JP5104428B2 - Organic semiconductor material and field effect transistor using the same - Google Patents

Description

  The present invention relates to an organic semiconductor material that can be formed by a simple process, and a field effect transistor using the organic semiconductor material thin film.

  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 display media, a technique using an active drive element (TFT element) as an image drive element has become mainstream in order to ensure uniformity of screen brightness, screen rewrite speed, and the like. For example, in a normal computer display, these TFT elements are formed on a glass substrate, and a liquid crystal, an organic EL element and the like are sealed.

  Here, semiconductors such as a-Si (amorphous silicon) and p-Si (polysilicon) can be mainly used for the TFT element, and these Si semiconductors (and metal films as necessary) are formed into a multilayer structure. The TFT element is manufactured by sequentially forming the drain and gate electrodes on the substrate. The manufacture of such a TFT element usually requires sputtering or other vacuum manufacturing processes.

  However, in the manufacture of such a TFT element, the vacuum system manufacturing process including the vacuum chamber must be repeated many times to form each layer, and the apparatus cost and running cost have become enormous. For example, in a TFT element, it is usually necessary to repeat processes such as vacuum deposition, dope, photolithography, development, etc. many times to form each layer, and the element is formed on a substrate through several tens of processes. Yes. A plurality of types of semiconductor layers, such as p-type and n-type, are also stacked on the semiconductor portion that is the key to the switching operation. In such a conventional manufacturing method using a Si semiconductor, it is not easy to change the equipment, for example, a design change of a manufacturing apparatus such as a vacuum chamber is required in response to the need for a large display screen.

  In addition, since the formation of such a conventional TFT element using a Si material includes a process at a high temperature, the substrate material is restricted to be a material that can withstand the process temperature. Therefore, in practice, glass must be used, and when the above-described thin display such as electronic paper or digital paper is configured using such a conventionally known TFT element, the display is heavy and flexible. Products that may break due to chipping or dropping impact. These characteristics resulting from the formation of TFT elements on a glass substrate are undesirable in satisfying the need for an easy-to-carry-type thin display accompanying the progress of computerization.

  On the other hand, in recent years, organic semiconductor materials have been energetically studied as organic compounds having high charge transport properties. In addition to charge transport materials for organic EL devices, these compounds include many organic laser oscillation devices such as those discussed in Science, 289, 599 (2000), and many such as Nature, 403, 521 (2000). It is expected to be applied to organic thin film transistors reported in this paper. If these organic semiconductor devices can be realized, there is a possibility of obtaining a semiconductor that can be made into a solution by simplifying the manufacturing process by vacuum or low pressure deposition at a relatively low temperature, and further improving the molecular structure appropriately. There is also a possibility of manufacturing by a printing method including an ink jet method by converting an organic semiconductor solution into an ink. Manufacturing by these low-temperature processes has been considered impossible for conventional Si-based semiconductor materials, but there is a possibility for devices using organic semiconductors, so the above-mentioned restrictions on substrate heat resistance are relaxed. For example, a TFT element may be formed on the transparent resin substrate. If a TFT element is formed on a transparent resin substrate and the display material can be driven by the TFT element, the display is lighter and more flexible than conventional ones, and will not crack even if dropped (or very difficult to break) It can be a display.

As organic semiconductors for realizing such TFT elements, there have heretofore been acenes such as pentacene and tetracene disclosed in JP-A-5-55568, and phthalocyanines including lead phthalocyanine disclosed in JP-A-5-190877. Low molecular weight compounds such as perylene and its tetracarboxylic acid derivatives, aromatic oligomers represented by thiophene hexamers called α-thienyl or sexualthiophene disclosed in JP-A-8-264805, and polythiophene Polymer compounds such as polythienylene vinylene and poly-p-phenylene vinylene have been proposed. (Many of these are described in Advanced Materials, 2002, No. 2, pages 99-117.)
Among them, an organic transistor element having an organic semiconductor layer composed of a pentacene thin film has attracted much attention as an organic transistor because of its high carrier (charge carrier) mobility. However, pentacene has poor solubility in a solvent. Since it is a compound, it is poor in suitability for forming a semiconductor thin film by a printing process including coating and an ink jet method, and in most cases, a vacuum deposition process is used for forming a pentacene thin film. In contrast, oligomers and polymers having a solubilizing group introduced therein, for example, oligomers or polymers having 3-alkylthiophene as a repeating unit, have relatively high carrier mobility and relatively good solvent solubility, so that coating and printing are possible. It is believed that a good quality organic semiconductor thin film can be obtained by a wet process such as a process.

