WO2007066466A1

WO2007066466A1 - Organic semiconductor material, organic semiconductor film, organic semiconductor device and organic thin film transistor

Info

Publication number: WO2007066466A1
Application number: PCT/JP2006/322228
Authority: WO
Inventors: Yasushi Okubo; Rie Katakura; Hidekane Ozeki
Original assignee: Konica Minolta Holdings, Inc.
Priority date: 2005-12-06
Filing date: 2006-11-08
Publication date: 2007-06-14
Also published as: JPWO2007066466A1; JP5223337B2

Abstract

Provided is an organic semiconductor material, which can be manufactured by simple coating process, has excellent characteristics as a transistor, and furthermore, is stable to oxygen in the air and sufficiently suppresses deterioration with time. An organic semiconductor film, an organic semiconductor device and an organic thin film transistor are also provided.

Description

Specification

Organic semiconductor materials, organic semiconductor films, organic semiconductor devices, and organic thin film transistors

Technical field

[0001] The present invention relates to an organic semiconductor material, an organic semiconductor film, an organic semiconductor device, and an organic thin film transistor.

Background technology

[0002] With the spread of information terminals, there is an increasing need for flat panel displays as displays for computers. In addition, with the advancement of information technology, there are increasing opportunities for information that was previously provided in paper media to be digitized, and electronic paper or digital paper has become popular as a thin, light, and easily portable mopile display medium. The need for this is also increasing.

[0003] Generally, in a flat display device, a display medium is formed using an element that utilizes liquid crystal, organic EL (organic electroluminescence), electrophoresis, or the like. Furthermore, in order to ensure uniformity of screen brightness and screen rewriting speed in these display media, technology that uses active drive elements (TFT elements) as image drive elements has become mainstream!/ヽ. For example, in a typical computer display, these TFT elements are formed on a glass substrate, and liquid crystals, organic EL elements, etc. are sealed.

[0004] Here, semiconductors such as a-Si (amorphous silicon) and p-Si (polysilicon) can be mainly used for TFT elements, and these S-conductors (and metal films as necessary) can be used. TFT devices are manufactured by multilayering and sequentially forming source, drain, and gate electrodes on a substrate. Manufacturing these TFT devices typically requires sputtering or other vacuum-based manufacturing processes.

[0005] However, in manufacturing such TFT devices, each layer must be formed by repeating a vacuum system manufacturing process including a vacuum chamber many times, which increases equipment costs and running costs. It had become enormous. For example, TFT devices typically require repeated vacuum deposition, doping, photolithography, development, and other steps to form each layer. The device is formed on the substrate through dozens of steps. The semiconductor part, which is the key to the switching operation, is made up of multiple types of semiconductor layers, such as p-type and n-type. With these conventional manufacturing methods using Si semiconductors, it is not easy to make changes to equipment, such as requiring major design changes to manufacturing equipment such as the vacuum chamber to meet the need for larger display screens.

[0006] Furthermore, since the formation of TFT elements using such conventional Si materials involves a high temperature process, there are restrictions on the substrate material being able to withstand the process temperature. Become. For this reason, in practice, glass must be used, and if the e-paper or digital paper mentioned earlier is constructed using such conventional TFT elements, the display This results in a product that is heavy and lacks flexibility, and may break due to the impact of a fall. These characteristics resulting from forming TFT elements on a glass substrate are desirable in meeting the need for easy-to-carry thin displays that accompany the advancement of information technology.

[0007] On the other hand, in recent years, research on organic semiconductor materials has been vigorously pursued as organic compounds with extremely high charge transport properties. These compounds have been used as charge-transporting materials for organic EL devices, as well as organic laser oscillation devices, such as those discussed in Non-Patent Document 1, and have been reported in numerous papers, such as Non-Patent Document 2. There are high expectations for its application to organic thin film transistor devices (organic TFT devices). If these organic semiconductor devices can be realized, it will be possible to simplify the manufacturing process by vacuum or low-pressure evaporation at relatively low temperatures, and to obtain semiconductors that can be made into a solution by appropriately improving their molecular structure. It is thought that the organic semiconductor solution can be made into ink to produce it by printing methods, including inkjet methods. Although manufacturing using these low-temperature processes was thought to be impossible for conventional Si-based semiconductor materials, it is possible for devices using organic semiconductors, and the above-mentioned restrictions on substrate heat resistance may be relaxed. Therefore, it is possible to form, for example, a TFT device on a transparent resin substrate. If a TFT element could be formed on a transparent resin substrate and the display material could be driven by the TFT element, the display would be lighter and more flexible than conventional displays, and would not break even if dropped (or would be extremely durable). It would be possible to make the display (hard to break). [0008] However, the organic semiconductors that have been studied so far for realizing such TFT devices include acenes such as pentacene and tetracene (see, for example, Patent Document 1), and phthalocyanines including lead phthalocyanine. low-molecular compounds such as perylene and its tetracarboxylic acid derivatives (see, for example, Patent Document 2), and aromatic oligomers such as thiophene hexamers called oc chenille or sexithiophene (see, for example, Patent Document 3). ), naphthalene, compounds in which a 5-membered aromatic heterocycle is symmetrically condensed with anthracene (see, for example, Patent Document 4), mono-containing oligos and polydithienopyridines (for example, see Patent Document 5), and even polythiophenes. Sufficient solubility in solvents is only possible with limited types of compounds such as , polyth- erene-bi-rene, poly-p-phelene-bi-rene, and conjugated polymers (for example, see Non-Patent Documents 1 to 3). A material that exhibits sufficient carrier mobility/ONZOFF ratio while retaining properties has been found.

[0009]Recently, it has been reported that a single crystal of rubrene, which is a highly soluble acene compound, has extremely high mobility (for example, see Non-Patent Document 4). Single crystals are made by vapor phase growth, and films made by solution casting are usually amorphous and have sufficient mobility.

[0010] Compounds in which functional groups are added to pentacene, a compound with high carrier mobility, by vacuum evaporation have also been disclosed, and it has also been reported that relatively good carrier mobility can be obtained by solution coating. (For example, see Patent Document 6.) ₀

[0011] However, acene-based compounds such as rubrene and pentacene are easily oxidized by oxygen contained in the air and converted into oxidants called endoberoxides, which significantly deteriorates their performance as field effect transistors. However, there are still issues to be solved regarding the storage stability of the solution and the stability of the coated film.

