TW201000430A - Chemical compound used for organic thin film transistor and organic thin film transistor - Google Patents

Abstract

Disclosed is an organic thin film transistor, which is provided with at least three terminals of a gate electrode, a source electrode, and a drain electrode, an insulating layer, and an organic semiconductor layer, on a substrate and controls an electric current between the source-drain electrodes by applying a voltage to the gate electrode. The organic semiconductor layer comprises a specific organic compound having an aromatic hydrocarbon group or a heteroaromatic ring group and an acetylene structure at the center. The organic thin film transistor emits light by making use of an electric current flowing between the source-drain electrodes and controls the emitting light by applying a voltage to the gate electrode. Further, a chemical compound suitable for the organic thin film transistor is disclosed.

Description

201000430 VI. INSTRUCTION DESCRIPTION: No. C. The invention relates to an organic thin film transistor in which an organic thin film transistor is used in an organic semiconductor layer. [Prior Art 3] BACKGROUND OF THE INVENTION A thin film transistor (TFT) is widely used as a switching element for display of a liquid crystal display device $. The cross-sectional structure of a representative TFT is shown in Fig. 3. As shown in the figure, a typical TFT has a gate electrode, an insulator layer, and an organic semiconductor layer in this order, and the organic semiconductor layer has a source electrode and a drain electrode which are formed at predetermined intervals. The organic semiconducting layer is formed as a channel region, and a current flowing between the source electrode and the drain electrode is pressed by a voltage applied to the gate electrode, thereby performing a switching operation.

X is produced by using an amorphous or a polycrystalline stone in such a TFT system, and a chemical vapor deposition apparatus using the germanium for the production of a TFT is very expensive, and a display device using the TFT is used. The enlargement of the size is accompanied by a problem of greatly increasing the manufacturing cost. The process of forming an amorphous poem or a polycrystalline film into a film is performed at a very high temperature, and therefore, the type of material that can be used as a substrate is very limited. 'There is a problem that a lightweight resin substrate cannot be used. In order to solve such a problem, a TFT in which an organic substance is used in place of a non-daily or a polycrystalline germanium (hereinafter, abbreviated as Organic Tft 3 201000430) is disclosed. When a Tft is formed from an organic material, a vacuum deposition method, a coating method, and the like are known, and the film formation method used can suppress an increase in the production cost, and a film formation method such as a film can be realized. The required process temperature can be carried out at a lower temperature. 2 Large-scale 'Selection of materials for film formation, organic TFTs have limitations on the substrate used

The advantage of the organic eve, the practical application of the organic TFT is _, and a lot of research is organically used as an organic semiconductor for organic TFT, as a material of a ς-type FET (field effect transistor), a conjugated polymer or thiophene A condensed aromatic hydrocarbon material such as a multimeric complex, a metal phthalocyanine compound or a condensate is used in the state of a single substance or a compound of another compound. Further, as a material of the n-type FET, for example, m,5,8-naphthalene tetraphthalic anhydride (NTCDA), 11,11,12,12-tetracyanophthalene-2,6_salina methane (TCNNQD) is known. ), 1,4,5,8-naphthalene tetracarboxydiimide or fluorinated phthalocyanine. On the other hand, it is also used as an apparatus for electrical conduction, an organic electroluminescence (EL) element. In an organic EL device, a strong electric field of 105 V/cm or more is applied in a film thickness direction of an ultrathin film of 10 nm or less, and a charge is forcibly passed. In the case of an organic TFT, With an electric field of 1 〇 5 v/cm or less, there is a need to allow a charge to pass through a distance of several μm or more at a high speed, and the organic substance itself becomes more conductive. However, in the conventional organic TFT, the above-mentioned compound has a small field effect mobility, and the response speed is slow, and high-speed responsiveness as a transistor is problematic. Also, the switch ratio is also small. In addition, the switch ratio referred to here refers to the current flowing between the source and the drain when the gate voltage is applied (open) divided by the source and the voltage when the gate voltage is not applied (off) 201000430 The value obtained by the current flowing between the poles, the open current is the current value at which the gate voltage is increased, and the current flowing between the source and the drain is saturated (saturation current). As a material of the organic TFT, there are reports using the following materials as the crystal material (Non-Patent Documents 1 and 2). · Para-quarter phenyl (4Ph) having a plurality of combinations of stupid rings, and - Para-quinquephenyl (5Ph), para-sexiphenyl (6Ph). However, the degree of mobility is low, and it is not possible to exhibit the characteristics of the transistor if the substrate is not heated during the fabrication of the device. Further, Patent Document 1 discloses that once BiS(2-aCenyl)acetylene is used as the transistor material, high mobility is exhibited. However, in the present literature, the halogen atom-substituted naphthalene, anthracene, and fused tetraphenyl which are used as a raw material for the synthesis of the compound are disadvantageous in comparison with the benzene substituted by the _ atom. [Patent Document 1] US 7,109,519 B2 [Non-Patent Document 1] G. Horowitz et al., published in Synthetic Metals, Vol. 41-43, p. 1127, 1991 [Non-Patent Document 2] DJGundlach et al. Published in Applied Physics Letter, Vol. 71, page 3853, 1997

C. SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide a compound for an organic thin film transistor which is easily obtained by a general synthesis method and can be produced by a general synthesis method. Low cost, 5 201000430 and the object of the present invention also provides an organic thin film transistor, which is used as a rider semiconductor layer to correct the high response speed (drive speed). Disclosure of the Invention The present inventors have found that, in order to achieve the above object, the organic semiconductor layer of the organic thin (tetra) crystal can be synthesized simply and inexpensively by using the following formula (1). The compound for a thin film transistor can speed up the response speed (driving speed), and completed the present invention. Namely, the present invention is a compound for an organic thin film transistor having a structure of the following formula (1). [Chemical Formula 1] X Α "ι (1) In the formula (1), the X system does not have any of the three structures of the following formulas (2) to (4). [Chemical Formula 2]

In the formula, Ar is an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having a carbon number of 〇6 to 6 or a group having a structure obtained by linking 2 ingots. Each group may have a substituent. In the formula, R1 to R5 are each a hydrogen atom, a halogen atom, an alkyl group having a carbon number of 〜3〇, a dentate group having a carbon number of 1 to 30, an alkoxy group having a carbon number of 1 to 30, and a carbon number of 〜3.函 函 函 氧基 氧基 氧基 氧基 氧基 氧基 氧基 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 It may also be combined to form a ring structure containing tl atoms), a sulfur-burning ketone group having a carbon number of 1 to 30, a haloalkylthio group having a carbon number of 1 to 30, an aromatic hydrocarbon group having a carbon number of 6 to 60, and carbon. a group of 3 to 60 aromatic heterocyclic groups, a group having a structure in which the aromatic groups are bonded via 2 or more rings; an alkylene group having 3 to 20 carbon atoms; and an alkynyl acetylene group having 5 to 60 carbon atoms; (alkylsilyl acetylenic group) or cyano group, these groups may also have a substituent. In the formula, R6 to R15 are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, a haloalkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and a carbon number of 1 to 3; a haloalkoxy group, an alkylthio group having 1 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms, an alkylamino group having a carbon number of 30, and a dialkylamino group having 2 to 60 carbon atoms ( The alkyl groups may be bonded to each other to form a ring structure containing a nitrogen atom, an alkylthio group having 1 to 30 carbon atoms, a halogenated sulfuric acid group having a hindrance of 1 to 30, an aromatic hydrocarbon group having 6 to 60 carbon atoms, and a carbon number. An aromatic heterocyclic group of 3 to 60, which may have a substituted alkyl group of 3 to 20, an alkylsilyl acetylenic group or a cyano group, or a cyano group. Each group may have a substituent or may be formed by bonding adjacent groups to each other: an aromatic hydrocarbon group having a number of 6 to 60, an aromatic heterocyclic group having a carbon number of 3 to 6 Å, or a broken number of 6 to 6 60 saturated ring structure. Further, the present invention provides an organic thin film transistor which is provided on at least a substrate: a gate electrode, a source electrode, and a terminal of a terminal electrode, an insulator layer, and an organic semiconductor layer' and by applying a voltage to the gate The electrode controls the current between the source and the drain. In the organic thin film transistor, the organic semiconductor layer contains an organic compound having the structure of the above formula (1). Further, the present invention provides an organic thin film light-emitting transistor in which an organic thin film transistor emits light by a current flowing between a source and a drain, and emits light by applying a voltage to a gate electrode. The compound for an organic thin film transistor of the present invention is easily obtained, and since it can be synthesized by a general synthesis method, it can be synthesized at a low production cost. Once this compound is used as the organic semiconductor layer, a thin film transistor having a high-speed response speed (driving speed) can be provided. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an example of the structure of an element of an organic thin film transistor of the present invention. Fig. 2 is a view showing an example of the element structure of the organic thin film transistor of the present invention. Fig. 3 is a view showing an example of the element structure of the organic thin film transistor of the present invention. . Fig. 4 is a view showing an example of the element structure of the organic thin film transistor of the present invention. Fig. 5 is a view showing an example of the element structure of the organic thin film transistor of the present invention. Fig. 6 is a view showing an example of the element structure of the organic thin film transistor of the present invention. Fig. 7 is a view showing an example of the element structure of the organic thin film transistor in the embodiment of the present invention. Fig. 8 (1) to (4) are views showing a manufacturing procedure of a source electrode and a drain electrode having a hole injecting electrode and an electron transporting electrode. 201000430 Γ 系 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS BEST MODE FOR CARRYING OUT THE INVENTION The compound for organic thin film transistor of the present invention has the following formula (1) [Chemical Formula 3] In the above formula (1), the Ari carbon number is 6 An aromatic hydrocarbon group of ～60 or an aromatic heterocyclic group of carbon number (6), or a structure obtained by linking these aromatic groups via two or more rings, and each of these groups may have a substituent. In the above formula (1), VIII is preferably a substituted or unsubstituted aromatic hydrocarbon group having 6 to 6 Å carbon atoms. In the above formula (1), a substituted or unsubstituted aromatic heterocyclic group having 1 to 60 carbon atoms is preferred.

