-dihexyl-α-kinkethiophene, α, ω-bis (α, which is a thiophene hexamer having the same repeating unit as those polymers. Oligomers such as 3-butoxypropyl) -α-sexithiophene and styrylbenzene derivatives can also be preferably used.

Furthermore, metal phthalocyanines such as copper phthalocyanine and fluorine-substituted copper phthalocyanine described in JP-A-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 derivative, naphthalene 2,3,6,7 tetracarboxylic acid diimide and other naphthalene tetracarboxylic acid diimides, and anthracene 2,3,6,7-tetra Condensed ring tetracals such as anthracene tetracarboxylic acid diimides such as carboxylic acid diimides Examples thereof include boronic acid diimides, fullerenes such as C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ , C ₈₄ , carbon nanotubes such as SWNT, merocyanine dyes, and dyes such as hemicyanine dyes.

  Among these π-conjugated materials, thiophene, vinylene, chelenylene vinylene, phenylene vinylene, p-phenylene, a substituent thereof, or two or more of these are used as a repeating unit, and the number n of the repeating units is 4 to 4 At least 1 selected from the group consisting of an oligomer of 10 or a polymer in which the number n of repeating units is 20 or more, a condensed polycyclic aromatic compound such as pentacene, fullerenes, condensed ring tetracarboxylic diimides, and metal phthalocyanine Species are preferred.

  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.

  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 tetracyanoquinodimethane are used in the organic semiconductor layer. And materials that can accept electrons, such as derivatives thereof, materials that have functional groups such as amino groups, triphenyl groups, alkyl groups, hydroxyl groups, alkoxy groups, and phenyl groups, substituted amines such as phenylenediamine , So-called doping, containing materials that serve as donors of electrons such as anthracene, anthracene, benzoanthracene, substituted benzoanthracene, pyrene, substituted pyrene, carbazole and its derivatives, tetrathiafulvalene and its derivatives, etc. Processing Good.

  The doping means introducing an electron-donating molecule (acceptor) or an electron-donating molecule (donor) into the thin film as a dopant. Accordingly, 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.

(Method for producing organic semiconductor layer)
These organic semiconductor layers can be produced by vacuum deposition, molecular beam epitaxial growth, ion cluster beam method, low energy ion beam method, ion plating method, CVD method, sputtering method, plasma polymerization method, electrolytic polymerization method, chemical method, etc. A polymerization 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 die coating method, an ink jet method, an LB method, and the like can be mentioned and can be used depending on the material.

  However, among these, in terms of productivity, spin coating, blade coating, dip coating, roll coating, bar coating, die coating, and ink jet can be used to easily and precisely form thin films using organic semiconductor solutions. A method or the like is preferably used.

  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 film is formed by heat treatment of a precursor film formed by coating. A thin film of material may be formed.

  The film thickness of the organic semiconductor layer made of these organic semiconductor materials is not particularly limited, but the characteristics of the obtained transistor are often greatly influenced by the film thickness of the organic semiconductor layer. Although it depends on the type of semiconductor material, it is generally 1 μm or less, preferably 10 nm to 300 nm.

  When a fluid electrode material is ejected to an insulating region using an electrostatic suction ink jet method, an ink containing a conductive material is prepared. The solvent or dispersion medium used for the ink is an organic semiconductor (organic semiconductor layer). It is preferable to select a material with as little damage as possible. Although damage depends on the semiconductor material, for example, when pentacene is used, it is preferable to contain 50% by mass or more of water, more preferably 60% by mass or more, and particularly preferably 90% by mass or more. The solvent or dispersion medium to be contained.

  Moreover, the transparent conductive film etc. which were formed from the said material can also be used.

  Here, the term “transparent” means that the light transmittance (ultraviolet light to visible light as light) is at least 50% or more, preferably 80% or more.

《Middle layer》
The organic thin film transistor, which is a preferred embodiment of the thin film transistor of the present invention, preferably has an intermediate layer (also referred to as a semiconductor protective layer) 3a between the insulating region and the semiconductor layer in contact with the organic semiconductor layer. By providing the intermediate layer in contact with the organic semiconductor layer, deterioration of the organic semiconductor layer due to air or water can be suppressed. Further, by providing the intermediate layer, durability due to bending or the like is also improved, and thereby deterioration of characteristics as a transistor can be suppressed.

  Depending on the organic semiconductor material, the material that forms the ink repellent insulating region, and the type of the solvent, an effect of suppressing damage to the organic semiconductor layer when forming the insulating region can be obtained. it can.

  As the intermediate layer, a material that does not affect the organic semiconductor layer is selected after the manufacturing process of the organic semiconductor transistor or after the manufacturing.

  As such a material, although it depends on the kind of semiconductor material, a phenol resin such as polyvinylphenol or novolac resin, an epoxy resin, a hydrophilic polymer, or the like can be used.

  The hydrophilic polymer is a polymer having solubility or dispersibility with respect to water or an aqueous acid solution, an alkaline aqueous solution, an alcohol aqueous solution, and various surfactant aqueous solutions. For example, homopolymers and copolymers composed of components such as polyvinyl alcohol, HEMA, acrylic acid, and acrylamide can be suitably used. As other materials, materials containing inorganic oxides and inorganic nitrides are also preferable because they do not affect the organic semiconductor and do not affect other coating processes. Further, a material for a gate insulating layer described later can also be used.

(Method for forming intermediate layer)
The intermediate layer containing an inorganic oxide or an inorganic nitride is preferably formed by an atmospheric pressure plasma method.