[0012] Regarding the stability over time of such organic semiconductor elements, for example, in Japanese Patent Application Laid-open No. 2003-292588, US Patent Application Publication No. 2003Z136958, US Patent Application No. 2003Z160230, and US Patent Application No. 2003Z164495, ``The use of polymer TFTs in integrated circuit logic elements for microelectronics greatly increases their mechanical durability and extends their usable lifetime.

[0013] However, many semiconductor polythiophenes are oxidatively doped by surrounding oxygen. It is considered that it is not stable when exposed to air because its conductivity increases. This results in higher off-state currents for devices fabricated with these materials, and therefore lower current-on ratios. Therefore, many of these materials require extreme care to eliminate or minimize oxidative doping by excluding ambient oxygen during material processing and device fabrication. This precaution increases manufacturing costs, making certain polymer TFTs less attractive as an economical alternative to amorphous silicon technology, especially for large-area devices. These and other disadvantages are avoided or minimized in embodiments of the invention. Therefore, there is a need for an electronic device that has strong resistance to oxygen and exhibits a relatively high current ONZOFF ratio. I think it will prevent the crabs! This problem is becoming a major challenge for practical application.

[0014] As an example of acene-based compounds that are relatively stable against oxidation, it has been reported that some compounds in which the 6 and 13 positions of pentacene are substituted with a silyl ethyl group have good coating film stability. (For example, see non-patent documents 5, 6 and patent document 7.) ₀

[0015] However, in these reports, the text only states the qualitative properties that the stability against acidity has improved, and the stability is still not sufficient for practical use. Not obtained.

[0016] In addition, by substituting a part of the pentacene mother nucleus of a compound in which the 6th and 13th positions of pentacene are substituted with a silyletyl group with an electron-withdrawing group such as a halogen atom or a cyano group, the acidity of the compound can be improved. Although attempts have been made to deepen the reduction potential, the mobility of these compounds remains at a maximum of 4.5 x 10-2 ^cm2 ^ZVs (for example, see Non-Patent Document 7).

[0017] In addition, as compounds having an acene core larger than that of anthrazithiophene, bis(triisopropylsilylethyl)tetradithiophene (6-ring acene), bis(triisopropylsilyletinyl)pentadithiophene Phene (7-ring acene) can be synthesized (for example, see Non-Patent Document 8), but bis(triisoprobylsilylacetyl)pentadithiophene is not the desired compound, but the acene mother. It has been reported that a dimer in which the nucleus and ethynyl group are bonded by a Diels-Alder reaction has been obtained. [0018] In addition, it is said that bis(tri-t-butylsilylethyl)pentadithiophene, which has a larger terminal ethynyl group, does not produce dimers and that the target compound can be stably isolated, but there are no questions regarding stability. The description is only qualitative, and the semiconductor characteristics have not been measured.

[0019] As described above, an organic semiconductor material that has both high mobility and durability has not yet been obtained.

Patent document 1: Japanese Patent Application Laid-Open No. 55568

Patent Document 2: Japanese Unexamined Patent Publication No. 5-190877

Patent Document 3: Japanese Unexamined Patent Publication No. 8-264805

Patent Document 4: Japanese Unexamined Patent Publication No. 11-195790

Patent document 5: Japanese Patent Application Publication No. 2003-155289

Patent Document 6: International Publication No. 03Z016599 Pamphlet

Patent Document 7: US Patent No. 6690029B1

Non-patent literature 1: Science magazine, volume 289, page 599 (2000)

Non-patent document 2: Nature magazine, volume 403, page 521 (2000)

Non-patent document 3: "Advanced Material" magazine, 2002, No. 2, page 99

Non-patent document 4: Science, vol. 303 (2004), page 1644

Non-patent document 5: Org. Lett., vol. 4 (2002), page 15

Non-patent document 6:J. Am. Chem. Soc., vol. 127 (2005), page 4986

Non-patent document 7: Org. Lett., vol. 7 (2005), page 3163

Non-patent document 8: Org. Lett., vol. 6 (2004), page 3325

Disclosure of invention

Problems that the invention seeks to solve

[0020] The present invention has been made in view of the above-mentioned problems, and its purpose is to be able to manufacture it by a simple coating process, to have good characteristics as a transistor, and to be resistant to oxygen in the air. An object of the present invention is to provide an organic semiconductor material that is stable and sufficiently suppressed from deteriorating over time, and an organic semiconductor film, an organic semiconductor device, and an organic thin film transistor using the same. Means to solve problems

[0021] The above object of the present invention was achieved by the following configuration.

[0022] 1. An organic semiconductor material characterized by comprising a compound represented by the following general formula (1) [0023] [Chemical formula 1] General formula <1)

[0024] (In the formula, L represents a divalent linking group, Υ and Ζ are an aromatic hydrocarbon ring or an aromatic

1 1 1

Represents a heterocycle. R is an alkyl group, cycloalkyl group, aralkyl group, aryl group or

1

represents a heteroaryl group, and the alkyl group, cycloalkyl group, aralkyl group, aryl group, and heteroaryl group further form a group bonded via an oxygen, sulfur, nitrogen, or silicon atom, respectively. You may. m represents an integer from 1 to 5, and nl represents an integer from 0 to 3. ) 2. The organic semi-organic semiconductor according to 1 above, wherein L is a group having an ethyl group.

1

conductor material.

[0025] 3. The organic semiconductor material as described in 1 or 2 above, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

[0026] [Case 2] —General formula (2)

[0027] (In the formula, Y and Ζ represent an aromatic hydrocarbon ring or an aromatic heterocycle. R is an

2 2 2 represents a kyl group, a cycloalkyl group, an aralkyl group, an aryl group, or a heteroaryl group, and each of the alkyl group, cycloalkyl group, aralkyl group, aryl group, and heteroaryl group is , may form a group bonded via a sulfur, nitrogen, or silicon atom. m represents an integer from 1 to 5, and n2 represents an integer from 1 to 2. )

4.The above Rί tertiary alkyl group, tertiary alkyloxy group, alkylsilyl group, alkyl

2

3. The organic semiconductor material described in 3 above, which represents a luciloxy group or an (alkylsilyl)alkyl group.