  An oligomer or polymer of 3-alkylthiophene is believed to move carriers by stacking some or all of the molecules so that the π orbital plane overlaps another molecule or part of a polymer chain. When stacking, the alkyl side chain extending from the 3rd position of the thiophene ring is considered to overlap between the molecules or a part of the polymer chain so as to fill the gap between each other. Poly-3-alkylthiophene appears to be able to form thin films with relatively high carrier mobility. This is a head-to-tail type thin film formed by oligo or polythiophene having regio specificity in which the 2-position of 3-alkylthiophene binds to the 5-position of the adjacent 3-alkylthiophene molecule. It is consistent with the facts well known to those skilled in the art that it has a higher carrier mobility than a thin film formed by oligo or polythiophene with a random binding mode without.

  However, these 3-alkylthiophene oligomers or polymers have side chains extending at an acute angle with respect to the direction in which the conjugated main chain extends. Therefore, even if they are oligomers or polymers having the same molecule or partial structure, the molecules are the same. In the case of orientation (that is, the following formula (a)), it is possible to have a good stack structure in which the side chains are not repelled and the π orbits overlap each other. The following formula (b)), side chains repel each other, and π orbitals cannot be superimposed on each other.

  That is, the oligomer or polymer of 3-alkylthiophene may not be able to superimpose the extended π orbital planes depending on the direction of the molecules that are approaching each other. In this case, the direction of the molecular chain is not reversed. There is a problem that a stacked structure cannot be taken as long as possible.

  Accordingly, an object of the present invention is to provide an organic semiconductor material that does not require a special alignment technique and can obtain a thin film with high carrier mobility by a simple method. In particular, the molecular orientation is reversed. However, another object is to provide a novel organic semiconductor material in which the angle between the main chain direction and the side chain is adjusted so that π orbits can be overlapped, and another object is easy to manufacture using the organic semiconductor material and An object is to provide a field effect transistor (organic thin film transistor) having high carrier mobility.

The above object of the present invention has been achieved by the following means (1) to (4). 1 to 8 are means to be referred to.
(1) A conjugated oligomer or polymer comprising a main chain having an extended conjugated bond, and a side chain linked at a bond angle of 80 to 100 degrees with a one-dimensional extension direction formed by the entire main chain. There are composed of only a thiophene ring, an organic semiconductor material and having a fused imidazole ring in the 3-position and 4-position of all thiophene rings constituting the conjugated oligomer or polymer.
(2) The organic semiconductor material as described in (1) above, wherein the side chain is a linear alkyl group.
(3) A field effect transistor comprising the organic semiconductor material according to (1) or (2).
(4) A charge transporting material and a gate electrode that is in direct or indirect contact with the charge transporting material, and an electric field is applied between the gate electrode and the charge transporting material so A field effect transistor for controlling the field effect transistor, wherein the charge transporting material is the organic semiconductor material described in (1) or (2).

  1. An organic semiconductor material comprising a conjugated oligomer or polymer comprising a main chain having an extended conjugated bond and a side chain extending in a direction substantially perpendicular to the substantial extension direction of the main chain.

  2. 2. The organic semiconductor material as described in 1 above, wherein the main chain is composed of a repeating unit containing at least one kind of aromatic ring.

  3. 3. The organic semiconductor material as described in 1 or 2 above, wherein the main chain is composed of a repeating unit containing at least either a thiophene ring or a p-phenylene ring.

  4). 4. The organic semiconductor material according to 1, 2 or 3, wherein the main chain is composed of a repeating unit containing at least a thiophene ring.

  5). 5. The organic semiconductor material as described in 3 or 4 above, wherein the substituted thiophene ring contained in the main chain has a structure in which an aromatic 5-membered ring is condensed at the 3-position and 4-position of thiophene.