V, as a specific example of the above-mentioned aromatic hydrocarbon group, may be exemplified by substituted benzene, naphthalene, anthracene, fused tetraphenyl cresine, phenanthrene, phenanthrene, ternary triphenyl, and cornnulene. ), 蔻, male burial 4 - (hexabenzotriphenylene), hexabenzocoronene (hexabenzocoronene), tricyclopentadiene and triphenylene (sumanene) and other residues. Specific examples of the aromatic heterocyclic group of Ar! include, by way of substitution, pyridine, pyrazine, quinoline, naphthyridine, benzopyrazine, phenazine, diazaanthracene, . Bibiquinoline, pyrimidine and quinazoline 9 201000430 (pyrimidoquinazoline), ° ratio ° Qin Qinlin, Fei Luolin, ° card ° sit, two stupid and sighed, swearing and swearing, two orders. Diphene, dibenzofuran, benzodiazepine, dithiaindacene, dithiaindenoindene, dibenzoselenophene, diterpenoid Diselena-indacene, diselena-indenoindene, dibenzosilole, [1] benzothieno[3,2-b]benzo Residues of thiophene and the like. The structure in which the above-mentioned aromatic groups are linked by two or more rings is a combination of the specific examples of the aromatic hydrocarbon group and the aromatic heterocyclic group, and specific examples thereof include: Benzene, terphenylene, binaphthyl, hydrazine, phenylthiophene, thienylnaphthalene, fluorenyl hydrazine, phenylnaphthalene, phenylhydrazine, acridinylnaphthalene. Residues such as bite base, singer, triple thiophene, etc. In the above formula (1), the substituent may have a substituent, and preferably has a group selected from the group consisting of benzene, naphthalene, anthracene, fused tetraphenyl, pentacene, phenanthrene, chopsticks. Bipyridine, pyrazine, quinoline, naphthyridine, benzopyrazine, phenazine, diazaanthracene, pyridoquinoline, pyrimidoquinazoline, pyrazinquinoxaline, phenanthroline, anthracene Oxazole, dibenzothiophene, thienothiophene, dithiophene, 1%, [1] exemplified by α-seceno[3,2-b]benzophenone, extended di-phenyl, terphenylene , binaphthyl, hydrazine, thiophene, thienylnaphthalene, thiophene, phenylnaphthalene, phenyl hydrazine. Pyridylnaphthalene, „pyridinyl hydrazine, bithiophene, and terphenylthiophene. As the above hydrazine 12 substituent, it may be listed as an aromatic hydrocarbon group, an aromatic heterologous group, an alkyl group, an alkoxy group, an aryloxy group, or an aromatic group. Sulfur group, alkoxycarbonyl group, 10 201000430 amine group, south atom, cyano group, nitro group, hydroxyl group, carboxyl group, etc. In the formula (1), the X system can be represented by the following formulas (2) to (4). Any of the structures. [Chemical Formula 4]