[0028] 5. Organic semiconductor material characterized by containing a compound represented by the following general formula (3) [0029] [Chemical formula 3]

-

[0030] (In the formula, Y and Z represent an aromatic hydrocarbon ring or an aromatic heterocycle, and L is a single bond.

3 3 3

, represents an oxygen atom, or an alkylene group. R to R are alkyl groups and cycloalkyl groups, respectively.

3 5

represents an aryl group, an aryl group or an alkylsiloxy group. n3 represents an integer from 1 to 2. ) 6. The organic compound according to 5 above, wherein Z represents a benzene ring and n3 is 2.

3

semiconductor material.

[0031] 7. An organic semiconductor film containing the organic semiconductor material according to any one of items 1 to 6 above.

[0032] 8. The organic semiconductor material according to any one of 1 to 6 above is dissolved in an organic solvent, and the resulting solution is applied and dried. The organic semiconductor film described in 7.

[0033] 9. An organic semiconductor device using the organic semiconductor material according to any one of items 1 to 6 above.

[0034] 10. An organic thin film transistor characterized in that the organic semiconductor material according to any one of items 1 to 6 above is used for a semiconductor layer.

Effect of the invention

[0035] The present invention provides an organic semiconductor material that is manufactured by a simple process, has good characteristics as a transistor, and has suppressed deterioration over time, an organic semiconductor film using the same, an organic semiconductor device, and an organic thin film transistor. I was able to provide it. Brief description of the drawing

[0036] [FIG. 1] A diagram showing a configuration example of an organic TFT according to the present invention.

[Figure 2] This is an example of a schematic equivalent circuit diagram of the organic TFT of the present invention.

[Figure 3] A schematic diagram showing an example of an organic EL element having a sealing structure.

[Figure 4] A schematic diagram showing an example of a substrate having a TFT used in an organic EL element.

Explanation of symbols

[0037] 1 Organic semiconductor layer

2 source electrode

3 Drain electrode

4 Gate electrode

5 Insulating layer

6 Support

7 Gate bus line 8 source line

10 Organic thin film transistor sheet

11 Organic thin film transistor

12 Output elements

13 Storage capacitor

14 Vertical drive circuit

15 Horizontal drive circuit

101, 201 board

102 Organic EL element

102a, 202 anode

102b Organic EL layer

102c, 204 cathode

103 Sealing film

205 Drive element

206 Hole transport layer

207 Luminescent layer

208 Electron transport layer

601 Board

602TFT

BEST MODE FOR CARRYING OUT THE INVENTION

[0038] In the organic semiconductor material of the present invention, by having the structure defined in any one of claims 1 to 6, it can be manufactured by a simple process and has good characteristics as a transistor. In addition, we were able to provide an organic semiconductor material whose deterioration over time is suppressed, an organic semiconductor film using the same, an organic semiconductor device, and an organic thin film transistor.

[0039] Details of each component according to the present invention will be sequentially explained below.

[0040] Acene-based compounds, which are one of the conventionally known organic semiconductor materials, deteriorate mainly due to Diels-Alder-like 1, 4-addition of oxygen molecules to the acene core over time. It is known that the disease progresses. [0041] In addition, in the above-mentioned bis(triisoprobylsilyl)pentadithiophene, the molecule itself

An inferiority mechanism is known in which Diels-Alder adhesion occurs between the -ru group and the acene mother nucleus, resulting in dimerization.

[0042] In order to prevent such a Diels-Alder reaction, the dienophile compound (acene core) is substituted with a sterically large substituent such as a tertiary butyl group or a trimethylsilyl group. It is known that it is effective to prevent compounds (such as oxygen) from coming close to the reaction site of the compound.

[0043] The compounds disclosed in the aforementioned Non-Patent Documents 5 to 7 also have a certain degree of stability due to such a sterically large substituent, the trialkylsilyl ethyl group. It is estimated to be.

[0044] However, even these compounds still lacked stability for practical use, so the present inventors conducted extensive studies to find a more stable substituent. As a result, an aromatic ring has a steric size equivalent to or larger than that of a trialkylsilyl group, does not cause an elimination reaction like a trialkylsilyl group, and has a specific substituent as a substituent. (Here, the aromatic ring refers to an aromatic hydrocarbon ring, an aromatic heterocycle, etc.) By adding an acene core to the acene core, deterioration by dienophiles such as oxygen can be prevented over a long period of time. The present inventors discovered that a compound with good solubility and good semiconductor properties can be obtained, leading to the completion of the present invention.

[0045] [Organic semiconductor material]

The organic semiconductor material of the present invention is characterized in that it is an organic semiconductor material consisting of an athene compound substituted with an aromatic group having a specific substituent, as represented by the above general formula (1).

[0046] In the above general formula (1), L represents a divalent linking group, and Y and Z represent an aromatic hydrocarbon ring.

1 1 1

or represents an aromatic heterocycle. R is an alkyl group, a cycloalkyl group, an aralkyl group,

1

represents an aryl group or a heteroaryl group, and the alkyl group, cycloalkyl group, aryl group, aryl group, and heteroaryl group are further bonded via an oxygen, sulfur, nitrogen, or silicon atom, respectively. may also form a group. m represents an integer from 1 to 5, and nl represents an integer from 0 to 3. [0047] The acene-based core used in the molecular skeleton of the organic semiconductor material of the present invention needs to be an acene-based core in which three or more substituted or unsubstituted rings (0≤nl) are condensed.

[0048] The acene-based mother nucleus is a ring structure in which aromatic rings (here, the aromatic ring refers to an aromatic hydrocarbon ring or an aromatic heterocycle) are linearly condensed. be. Acene-based cores with less than 3 rings are not preferred because their mobility as a semiconductor will be insufficient. On the other hand, the greater the number of condensed rings, the more easily they are oxidized by oxygen, so the number of condensed rings in the acene-based mother nucleus is preferably 9 rings or less (nl≤3)!/. More preferably, it is an acene compound in which 5 to 7 rings (nl = 1 to 2) are condensed.