  6). 6. The organic semiconductor material according to any one of 1 to 5, wherein the side chain is a linear alkyl group.

  7). A field effect transistor comprising the organic semiconductor material described in any one of 1 to 6 above.

  8). It is composed of a charge transporting material and a gate electrode that is in direct or indirect contact with the charge transporting material, and an electric field is applied between the gate electrode and the charge transporting material to control the current in the charge transporting material. 7. A field effect transistor according to claim 1, wherein the charge transporting material is the organic semiconductor material described in any one of 1 to 6 above.

  An organic semiconductor material that can be formed by a simple process was obtained, an organic field effect (thin film transistor) using the organic semiconductor material thin film, a switching element could be configured, and it was proved that it could be used for a circuit such as a display panel.

  Hereinafter, an organic semiconductor material and a field effect transistor using the material will be described.

  The organic semiconductor material according to the present invention is an oligomer or polymer having an extended conjugated bond, and has a side chain extending in a direction perpendicular to the substantial extension direction of the main chain. The substantial extension direction of the main chain here is a one-dimensional direction formed by the entire main chain when the oligomer or polymer formed by expanding the conjugation has a linear structure. It does not mean the bond angle inside or between individual repeating units. For example, in the case of poly-p-phenylene, since the repeating units continue in the same direction as the bonding angle between the p-phenylenes which are repeating units, in this case, the bonding angle between the repeating units and the substantial extension direction of the main chain In the case of polythiophene, the main chain may be bent depending on the thermal motion of molecules, the cooling rate when a thin film is formed, the state of the substrate, and other factors. However, in the absence of such factors, the polythiophene main chain is considered to extend linearly. In this case, the bond angle between the individual thiophene rings and the direction in which the main chain extends, that is, the substantial extension direction, are as follows. So different.

  The side chain of the material according to the present invention extends in a direction substantially perpendicular to the substantial extension direction of the main chain. The term “substantially orthogonal” as used herein refers to a partial structure in which a conjugated bond of a repeating unit is extended or a bond in which a side chain is linked to a cyclic structure condensed with a partial structure in which a conjugated bond is extended. The angle is perpendicular to the extension direction, and the side chain bond angle in the portion is not 90 degrees. The term “substantially orthogonal” here does not necessarily have to be exactly 90 degrees, and can be regarded as being substantially orthogonal if it is within the range of 80 to 100 degrees. . Furthermore, as is well known to researchers working in the art, the bond between the side chain and the main chain changes the angle due to the thermal motion of the molecule, etc., but this direction is used to describe the molecular structure of the molecule. It is the direction when it is considered to be in the most stable state, that is, in an energetically low state, similar to the “bond angle” used in the above. The bond angle between atoms also changes due to thermal motion, but when a researcher working in the field uses the term “bond angle”, it ignores the effect and talks about the bond angle in the most stable state. It is the same. Further, the side chain does not need to extend in the same plane as the surface formed by the extended π orbit formed by the main chain, and may form an angle in any direction above and below the expanded π orbit plane. . That is, in the mapping of the structure of the most stable state of the molecule to the plane parallel to the expanded π orbital plane formed by the main chain, if the main chain extends in a direction perpendicular to the substantial extension direction of the main chain, This is included in the category of the organic semiconductor material according to the present invention.

  The material according to the present invention preferably contains at least one kind of aromatic ring in the repeating unit. Examples of the aromatic ring include a benzene ring, a thiophene ring, a furan ring, a selenophene ring, a pyrrole ring, and a pyridine ring, which may be substituted, or condensed with other aromatic rings to form a polycyclic aromatic ring. An aromatic ring may be formed. The repeating unit containing these aromatic rings includes a structure in which these aromatic rings are linked by a conjugated bond or a structure formed by bonding with an ethylene-1,2-diyl group or an acetylenediyl group. In this structure, a conjugated bond can be formed inside the repeating unit and between the repeating units. Among these repeating units, a repeating unit containing a thiophene ring or a benzene ring is preferable. In the case of a benzene ring, it is particularly preferable that the repeating unit is incorporated in the repeating unit as a p-phenylene substituent. More preferably, it is a repeating unit having a structure in which a substituted thiophene ring is incorporated, and more preferably a repeating unit having a structure in which an aromatic 5-membered ring is condensed at positions 3 and 4 of thiophene. Examples of the aromatic ring to be condensed with respect to the ring include an imidazole ring, an oxazole ring, a thiazole ring, a selenazole ring, and a pyrrole ring.