  The method of forming a thin film by the plasma method under atmospheric pressure is a process in which a thin film is formed on a substrate by discharging at atmospheric pressure or a pressure near atmospheric pressure to excite a reactive gas to form a thin film on a substrate. JP-A-11-61406, JP-A-11-133205, JP-A-2000-121804, JP-A-2000-147209, JP-A-2000-185362, etc. (hereinafter also referred to as atmospheric pressure plasma method) Called). Accordingly, a highly functional thin film can be formed with high productivity.

<< Gate insulating layer and method for forming the same >>
Although various insulating films can be used as the gate insulating layer 2a of the thin film transistor of the present invention, an inorganic oxide film having a high relative dielectric constant is particularly 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.

(Method for forming gate insulating layer)
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. 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 wet processes such as printing and ink jet patterning methods, etc. 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.

  Among these, the film formation by the atmospheric pressure plasma method or the anodic oxidation method described above is preferable.

  It is also preferable that the gate insulating layer is composed of an anodic oxide film or the anodic oxide 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. An oxide film is formed by anodizing. Any electrolyte solution that can form a porous oxide film can be used as the anodizing treatment. Generally, sulfuric acid, phosphoric acid, oxalic acid, chromic acid, boric acid, sulfamic acid, benzenesulfone, and the like can be used. Acids or the like, or mixed acids obtained by combining two or more of these or salts thereof are used. The treatment conditions for anodization vary depending on the electrolytic solution used, and thus cannot be specified in general. In general, the concentration of the electrolytic solution is 1% by mass to 80% by mass, and the temperature of the electrolytic solution is 5 ° C. to 70 ° C. A current density of 0.5 A / dm ^{2 to} 60 A / dm ² , a voltage of 1 V to 100 V, and an electrolysis time of 10 seconds to 5 minutes are suitable. A preferred anodizing treatment is a method in which an aqueous solution of sulfuric acid, phosphoric acid, boric acid, tartaric acid, or the like or a salt thereof is used as the electrolytic solution and the treatment is performed with a direct current, but an alternating current can also be used. Preferably the concentration of these acids is 5 wt% to 45 wt%, temperature 20 ° C. to 50 ° C. of the electrolytic solution at a current density of ^{0.5A / dm 2 ~20A / dm 2} 20 seconds to 250 seconds electrolytic treatment It is preferable to do this.

  In addition, as the organic compound film, polyimide, polyamide, polyester, polyacrylate, photo radical polymerization type, photo cation polymerization type photo curable resin, or a copolymer containing an acrylonitrile component, polyvinyl phenol, polyvinyl alcohol, novolac resin, Also, cyanoethyl pullulan or the like can be used.

  As the method for forming the organic compound film, the wet process is preferable. 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.

  Arbitrary alignment treatment may be performed between the gate insulating layer and the organic semiconductor layer. Silane coupling agents such as octadecyltrichlorosilane, trichloromethylsilazane, and self-assembled alignment films such as alkane phosphoric acid, alkanesulfonic acid, and alkanecarboxylic acid are preferably used.

<Constituent material of gate electrode>
As the constituent material of the gate electrode according to the present invention, the same material as that of the source electrode and the drain electrode can be used.

<Support>
In the present invention, the support is preferably a resin sheet made of a resin.

  Examples of the resin sheet include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), Examples thereof include a resin sheet film made of cellulose triacetate (TAC), cellulose acetate propionate (CAP) and the like. Thus, 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 addition, a sealing film can be provided on the organic thin film transistor of the present invention. Examples of the sealing film include the inorganic oxides and inorganic nitrides described above, and the sealing film is preferably formed by the atmospheric pressure plasma method described above. Thereby, the durability of the organic thin film transistor is improved.

<Underlayer>
The thin film transistor of the present invention preferably has at least one of an undercoat layer containing a compound selected from inorganic oxides and inorganic nitrides and an undercoat layer containing a polymer.

  Examples of the inorganic oxide contained in the undercoat layer include silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, barium zirconate titanate, lead zirconate titanate, titanate Examples thereof include lead lanthanum, strontium titanate, barium titanate, barium fluoride magnesium, bismuth titanate, strontium bismuth titanate, strontium bismuth tantalate, bismuth tantalate niobate, and yttrium trioxide. Examples of the inorganic nitride include silicon nitride and aluminum nitride.

  Of these, silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, and silicon nitride are preferable.

  In the present invention, the undercoat layer containing a compound selected from inorganic oxides and inorganic nitrides is preferably formed by the atmospheric pressure plasma method described above.

  Polymers used for the undercoat layer containing polymer include polyester resin, polycarbonate resin, cellulose resin, acrylic resin, polyurethane resin, polyethylene resin, polypropylene resin, polystyrene resin, phenoxy resin, norbornene resin, epoxy resin, vinyl chloride-vinyl acetate Copolymer, vinyl chloride resin, vinyl acetate resin, copolymer of vinyl acetate and vinyl alcohol, partially hydrolyzed vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer Polymer, ethylene-vinyl alcohol copolymer, polyvinyl alcohol, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, vinyl polymers such as ethylene-vinyl acetate copolymer, polyamide resin, ethylene-butadiene resin, Tajien - rubber-based resin such as acrylonitrile resin, silicone resins, and fluorine resins.

<< Method for Fabricating Thin Film Transistor Element >>
FIG. 5 is a diagram for explaining a manufacturing method of a thin film transistor of the present invention.

  A step of forming an insulating region having an electrode material repellent property containing silicon rubber by the electrostatic attraction type inkjet device of the present invention having a capacity per droplet of 1 to 400 fl of the present invention; FIG. 5 shows a method for manufacturing a thin film transistor element and a thin film transistor element sheet, which includes a step of forming each of a source electrode and a drain electrode by dividing a fluid electrode material supplied to an insulating region at the insulating region. To explain.

  In FIG. 5A, the gate electrode 2, the gate insulating layer 2a, and the organic semiconductor layer 3 are formed on the support 1 in this order using the materials and the formation method described above.