[0049] Examples of the acene-based core of the compound represented by the above general formula (1) include anthracene, pyridoquinoline, biladinoquinoxaline, pyrimidoquinazoline, pyridazinophthalazine, 1, 2, 5, 6- Tetraazaanthracene, benzodifuran, benzodithiophene, pyroindole, benzobisoxazole, benzobisthiazole, benzodiimidazole, pentacene, 1, 8 diazapentacene, 2, 9 diazapentacene, 1, 4, 8, 11-tetraazapentacene, 5, 7, 12, 14-tetraazapentacene, anthradithiophene, anthradifuran, anthradipyrrole, anthrabisoxazole, anthrabisthiazole, anthradiimidazonole, heptacene, 1 , 10-diazaheptacene, pentadithiophene, nonacene, etc. These acene-based cores may have substituents as described below.

[0050] As the linking group L, any divalent linking group can be used without limitation. Linking group L and

1 1 Examples include alkylene groups such as methylene, ethylene and hexamethylene groups, alkylene groups such as bilene groups and 1,2-dichloroethylene groups, and alkylene groups such as ethyl groups. group, cyclohexane, cycloalkylene group such as 1,4 diyl group, arylene group such as phelene group, ether group, amino group, thioether group, carbol group, thiocarbol group, carbolimino group , a sulfiel group, a sulfol group, a single bond, and the like.

[0051] A plurality of these may be bonded in series to form a single linking group, or may be introduced as a substituent that replaces some hydrogen atoms of the linking group to have a branched structure. It may also have a substituent as described below.

[0052] The aromatic hydrocarbon ring or aromatic heterocycle represented by Y and Z has a condensed ring number of 1 to 1.

1 1

3, aromatic hydrocarbon rings or aromatic heterocycles can be used without restriction. Wear.

[0053] However, if a fused polycycle is used, the solubility of the compound decreases, so a monocyclic aromatic hydrocarbon ring or an aromatic heterocycle is preferred. Examples of such monocyclic aromatic hydrocarbon rings or aromatic heterocycles include six-membered ring structures such as benzene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, and tetrazine ring; , pyrrole ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, furan ring, benzofuran ring, isobenzofuran ring, oxazole ring, isoxazole ring, furazane ring, thiophene ring, thiazole ring, etc. Either can be used without restriction.

[0054] The present invention is characterized in that the aromatic hydrocarbon ring or aromatic hydrocarbon ring represented by Y and Z above is

1 1

The aromatic heterocycle has one or more substituents R. Substituent R is an alkyl group, a

1 1

It represents a substituent selected from a chloroalkyl group, an aralkyl group, an aryl group, a heteroaryl group, or a group in which the above group is bonded via an oxygen, sulfur, nitrogen, or silicon atom. These may be bonded to each other to form a ring, and may further have a substituent as described below.

[0055] Compounds without substituent R as described above have low solubility and cannot be diluted by solution coating.

1

It is difficult to form a film, and steric hindrance is not sufficient to prevent the acene core and oxygen molecules from deteriorating through the Diels-Alder reaction, resulting in insufficient stability.

[0056] Number of substituents R in the aromatic hydrocarbon ring or aromatic heterocycle represented by Y and Z

1 1 1 m is preferably an integer of 1 or more and 5 or less. When m is 0 (no substitution), the solubility or stability is insufficient as described above. Furthermore, introducing five or more substituents often involves synthetic difficulties, and if there are five or more substituents, the symmetry of the compound decreases, crystallinity decreases, and mobility may become insufficient. Preferable to be!/,.

[0057] A part of the above acene-based mother nucleus (the part represented by Z), the linking group L, and the substituent R force are respectively updated.

Examples of the substituents in 1 1 1 include the following substituents.

[0058] Alkyl group: For example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, neopentyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, pentadecyl group, etc. Cycloalkyl group: For example, cyclopentyl group, cyclohexyl group, etc.

Aralkyl group: For example, benzyl group, p-iso-propylbenzyl group, o-methylbenzyl group, etc.

Alkyl group: For example, bull group, allyl group, 1, 2-dichloroethylene group, etc. Alkyl group: Etyl group, propargyl group, jetyl group, etc.

Aryl group (also referred to as aromatic carbocyclic group, aromatic hydrocarbon group, etc.): For example, phenyl group

, p-chlorophenol group, tolyl group, xylyl group, mesityl group, biphelyl group, etc., as well as naphthalene ring, anthracene ring, azulene ring, acenaphthene ring, fluorene ring, phenanthrene ring, indene ring, pyrene ring , tetracene ring, pentacene ring, hexacene ring, benzopyrene ring, benzazurene ring, talicene ring, benzochrysene ring, acenaphthene ring, acenaphthylene ring, triphenaphthylene ring, coronene ring, benzocoronene ring, hexabenzocoronene ring, benzofluorene ring , fluoranthene ring, perylene ring, naphthoperylene ring, pentabenzoperylene ring, benzoperylene ring, pentaphene ring, picene ring, pyranthrene ring, coronene ring, naphthocoronene ring, fovalene ring, anthranthrene ring Etc. Derived substituents etc,

Heteroaryl group (also referred to as aromatic heterocyclic group, heteroaromatic ring group, etc.): For example, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, tetrazine ring, quinoline ring, isoquinoline ring, ataridine ring, Nanthridine ring, quinoxaline ring, cinnoline ring, phthalazine ring, quinazoline ring, naphthyridine ring, pteridine ring, phenazine ring, phenantholine ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, indole ring, benzimidazole ring, Rubazole ring, purine ring, pyrrolopyrrole ring, pyrazolotriazole ring, benzoquinoline ring, rubbazole ring, azacarbazole ring, phenazine ring, phenanthridine ring, phenantophosphorus ring, carboline ring, cyclazine ring, kindlin ring, Thevezine ring, Kundrin ring, triphenodithiazine ring, triphenodioxazine ring, phenanthrazine ring, anthrazine ring, perimidine ring, diazatribazole ring (where any one of the carbon atoms constituting the carboline ring ), phenanthyl ring, furan ring, benzofuran ring, isobenzofuran ring, dibenzofuran ring, oxazole ring, isoxazole ring, oxadiazole ring, furazane ring, thiophene ring, benzothio ring Phen ring, thieno[2, 3- a]thiophene ring, thieno[2, 3- b]thiophene ring, anthradithiophene ring, dithiafulvene ring, thiazole ring, benzothiazole ring, dibenzothiophene ring, benzodithiophene ring, anthradithiophene ring Substituents derived from the thiophene ring, thiophthene ring, etc.