In the formulae (2) to (4), each of R1 to R5 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, a chiral alkyl group of a carbon number, an alkoxy group having a carbon number, and carbon. a 1 to 30-tooth alkoxy group, a C 1 to 30 alkylthio group, a C 1 to 30 haloalkylthio group, a C 1 to 30 alkylamino group, and a C 2 to 60 dioxane Amino groups (alkyl groups may also be bonded to each other to form a ring structure containing a nitrogen atom), a carbon number of oxathiol groups, a halogenated thiol group having a carbon number of 1 to 30, and a carbon number of 6 to 60 a hydrocarbon group, an aromatic heterocyclic group having 3 to 60 carbon atoms, a group having a structure in which the aromatic groups are bonded via two or more rings; a calcined carbon group having a carbon number of 3 to 20, and a number of 5 to 60 /% alkylsilyl acetylenic group or cyano group, these groups may also have a substituent. In the above formula (1), each of R6 to R15 is a halogen atom, a halogen atom, a condensed group having 1 to 30 carbon atoms, a halogen group having 1 to 30 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, and charcoal. a halogenated alkoxy group having a number of 1 to 30, a sulfur-burning group having a hindrance of 1 to 30, a sulfur-burning sulfur group having a hindrance of 1 to 3 Å, an alkyl group having a carbon number of 1 to 30, and a carbon number of 2 to 6 Å. Dialkylamino group (the base can also be combined to form a ring structure containing a nitrogen atom), a sulphur-burning base having a carbon number of 丨~3〇, an iS institute sulfur-based base having a carbon number of 1 to 30, and a carbon number of 6~ 60 aromatic hydrocarbon group, carbon number 3 to 60 aromatic heterocyclic group, carbon number 3 to 2 fluorene fluorenyl group, carbon number 11 201000430 5~60 of aikylsilyl acetylenic group or cyano group Each of the groups may have a substituent. Further, among R6 to r15, an aromatic hydrocarbon group having an interference ratio of 6 to 60 and an aromatic heterocyclic ring having a carbon number of 3 to 60 may be formed by bonding adjacent groups to each other. a saturated or cyclic structure having a carbon number of 6 to 60. In the above formula (1), R1 to R are preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkylsilyi acetylenic group having a carbon number of 5 to 60, or a carbon number. 3 〇 alkyl or cyano. In the above formula (1), among R6 to R15, at least two adjacent groups are preferably bonded to each other to form an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 3 to 60 carbon atoms. Further, the compound for an organic thin film transistor of the present invention basically exhibits two polarities of p-type (hole conduction) and n-type (electron conduction), and can be used as ρ by a combination of source and electrodeless electrodes to be described later. The type element is driven as an n-type element. However, in the above formula (1), by using the electron accepting group as a substituent on An or Ri~Ris, the lowest unoccupied orbit (LUMO) is lowered, which is effective. It is the function of n-type semiconductors. The electron accepting group is preferably a hydrogen atom, a dentate atom, a cyano group, an alkyl group having 1 to 30 carbon atoms, a haloalkoxy group having 1 to 30 carbon atoms, and a tooth having a carbon number of 1 to 30. Sulfur brewing base. Further, by using the electron supply group as the substituent on R1 to R15 and An to raise the highest occupied orbital level, it can function as a germanium type semiconductor. The electron supply property is preferably a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, or a dialkyl having 2 to 60 carbon atoms. Amino groups (amine groups may also be bonded to each other to form a ring structure containing a nitrogen atom). 12 201000430 Specific examples of the respective groups shown by R1 to R15 in the formula (1) will be described below. Examples of the i-electron atom include fluorine, gas, bromine and iodine atoms. As the alkyl group, a mercapto group, an ethyl group, a propyl group, an isopropyl group, an η-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, a η-fluorenyl group, an η-hexyl group, and the like are exemplified. Η-heptyl, η-octyl, η-fluorenyl, η-fluorenyl, η-undecyl, η-dodecyl, η-tridedecyl, η-tetradecyl, η-pentadecayl, Η-hexadecyl, η-heptadecyl, η-octadecyl, η-ninedecyl, η-twenthylene, η-dioxin-alkyl, η-twenthyl, η- Twenty-three burnt base, η- twenty-four burnt base, η- twenty-fifth burnt base, η-tifteen burntyl group, η-27 heptane > base, η-octadecyl burnt, η- Twenty-nine burning base, η-thirty yard base, etc. As the above haloalkyl group, for example, a chloromethyl group, a 1-oxyethyl group, a 2-oxyethyl group, a 2-chloroisobutyl group, a 1,2-dichloroethyl group, a 1,3-dichloro group can be exemplified. Isopropyl, 2,3-dioxa-t-butyl, 1,2,3-trichloropropyl, bromomethyl, 1-bromoethyl, 2-bromoethyl, 2-bromoisobutyl, 1,2-dibromoethyl, 1,3-dibromoisopropyl, 2,3-dibromo-t-butyl, 1,2,3-tribromopropyl, iodonyl, 1-iodoethyl Base, 2-decylethyl, 2-mothisobutyl, 1,2-diethylidene, 1,3-diironisopropyl, 2,3-diiodo-t-butyl, 1,2, 3-triiodopropyl, fluoromethyl, 1-fluoromethyl, 2-fluoromethyl, 2-fluoroisobutyl, 1,2-difluoroethyl, difluoromethyl, trifluoromethyl, five Fluoroethyl, perfluoroisopropyl, perfluorobutyl, perfluorocyclohexyl, and the like. The alkoxy group is represented by a group of -OX1, and examples of X1 include the same examples as those described for the alkyl group, and the il alkoxy group is represented by a group of -OX2, and as an example of X2, The same examples as those described for the above haloalkyl group can be exemplified. The alkylthio group is represented by the group of -SX1, and as an example of X1, 13 201000430 is the same example as that of the group, and the above-mentioned secret sulfur group is not the base of sx. The same examples as those described for the above-mentioned halogen group can be exemplified. The alkyl group is represented by a group of ΝΗχΙ, and the trialkyl group is not a base of ruthenium, and the oxime 1 and the group of X3 are each exemplified by the same examples as those described above. Further, the di-silmino group-finding group may be bonded to each other to form a ring structure containing a nitrogen atom, and examples of the ring structure include, for example, a ruthenium ruthenium, a ruthenium ruthenium, and the like. The alkyl sulfonium group is represented by the group of -SC^X1, and as an example of X1, the same example as the one described in the above-mentioned alkyl group can be exemplified, and the above-mentioned halogen sulphur base is not -S The group of 〇2X2, as an example of oxime 2, can be exemplified by the same examples as those described for the above haloalkyl group. The aromatic hydrocarbon group may, for example, be a phenyl group, a naphthyl group, a diphenyl group, a aryl group, a tetracenyl group or a condensed pentaphenyl group. For example, a di-sigma-phene-phenyl, a benzo-furanyl group, a benzothienyl group, a quinolyl group, a carbazolyl group, a dip-folfyl group, Two stupid and sold phenyl, stupid and thiadiazolyl and the like. The alkyl alkane group is represented by a group of _§ίχ1χ3χ4, and each of χ1, X3 and X4 is exemplified by the same examples as those described for the above-mentioned alkyl group. The alkylsilyl acetylenic group is a group in which the group represented by the group is bonded to an ethynyl group, and is exemplified by: monomethyl ethynyl group, triethyl hydrazine. Ethylene group, triisopropyl hydrazide group, and the like. ^5 _ν , κ κ ' as a group having a structure in which an aromatic hydrocarbon group having 6 to 60 carbon atoms and / 14 201000430 or an aromatic heterocyclic group having 3 to 60 carbon atoms are bonded via 2 rings or more The same example as the above Ar1 can be exemplified. Among the R6 to R15, the aromatic hydrocarbon group or the aromatic heterocyclic group which is formed by the adjacent groups being bonded to each other may be the same as those described for the aromatic hydrocarbon group or the aromatic heterocyclic group. The saturated cyclic structure may, for example, be a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or a 1,4-dioxanyl group. Examples of the substituent of R1 to R15 include an aromatic hydrocarbon group, an aromatic heterocyclic group, an alkyl group, an alkoxy group, an aryloxy group, an arylthio group, an alkoxycarbonyl group, an amine group, and an i atom. Cyano group, nitro group, hydroxyl group, carboxyl group and the like. Specific examples of the compound for an organic thin film transistor of the present invention are listed below, but the present invention is not limited thereto. [Chemical Formula 5] \ 15 201000430

(20) 16 201000430 201000430

18 201000430

19 201000430

(77) (78)

(87) The compound for an organic thin film transistor of the present invention can be synthesized by a known method, for example, by a head-coupling reaction shown below, and 20 201000430 is synthesized by a coupling reaction of a transition metal catalyst. [Chemical Formula 6]