  In FIG. 5 (2), the receiving layer 7 is further formed thereon using the above-described materials and forming methods.

  In FIG. 5 (3), furthermore, an insulating material droplet 6a having electrode material repellent properties is ejected by the electrostatic suction ink jet device.

  In FIG. 5 (4), an insulating material 6 having electrode material repulsion is formed by infiltrating the receiving layer 7 with an insulating material having electrode material repulsion containing silicon rubber.

  In FIG. 5 (5), the fluid electrode material 8 is further supplied (injected) from the upper side of the insulating region 6 so as to protrude from the left and right of the insulating region 6 by the electrostatic suction ink jet apparatus.

  In FIG. 5 (6), the fluid electrode material 8 is repelled and divided into 8a and 8b by the insulating region 6 having electrode material repulsion.

  In FIG. 5 (7), the flowable electrode materials 8a and 8b penetrate into the receiving layer 7 to form the source electrode 5 and the drain electrode 4, thereby completing one thin film transistor element.

  That is, the source electrode 5 and the drain electrode 4 are formed by the electrostatic suction ink jet apparatus.

  Further, the solvent or dispersion medium of the discharge liquid of the electrostatic suction type ink jet device used for forming the source electrode 5 and the drain electrode 4 contains 50% by mass or more of water.

  Although the bottom-gate thin film transistor has been described above, it is needless to say that it can be applied to a top-gate thin film transistor.

Hereinafter, a method for forming the insulating region 6 on the organic semiconductor layer 3 described with reference to FIGS. 5 (3, 4) and 5 (5, 6) and further forming source / drain electrodes will be described in detail. For easy understanding, layers other than the organic semiconductor layer 3, the insulating region 6 having electrode material repellent properties, the insulating material droplet 6a, the fluid electrode material 8a and 8b, and the fluid electrode material droplet 8c and 8c ₁ The material is omitted.

  FIG. 6 is a schematic view showing an example in which an insulating region is formed on an organic semiconductor layer by the electrostatic suction ink jet apparatus.

  First, a method for forming the insulating region 6 on the organic semiconductor layer 3 described with reference to FIGS.

  In FIG. 6, an insulating material droplet 6 a is discharged to the approximate center of the organic semiconductor layer 3 using the electrostatic suction ink jet apparatus. At this time, a nozzle (not shown) is moved in parallel with the organic semiconductor layer 3, and each droplet (6a) is ejected in a straight line so as not to be displaced in the horizontal direction in the drawing.

  Further, the ink droplets that have landed on a straight line are ejected in a superimposed manner as illustrated so that the edges of the ink droplets do not become uneven.

  In this case, when the above-described continuous discharge is performed, the edge is not uneven, and a good insulating region 6 can be formed.

  When the diameter of the landed ink droplet is equal to the required channel length, only one row is ejected. When the required channel length is larger than the diameter of the ink droplet, plural rows are ejected on the left and right in the figure, and the dots are arranged on the left and right in the figure. Discharge in a zigzag pattern so that there is no gap between them.

  In this manner, the insulating region 6 having electrode material repellent properties having a necessary channel length is formed.

  FIG. 7 is a schematic view showing an example of forming source / drain electrodes by an ink jet method.

  Next, a method for forming the source / drain electrodes described with reference to FIGS.

  In FIG. 7A, the diameter of at least the width of the insulating region 6 (channel length), preferably the width of the organic semiconductor layer 3 is set at the approximate center of the insulating region 6 by using the electrostatic suction ink jet apparatus. The fluid electrode material droplet 8c having the same is discharged. At this time, a nozzle (not shown) is moved in parallel with the insulating region 6, and each droplet (8c) is ejected in a straight line so as not to be displaced in the horizontal direction of the drawing.

  Further, the ink droplets that have landed on a straight line are ejected in a superimposed manner as illustrated so that the edges of the ink droplets do not become uneven.

  FIG. 7B shows a state where the ejected fluid electrode material droplets 8c are repelled and divided by the electrode material repellent property of the insulating region 6 and aggregated (8a, 8b) on the left and right sides of the insulating region 6. Show.

  FIG. 8 is a schematic view showing another example of forming source / drain electrodes by an ink jet method.

  Next, another example of forming source / drain electrodes will be described.

In FIG. 8A, at least a part of the fluid electrode material droplet 8c ₁ is insulative using the electrostatic attraction type ink jet device at a position spaced apart from the center of the insulating region 6 to the left and right in the drawing by a predetermined distance. The fluid electrode material droplet 8c ₁ is discharged so as to overlap the region 6. At this time, a nozzle (not shown) is moved in parallel with the insulating region 6 so that each droplet (8c ₁ ) is ejected in a straight line so as not to be displaced in the horizontal direction in the drawing.

  Further, the ink droplets that have landed on a straight line are ejected in a superimposed manner as illustrated so that the edges of the ink droplets do not become uneven.

FIG. 8B shows that the portion of the ejected fluid electrode material droplet 8c ₁ that overlaps the insulating region 6 is repelled by the electrode material repellent property of the insulating region 6 and agglomerates to the left and right of the insulating region 6 in the drawing. (8a, 8b) is shown.

<< Thin Film Transistor Element Sheet of the Present Invention and Method for Producing Thin Film Transistor Element Sheet by Inkjet Method >>
FIG. 9 is an explanatory view of one embodiment of a manufacturing process of a thin film transistor element of the thin film transistor element sheet of the present invention by an inkjet method.

  Here, with reference to FIG. 9, one mode of a manufacturing process of the thin film transistor element of the thin film transistor element sheet of the present invention by an inkjet method will be described. In FIG. 9, the production of the fluid electrode material repulsion region 6, the source electrode 5, the drain electrode 4, and the source bus line 12 will be described.