Heterocyclic group: epoxy ring, aziridine ring, thiirane ring, oxetane ring, azetidine ring, thiethane ring, tetrahydrofuran ring, dioxolane ring, pyrrolidine ring, virazolidine ring, imidazolysine ring, oxazolidine ring, tetrahydrothiophene ring, sulfolane ring, Thiazolidine ring, ε-proratatone ring, ε-prolatatum ring, piperidine ring, hexahydropyridazine ring, hexahydropyrimidine ring, piperazine ring, morpholine ring, tetrahydropyran ring, 1, 3-dioxane ring , 1, 4 dioxane ring, trioxane ring, tetrahydrothiopyran ring, thiomonoleforin ring, thiomonolephorin 1, 1-dioxide ring, bilanose ring, jazabicyclo [2, 2, 2]-octane ring, etc. ,

Alkoxy group: For example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.

Cycloalkoxy group: For example, cyclopentyloxy group, cyclohexyloxy group, etc. Aryloxy group: For example, phenoxy group, naphthyloxy group, etc.

Alkylthio group: For example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.

Cycloalkylthio group: For example, cyclopentylthio group, cyclohexylthio group, etc. Arylthio group: For example, phenylthio group, naphthylthio group, etc.

Alkoxycarboxylic group: For example, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarboxylic group, octyloxycarboxylic group, dodecyloxycarboxylic group, etc.

Paryloxycarbonyl group: For example, pheryloxycarbonyl group, naphthyloxycarbonyl group, etc.

Sulfamoyl group: For example, aminosulfol group, methylaminosulfol group, dimethylaminosulfol group, butylaminosulfol group, hexylaminosulfol group, cyclohexylaminosulfol group, octylamino group Sulfol group, dodecylaminosulfol group, phenylaminosulfol group, naphthylaminosulfol group, 2-pyridylaminosulfol group, etc.

Acyl group: For example, acetyl group, ethyl carboxyl group, propyl carboxyl group, pentyl carboxyl group, cyclohexyl carboxyl group, octyl carpol group, 2-ethylhexyl carboxyl group, dodecyl carboxyl group fluorine group, fluorocarbon group, naphthylcarboxylic group, pyridylcarboxylic group, etc.

Acyloxy group: For example, acetyloxy group, ethylcarboxy group, butylcarboxy group, octylcarboxy group, dodecylcarpoloxy group, phenolcarboxy group, etc.

Amide group: For example, methylcarbolamino group, ethylcarbolamino group, dimethylcarbolamino group, propylcarbolamino group, pentylcarbolamino group, cyclohexylcarbolamino group, 2-ethylhexylcarbolamino group, octylcarbolamino group Boramino group, dodecylcarpolamino group, phenolcarpolamino group, naphthyl carbonylamino group, etc.

Rubamoyl group: For example, aminocarboxylic group, methylaminocarboxylic group, dimethylaminocarboxylic group, propylaminocarboxylic group, pentylaminocarboxylic group, cyclohexylaminocarboxylic group , octylaminocarboxylic group, 2-ethylhexylaminocarboxylic group, dodecylaminocarboxylic group, phelaminocarboxylic group, naphthylaminocarboxylic group, 2-pyridylaminocarboxylic group etc,

Ureido group: For example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, ferureido group, naphthylureido group, 2-pyridylaminoureido group, etc.

Amino group: For example, amino group, ethylamino group, dimethylamino group, butylamino group, pentylamino group, 2-ethylhexylamino group, dodecylamino group, allino group, naphthylamino group, 2-pyridylamino group, etc.

Halogen atoms: For example, fluorine atoms, chlorine atoms, bromine atoms, etc.

Fluorinated hydrocarbon groups: For example, fluoromethyl group, trifluoromethyl group, pentafluoroethyl group, pentafluorophel group, etc. Silyl group: For example, trimethylsilyl group, triisoprobylsilyl group, tricyclohexylsilyl group, trifluorsilyl group, fluorethylsilyl group, trimethoxysilyl group, triethoxysilinole group, silatrane group,

Siloxy group: For example, trimethylsiloxy group, triisoprobylsiloxy group, tricyclohexylsiloxy group, triphenolsiloxy group, phenolsiloxy group,

(Alkylsilyl)alkyl group: (triethylsilyl)methyl group, (triisoprobylsilyl) propyl group, bis(trimethylsilyl)methyl group, tris(trimethylsilyl)methyl group, sulfiel group: For example, methylsulfyl group, ethylsulfyl group group, butylsulfyl group, cyclohexylsulfyl group, 2-ethylhexylsulfiel group, dodecylsulfyl group, phenylsulfyl group, naphthylsulfyl group, 2-pyridylsulfyl group, etc. ,

Sulfol group: For example, methylsulfol group, ethylsulfol group, butylsulfol group, cyclohexylsulfol group, 2-ethylhexylsulfol group, dodecylsulfol group, etc., phenylsulfol group, Naphthylsulfol group, 2-pyridylsulfol group, etc.

Other substituents: cyano group, nitro group, hydroxy group, mercapto group, alkylsilyl group, disulfide group, sulfoximine group, oxo group (=0), thione group (=S), phosphate ester group, thiophosphate ester group, phosphorylamino group, phosphite group, etc. These substituents may be further substituted with the above substituents. Moreover, a plurality of these substituents may be bonded to each other to form a ring.

[0059] Among the structures represented by the above general formula (1), preferably the linking group L is an ethynyl group.

1

A compound is preferred.

[0060] It is known that the conductivity of organic semiconductors mainly propagates in the direction perpendicular to the plane formed by the acene-based cores, and the greater the overlap between the acene-based cores, the better the semiconductor properties. be able to.

[0061] The aromatic group Y connected to the acene-based core is a sterically large group having m substituents R.