Further, in an electronic device such as a transistor, a device having a high field effect mobility or a high switching ratio can be obtained by using a material of high purity. Therefore, depending on the demand, it is preferably purified by column chromatography, recrystallization, distillation, sublimation or the like. It is preferred to repeat the purification methods or to increase the purity by combining a plurality of methods. Further, as a final step of the purification, it is preferred to repeat the sublimation purification step at least twice or more. By using these methods, it is preferred to use a material having a purity of 90% or more as determined by HPLC, more preferably 95% or more, and particularly preferably a material having a purity of 99% or more, whereby the organic thin film transistor can be improved. The field effect mobility and switching ratio play the performance of the original material. Next, the element structure of the organic thin film transistor of the present invention will be described. The element structure of the organic thin film transistor of the present invention has at least three terminals of a gate electrode, a source electrode and a drain electrode, an insulator layer and an organic semiconductor layer, and the source and the drain are controlled by applying a voltage to the gate electrode. A thin film transistor between currents. Further, the organic semiconductor layer is characterized by containing the above compound for an organic thin film transistor of the present invention. Typically, an organic thin film crystal system is disposed on a substrate. The structure of the transistor is not particularly limited, and any member having a known element structure may be used in addition to the composition of the organic semiconductor layer. Next, a specific example of the element structure of the organic thin film transistor will be described by way of a drawing of 21 201000430. Fig. 1 to Fig. 4 are views showing an example of the element structure of the organic thin film transistor of the present invention. The organic thin film transistor 1 of Fig. 1 is formed on a substrate 10, and has a source electrode 11 and a drain electrode 12 which are opposed to each other at a predetermined interval. Further, the organic semiconductor layer 13 is formed to cover the gap between the source electrode 11, the drain electrode 12, and the source electrode 11 and the drain electrode 12, and to laminate the insulator layer 14. A gate electrode 15 is formed on the upper portion of the insulator layer 14 and at a gap between the source electrode 11 and the drain electrode 12. The organic thin film transistor 2 of Fig. 2 has a gate electrode 15 and an insulator layer 14 in this order on the substrate 10, and has a pair of source electrodes 11 and 形成 formed at predetermined intervals on the insulator layer 14. The electrode 12 has an organic semiconductor layer 13 formed thereon. The organic thin film transistor 3 of FIG. 3 has a gate electrode 15, an insulator layer 14, and an organic semiconductor layer 13 sequentially on the substrate 10. The organic semiconductor layer 13 is formed at a predetermined interval to form a pair. Source electrode 11 and drain electrode 12. The organic thin film transistor 4 of Fig. 4 has an organic semiconductor layer 13 on a substrate 10, and has a pair of source electrodes 11 and drain electrodes 12 formed at predetermined intervals on the organic semiconductor layer 13. Further, the insulator layer 14 and the gate electrode 15 are sequentially provided. The organic thin film electro-crystal system of the present invention has a structure of a field effect transistor (FET). As described above, there are several kinds of structures depending on the position of the electrodes, the order of lamination of the layers, and the like. The organic thin film electro-crystal system has: 22 201000430 an organic semiconductor layer (organic compound layer), a source electrode and a drain electrode which are opposed to each other at a predetermined interval, and each of which is separated from the source electrode and the drain electrode by a predetermined distance The open gate electrode controls the current flowing between the source and the drain electrode by applying a voltage to the gate electrode. Here, the distance between the source electrode and the drain electrode depends on the use of the organic thin film transistor of the present invention, and is usually lp.lpm~lmm, preferably Ιμηη~ΙΟΟμιη, more preferably 5μηι~ΙΟΟμηι. A variety of structures have been proposed for the organic thin film transistor. The organic thin film electromorphic system of the present invention controls the current flowing between the source electrode and the drain electrode by applying a voltage to the gate electrode, thereby It is found that the mechanism having the effect of switching operation or amplification is not limited to the above-described element structure. For example, Yoshida et al. of the Industrial Technology Research Institute, in the 49th Session of the Joint Symposium on Applied Physics, presented in the draft 27a-M-3 (March 2002). Top and bottom contact ) organic thin film transistor (see Figure 5), or the organic thin film transistor of the vertical shape proposed by Kudo et al., Chiba University, et al., 118-A (1998), page 1440 (see page 6) Figure), with such a component structure can also be. Hereinafter, the structural member of the organic thin film transistor will be described. (Organic semiconductor layer) The organic semiconductor layer in the organic thin film transistor of the present invention contains the above compound for an organic thin film transistor of the present invention. The film thickness of the organic semiconductor layer is not particularly limited, but is usually from 5 nm to 1 μm, preferably from 2 nm to 250 nm. 23 201000430 Further, the method for forming the organic semiconductor layer is not particularly limited, and a known method such as a molecular wire evaporation method (MBE method), a vacuum evaporation method, a chemical vapor deposition, or a solution in which a material is dissolved in a solvent can be applied. Printing, coating method and drying, electropolymerization, molecular beam evaporation, self-assembly by solution, and the like, by dipping method, spin coating method, casting method, bar coating method, roll coating method, etc. In combination, the organic semiconductor layer is formed of the material of the organic semiconductor layer described above. When the crystallinity of the organic semiconductor layer is increased, the field effect mobility is improved, and when a film is formed from a vapor phase (steaming, subtraction, plating, etc.), it is preferred to maintain the substrate temperature in the film formation at a high temperature. The temperature is preferably from 50 to 250 ° C, more preferably from 70 to 150 ° C. Further, regardless of the film formation method used, in order to obtain a high performance device, it is preferred to carry out annealing after film formation. The annealing temperature is preferably 50 to 200 ° C, more preferably 70 to 200 ° C, and the annealing time is preferably 10 minutes to 12 hours' more preferably 1 to 10 hours. In the present invention, a mixed film of a plurality of materials may be used in the organic semiconductor layer, using a combination of a plurality of materials, a combination of a plurality of materials, or a known semiconductor such as fused pentene or a thiophene oligomer. A plurality of layers formed of different materials may be laminated. (Substrate) The substrate in the organic thin film transistor of the present invention serves as a structure for supporting the structure of the organic thin film transistor, and as the material thereof, an inorganic compound such as a metal oxide or a nitride may be used in addition to glass. , plastic film (PET, PES, PC) or metal substrate, or such composites, or laminates. Further, when the structure of the organic thin film 24 201000430 can be sufficiently supported by structural elements other than the substrate, the substrate may not be used. x, the material of the board, mostly the time (si) wafer. In this case, the 'si itself can be used as both a gate electrode and a substrate. Further, the surface of &<lt; can be oxidized and opened; and Si 〇 2 can be used as an insulating layer. In this case, on the Si substrate, the gate electrode layer for the wire connection is used as the gate electrode layer. A metal (electrode) such as AU is used. In the organic thin film transistor of the present invention, as a material for the interelectrode electrode to be reduced to the electrode of the electrode, it is possible to use platinum, gold, silver, nickel, chromium, and the like. Limiting bismuth, indium, palladium, ruthenium, osmium, iridium, aluminum, lanthanum, tin, antimony, lead, antimony, indium tin oxide (IT〇), zinc oxide, rhodium, , / ^, tin oxide graphite, silver paste and Broken ointment, bell, sputum, sodium, magnesium, glass fierce, wrong, recorded, sharp, nano, sodium-bell alloy, magnesium, lithium, slavery, magnesium/silver mixture, occupational compound, magnesium/indium Compound = copper mixed mixture, lithium/aluminum mixture, and the like. Aluminum/aluminum is used as a method for forming the above-mentioned electrodes, such as electron beam, lining, electro-conducting material, reading, neon, electroless, electroless plating, spin coating, printing or inkjet, etc. 'There are the following methods: to make it again according to the shadow method or the photoresist method (pulse, the method of forming the electrode by the light microfilm known from the above, the transfer of the conductivity, the blackening, etc. 々 (3) The method of falling metal in aluminum or steel, etc. "Form, forming an anti-touch layer (kiss _ engraved 25

The thickness of the electrode to be formed by the 2U1UUU4JU is preferably in the range of 4 nm to 300 nm, preferably φ2. Within the range of $. Further, since the thickness is not high, the electric resistance becomes high, and the voltage does not become thicker than the organic semiconductor layer, and the formation of the film is less time consuming, and the layer can be layered by the case of the protective layer. Underneath, there will be no unevenness of the surface of the present invention. The organic thin Β ^ 柘, the gate electrode and the "aa a, as a source electrode, the electrodepositive electro-chemical material of the dissolution method, preferably using the above-mentioned guide formed by the object, especially *! a fluid electrode material such as an ink or a dispersion, or a metal particle of copper: a conductive polymer or platinum, gold or yttrium as a dispersion containing metal fine particles, for example, a known conductive material may be used. It is preferable to use a dispersion containing metal fine particles having a normal plate diameter of 0.5 nm to 50 nm and 1 nm to 1 Å. As a material of the metal fine particles, for example, platinum, gold, rhodium, or the like can be used. Nickel, copper, iron, tin, antimony, lead, antimony, palladium, iridium, osmium, iridium, aluminum, trafic, sputum, turn, crane, reed, etc. It is preferred to use a dispersion to form an electrode, The dispersion is formed by using a dispersion stability mainly composed of an organic material, and dispersing the metal fine particles in a dispersion medium of water or an arbitrary organic solvent. As a method of producing such a dispersion of metal fine particles , for example: a physical formation method such as a vapor evaporation method, a sputtering method, or a metal vapor synthesis method, or a colloid method, a coprecipitation method, or the like, to reduce the metal ions in a liquid phase at 26 201000430 to form a gold-based wt, .a ' The chemical formation method of the particles is better than that of the Japanese special edition No. 11-76800, such as the Eighth*E newspaper, the Japanese special Kaiping 11-80647, the Japanese special Kaiping 1 319, 538, the gossip, the beer eight + the bun, and the Japanese special 2000-239853 胶 遽 遽 α α α α α α 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 2001 The dispersion of metal fine particles produced by the evaporation method in the gas described in the special publication of the Japanese Patent Publication No. 2000-124157, JP-A-2000-123634. The use of the special metal particles to divide the ugly. The object can be patterned by direct inkjet method, or it can be formed by coating a film into a dynasty lithography or laser ablation.

A method of patterning a stamp, a lithographic plate, a screen printing, or the like. After the former «(4) is shaped, the solvent is dried, and then heated to a predetermined shape in the range of 10 (TC~3〇〇t, preferably 15〇L〇C 1 as needed, thereby thermally fusion of the metal micro-teaching And forming an electrode pattern having a desired shape. j. As a material of the gate electrode, the source electrode, and the drain electrode, it is preferable to use a known conductive polymer capable of improving conductivity by doping. Appropriate system of the village: lead amine, material aggregate, Y package 1± polycetin (a complex of polydioxyethylphene and polyphenylethylene acid, etc.), polydioxyethyl a compound of PEDQT and a polystyrene (tetra) acid, etc. The contact resistance between the source electrode and the organic semiconductor layer of the gate electrode can be reduced by the materials. The formation method can also be performed by an inkjet method. The patterning can also be formed by lithography or laser ablation of the coating film. Further, the method of patterning is performed by a printing method such as letterpress gravure and lithographic screen printing. 27 201000430, _Yes, formation source The material of the electrode and the drain electrode, the foregoing example: the contact surface of the car and the organic semiconductor layer The electric resistance is smaller. This t electric steep resistance 'that is, the current control residual (4) should be related to the field effect mobility U; ^ to the large mobility, as small as possible, the resistance is necessary. The relationship between the working function of the electrode material and the energy level of the organic semiconductor layer. The working function (w) of the electrode material is taken as a, the ionization potential (Ip) of the organic semiconductor layer is taken as b, and the electron affinity of the organic semiconductor layer (10) is taken as It is preferable to satisfy the following relationship: c, any of a, b & c is a positive value based on the vacuum level. In the case of a P-type organic thin film transistor, it is preferable to satisfy Ba < 1.5eV (formula (1))' is better to satisfy ba < l_〇ev. In the relationship with the organic semiconductor layer, if the above relationship can be maintained, a high-performance device can be obtained, in particular, as much as possible The working function of the electrode material is preferably 4.0 eV or more, and more preferably the working function is 42 eV or more. The working function value of the metal is described, for example, in the Chemical Handbook Basics, 11-493 (Revised 3 version) Learn to compile a good model of the company will issue 1983 Any one of the active metals having a work function of 4.OeV or more listed in the above table, the high work function metals are mainly: Ag (4_26, 4.52, 4.64, 4.74 eV), Al (4.06, 4.24). , 4.41eV), Au (5.1, 5.37, 5.47eV), Be (4.98eV), Bi (4.34eV), Cd (4.08eV), Co (5.0eV), Cu (4.65eV), Fe (4.5, 4.67 , 4.81eV), Ga(4.3eV), Hg(4.4eV), Ir(5.42, 5.76eV), Mn(4.1eV), Mo(4.53, 4.55, 4.95eV), Nb(4.02, 4.36, 4.87eV) , Ni (5.04, 5.22, 5.35eV), Os (5.93eV), Pb (4.25eV), Pt (5.64eV), Pd (5.55eV), 28 201000430