  In FIG. 9, first, a channel region (layer) made of the organic semiconductor layer 3 is provided so as to intersect the gate bus line 11 also serving as a gate electrode, and a fluid electrode material repulsion region (layer) 6 is formed. Ink made of a dispersion or solution containing a conductive electrode material is supplied to both sides of the fluidic electrode material repellent region 6 or is supplied onto the repellent region 6 to divide the fluidic electrode material, and the source electrode 5 The drain electrode 4 and the pixel electrode 4a are formed.

  Here, the fluid electrode material repulsion region 6 is formed by the electrostatic suction ink jet apparatus.

  The other regions (layers) may be subjected to multiple ejection by changing the ejection position with the electrostatic suction type ink jet apparatus, or may be formed by multiple ejection with coarser positions being changed with a normal inkjet.

  Similarly, the source bus line 12 is formed by the electrostatic suction type ink jet apparatus. If the source bus line is formed before the source electrode is formed, undesired spreading of the droplets of the source electrode material is suppressed.

  FIG. 10 is an equivalent circuit diagram showing an embodiment of a thin film transistor element sheet in which a plurality of thin film transistor elements of the present invention are arranged.

  The thin film transistor element sheet 10 has a large number of thin film transistor elements 14 arranged in a matrix with a support made of a resin substrate. 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 organic transistor element 14, and the output element 16 is, for example, a liquid crystal, an electrophoretic element or the like, 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.

  Such a sheet in which TFT elements are two-dimensionally arranged on a flexible resin support increases the adhesion between the support and the TFT constituent layer and is resistant to bending of the support with excellent mechanical strength. It can be made resistant.

  Next, FIGS. 11A, 11B, and 11C illustrate some of the aspects of the thin film transistor element sheet in which the semiconductor layer of the present invention shown in FIG. 10 contains an organic semiconductor material.

  FIG. 11 is a schematic view showing an aspect of an organic thin film transistor forming one pixel of the thin film transistor element sheet of the present invention.

  In the thin film transistor element shown in FIG. 11A, since the gate bus line 11 (here, the gate bus line 11 is covered with a gate insulating layer (not shown)), the existence position is indicated by a dotted line. The organic semiconductor layer 3 is provided so as to intersect with the liquid electrode material repulsion region 6 (also referred to as a layer) on the organic semiconductor layer 3. A drain electrode 4 and a source electrode 5 are provided on both sides. Here, the gate bus line 11 serves as a gate electrode.

  FIG. 11B is different from FIG. 6A in that the gate electrode branches from the gate bus line 11. The organic semiconductor layer 3 is disposed on a gate electrode branched from the gate bus line 11, a source electrode 5 and a drain electrode are disposed in contact therewith, and a pixel electrode 4 a is further formed on the drain electrode 4. However, the pixel electrode 4 a may also serve as the drain electrode 4.

  FIG. 11C is a schematic diagram showing that the source electrode 5, the drain electrode 4, and the pixel electrode 4a are formed from two ink jet dots. After the flowable electrode material repulsion region 6 and the source bus line 12 are formed, a droplet of the flowable electrode material is discharged onto the organic semiconductor layer 3 and the portion of the flowable electrode material repulsion region 6 formed thereon. The flowable electrode material is self-organized on 6. Accordingly, both the source electrode and the drain electrode are formed by one droplet, and the source electrode is joined to the source bus line. Similarly, the pixel electrode 4 a is formed from one inkjet droplet and is joined to the drain electrode 4. Here, the pixel electrode 4a is separated from the source electrode 5 and the source bus line 12 by the fluid electrode material repulsion region 6, thereby preventing a short circuit. Each of the fluid electrode material droplets described above may be controlled to an arbitrary liquid amount in accordance with a desired size of the electrode that can be finally formed. For example, in order to further enlarge the pixel electrode 4a, a simple electrode can be formed by enlarging a droplet for the pixel electrode and discharging the droplet to a desired position with the electrostatic suction ink jet apparatus.

  Even if the drain electrode forms the pixel electrode 4a, or the drain electrode 4 is connected to the pixel electrode 4a, and the pixel electrode and the source bus line are separated by the insulating region. Good.

A plurality of thin film transistor elements each having a channel region, a source electrode, and a drain electrode, each including a gate electrode, a gate insulating layer, and a semiconductor layer, are connected to each other via a gate bus line and a source bus line. The manufacturing method of the thin film transistor element sheet
On the channel region or the support, an insulating region having electrode material repellent property is directly or via another layer, and the capacity per droplet of ejected droplet is 1 to 400 fl and the nozzle diameter is 1 to 20 μm. Forming by the electrostatic attraction type ink jet device, and then the fluid electrode material is supplied onto the channel region or the support directly or through another layer, and the fluidity is supplied by the insulating region. The electrode material is divided and includes at least the step of forming the source electrode and the drain electrode, which will be described below.

<< Structure of insulating region having repulsive property of electrode material of thin film transistor element sheet >>
Insulating material having electrode material repellent property and insulating region The formation method by the electrostatic attraction type ink jet device is the same as that described in the thin film transistor.

<< Structure of fluid electrode material, source electrode, drain electrode, etc. of thin film transistor element sheet >>
The fluid electrode material of the thin film transistor element sheet and the method for forming the source / drain electrodes are the same as described above.

  In addition, materials such as a gate electrode, a semiconductor layer, an intermediate layer, a gate insulating layer, and a support used for the thin film transistor element sheet are the same as those described in the thin film transistor, and they are formed in the same manner as the thin film transistor.

  For example, the fluid electrode material is supplied by the electrostatic suction ink jet apparatus.

  Next, the aspect which forms an insulating area | region in the shape of a line on an element sheet | seat is demonstrated.