1 1

It is a substituent, and if it exists near the acene-based mother nucleus, it may reduce the stack area of the acene-based mother nuclei and deteriorate the semiconductor properties. It is preferable to be located at a certain distance without interfering with the stacking of the player.

[0062] Unlike alkylene groups, alkenylene groups, etc., the ethynyl group is a linear linking group and has the same size and thickness as the acene-based core, so it does not inhibit the stacking of the acene-based core.

[0063] Furthermore, the ethynyl group is a relatively electron-withdrawing substituent, and has the effect of lowering the redox potential of the acene-based mother nucleus and preventing oxidative deterioration.

[0064] Furthermore, since the ethynyl group has a rigid structure, the crystallinity of the compound becomes high, and as a result, the arrangement of the compound in the coating film becomes uniform, making it possible to obtain a thin film with higher mobility. A thin film with such high crystallinity has the effect of making it difficult for deteriorating factors such as oxygen and moisture to penetrate into the thin film, making it less likely that deterioration will occur.

[0065] In order to further enhance the stability of the compound, it is preferable that at least one substituent R is present at the ortho position of the linking group L so that oxygen cannot approach sterically. death

1 1

Therefore, a compound represented by the above general formula (2) is preferable.

[0066] In the above general formula (2), Y and Z are substituted or unsubstituted hydrocarbon aromatic rings or

twenty two

represents a heteroaromatic ring. R is an alkyl group, cycloalkyl group, aralkyl group, aryl group

2

represents a substituent selected from a group consisting of a heteroaryl group, a heteroaryl group, or a group in which the above group is bonded via an oxygen, sulfur, nitrogen, or silicon atom. m represents an integer from 1 to 5, n2 represents an integer from 1 to 2

[0067] With such a structure, a coating film with even higher stability can be obtained.

[0068] The substituent R is more preferably a tertiary alkyl group, a tertiary alkyloxy group, or a silicate group.

2

siloxy, and (alkylsilyl)alkyl groups are selected substituents. Tertiary alkyl groups, tertiary alkyloxy groups, silyl groups, and siloxy groups are the most sterically large substituents among the above-mentioned substituents because they have a four-way branched structure. This is because it has a high ability to protect power.

[0069] More preferred is a compound having a structure represented by the above general formula (3).

[0070] In the above general formula (3), Y and Z are substituted or unsubstituted hydrocarbon aromatic rings or

3 3

represents a heteroaromatic ring, L is a single bond, an oxygen atom, or an alkylene group.

3

Represents a group. R to R are from alkyl group, cycloalkyl group, aryl group, siloxy group

3 5

Represents a selected substituent. n3 represents an integer from 1 to 2. [0071] As shown in the above general formula (3), by substituting sterically large silyl groups on both sides of the ortho position of the ethyl group, addition of oxygen to the acene core can be further prevented.

[0072] Among these, r=2 and the aromatic ring represented by Z is an unsubstituted benzene ring.

3

It is a compound whose parent nucleus is heptacene. With such a structure, it is possible to increase the overlap of the π-conjugated planes between molecules in the coated film, so it is possible to obtain an organic semiconductor film with excellent mobility.

[0073] The molecular weight of the compounds represented by the above general formulas (1) to (3) is preferably in the range of 300 to 5000. By setting the molecular weight to 300 or more, the volatility of the compound can be made sufficiently low, and contamination due to volatilization during production can be prevented. Furthermore, by setting it to 5000 or less, the solubility in the solvent can be kept within a good range. In addition, it is possible to improve the stacking properties between molecules, and it is possible to improve TFT performance. The molecular weight is more preferably in the range of 500 to 2000. Note that the molecular weight of the organic semiconductor material of the present invention can be measured using a mass spectrometer or the like.

[0074] Specific examples of compounds represented by general formulas (1) to (3) according to the present invention are shown below, but the present invention is not limited thereto.

[0075] [C4]

[S^] [9 00]

ZZZie/900Zdf13d 61· 991?990/.00ί OAV

[0077] [6] [ W [8Z00]

9917990/Ζ.00Ζ OAV

[8^ ] [6 00]

ZUZ£/900Zdf/X3d zz 99f990//.00l OAV

[0080] [9]

[0I^ ] [Ϊ800]

ZZZrC/900Zdf X3d z 99t990 excitation ί ΟΛ\

36

WC ₄ H ₉ ' / · 丫\ C ₄ H _g (t)

_h3NH3 _{_}

[0083] [C12]

[0084] [C13]

[0085] [C14]

[0086] [C15]

In addition, the above-mentioned compound can be synthesized with reference to the following literature.

'(Alkylsilyl)phelacetylene compounds: For example, J. Am. Chem. Soc., vol. 99(1977), ρ2010, etc., or Chem. Lett., (1991), pl259, etc.

'(Alkylsiloxy)phelacetylene compounds: For example, J. Mater. Chem., vol. 12(2002)ρ2009, etc. -Addition reaction of aryl acetylene compound to acene core: For example, the above-mentioned non-patent document 6,

J. Org. Chem., vol. 34 (1969), pi 734 etc.

[Organic semiconductor film, organic semiconductor device, organic thin film transistor]

The organic semiconductor film, organic semiconductor device, and organic thin film transistor of the present invention will be explained.

[0088] When the organic semiconductor material of the present invention is used in an organic semiconductor film, an organic semiconductor device, or a semiconductor layer of an organic thin film transistor, it is possible to provide an organic semiconductor device or an organic thin film transistor that drives well. Organic thin film transistors are of the top-gate type, which has a source electrode and drain electrode connected to each other by an organic semiconductor as a semiconductor layer on a support, and a gate electrode on top of the source and drain electrodes via a gate insulating layer; It is broadly divided into the bottom-gate type, which has a gate electrode on top, and a source and drain electrode connected by an organic semiconductor via a gate insulating layer.

[0089] In order to install the organic semiconductor material of the present invention in the semiconductor layer of an organic semiconductor film, an organic semiconductor device, or an organic thin film transistor, it can also be installed on a substrate by vacuum evaporation.

It is preferable that a solution prepared by dissolving it in an appropriate solvent and adding additives as necessary is placed on the substrate by cast coating, spin coating, printing, an inkjet method, an ablation method, or the like.