Re (4.72 eV), Ru (4.71 eV), Sb (4.55, 4.7 eV), Sn (4.42 eV), Ta (4.0, 4.15, 4.8 eV), Ti (4.33 eV), V (4.3 eV), W ( 4.47, 4.63, 5.25eV), Zr (4.05eV). Among them, noble metals (Ag, Au, Cu, Pt), Ni, Co, Os, Fe, Ga, Ir, Mn, Mo, Pd'Re, Ru, V., W are preferable. The metal is preferably a conductive polymer such as ITO, polyaniline or PEDOT: PSS (polydioxyethylthiophene: polystyrenesulfonate) and carbon. As the electrode material, even if one or more kinds of substances having a high work function are contained, it is not particularly limited as long as the work function satisfies the above formula (I)'. In the case of the n-type organic thin film transistor, it is preferable to satisfy a_c < 15 ev (formula (II)), and it is more preferable to satisfy a-c < loev. In the relationship with the organic semiconductor layer, as long as the above relationship can be maintained, a high-performance device can be obtained, and in particular, the working function of the electrode material is preferably as small as possible, preferably a work function of 4.3 eV. Preferably, the following is a work function of 3.7 eV or less. As a specific example of the low work function metal, for example, it is described in pages 11-493 of the Chemical Handbook Basics (revised 3rd edition of the Japanese Chemical Society, Maruzen Co., Ltd. issued in 1983), and may be selected from the above table having 4 3ev or The effective metals of the following working functions are, for example, Ag (4.26 eV), Al (4.06, 4.28 eV), Ba (2.52 eV), Ca (2.9 eV), Ce (2.9 eV), Cs (1.95 eV). , Er (2.97eV), Eu (2.5eV), Gd (3_leV), Hf (3.9eV), In (4_09eV), Κ (2·28), La (3.5eV), Li (2.93eV), Mg ( 3.66eV), Na (2.36eV), Nd (3.2eV), Rb (4.25eV), Sc (3.5eV), Sm (2.7eV), Ta (4.0, 4.15eV), Y (3.1eV), Yb ( 2.6 eV), Zn (3.63 eV), and the like. Among them, compared with 29 201000430, Ba, Ca, Cs, Er, Eu, Gd Hf, K, La, Li, Mg, Na,

In contact with moisture or oxygen, it is coated with a stable metal in the air (such as a metal such as Ag or Au). The film thickness required for coating needs to be as thick as 1 Gnnm, although the thickness of the metal may be free from oxygen or water, but in practice, the work function satisfies the above formula (II) for reasons of improving productivity and the like. And, since the low work function metal is easily deteriorated once with the atmosphere, it is preferably viewed as needed, preferably Ιμηη or less. In the organic thin film transistor of the present invention, for example, for the purpose of improving the implantation efficiency, a buffer layer may be disposed between the organic semiconductor layer and the source electrode and the drain electrode. As the buffer layer, the n-type organic thin film transistor is preferably a compound having an alkali metal or an alkaline earth metal ion of LiF, Li20, CsF, NaC03, KCl, MgFrCaCO3 or the like which is used in the cathode of the organic EL. Further, a compound used as an electron injecting layer or an electron transporting layer may be inserted into an organic EL such as Alq. For the P-type organic thin film transistor, a cyano compound such as FeCl3, TCNQ, F4-TCNQ, HAT, etc., CFx or Ge〇2, Si〇2, Mo03, V2O5, V〇2, \^2〇3, ^ίηΟ, M!n3〇4, Zr〇2, λν〇3, Ti〇2, Iri2〇3,