  FIG. 12 is an explanatory diagram of a first mode in which an insulating region is formed in a line shape on an element sheet.

  FIG. 13 is an explanatory diagram of a second mode in which an insulating region is formed in a line shape on an element sheet.

  FIG. 14 is an explanatory diagram of a third mode in which an insulating region is formed in a line shape on an element sheet.

  FIG. 15 is an explanatory diagram of a fourth aspect in which the insulating region is formed in a line shape on the element sheet.

  In FIG. 12, the organic semiconductor layer 3 is formed by, for example, an electrostatic suction ink jet apparatus that discharges a solution or dispersion of an organic semiconductor material so as to intersect the gate bus line 11. Next, the insulating region 6 is formed in a line shape while conveying a support (not shown) in a direction intersecting the gate bus line 11.

The method of forming the insulating region 6 in a line shape (also called a line pattern) is preferable.
This is a patterning method using the electrostatic suction type ink jet apparatus.

  A channel region is formed by lines of the insulating region 6 formed on the element sheet, and regions 20 and 21 are formed by simultaneously forming A and B lines.

  After forming the insulating region, the fluid electrode material is supplied to the region 20 to form the source electrode and the source bus line, and the fluid electrode material is supplied to the region 21 to form the drain electrode 4 and the pixel electrode 4a. Further, the region 21 forms a storage capacitor with the adjacent gate bus line.

  Here, after the step of forming the insulating region having the electrode material repellent property, the fluid electrode material may be supplied to the entire surface of the sheet.

  In FIG. 12, the gate bus line is also used as the gate electrode. As a result, even if the semiconductor layers 6, A, and B of each pixel are displaced in the gate bus line direction, the TFT sheet can be manufactured without any problem. Is done.

  13 has the same configuration as that of FIG. 12 except that the channel region made of the organic semiconductor layer 3 is formed on the line of the fluid electrode material repulsion region 6. The insulating region 6 is formed by the electrostatic suction ink jet device.

  In FIG. 14, the gate electrode is formed by branching from the gate bus line 11, and a channel region made of the organic semiconductor layer 3 is provided at the branch portion.

  15 is the same as FIG. 14 except that the capacitor line 22 is provided so as to face the gate bus line 11.

  Here, the channel region (also referred to as a layer) made of a semiconductor layer constituting the thin film transistor element is preferably provided so as to intersect with the gate bus line constituting the element. Here, “intersect” includes a state in which a gate bus line and a channel region formed of a semiconductor layer are in contact with each other.

  Layer formation by the ink jet method including the electrostatic attraction type ink jet apparatus described above is performed while transporting the support of the thin film transistor or the support of the thin film transistor element sheet.

  12 to 15, the above electrode material is used as a constituent material of a source electrode, a drain electrode, a source bus line, and a gate bus line, and a conductive paste (mainly composed of conductive polymer or metal fine particles) Or ink), for example, an aqueous dispersion of polystyrene sulfonic acid and poly (ethylenedioxythiophene) (Bayer Bay P manufactured by Bayer), silver paste, or aqueous dispersion of metal fine particles described in JP-A-11-80647 A liquid is preferably used.

  The thin film transistor element sheet is manufactured by the manufacturing method described above.

<< Structure of electric circuit having thin film transistor element >>
FIG. 16 is a structural diagram of a thin film transistor element.

  The electric circuit 100 of the present invention has the organic thin film transistor element shown in FIG. 16, and includes a support 1, a gate electrode 2, an insulating layer 2a, an organic semiconductor layer 3, a protective layer (intermediate layer) 3a, and a drain / source electrode 4. 5. The material, configuration, and formation method of the insulating region 6, the image receiving layer 7 and the like are the same as the material, configuration, and formation method of the above-described thin film transistor and thin film transistor element sheet.

  That is, as described in the thin film transistor and thin film transistor element sheet, the thin film transistor element in the electric circuit 100 has at least the gate electrode 2, the organic semiconductor layer 3, the source electrode 5 and the drain electrode 4 on the support 1. A step of forming the insulating region 6 having repulsion by the electrostatic suction type ink jet apparatus having a capacity per droplet of 1 to 400 fl, and then supplying a fluid electrode material to the insulating region 6 The fluid electrode material is divided at the insulating region 6 to have an organic thin film semiconductor manufactured through a process in which each of the source electrode 5 and the drain electrode 4 is formed.

  The insulating region 6 contains silicon rubber and is formed by a step of supplying an insulating region forming material to the receiving layer 7. The source electrode 5 and the drain electrode 4 are made of a fluid electrode material. It is an electric circuit having a thin film transistor element formed by supplying to the receiving layer 7.

  The insulating region 6 is formed on the organic semiconductor layer 3 containing an organic semiconductor material, and an intermediate layer 3 a is provided between the insulating region 6 and the organic semiconductor layer 3.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

Example 1
<< Production of Thin Film Transistor >>
As described below, a bottom-gate thin film transistor having a layer structure as shown in FIG. In addition, a manufacturing procedure of the thin film transistor will be described as steps (1) to (3) with reference to (1) and (3) to (6) of FIG. 1B and FIG. 5B are drawings showing the same configuration.

Step (1): (1) in FIG.
A gate electrode 2, a gate insulating layer 2a, and an organic semiconductor layer 3 were formed on the support 1 as described below to obtain a layer structure as shown in FIG.
(Production of support)
The surface of the support 1 made of a PES film having a thickness of 200 μm is subjected to a corona discharge treatment under conditions of 50 W / m ² / min, and a coating solution having the following composition is applied so as to have a dry film thickness of 2 μm. After drying for 5 minutes, it was cured for 4 seconds from a distance of 10 cm under a 60 W / cm high-pressure mercury lamp.