The side chain of the organic semiconductor material according to the present invention is not particularly limited as long as it is substantially orthogonal to the substantial extension direction of the main chain, but a branched or sterically bulky substituent is included. What it does not have is preferable. Among these, a linear alkyl group is preferable, but this may be substituted. The methylene (—CH ₂ —) moiety in the side chain may be replaced with an oxygen atom or a sulfur atom to form an ether bond or thioether bond, or may be replaced with a benzene ring. Some or all of the hydrogen atoms in the alkyl chain may be replaced by halogen atoms, and preferred halogen atoms in this case include chlorine atoms or fluorine atoms. Furthermore, an aromatic group (phenyl group, naphthyl group, tolyl group, pyridyl group, pyrazolyl group, quinolyl group, imidazolyl group, benzthiazolyl group, etc.) or cyano group which may be substituted is bonded to the end part of the side chain. Also good.

  Although the example of the extended conjugated oligomer or polymer which concerns on this invention is given to the following, the aspect of this invention is not restrict | limited by this compound example. In addition, m described in the following compound examples shows a polymerization degree, and all are obtained by gel electrophoresis chromatography (polystyrene standard).

  The organic semiconductor material according to the present invention is described in J. Org. Heterocycl. Chem. , 1991, 1449-1451, Chem. Ber. , 1986, 3198-3203, J. Am. Org. Chem. 1994, 3077-3081, Phosphorous, Sulfur, Silicon, Rel. Elem. 1994, 507-508, Heterocycles, 1995, 2691, Tetrahedron Lett. 1989, 7249-7252, 2001, 7435-7438, 5327-5329, 6877-6881, J. Org. Org. Chem. , 1983, 4713-4714, J. Am. Chem. Soc. Perkin Trans2. 1999, 505-504; Med. Chem. 199, 9222-2925, 1992, 438-450, 1992, 3792-3802, J. Am. Am. Chem. Soc. , 1954, 1068-1072, Synthesis, 1975, 451, Monatsh. Chem. , 1976, 299-305, Polymer Journals, 2001, 221-226, Chem. Rev. , 2002, 1359-1469 and the like, and can be synthesized by using known chemical reactions, and in synthesizing a polymer, a gas phase polymerization method, an electropolymerization method, or the like can be used depending on the substrate. It is also possible to use known polymerization methods. The reaction may be carried out continuously or while isolating and purifying the intermediate product through steps. As a typical synthesis example, the synthesis route of Exemplary Compound 3 is shown below. As described above, the reactions at each stage of this compound synthesis are well-known reactions to researchers working in the field.

  <Synthesis Example> Exemplary Compound 3

(Synthesis of Intermediate 2)
Chlorohexane (6.3 g) was added to 10 g of thienomercaptoimidazole (1) dissolved in 100 ml of methanol, 15 ml of 28% methanol solution of sodium methoxide was added, and the mixture was stirred at reflux temperature for 3 hours. The obtained mixed solution was poured into 300 ml of water, and the organic substance extracted with ethyl acetate was purified by silica gel column chromatography to obtain 4.9 g of intermediate 2 (hexylthiothienoimidazole). (Yield 33%)
(Synthesis of Intermediate 3)
4.5 g of the intermediate 2 was converted to a 1,2-diculoethane solution, and 7 g of N-bromosuccinimide was added as a solid to the solution, followed by stirring at room temperature for 3 hours. After concentration of the obtained mixture, organic substances were extracted with ethyl acetate and purified by silica gel column chromatography to obtain 7.1 g of intermediate 3 (hexylthiodibromothienoimidazole). (Yield 95%)
(Synthesis of Exemplary Compound 3)
Under a nitrogen atmosphere, a solution obtained by dissolving 7 g of 30 g of Intermediate 3 in 30 ml of tetrahydrofuran was gradually added dropwise to magnesium particles (0.5 g) placed in tetrahydrofuran to maintain a state where fine foaming from the magnesium particles was maintained. Then, the dropwise addition of the solution of Intermediate 3 was continued. After completion of the dropwise addition, the obtained solution was stirred at 50 ° C. for 1 hour to complete the reaction between the intermediate 3 and magnesium. After the reaction mixture was allowed to cool, this solution was extracted from the reaction vessel with a syringe, and a suspension in which 0.4 g of (1,3-bis (diphenylphosphino) propane) nickel chloride was dispersed in 15 ml of tetrahydrofuran was contained. The reaction vessel was added to a nitrogen atmosphere. The mixture was heated to 50 ° C. and stirred for 12 hours. The obtained reaction mixture was poured into dilute hydrochloric acid to stop the reaction, and insoluble matter was collected by filtration and washed with water, methanol and an aqueous solution of ethylenediaminetetraacetic acid to obtain 1.2 g of dark brown solid of Exemplified Compound 3.