Metals such as ZnO, NiO, Hf02, Ta2〇5, Re〇3, and Pb02, metal oxides other than metal-based metals, and inorganic compounds such as ZnS and ZnSe. In most cases, these oxides cause oxygen defects, which are suitable for hole injection. Further, in an organic EL element such as TPD or NPD or an organic EL element such as CuPc, a compound used as a hole injection layer or a hole transport layer may be used. Further, it is preferred to form two or more kinds of the above compounds. The buffer layer lowers the threshold voltage by lowering the injection barrier of the carrier, and it is known that the effect of driving the transistor at a low voltage is known, but it has been found that the compound having the effect of the present invention has not only a low voltage effect but also an effect of improving mobility. . This is because at the interface between the organic semiconductor and the insulator layer, there is a carrier ,3, and once the gate voltage is applied to cause the carrier to be implanted, the carrier just opened to the implant is used to plug the trap, but by inserting The buffer layer is trapped at a low voltage, so the mobility is improved. The buffer layer may be present between the electrode and the organic semiconductor layer in a thin layer, and has a thickness of 0.1 nm to 30 nm, preferably 〇3 nm to 20 nm. (Insulator Layer) The material of the insulating layer of the organic thin film transistor of the present invention is not particularly limited as long as it can be formed into an electrically insulating film, and a metal oxide (oxide containing cerium) can be used. A metal nitride (sand-containing nitride), a south molecule, an organic low molecule, etc., which have an electrical resistivity of 1 ODcm or more at room temperature, are particularly preferably an inorganic oxide film having a relatively high permittivity. . As the inorganic oxide, for example, cerium oxide, aluminum oxide, oxidation group, titanium oxide, tin oxide, cerium oxide, barium titanate, barium zirconate titanate, and acid acid titanate (lead) Zirconate titanate), lead titanate tantalum, barium titanate, barium titanate, barium magnesium fluoride, barium oxide, oxyfluoride, magnesium oxide, secret oxide, titanic acid, sharp oxide, barium titanate The group acid grade, the pentoxide group, the group acidity grade, the strontium (tri〇xide yttrium) and the combination of these are preferably cerium oxide, aluminum oxide, oxidation button, titanium oxide. 31 201000430 Further, inorganic oxides such as tantalum nitride (Si3N4, SixNy (x, y> 0)), and aluminum nitride are also suitable. And the 'insulator layer may also be formed by a precursor material containing an alkoxide metal' which is formed by coating a solution of the precursor substance on, for example, a substrate, and then treating it with a chemical solution containing a heat treatment to form an insulator layer. As the metal in the alkoxide metal, for example, a transition metal, an actinosteroid, or a member selected from a main group element, specifically, for example, barium (Ba), strontium (Sr), and titanium (Ti) ) '铋(Bi), 钽(Ta), vermiculite (Zr), iron (Fe), recorded (Νι), 猛 (Μη), lead (Pb), lanthanum (La), chain (Li), sodium ( Na), potassium (6), strontium (Rb), strontium (Cs), strontium (Fr), strontium (Be), magnesium (Mg), calcium (Ca), strontium (Nb), strontium (T1), mercury (Η§ ), copper (Cu), cobalt (Co), rhodium (Rh), antimony (Sc), and antimony (Y). Further, examples of the alkoxide in the alkoxide metal include, for example, an alcohol containing methanol, ethanol, propanol, isopropanol, butanol or isobutanol, and methoxyethanol. Ethoxyethanol, propoxyethanol, butoxyethanol, pentyloxyethanol, heptoxyethanol, decyloxypropanol, ethyl lactylpropanol, propoxypropanol, butoxypropanol, pentane A substance derived from an oxypropanol, an alkoxy alcohol of heptyloxypropanol or the like. In the X-month of the test, the insulator layer is formed by the above-mentioned materials, and the polarization in the insulating crucible is easily generated, which can reduce the critical electric resistance of the transistor operation, especially in the above materials, especially once by Si3N4, SixNy, (Υ> When a tantalum nitride is formed to form an insulator layer, a depleuon layer is more likely to be generated, and the threshold voltage of the transistor operation can be further reduced. As the insulator layer using an organic compound, polyimine, 32 201000430 polyamide, polyester, polyacrylic acid, photoradical polymerization, photocationic polymerization photocurable resin, copolymer containing acrylonitrile can be used. , polyvinyl benzene, polyethylene glycol, acid resin and cyanoethyl pullulan (cyanoethyl pullulan). Others, added to wax, polyethylene, polychloroprene, polyethylene terephthalate, polyformal, polyethylene, polypyridyl ethylene, polydecyl acrylate, polysulfone, polycarbonate , polyimidocyanoethyl pullulan, poly(ethyl benzoate) (PVP), poly(methyl methacrylate) (PMMA), polycarbonate (PC), polystyrene ( PS), polyolefin, polypropylene decylamine, poly(acrylic acid), phenolic resin, resole phenolic resin, polyimine, polyxylylene, epoxy resin, high dielectric of polytriglucose, etc. A polymer material having a coefficient can also be used. As the organic compound material or polymer material used for the insulator layer, a material having water repellency is particularly preferable. By using a material having water repellency, the interaction between the insulator layer and the organic semiconductor layer can be suppressed, and the organic semiconductor system can improve the crystallinity of the organic semiconductor layer by utilizing the original cohesiveness, thereby improving the device performance. As an example of such materials, for example, a Yasuda expert published in jpn. j. Appl. phys. Vol. 42 (2003) pp_66M-66l8 contains a polypyrene (p〇iy_p_Xyiyiene) derivative or Jan〇s Veres et al., published in Chem. Mater., Vol. 16 (2004) ρρ·4543-4555. Further, when the top gate structure shown in Figs. 1 and 4 is used, the organic compound is used as the material of the Saki Prefecture, and the damage caused by the organic semiconductor layer is reduced to form a film. And an effective method. 33 201000430 The insulator layer may be a mixed layer of a plurality of inorganic or organic compound materials as described above, and the plurality of inorganic or organic compound material (four) layer structures may be used. In this case, the material of the apparatus can be controlled by the material of the electric coefficient and the material having the water repellency as needed. Further, the insulator layer may also contain an anodized film or the anode anodic film. As the structure thereof, it is preferable to use an anodized lining or a (iv) hole. The anodized film system can be formed by anodizing a metal which can be anodized by a known method. The method of the anodizing treatment is not particularly limited, and a known method can be used. An oxidized coating film can be formed by performing anodizing treatment. As an electrolytic solution used for anodizing, as long as it is ruthenium Any electrolyte solution can be used to form a porous oxide film, and generally, sulfuric acid, phosphoric acid, citric acid, chromic acid, boric acid, amine sulfonic acid, benzenesulfonic acid or the like, or a mixed acid of two or more of these acids or the like is used. Acid salt. The treatment conditions for anodization are various due to various changes in the electrolyte used, and the general suitable range is: electrolyte The concentration is the mass of the rib. The temperature of the electrolyte is 5 to 70 ° C, the current density is 〇·5~6〇A/cm2, the voltage is 100 volts, and the electrolysis time is 10 seconds to 5 minutes. Preferably, the anodizing treatment is a method of treating a direct current using an aqueous solution of sulfuric acid or tannic acid as an electrolytic solution, but an alternating current can also be used. The concentration of the acid is preferably Μ% by mass, and it is preferred to carry out electrolytic treatment for 20 to 25 sec under the temperature of the electrolyte of 20 to 5 (rc, current density: 〇 5 to 20 A/cm 2 ). Also:,,, as the thickness of the insulator layer, the thickness of the layer is too thin, which will cause the expansion. 201000430 The actual voltage applied to the organic semiconductor becomes larger, although the driving voltage and threshold voltage of the device itself can be reduced, but it will cause The leakage current between the source and the gate becomes large, and the necessity of selecting an appropriate film thickness is usually 1 Onm to 5 μm, preferably 50 nm to 2 μm, more preferably 100 nm to Ιμηι. Further, the foregoing insulator layer and Any alignment treatment may be applied between the organic semiconductor layers. As a preferred example, a water repellency treatment is applied to the surface of the insulator layer to reduce the interaction between the insulator layer and the organic semiconductor layer, and to improve the organic semiconductor. The method for crystallizing the layer, specifically, for example, in the liquid phase or in the gas phase, the sulphur coupling agent (for example, hexamethyldioxane, tristearyl decane, three) Chloroquinone decazane, or A self-assembled alignment film material of phosphoric acid, an alkanesulfonic acid, an alkanecarboxylic acid or the like is brought into contact with the surface of the insulating film to form a self-assembled film, and then subjected to an appropriate drying treatment. Further, if it is used for liquid crystal alignment, It is preferable to provide a film made of polyimide or the like on the surface of the insulating film, and a method of performing a bristle treatment on the surface thereof. As a method of forming the insulator layer, a vacuum vaporization method or a molecular line can be used as an example. Crystal growth method, agglomerated ion beam method, low-energy ion beam method, ion ore method, chemical vapor deposition method, de-bonding method, 曰本特开平11-61406, Japanese Patent Laid-Open No. 11-133205, 曰Dry process such as the normal-electrode slurry method described in JP-A-2000-147209, JP-A-2000-185362, or JP-A-2000-185362, or a spray coating method, a spin coating method, or a plating method A wet process such as a coating method, a immersion plating method, a casting method, a roll coating method, a bar coating method, a die coating method, or the like, a method of patterning by printing or inkjet, or the like. 35 201000430 Wet It can be used: a dispersion aid of a surfactant or the like is used, a fine particle of an inorganic oxide is dispersed in a solution of any organic solvent or water, coated or dried, or an oxide precursor, for example, A so-called sol-gel method in which a solution of an alkoxide body is applied and dried. As a method of forming the organic thin film transistor of the present invention, it can be by a non-specific known method, but conforms to the desired element structure once A series of device manufacturing steps before substrate formation, gate electrode formation, insulator layer formation, organic semiconductor layer formation, source electrode formation, and gate electrode formation are not formed in contact with the atmosphere at all, and are not in contact with the atmosphere. It is preferable because it can prevent the performance of the element due to moisture or oxygen in the atmosphere. In the case where it is necessary to contact the atmosphere once, it is preferred that the step after the film formation of the organic semiconductor layer is a step of not contacting the atmosphere at all, immediately before the film formation of the organic semiconductor layer, by Ultraviolet irradiation, ultraviolet/ozone irradiation, oxygen plasma, argon plasma, etc., the surface of the organic semiconductor layer is laminated (for example, in the case of an element, a portion of the surface of the source electrode and the drain electrode is laminated on the insulating layer) After the purification and activation, the organic semiconductor layer is laminated. Further, among the p-type TFT materials, if the oxygen is adsorbed by contact with the atmosphere, the performance may be improved. Therefore, the material may be appropriately brought into contact with the atmosphere depending on the material. Further, considering, for example, the influence of oxygen, water or the like contained in the atmosphere on the organic semiconductor layer, a gas barrier layer may be formed on all or a part of the outer peripheral surface of the organic transistor element. For the material forming the gas barrier layer, materials commonly used in the field can be used, for example, polyethylene 36 201000430 alcohol, ethylene-vinyl alcohol copolymer, polyethylene, polydivinylidene, polychlorotrifluorochloride Ethylene and the like. Further, an insulating inorganic substance as exemplified in the above insulator layer may be used. In the present invention, it is possible to provide an organic thin film light-emitting transistor which emits light by applying a voltage to a gate electrode by applying a current flowing between a source electrode and a drain electrode. That is, an organic thin film transistor can be used as the light-emitting element (organic EL). Since the light-emitting transistor and the light-emitting element can be integrated and controlled, it is possible to reduce the cost by increasing the aperture ratio of the display or simplifying the manufacturing process, which brings great practical benefits. When it is used as an organic photoelectric crystal, it is necessary to inject a hole from one side of the source electrode and the drain electrode and inject electrons from the other side, and it is preferable to improve the light-emitting performance to satisfy the following conditions. In the organic thin film light-emitting transistor of the present invention, in order to improve the injection property of the hole, it is preferable that at least one of the source electrode and the drain electrode is a hole injecting electrode. The hole injection electrode contains an electrode having a working function of 4.2 eV or more. In addition, the upper limit of the working function of the hole injection electrode is, for example, 7.0 eV. Further, in order to improve the injectability of electrons, it is preferable that at least one of the source electrode and the anode electrode is an electron injecting electrode. The electron injecting electrode is an electrode containing a substance having a working function of 4 to 3 eV or less. Further, the lower limit of the work function of the electron injection electrode is, for example, 1.8 eV. More preferably, the organic thin film light-emitting electric crystal system includes one of a source electrode and a drain electrode, and is an electrode for injecting electrons, and the other is an electrode for electron injection. 37 201000430 Further, in order to improve the injectability of the hole, it is preferable that a hole injection layer is interposed between the electrode of at least one of the source electrode and the drain electrode and the organic semiconductor layer. The hole injection layer can be exemplified by using an amine-based material which is a hole injecting material and a hole transporting material in the organic EL element. Further, in order to improve the injectability of electrons, it is preferable that an electron injecting layer is interposed between at least one of the source electrode and the drain electrode and the organic semiconductor layer. Similarly to the hole, the electron injecting layer can preferably use an electron injecting material for the organic EL element, and the organic thin film emitting transistor has a hole in which the electrode of one of the source electrode and the drain electrode has a hole injection layer. And the other electrode has an electron injection layer. [Examples] Next, the present invention will be described in further detail by way of examples. Synthesis Example 1 (Synthesis of Compound (46)) Compound (46) was synthesized in the following manner. The synthetic path is shown below. [Chemical Formula 7]