Dipentaerythritol hexaacrylate monomer 60g
Dipentaerythritol hexaacrylate dimer 20g
Dipentaerythritol hexaacrylate trimer or higher component 20g
Diethoxybenzophenone UV initiator 2g
Silicone surfactant 1g
75g of methyl ethyl ketone
Methyl propylene glycol 75g
Further, a 50 nm-thick silicon oxide film was provided on the layer by continuous atmospheric pressure plasma treatment under the following conditions to form an undercoat layer (not shown).
(Used gas)
Inert gas: helium 98.25% by volume
Reactive gas: oxygen gas 1.5 volume%
Reactive gas: Tetraethoxysilane vapor (bubbled with helium gas) 0.25% by volume
(Discharge conditions)
Discharge output: 10 W / cm ²
(Electrode condition)
The electrode is coated with 1 mm of alumina by ceramic spraying on a stainless steel jacket roll base material having cooling means with cooling water, and then a solution obtained by diluting tetramethoxysilane with ethyl acetate is applied and dried, and then sealed by ultraviolet irradiation. This is a roll electrode having a dielectric (relative dielectric constant of 10) adjusted so that the surface roughness (Rmax) specified in JIS B 0601 is 5 μm by performing hole treatment, smoothing the surface, and being grounded . On the other hand, as the application electrode, a hollow rectangular stainless steel pipe was coated with the same dielectric as described above under the same conditions.
(Gate electrode formation process)
Photosensitive resin 1 having the following composition was applied on the undercoat layer and dried at 100 ° C. for 1 minute to form a photosensitive resin layer having a thickness of 2 μm. (Photosensitive resin 1)
Dye A 7 parts novolak resin (phenol and m-, p-mixed novolak resin co-condensed with cresol and formaldehyde (Mw = 4000, phenol / m-cresol / p-cresol molar ratio 5/57/38, respectively) 90 parts Crystal violet 3 parts Propylene glycol monometal ether 1000 parts After exposing the gate electrode pattern at an energy density of 200 mJ / cm ² with a semiconductor laser with an oscillation wavelength of 830 nm and an output of 100 mW, the resist image is developed with an aqueous alkali solution. Obtained.

Further, after forming an aluminum film having a thickness of 300 nm on the entire surface by sputtering, the remaining part of the photosensitive resin layer was removed by MEK, whereby the gate electrode 2 was produced.
(Anodized film forming process)
After thoroughly cleaning the above film substrate, the thickness of the anodic oxide film is 120 nm using a direct current supplied from a 100 V constant voltage power source in a 50 g / L ammonium borate aqueous solution for 5 minutes. An anodized film (not shown) was prepared and washed thoroughly with ultrapure water.
(Gate insulation layer formation process)
Further, the gas used in the atmospheric pressure plasma method described above was changed to the following at a film temperature of 200 ° C. to provide a gate insulating layer 2a which is a silicon oxide layer having a thickness of 30 nm.
(Used gas)
Inert gas: helium 98.25% by volume
Reactive gas: oxygen gas 1.5 volume%
Reactive gas: Tetraethoxysilane vapor (bubbled with helium gas) 0.25% by volume
Surface treatment with HMDS (hexamethyldisilazane) was performed on the surface of the gate insulating layer.
(Organic semiconductor layer formation process)
Next, a chloroform solution of a compound (pentacene precursor) described in US Publication No. US20030193664 is discharged onto the gate insulating layer 2a to a region where a channel is to be formed using a piezo ink jet method, and nitrogen gas is discharged. Among them, the film was dried at 50 ° C. for 3 minutes and subjected to a heat treatment at 200 ° C. for 10 minutes to form an organic semiconductor layer 3 which is a pentacene thin film having a thickness of 50 nm.

Step (2): (3), (4) in FIG. 5: Formation of insulating region 6 As shown in (3), (4) in FIG. E ″ (isoparaffin hydrocarbon, manufactured by Exxon Chemical Co., Ltd.) A liquid diluted with a single solvent to a solid content concentration of 10.3% by mass was measured by an electrostatic suction ink jet apparatus having a nozzle having an inner diameter of 5 μm as shown in FIG. As shown in FIG. 5, after the ink droplet 6a was ejected, it was dried to form an insulating region (layer) 6 made of silicon rubber having a width of 3 μm in the receiving layer 7 as shown in FIG.
(Composition of Composition 2)
α, ω-divinylpolydimethylsiloxane (molecular weight about 60,000) 100 parts HMS-501 (both end methyl (methylhydrogensiloxane)
(Dimethylsiloxane) copolymer, number of SiH groups / molecular weight = 0.69 mol / g,
7 parts Vinyltris (methylethylketoxyimino) silane 3 parts SRX-212 (platinum catalyst, manufactured by Toray Dow Corning Silicon Co., Ltd.)
Part 5 Note that FIG. 1B and FIG. 5B have the same configuration.

Moreover, the preparation method of the coating liquid for forming the receiving layer 7 is as follows.
(Preparation of receiving layer coating solution)
Colloidal silica (manufactured by Nissan Chemical Industries, Ltd .: primary particle size 10 nm to 20 nm, 20% aqueous dispersion) in 3 kg, Aerosol 300 (primary particle size 7 nm) manufactured by Nippon Aerosil Co., Ltd., which is a vapor phase method silica After suction dispersion, pure water was added to prepare a 7 L dispersion. Further, 0.7 L of an aqueous solution containing 27 g of boric acid and 23 g of borax was added, and 1 g of an antifoaming agent (SN381: manufactured by San Nopco) was added.

The mixture was dispersed twice with a high-pressure homogenizer at a pressure of 2.45 × 10 ⁷ Pa to prepare a silica mixed water dispersion. While stirring at 40 ° C., 1 L of a 5% aqueous solution of polyvinyl alcohol was mixed with 1 L of this silica-mixed aqueous dispersion to prepare a receiving layer coating solution. The coating liquid was discharged as ink droplets on the surface of the organic semiconductor layer by a piezo-type ink jet device and dried at 100 ° C. in nitrogen gas to form a receiving layer having a thickness of 0.3 μm.