  The organic semiconductor material according to the present invention can be applied by dissolving in a solvent such as ethanol, methanol, tetrahydrofuran, dioxane, methyl ethyl ketone, chloroform, methylene chloride, N-methylpyrrolidone, N, N-dimethylformamide as a solvent. Further, if necessary, an aqueous or oil-based ink to which an appropriate additive is added can be prepared and printed by screen printing, an ink jet method, or the like. Furthermore, transfer may be performed to a substrate on which an electric element is to be formed by an ablation method using a substrate coated with the organic semiconductor material and an appropriate photothermal conversion material.

  The thin film thus formed may be annealed at a temperature not exceeding 200 ° C., for example, during drying after coating. Annealing may be performed in air, but may be performed in an inert atmosphere such as nitrogen or argon, or may be performed in a hydrogen atmosphere.

  In addition, the organic semiconductor materials according to the present invention include Lewis acids (iron chloride, aluminum chloride, antimony bromide, etc.), halogens (iodine, bromine, etc.), hydrohalic acids or salts thereof, sulfonic acids or salts thereof (polystyrene). A sodium salt of sulfonic acid, potassium p-toluenesulfonate, etc.) may be doped, and the conductivity can be adjusted by doping.

  Field effect transistors comprising these organic semiconductor materials can be advantageously used for the production of various devices such as switching elements as thin film field effect transistors.

  That is, a field effect transistor using an organic thin film made of these organic semiconductor materials uses the organic semiconductor material according to the present invention as a charge transporting material, and a gate insulating layer made of a dielectric, for example, in the charge transporting material layer. And a source electrode and a drain electrode provided in contact with the charge transporting material layer. By applying an electric field between the gate electrode and the source electrode, the source and drain electrodes are formed. The current between them (ie the current in the charge transport material layer) is controlled.

  Next, field effect transistors using these organic semiconductor materials and thin films thereof will be described.

  The gate electrode, the source electrode, and the drain electrode used in the field effect transistor are not particularly limited as long as they are conductive materials. Platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, Indium, palladium, tellurium, rhenium, iridium, aluminum, ruthenium, germanium, molybdenum, tungsten, tin oxide / antimony, indium tin oxide (ITO), fluorine-doped zinc oxide, zinc, carbon, graphite, glassy carbon, silver paste and Carbon paste, lithium, beryllium, sodium, magnesium, potassium, calcium, scandium, titanium, manganese, zirconium, gallium, niobium, sodium, sodium-potassium alloy, magnesium, lithium, aluminum Magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide mixture, lithium / aluminum mixture, etc. are used, in particular, platinum, gold, silver, copper, aluminum, indium, ITO and carbon are preferred. Alternatively, a known conductive polymer whose conductivity is improved by doping or the like, for example, conductive polyaniline, conductive polypyrrole, conductive polythiophene, a complex of polyethylenedioxythiophene and polystyrenesulfonic acid, or the like is also preferably used. Of the source electrode and the drain electrode, those having low electrical resistance at the contact surface with the organic semiconductor material layer are preferable.