(46) In a 300 ml three-necked flask, 4-bromo-P-tetraphenyl 3.00 g (8.87 mmol) and tetrakis(triphenylphosphine) were placed! 0.513 g (0.443 mmol) and cuprous copper (I) 0.169 g (0.886 mmol) were subjected to argon substitution. Hereto, 22 ml of triethylamine and 3.09 g (26.6 mmol) of 2-ethynylnaphthalene were added, and under reflux of argon, 9 38 201000430 hours of heating was refluxed. The solid obtained by filtration of the reaction mixture was washed with chlorobenzene and methanol to give the compound (46) 2.36 g (5.77 mmol, yield 65%). The object was confirmed by measurement by 9 〇 MHz W-NMR and FD-MS (field-induced desorption mass spectrometry). The measurement results of FD-MS are shown below. The theoretical calculation of FD-MS is C48H30S2 = 378, and m/z = 378 (Μ + 9 100) is found. Further, the compound was sublimed and purified at 26 °C. The compound (46) obtained by sublimation purification had a purity of 99.5%. Further, in Synthesis Example 1, the apparatus and measurement conditions used for the measurement of FD-MS are shown below. <FD-MS measurement> Apparatus: HX11(R) (manufactured by Sakamoto Electronics Co., Ltd.) Condition: Accelerating voltage: 8 kV Scanning range Example 1 (manufacturing of organic thin film transistor) By the following procedure, the manufacturing method shown in Fig. 7 was produced. Organic thin film transistor. First, the glass substrate was ultrasonically washed for 30 minutes by a neutral detergent, pure water, acetone, and ethanol, and then a gold (An) ' of 4 〇 nm was formed by sputtering to form a gate. Electrode 15. Next, the substrate 1〇 was set in the film formation portion of the thermal chemical > fly phase > On the other hand, a petri dish is placed on the evaporation portion of the raw material. The petri dish is filled with an insulator layer material, and a polyparaphenylene derivative [Parylene] (trade name; diX-C ' The third chemical formation of Du) 250mg. The hot chemical vapor deposition apparatus was vacuumed by a vacuum pump 39 201000430, and after depressurization to 5 Pa, the evaporation section was heated to (10) seven, the polymerization section was heated to 680 C, and placed for 2 hours to form on the gate electrode 15. Insulator layer 14° having a thickness of ^^^ Next, the substrate was placed in a vacuum vapor deposition apparatus (manufactured by ULVAC, ΕΧ-4〇0), and the compound was applied to the insulator layer at a deposition rate of 0.05 nm/s. 46) An organic semiconductor layer 13 having a film thickness of 50 nm is formed. Next, through the metal mask, gold is formed to a thickness of 50 ι nm, thereby forming a source electrode n and a non-polarity (four) having a spacing (channel length L) of 7 Å and not continuing. At this time, the width of the source electrode and the drain electrode (channel width w) was ▲ to form an organic thin film transistor 3. V. "w --TV V \厂甲J 拽 -------- The gate electrode of the 溥 film transistor, the voltage is applied to the source. In this case, the % hole is induced into the channel region (10) of the organic semiconductor layer (10) and the poleless ',) to act as a P-type transistor. As a result, the current-to-switch ratio between the source and the 2 electrode of the current saturation region is 3x1q5. Further, the field effect mobility μ of the nose outlet hole is 6xi〇-2cm2/Vs by the following formula (8). ^-(W/2L) . 〇μ . (Vg-Vt)2 (a) —A· Channel ping Id source current between the source and the drain, W system channel width, L system value electrode insulator layer The capacitance per unit area, % is the gate threshold ^, VG system gate voltage. Only &^]2 (manufacture of organic thin film transistor) The material of the compound 1 organic semiconductor layer was replaced by the compound (28) instead of the film electrocrystal. In the same manner as in the first embodiment, an organic thin tantalum transistor obtained by thinning is produced, and in the same manner as in the embodiment 40 201000430, the gate voltage VG of -40 V is used to drive p. Type transistor. The switching ratio of the current between the source and the drain electrode was measured, and the calculation results of the field effect mobility μ of the hole are shown in Table 1. (Example 3) (Production of Organic Thin Film Transistor) An organic thin film transistor was produced in the same manner as in Example 1 except that the compound (61) was used instead of the compound (46). With respect to the obtained organic thin film transistor, a p-type transistor was driven at a gate voltage VG of -40 V in the same manner as in the first embodiment. The switching ratio of the current between the source and the drain electrode was measured, and the calculation results of the field effect mobility μ of the hole are shown in Table 1. Example 4 (Production of Organic Thin Film Transistor) As a material of the organic semiconductor layer, an organic thin film transistor was produced in the same manner as in Example 1 except that the compound (62) was used instead of the compound (46). With respect to the obtained organic thin film transistor, a p-type transistor was driven at a gate voltage VG of -40 V in the same manner as in the first embodiment. The switching ratio of the current between the source and the drain electrode was measured, and the calculation results of the field effect mobility μ of the hole are shown in Table 1. Example 5 (Production of Organic Thin Film Transistor) As a material of the organic semiconductor layer, an organic thin film transistor was produced in the same manner as in Example 1 except that the compound (86) was used instead of the compound (46). With respect to the obtained organic thin film transistor, a p-type transistor was driven at a gate voltage VG of -40 V in the same manner as in the first embodiment. The switching ratio of the current between the source and the drain electrode was measured, and the calculation results of the field effect mobility μ of the hole are shown in Table 1. 41 201000430 Comparative Example 1 (Production of Organic Thin Film Transistor) As a material of the organic semiconductor layer, in addition to the use of p-biphenylbenzene (Comparative Compound 1, hereinafter referred to as 6Ph) in place of the compound (46), 1 In the same way, an organic thin film transistor was fabricated. With respect to the obtained organic thin film transistor, a p-type transistor was driven at a gate voltage VG of -40 V in the same manner as in the first embodiment. The switching ratio of the current between the source and the drain electrode was measured, and the calculation results of the field effect mobility μ of the hole are shown in Table 1. Comparative Example 2 (Production of Organic Thin Film Transistor) As a material of the organic semiconductor layer, in place of the compound (46), in place of the compound (46), except that bisanthracenyl acetylene (hereinafter referred to as Comparative Compound 2, hereinafter referred to as ΒΑΑ) was used. In the same manner as in Example 1, an organic thin film transistor was produced. With respect to the obtained organic thin film transistor, a p-type electric crystal was driven at a gate voltage VG of -40 V in the same manner as in the first embodiment. The switching ratio of the current between the source and the drain electrode was measured, and the calculation results of the field effect mobility μ of the hole are shown in Table 1. [Table 1] Compound type of organic semiconductor layer Type of field effect mobility (cm2/Vs) Switching ratio Example 1 (46) P type 6xl〇·2 5χ105 Example 2 (28) P type 3xl0'2 3χ105 Example 3 (61) P type 2χ10'2 2χ105 Example 4 (62) P type 3χ1〇·2 4χ105 Example 5 (86) P type 2χ1〇·2 3χ105 Comparative example 1 6Ph P type 6χ10'6 2χ102 Comparative example 2 BAA P type 9χ1〇·3 2χ104 [Chemical Formula 8] 42 201000430

(28)

η::Manufacture of organic thin film light-emitting transistors)