Step (3): (5) to (7) in FIG. 5: Formation of source electrode 5 and drain electrode 4 As shown in FIG. 5 (5), electrodes are formed on the surface of the insulating region 6 described above. A water dispersion of polystyrene sulfonic acid and poly (ethylenedioxythiophene) (Bayer's Baytron P), which is a material, is ejected as ink droplets 8 by the above-described inkjet device, and as shown in FIG. When the ink droplets 8a and 8b were divided on both sides of the region 6, the ink droplets 8a and 8b were separated and dried at 60 ° C., thereby producing the source electrode 5 and the drain electrode 6 as shown in FIG.

  Here, the steps shown in FIG. 5 (3) and FIG. 5 (5) are shown as plan views of the support 1 from above, as shown in FIG. 6 and FIG. 7 (a), respectively.

  In FIG. 5 (5), the electrode forming material immediately after ejection is present as ink droplets 8 on both the insulating region 6 and the organic semiconductor layer 3, but after a predetermined time has elapsed, (6) in FIG. As shown in FIG. 3, the ink droplet 8a and the ink droplet 8b are divided on both sides of the region 6 due to the electrode material repellent property of the insulating region 6. Finally, the ink droplet 8 a forms the source electrode 5 and the ink droplet 8 b forms the drain electrode 4.

  A thin film transistor was manufactured as described above.

  The obtained thin film transistor showed good operating characteristics of a p-channel enhancement type FET, and the carrier mobility in the saturation region was 0.2. Further, when Vd (source / drain bias) was −50 V, the ratio (on / off ratio) of drain current values when Vg (gate bias) was −30 V and 0 V was 500,000.

Example 2
As described below, a thin film transistor element sheet having the configuration shown in FIGS.

<< Production of Thin Film Transistor Element Sheet >>
Process (1)
On the support (not shown), the gate bus line 11 (when the gate bus line also serves as the gate electrode, the gate electrode is not shown) and the organic semiconductor layer 3 were provided as follows.
(Preparation of support 1)
It was produced in the same manner as in Example 1.
(Gate electrode formation process)
On the undercoat layer, the photosensitive resin 1 of Example 1 was applied in the same manner as in Example 1, and dried at 100 ° C. for 1 minute to form a photosensitive resin layer having a thickness of 2 μm. did. (Photosensitive resin 1)
The gate bus line and gate electrode patterns were exposed at an energy density of 200 mJ / cm ² with a semiconductor laser having an oscillation wavelength of 830 nm and an output of 100 mW, and then developed with an alkaline aqueous solution to obtain a resist image.

Further, a 300 nm thick aluminum film was formed on the entire surface by sputtering, and then the remaining part of the photosensitive resin layer was removed by MEK, whereby the gate bus line 11 and the gate electrode were produced. .
(Anodized film forming process)
After thoroughly washing the above film substrate, an anodized film is produced in a 50 g / L ammonium borate aqueous solution using a direct current supplied from a constant voltage power source of 100 V for 5 minutes, and washed thoroughly with ultrapure water. did.
(Gate insulation layer formation process)
Further, in the same manner as in Example 1, a gate insulating layer which is a silicon oxide layer having a thickness of 30 nm was provided at a film temperature of 200 ° C., and HMDS treatment was similarly performed.
(Organic semiconductor layer formation process)
Next, on the gate insulating layer (not shown), a chloroform solution is discharged onto the region where a channel is to be formed using a piezo-type ink jet method as described above. When it was partially dried and heat-treated at 200 ° C. for 10 minutes, an organic semiconductor layer 3 that is a pentacene thin film having a thickness of 50 nm was formed.
(Formation of intermediate layer): PVA layer (thickness 0.3 μm) is provided On the organic semiconductor layer 3, an aqueous solution obtained by dissolving sufficiently purified polyvinyl alcohol in water purified by an ultrapure manufacturing apparatus is used. And dried well at 100 ° C. in a nitrogen gas atmosphere to form an intermediate layer made of polyvinyl alcohol.

Process (2)
(Formation of fluid electrode material repulsion region 6, A, B)
Further, a liquid obtained by diluting the following composition 2 with Isopar E ″ (isoparaffinic hydrocarbon, manufactured by Exxon Chemical Co., Ltd.) alone is used to eject ink droplets by an electrostatic suction ink jet apparatus having a nozzle having an inner diameter of 5 μm. Then, it was dried and cured to form fluid electrode material repulsion regions (layers) 6, A and B made of silicon rubber having a width of 3 μm.
(Composition of Composition 2)
α, ω-divinylpolydimethylsiloxane (molecular weight about 60,000) 100 parts HMS-501 (both end methyl (methylhydrogensiloxane)
(Dimethylsiloxane) copolymer, SiH group number / molecular weight =
0.69 mol / g, manufactured by Chisso Corp.) 7 parts Vinyltris (methylethylketoxyimino) silane 3 parts SRX-212 (platinum catalyst, manufactured by Toray Dow Corning Silicon Co., Ltd.)
5 parts Carbon black 5% dispersion 15 parts Further, the intermediate layer other than the region where the fluid electrode material repulsion regions 6, A and B were provided was removed by water treatment or the like, and rinsed well with ultrapure water.