  As a method for forming an electrode, a method for forming an electrode using a known photolithographic method or a lift-off method from a conductive thin film formed using a method such as vapor deposition or sputtering using the above as a raw material, or a metal foil such as aluminum or copper There is a method of etching using a resist by thermal transfer, ink jet or the like. Alternatively, the conductive polymer solution or dispersion, or the conductive fine particle dispersion may be directly patterned by ink jetting, or may be formed from the coating film by lithography, laser ablation, or the like. Furthermore, a method of patterning an ink containing a conductive polymer or conductive fine particles, a conductive paste, or the like by a printing method such as a relief printing plate, an intaglio printing plate, a planographic printing plate or a screen printing can be used.

  Further, the signal lines, the scanning lines, the display electrode materials, the formation method, and the like in the case of producing these as TFT sheets are the same as described above.

  Various insulating films can be used for the gate insulating layer used in these organic semiconductor materials and thin film field effect transistors, and 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 trioxide yttrium. Of these, silicon oxide, aluminum oxide, tantalum oxide, and titanium oxide are preferable. Inorganic nitrides such as silicon nitride and aluminum nitride can also be suitably used.

  Examples of the method for forming the film include a vacuum process, a molecular beam epitaxial growth method, an ion cluster beam method, a low energy ion beam method, an ion plating method, a CVD method, a sputtering method, an atmospheric pressure plasma method, and the like, spraying Examples include a wet process such as a coating method, a spin coating method, a blade coating method, a dip coating method, a casting method, a roll coating method, a bar coating method, a coating method such as a die coating method, and a patterning method such as printing or inkjet. 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 necessary, 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 atmospheric pressure plasma method and the sol-gel method are preferable.

  Plasma film formation under atmospheric pressure refers to 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. No. 11-133205, JP-A No. 2000-185362, JP-A No. 11-61406, JP-A No. 2000-147209, JP-A No. 2000-121804, etc. (hereinafter also referred to as atmospheric pressure plasma method). Accordingly, a highly functional thin film can be formed with high productivity.

  Examples of the organic compound film used as the insulating layer include polyimide, polyamide, polyester, polyacrylate, photo radical polymerization type, photo cation polymerization type photo curable resin, copolymer containing acrylonitrile component, polyvinyl phenol, polyvinyl There are phosphazene compounds including alcohol, novolac resin, cyanoethyl pullulan, polymer, and elastomer. 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.

  In the present invention, a material having a functional group such as acrylic acid, acetamide, dimethylamino group, cyano group, carboxyl group, nitro group, benzoquinone derivative, tetracyanoethylene and tetracyanoquinodimethane is used in the organic semiconductor material layer. And materials that serve as acceptors for accepting electrons such as derivatives thereof, materials having functional groups such as amino group, triphenyl group, alkyl group, hydroxyl group, alkoxy group, and phenyl group, substituted amines such as phenylenediamine Materials such as donors such as anthracene, anthracene, benzoanthracene, substituted benzoanthracenes, pyrene, substituted pyrene, carbazole and derivatives thereof, tetrathiafulvalene and derivatives thereof, and so-called doping Processing may be performed.