[0090] In this case, the solvent for dissolving the organic semiconductor material of the present invention is not particularly limited as long as it can dissolve the organic semiconductor material and prepare a solution with an appropriate concentration. Chain ether solvents such as ethyl ether and diisopropyl ether, cyclic ether solvents such as tetrahydrofuran and dioxane, ketone solvents such as acetone and methyl ethyl ketone, and halogenated solvents such as chloroform and 1,2-dichloroethane. Examples include alkyl solvents, aromatic solvents such as toluene, o-dichlorobenzene, nitrobenzene, and m-talesol, N-methylpyrrolidone, and disulfuric acid. Among these solvents, solvents containing non-halogen solvents are preferred, and it is preferable to use non-halogen solvents. In addition, when coating on an insulating film whose surface has been hydrophobized, it is preferable to use a nonpolar solvent whose surface energy is lower than that of the hydrophobized surface. Cyclohexane, toluene, etc. are preferred. [0091] In the organic thin film transistor of the present invention, it is preferable that the organic semiconductor material of the present invention is used in the semiconductor layer. The semiconductor layer is preferably formed by applying a solution or dispersion containing these organic semiconductor materials.

[0092] In the present invention, the materials forming the source electrode, drain electrode, and gate electrode are not particularly limited as long as they are conductive materials, and include platinum, gold, silver, nickel, chromium, copper, iron, tin, Antimony, tantalum, indium, palladium, tellurium, rhenium, iridium, anoremium, ruthenium, germanium, molybdenum, tungsten, 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, anoremium, magnesium Z copper mixture, magnesium Z silver mixture, magnesium Z aluminum mixture, magnesium Z indium mixture, aluminum Z oxidium aluminum mixture, lithium Z aluminum mixture, etc. are used, but in particular, Platinum, gold, silver, copper, aluminum, indium, ιτο and carbon are preferred. Alternatively, known conductive polymers whose conductivity has been improved by doping etc., such as conductive polyaline, conductive polypyrrole, conductive polythiophene, a complex of polyethylene dioxythiophene and polystyrene sulfonic acid, etc., can also be suitably used. . Among these, those with low electrical resistance at the contact surface with the semiconductor layer are preferred.

[0093] As a method for forming an electrode, a conductive thin film is formed using a method such as vapor deposition or sputtering using the above raw materials, and an electrode is formed using a known photolithography method or a lift-off method, or a method using aluminum, copper, etc. There is a method of etching on metal foil using a resist such as thermal transfer or inkjet. Further, a solution or dispersion of a conductive polymer or a dispersion of conductive fine particles may be directly patterned by inkjet, or it may be formed from a 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 letterpress, intaglio, planography, or screen printing can also be used.

[0094] Various insulating films can be used as the gate insulating layer, especially those with a high dielectric constant. An inorganic acid film is preferred. Inorganic acids include silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, barium zirconate titanate, lead zirconate titanate, and titanate. Examples include lanthanum lead, strontium titanate, barium titanate, barium magnesium fluoride, bismuth titanate, strontium bismuth titanate, strontium bismuth tantanoleate, bismuth tantanoleate niobate, and yttrium trioxide. Among them, silicon oxide, aluminum, tantalum, and titanium are preferred. Inorganic nitrides such as silicon nitride and aluminum nitride can also be suitably used.

[0095] Methods for forming the above film include vacuum evaporation, molecular beam epitaxial growth, ion cluster beam, low energy ion beam, ion plating, CVD, sputtering, atmospheric pressure plasma, etc. Dry process, coating methods such as spray coating method, spin coating method, blade coating method, dip coating method, casting method, roll coating method, bar coating method, die coating method, etc., and patterning method such as printing and inkjet method. There are wet processes such as , which can be used depending on the material.

[0096] The wet process is a method in which fine particles of an inorganic oxide are dispersed in any organic solvent or water using a dispersion aid such as a surfactant if necessary, and then dried. For example, a so-called sol-gel method is used in which a solution of an alkoxide is applied and dried. Preferred among these are the atmospheric pressure plasma method and the sol-gel method.

[0097] A method for forming an insulating film by plasma film forming treatment under atmospheric pressure is a process in which a thin film is formed on a substrate by discharging at or near atmospheric pressure to excite a reactive gas with plasma. The method is described in JP-A-11-61406, JP-A-11-133205, JP-A-2000-121804, JP-A-2000-147209, JP-A-2000-185362, etc. (see below) , also called atmospheric pressure plasma method). This allows highly functional thin films to be formed with high productivity.

[0098] In addition, as the organic compound film, polyimide, polyamide, polyester, polyarylate, photo-curing resin of photo-radical polymerization type, photo-active thion polymerization type, or copolymer containing acrylonitrile component, polybyrphenol, Polybulic alcohol, novolac olefin, cyanoethyl pullulan, and the like can also be used. As a method for forming organic compound films The wet process is preferable. An inorganic acid film and an organic acid film can be laminated and used together. Further, the thickness of these insulating films is generally 5011111 to 3111, preferably 100 nm to 1 μm.

[0099] Further, the support is made of glass or a flexible resin sheet, and for example, a plastic film can be used as the sheet. Examples of the plastic film include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether sulfone (PES), polyetherimide, polyetheretherketone, polyphelene sulfide, polyarylate, polyimide, polycarbonate ( Examples include films that can be made from strong materials such as PC), triacetylcellulose (TAC), diacetylcellulose (DAC), and cellulose acetate propionate (CAP). In this way, by using a plastic film, it is possible to achieve a lighter weight compared to the case where a glass substrate is used, and it is possible to improve portability and resistance to impact.

[0100] Below, an organic thin film transistor using an organic semiconductor film formed using the organic semiconductor material of the present invention will be described.

[0101] FIG. 1 is a diagram showing a configuration example of an organic thin film transistor of the present invention. In the same figure (a), a source electrode 2 and a drain electrode 3 are formed using metal foil or the like on a support 6, an organic semiconductor layer 1 made of the organic semiconductor material of the present invention is formed between the two electrodes, and then An organic thin film transistor is formed by forming an insulating layer 5 and further forming a gate electrode 4 thereon. Figure (b) shows the organic semiconductor layer 1 formed between the electrodes in (a) by using a coating method or the like to cover the entire surface of the electrodes and support. (c) shows a structure in which an organic semiconductor layer 1 is first formed on a support 6 using a coating method or the like, and then a source electrode 2, a drain electrode 3, an insulating layer 5, and a gate electrode 4 are formed.