Step (3): Formation of source electrode 5, drain electrode 4, pixel electrode 4a, and source bus line 0.01% by mass of a nonionic surfactant (for example, NP15 manufactured by Nikko Chemicals), which is an electrode forming material, was added. An aqueous dispersion of polystyrene sulfonic acid and poly (ethylenedioxythiophene) (Bayer's Baytron P) is applied, and when the coating film is divided by the flowable electrode material repulsion regions 6, A, B, it is dried at 60 ° C. A film of the electrode forming material having a film thickness of 0.2 μm was formed. Further, a silver paste is applied. Similarly, when the coating film is divided by the flowable electrode material repulsion regions 6, A and B, the film is dried at 60 ° C. and heat-treated at 200 ° C. A coating film was formed.

  A channel region is formed by lines of the insulating region 6 formed on the element sheet, and regions 20 and 21 are formed by simultaneously forming A and B lines.

A fluid electrode material is supplied to the region 20 to form a source electrode and a source bus line, and a fluid electrode material is supplied to the region 21 to form the drain electrode 4 and the pixel electrode 4a. Further, the region 21 forms a storage capacitor with the adjacent gate bus line. Through the above steps, the thin film transistor element sheet of the present invention can be manufactured and driven well.

  With the inventions described in configurations 1 to 7, there is no performance variation, short channel length, high performance, low cost, and accuracy without using advanced vacuum equipment or vacuum systems or photolithography that require complicated processing steps. A thin film transistor with a high level can be provided.

  According to the inventions described in configurations 8 to 10, a thin film transistor having the above-described effects can be easily and efficiently manufactured without using a vacuum system or photolithography that requires advanced vacuum system facilities or complicated processing steps. A method for manufacturing a thin film transistor with high manufacturing stability can be provided.

  According to the inventions described in configurations 11 to 18, a thin film transistor element sheet in which a plurality of thin film transistor elements having the above-described effects are connected without using a vacuum system or photolithography that requires advanced vacuum system facilities or complicated processing steps, In addition, it is possible to provide a method for manufacturing a thin film transistor element sheet that is efficiently manufactured and has high manufacturing stability.

  According to the invention described in Structure 19, a thin film transistor element sheet in which a plurality of organic thin film transistor elements exhibiting the above-described effects are connected can be provided.

  Further, according to the inventions described in configurations 1 to 7, it is possible to provide an electric circuit including a thin film transistor element that exhibits the above-described effects.

Claims (19)

  In the thin film transistor having at least a gate electrode, a semiconductor layer, a source electrode, and a drain electrode, an insulating region having an electrode material repellent property is formed on the support by an electrostatic suction ink jet apparatus having a nozzle inner diameter of 30 μm or less. The flowable electrode material is supplied to the insulating region, and the flowable electrode material is divided by the insulating region, thereby producing each of the source electrode and the drain electrode. A thin film transistor.   2. The thin film transistor according to claim 1, wherein the insulating region contains silicon rubber.   2. The thin film transistor according to claim 1, wherein the insulating region is formed by a step of supplying an insulating region forming material to the receiving layer.   2. The thin film transistor according to claim 1, wherein the source electrode and the drain electrode are formed by supplying the fluid electrode material to the receiving layer.   2. The thin film transistor according to claim 1, wherein the insulating region is formed on the semiconductor layer by the step of forming the insulating region on the semiconductor layer.   The thin film transistor according to claim 1, wherein an intermediate layer is provided between the insulating region and the semiconductor layer.   The thin film transistor according to claim 1, wherein the semiconductor layer includes an organic semiconductor material.   2. The method of manufacturing a thin film transistor according to claim 1, wherein a step of forming an insulating region having electrode material repulsion by the electrostatic attraction type ink jet device, and a fluid electrode material supplied to the insulating region A method for manufacturing a thin film transistor, characterized by comprising a step of forming each of a source electrode and a drain electrode by being divided at the insulating region.   9. The thin film transistor according to claim 8, wherein the insulating region contains silicon rubber, and the supply of the fluid electrode material to the insulating region is performed by the electrostatic suction ink jet apparatus. Manufacturing method.   10. The method for manufacturing a thin film transistor according to claim 9, wherein the fluid electrode material supplied from the electrostatic attraction type ink jet device includes 50% by mass or more of water as a solvent or a dispersion medium. .   A thin film transistor element sheet in which a plurality of thin film transistor elements each having a channel region including a gate electrode, a gate insulating layer, and a semiconductor layer, a source electrode, and a drain electrode are connected to each other via a gate bus line and a source bus line on a support. A step of forming an insulating region having an electrode material repellent property on the channel region or the support directly or via another layer by the electrostatic suction ink jet apparatus, The conductive electrode material is supplied onto the channel region or the support directly or via another layer, and the fluid electrode material is divided by the insulating region so that at least the source electrode and the drain electrode are provided. A method for manufacturing a thin film transistor element sheet, comprising a step of forming a thin film transistor element sheet.   12. The method for manufacturing a thin film transistor element sheet according to claim 11, wherein the channel region intersects the gate bus line.   The method for manufacturing a thin film transistor element sheet according to claim 11, wherein the support is a resin substrate.   The drain electrode forms a pixel electrode, or the drain electrode is connected to the pixel electrode, and the pixel electrode and the source bus line are separated by the insulating region. A method for producing a thin film transistor element sheet according to claim 11.   12. The method of manufacturing a thin film transistor element sheet according to claim 11, wherein the fluid electrode material is supplied by the electrostatic suction ink jet apparatus.   The method for producing a thin film transistor element sheet according to claim 11, wherein the semiconductor layer contains an organic semiconductor material.   12. The method of manufacturing a thin film transistor element sheet according to claim 11, further comprising a step of supplying a fluid electrode material to the entire surface of the sheet after the step of forming the insulating region having the electrode material repellent property. .   12. The method for producing a thin film transistor element sheet according to claim 11, wherein the thin film transistor element sheet is produced while transporting the support.   A thin film transistor element sheet manufactured by the manufacturing method according to claim 11.

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