The doping means introducing an electron-donating molecule (acsector) or an electron-donating molecule (donor) into the thin film as a dopant. Either an acceptor or a donor can be used as the dopant used in the present invention. As the acceptor, halogen such as Cl ₂ , Br ₂ , I ₂ , ICl, ICl ₃ , IBr, IF, etc., Lewis acid such as PF ₅ , AsF ₅ , SbF ₅ , BF ₃ , BC 1 ₃ , BBr ₃ , SO ₃ , HF HC1, HNO ₃ , H ₂ SO ₄ , HClO ₄ , FSO ₃ H, ClSO ₃ H, CF ₃ SO ₃ H and other protonic acids, acetic acid, formic acid, amino acids and other organic acids, FeCl ₃ , FeOCl, TiCl ₄ , Transition metals such as ZrCl ₄ , HfCl ₄ , NbF ₅ , NbCl ₅ , TaCl ₅ , MoCl ₅ , WF ₅ , WCl ₆ , UF ₆ , LnCl ₃ (Ln = La, Ce, Nd, Pr, etc. and lanthanoids and Y) Examples thereof include compounds, Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , PF ₆ ⁻ , AsF ₅ ⁻ , SbF ₆ ⁻ , BF ₄ ⁻ , electrolyte anions such as sulfonate anions, and the like. As donors, alkaline metals such as Li, Na, K, Rb, and Cs, alkaline earth metals such as Ca, Sr, and Ba, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, and Dy , Ho, Er, Yb and other rare earth metals, ammonium ions, R ₄ P ⁺ , R ₄ As ⁺ , R ₃ S ⁺ (R is an alkyl group, aryl group, etc.), acetylcholine, and the like. As a method for doping these dopants, either a method of preparing a thin film of an organic semiconductor material in advance and introducing a dopant later, or a method of introducing a dopant when forming a thin film of an organic semiconductor material can be used. As the doping of the former method, gas phase doping using a dopant in a gas state, liquid phase doping in which a solution or liquid dopant is brought into contact with the thin film, and solid doping in which a dopant in the solid state is brought into contact with the thin film and diffusion doping is performed. A method of phase doping can be mentioned. In liquid phase doping, the efficiency of doping can be adjusted by applying electrolysis. In the latter method, a mixed solution or dispersion of an organic semiconductor compound and a dopant may be simultaneously applied and dried. For example, when using a vacuum evaporation method, a dopant can be introduce | transduced by co-evaporating a dopant with an organic-semiconductor compound. When a thin film is formed by a sputtering method, a dopant can be introduced into the thin film by sputtering using a binary target of an organic semiconductor compound and a dopant. Still other methods include chemical doping such as electrochemical doping, photoinitiated doping, and physical methods such as ion implantation shown in the publication {Industrial Materials, Vol. 34, No. 4, p. 55, 1986}. Any of the chemical dopings can be used.

  As a method for producing an organic semiconductor material thin film, in addition to the above-described printing, screen printing, inkjet printing, and other printing methods, a vacuum deposition method, a molecular beam epitaxial growth method, an ion cluster beam method, a low energy ion beam method, an ion plating method. Method, CVD method, sputtering method, plasma polymerization method, electrolytic polymerization method, chemical polymerization method, spray coating method, spin coating method, blade coating method, dip coating method, cast method, roll coating method, bar coating method, die coating method and Examples include the LB method, which can be used depending on the material. However, among these, in terms of productivity, spin coating methods, blade coating methods, dip coating methods, roll coating methods, bar coating methods, die coating methods, etc. that can easily and precisely form thin films using organic semiconductor material solutions. A coating method is preferred. The thickness of the thin film made of these organic semiconductor materials is not particularly limited, but the characteristics of the obtained transistor are often greatly influenced by the thickness of the active layer made of the organic semiconductor material. Although it varies depending on the type of organic semiconductor material, it is generally 1 μm or less, preferably 10 to 300 nm.

  Also, it does not require a high temperature for its formation and does not require a heat-resistant substrate such as a glass substrate, so an organic semiconductor material thin film, a field effect transistor using this, a switching element, etc. on an insulating support such as various plastic films The TFT sheet serving as a driving element for driving the display material in units of each pixel used in various display panels can be made flexible.

  As the flexible insulating sheet, for example, a plastic film can be used as the sheet. Examples of plastic films include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), and cellulose triacetate. Examples thereof include films made of (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.

  Furthermore, a plasticizer such as trioctyl phosphate or dibutyl phthalate may be added to these plastic films, or a known ultraviolet absorber such as benzotriazole or benzophenone may be added. In addition, a resin prepared by applying a so-called organic-inorganic polymer hybrid method in which a raw material of an inorganic polymer such as tetraethoxysilane is added and the molecular weight is increased by applying energy such as a chemical catalyst, heat, or light. It can also be used as a raw material.

(Embodiment of the Invention)
Below, the field effect transistor using the organic-semiconductor material thin film which consists of an electroconductive material concerning this invention is demonstrated.

  FIG. 1 shows a schematic configuration example of a field effect transistor using the organic semiconductor material of the present invention. In FIG. 2A, a source electrode 2 and a drain electrode 3 are formed on a support 6 with a metal foil or the like, and an organic semiconductor material layer 1 made of the conductive material of the present invention is formed between both electrodes. A field effect transistor is formed by forming an insulating layer 5 on the substrate and further forming a gate electrode 4 thereon. FIG. 2B shows the organic semiconductor material layer 1 formed between the electrodes in FIG. 1A so as to cover the entire surface of the electrode and the support using a coating method or the like. (C) shows that the organic semiconductor material layer 1 is first formed on the support 6 by using a coating method or the like, and then the source electrode 2, the drain electrode 3, the insulating layer 5, and the gate electrode 4 are formed.