- The order of j ^ is made to manufacture an organic thin film light-emitting transistor. First, the Si substrate (P-type specific resistance (1) (10) also serves as a gate electrode) is oxidized. A thermal oxide film of 3 〇〇 nm is formed on the substrate as an insulator layer. i, after the S1〇2 film formed on the other side of the substrate is completely removed by the dry material, II is formed by the hetero-method filming into a film thickness of 2 〇nm, and by 'sputtering' On the upper side, gold (Au) is formed into a film thickness of 10011111 to serve as a gate electrode. The substrate was subjected to ultrasonic cleaning for 30 minutes by a neutral detergent, pure water, acetone, and ethanol. Then, it was set in a vacuum vapor deposition apparatus (EX-900, manufactured by ULVAC Co., Ltd.), and the compound 43 (2010) was formed into a film at a vapor deposition rate of 0 05 nm/s on the insulator layer (Si 2 ). An organic semiconductor light-emitting layer having a thickness of 100 nm. Next, the electrode electrode of the source electrode (Au)#; the electrode of the electron transporting electrode is formed as shown in the first paragraph. Specifically, as in the above, a metal mask having a channel length of 75 Å and a channel width of 5 mm is provided, and the substrate 2 is formed into an organic semiconductor light-emitting layer, and is slanted by 45 degrees with respect to the evaporation source. In the mask, gold 22 is formed into a film thickness of 5 Gnm (Fig. 8 (1) (2)). Next, the substrate was tilted by 45 degrees in the opposite direction, and the magnesium 23 was steamed to have a film thickness of (10) (10) (Fig. 8 (3)). In this way, the source electrode and the secret electrode including the electron-transporting electrode 23 (Mg) having the hole injecting electrode 2 are formed so as to be thin, so as to form an organic thin film light-emitting transistor (Fig. 8 (4) ). Once -100V is applied between the source and the drain, and the Qiaolin to the free electrode is applied, the blue light of the ed/m2 is obtained. The luminescence spectrum is shown in Fig. 9. Industrial Applicability As described in detail above, the organic thin tantalum transistor of the present invention has a high response speed (driving speed) by using a compound having a specific structure having a high electron mobility as a material of the organic semiconductor layer, and the switch A large-sized, high-performance transistor can also be used as a light-emitting organic thin film light-emitting transistor. The contents of the documents described in this specification are all incorporated herein by reference. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an example of the structure of an element of an organic thin film transistor of the present invention. 44 201000430 Fig. 2 is a view showing an example of the element structure of the organic thin film transistor of the present invention. Fig. 3 is a view showing an example of the element structure of the organic thin film transistor of the present invention. . Fig. 4 is a view showing an example of the element structure of the organic thin film transistor of the present invention. Fig. 5 is a view showing an example of the element structure of the organic thin film transistor of the present invention. Fig. 6 is a view showing an example of the element structure of the organic thin film transistor of the present invention. Fig. 7 is a view showing an example of the element structure of the organic thin film transistor in the embodiment of the present invention. Fig. 8 (1) to (4) show patterns of manufacturing steps of the source electrode and the drain electrode of the electron injecting electrode and the electron transporting electrode. Fig. 9 is a view showing the luminescence spectrum of the organic thin film luminescent transistor of the present invention obtained in Example 6. [Description of main component symbols] 13.. Organic semiconductor layer 14.. Insulator layer 15.. Gate electrode 20.. Substrate 21.. Metal mask 22.. Hole injection electrode (Gold) 23.. Electron transporting electrode (magnesium) 1.. Organic thin film transistor 2. Organic thin film transistor 3. Organic thin film transistor 4. Organic thin film transistor 10.. . Source electrode 12...汲 electrode 45

Claims (1)

201000430 VII. Patent application scope: 1. A compound for an organic thin film transistor having the structure of the following formula (1): [Chemical Formula 1] Χ^^-ΑΙΊ (1) wherein X represents the following formula (2) Any one of the groups shown in the above-mentioned (4); Ar! is an aromatic hydrocarbon group having 6 to 60 carbon atoms; an aromatic heterocyclic group having 1 to 60 carbon atoms; or having such an aromatic group linked via 2 or more rings; a group having a structure, wherein each of the groups may have a substituent; [Chemical Formula 2] An alkyl group, a haloalkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a haloalkoxy group having 1 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms, and a carbon number of 1 to 30 i alkylthio group, alkylamino group having 1 to 30 carbon atoms, dialkylamino group having 2 to 60 carbon atoms (alkyl groups may be bonded to each other to form a ring structure containing a nitrogen atom), and carbon number is 1 to 30. An alkylthio group, a halogen alkylthio group having 1 to 30 carbon atoms; an aromatic hydrocarbon group having 6 to 60 carbon atoms; an aromatic heterocyclic group having 3 to 60 carbon atoms; a group having a structure obtained by linking; an alkylene group having 3 to 20 carbon atoms; an alkylsilyl acetylenic group having a carbon number of 5 to 60; or a cyano group, wherein each of the groups may have a substituent; Each of R15 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, 46 201000430, a haloalkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and a halogen having 1 to 30 carbon atoms. An oxy group, an alkylthio group having 1 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms, an alkylamino group having 1 to 3 carbon atoms, and a dialkylamino group having 2 to 60 carbon atoms (alkyl group) Can also be combined with each other to form a ring structure containing a nitrogen atom), carbon number 1 to 3 Alkanethiol group of 0, haloalkyl sulfonyl group having 1 to 30 carbon atoms, aromatic hydrocarbon group having 6 to 60 carbon atoms, aromatic heterocyclic group having 3 to 60 carbon atoms, alkyl alkane group having 3 to 20 carbon atoms And an alkylsilyl acetylenic group or a cyano group having a carbon number of 5 to 60, and each of the groups may have a substituent 'or a carbon number of 6 to be formed by linking adjacent groups to each other. An aromatic hydrocarbon group, an aromatic heterocyclic group having 3 to 60 carbon atoms or a saturated cyclic structure having a carbon number of 6 to 60). 2. The compound for an organic thin film transistor according to the first aspect of the invention, wherein in the above formula (1), the 'Ar! is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 6 carbon atoms. 3. The compound for an organic thin film transistor according to the scope of the invention, wherein in the above formula (1), An is a substituted or unsubstituted carbon number of an aromatic heterocyclic group. A compound for an organic thin film transistor according to the first aspect of the invention, wherein in the above formula (1), the oxime is a substituted or unsubstituted aromatic group having 6 to 6 carbon atoms, and/or substituted Or an unsubstituted carbon number 丨~6〇 of an aromatic heterocyclic group obtained by linking two or more rings. Use the compound, in . Bisazine, quinoline, , phenazine, diazepine, and the compound for an organic thin film transistor according to the first aspect of the patent application. In the above formula (1), the group is: benzene, I 47 201000430 (diazaanthracene). Compared with 11 and Lin Lin, σ close bite and Yu Lin. Biazine mouth i: 嗔琳, 菲罗琳, miso, and two stupid. Sai,. The plug is ok. Cephthophene, diphenanthrinothiophene, [1] benzothieno[3,2-b]benzothiophene, terphenyldiphenyl, terphenylene, binaphthyl, hydrazine, phenyl sigma, Πsecenylnaphthalene, thienyl I, phenylnaphthalene, phenylhydrazine, D-pyridylnaphthalene, σ-pyridylhydrazine, bithiophene, and tert-thiophene. 6. The compound for an organic thin film transistor according to the first aspect of the invention, wherein in the above formula (1), each of R1 to R15 is a hydrogen atom, a halogen atom, a carbon number of 1 to 30, and a carbon number of 5~ 60 alkylsilyl acetylenic group, a charcoal number of 1 to 30 halogenated or cyano group. 7. The compound for an organic thin film transistor according to the first aspect of the invention, wherein in the above formula (1), at least two adjacent groups of R6 to R15 are bonded to each other to form an aromatic hydrocarbon group having 6 to 60 carbon atoms, or An aromatic heterocyclic group having 3 to 60 carbon atoms. 8. An organic thin film transistor having a gate electrode, a source electrode, and a drain terminal, an insulator layer, and an organic semiconductor layer, and controlling the source and the drain by applying a voltage to the gate electrode In the organic thin film transistor, the organic thin film comprises the compound for an organic thin film transistor according to any one of claims 1 to 7. 9. The organic thin film transistor of claim 8, wherein the light is emitted by a current flowing between the source electrode and the drain electrode, and the light is controlled by applying a voltage to the gate electrode. 10. The organic thin film transistor according to claim 9 wherein the source 48 201000430 one of the electrode and the drain electrode is composed of a substance having a working function of 4_2 eV or more, and the other is a working function of 4.3 eV or less. The composition of matter. 11. The organic thin film transistor of claim 8, wherein a buffer layer is provided between the source electrode and the drain electrode and the organic semiconductor layer. 49