  In FIG. 4D, after forming the gate electrode 4 on the support 6 with a metal foil or the like, the insulating layer 5 is formed, and the source electrode 2 and the drain electrode 3 are formed on the metal foil or the like on the insulating layer 5. An organic semiconductor material layer 1 made of the conductive material of the present invention is formed between the electrodes. In addition, it is also possible to adopt a configuration as shown in FIGS.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

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

Example 1
1 g of a regioregular body of poly (3-n-hexylthiophene-2,5-diyl) (manufactured by Aldrich, average molecular weight 90000 measured by gel electrophoresis chromatography) was dissolved in 10 ml of chloroform, and this was dissolved in polyethersulfone (PES). On the film, the polymer film was formed by apply | coating with an applicator (thickness 120 micrometers), and drying naturally, and the organic-semiconductor material A was obtained.

  Using a solution obtained by dissolving 100 mg of Exemplified Compound 3 (average polymerization degree 6 measured by gel electrophoresis chromatography) synthesized according to the synthesis route in 1 ml of chloroform, a polymer film is formed in the same manner as in the organic semiconductor material A, An organic semiconductor material B was obtained.

  The organic semiconductor materials A and B were each immersed in a 2 mol / L hydrochloric acid aqueous solution at 20 ° C. for 12 hours and vacuum-dried at 40 ° C. Then, the electrical conductivity of the sample was measured. The relative value of the electrical conductivity of the organic semiconductor material B with a conductivity of 100 was 161, and it was confirmed that the electrical conductivity of the organic semiconductor material B of the present invention was greatly improved.

Example 2
A thermal oxide film having a thickness of 300 nm was formed on an n-type doped silicon substrate, and then gold having a thickness of 50 nm was deposited on the oxide film, and source and drain electrodes having a gap of 10 μm were formed by photolithography. Next, an organic semiconductor material layer having a thickness of 30 nm was formed by spin-coating a well-purified chloroform solution of Exemplified Compound 3 of the present invention to obtain an organic field effect transistor (thin film transistor).

  The produced organic field effect transistor exhibits a switching function by ON / OFF of the voltage between the gate and source electrodes (gate voltage), and also has a high current value in a switching ON state at a low gate voltage. It was confirmed that the / OFF ratio is high and has a good switching function.

  The organic field effect transistor (thin film transistor) formed according to the present invention can be formed by patterning with a simple and efficient process using coating or the like than that formed by the conventional method. A large amount of equipment is not required, and high-accuracy patterning can be efficiently performed at low cost.

  In addition, despite the fact that the constituent layers such as the organic semiconductor material layer are formed by a simple method such as a coating method, the accuracy of electrode pattern formation is good. There are few variations that become barriers.

It is a figure which shows the schematic structural example of the field effect transistor using an organic electroconductive material.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Organic-semiconductor material layer 2 Source electrode 3 Drain electrode 4 Gate electrode 5 Insulating layer 6 Support body

Claims (4)

A conjugated oligomer or polymer comprising a main chain having an extended conjugated bond and a side chain linked at a bond angle of 80 to 100 degrees with a one-dimensional extension direction formed by the whole main chain, wherein the main chain is a thiophene ring It is composed of only an organic semiconductor material and having a fused imidazole ring in the 3-position and 4-position of all thiophene rings constituting the conjugated oligomer or polymer. The organic semiconductor material according to claim 1, wherein the side chain is a linear alkyl group. A field effect transistor comprising the organic semiconductor material according to claim 1. It is composed of a charge transporting material and a gate electrode that is in direct or indirect contact with the charge transporting material, and an electric field is applied between the gate electrode and the charge transporting material to control the current in the charge transporting material. 3. A field effect transistor according to claim 1, wherein the charge transporting material is the organic semiconductor material according to claim 1.

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