[0102] Figure (d) shows that after a gate electrode 4 is formed on a support 6 using metal foil or the like, an insulating layer 5 is formed, and a source electrode 2 and a drain electrode 3 are formed on the support 6 using metal foil or the like. An organic semiconductor layer 1 made of the organic semiconductor material of the present invention is formed between the electrodes. Other configurations as shown in (e) and (f) of the same figure can also be adopted.

[0103] FIG. 2 is a diagram showing an example of a schematic equivalent circuit diagram of an organic thin film transistor sheet.

[0104] Organic thin film transistor sheet 10 is a large number of organic thin film transistors arranged in a matrix 1 Has 1. 7 is a gate bus line of each organic thin film transistor 11, and 8 is a source bus line of each organic thin film transistor 11. An output element 12 is connected to the source electrode of each organic thin film transistor 11, and this output element 12 is, for example, a liquid crystal, an electrophoretic element, etc., and constitutes a pixel in a display device. The pixel electrode may also be used as an input electrode for a photosensor. In the illustrated example, a liquid crystal is used as an output element, and an equivalent circuit that also includes a resistor and a capacitor is shown. 13 is a storage capacitor, 14 is a vertical drive circuit, and 15 is a horizontal drive circuit.

[0105] The performance required for organic thin film transistors varies depending on the application, but for example, in applications such as electronic paper, the carrier mobility is 0.01 (1.0 x 10— ² )~: L Ocm ² /Vsec is preferably in the range. The ON/OFF ratio is preferably in the range from 1.0 x 10 ⁵ to 1.0 x 10 ⁷ . With such a range, the display can be driven at a sufficient speed and good gradation can be imparted to the display.

Example

[0106] Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto.

[0107] Here, the structural formulas of compounds used in Examples are shown.

[0108] [C16]

Comparative compound (3) ratio

[0109] Example 1

《Fabrication of organic thin film transistor 1》: Comparison using compound 2

A 200 nm thick thermal oxide film was formed on a Si wafer with a specific resistance of 0.01 Ω'cm to serve as a gate insulating layer, and then surface treatment was performed using octadecyltrichlorosilane.

[0110] Comparative compound 2 was dissolved on the Si wafer subjected to such surface treatment at a concentration of 0.5% by mass in toluene in which nitrogen was bubbled for 30 minutes in a nitrogen atmosphere. Apply a spin coat (rotation speed: 2500 rpm, 15 seconds) and dry naturally. A test film was formed and heat treated at 50°C for 30 minutes in a nitrogen atmosphere.

[0111] Further, gold was deposited on the surface of this film using a mask to form a source electrode and a drain electrode. An organic thin film transistor 1 was fabricated with a source electrode and a drain electrode each having a width of 100 m and a thickness of 200 nm, a channel width W = 3 mm, and a channel length L = 20 μm.

[0112] Comparative compound 2 (2, 3, 9, 10-tetrahexylpentacene) was synthesized by the method described in Organic Letters, vol. 2 (2000), p85.

[0113] <Preparation of organic thin film transistor 2>: Comparison using compound 3

Organic thin film transistor 2 was produced in the same manner as organic thin film transistor 1 except that comparative compound 2 was changed to comparative compound 3. Comparative compound 3 was synthesized by the method described in J. Org. Chem., vol. 34 (1969), p. 1734.

[0114] <<Preparation of organic thin film transistor 3>>: Use of comparative compound 4

Organic thin film transistor 3 was manufactured in the same manner as organic thin film transistor 1 except that comparative compound 2 was changed to comparative compound 4. In addition, Comparison Compound 4 was synthesized using the above-mentioned non-patent document 6, supporting information 7 using the same method.

[0115] <<Preparation of organic thin film transistor 4>>: Use of comparative compound 5

Organic thin film transistor 4 was manufactured in the same manner as organic thin film transistor 1 except that comparative compound 2 was changed to comparative compound 5. Comparative compound 5 was synthesized using the method described in Non-Patent Document 8, supporting information 7.

[0116] 《Fabrication of organic thin film transistors 5 to 9》

Organic thin film transistors 5 to 9 were produced in the same manner as in the production of organic thin film transistor 1, except that the organic semiconductor material of the present invention listed in Table 1 was used instead of comparative compound 2.

[0117] 《Evaluation of carrier mobility and ONZOFF ratio》

For the obtained organic thin film transistors 1 to L0, the carrier mobility and ONZO FF ratio of each element were measured immediately after the element was fabricated. In the present invention, the carrier mobility was determined from the saturation region of the IV characteristic, and the ONZOFF ratio was determined from the ratio of the drain current values when the drain bias was set to -50V and the gate bias was set to -50V and 0V.

[0118] Similar evaluations were conducted after placing each device in an environmental chamber at 40°C and 90% RH for 48 hours. We remeasured the rear mobility and ONZOFF ratio.

[0119] The results obtained are shown in Table 1.

[0120] [Table 1]

[0121] From the results in Table 1, Comparative Compound 2 was able to form a coating film and was confirmed to be driven as a semiconductor, but the performance deteriorated significantly after the durability test. You can see that it is a material.

[0122] Comparative Compound 3 was similarly observed to have improved solubility compared to Comparative Compound 2, but it was not possible to dissolve all of it at the above concentration. Perhaps for this reason, the mobility of the obtained thin film was also low at 10 ³ .

[0123] Organic semiconductor devices ₃ and 4 showed sufficient TFT performance immediately after coating film formation, but after the durability test, the mobility was ^10-3 and the ONZOFF ratio was ^10-4 , indicating that the drive of the display was poor. Not held up to possible value.

[0124] On the other hand, organic thin film transistors 5 to 9 fabricated using the organic semiconductor material of the present invention exhibited excellent characteristics in both the carrier mobility 'ON/OFF ratio immediately after fabrication, and the mobility remained low even after the durability test. is ^10-2 or more, and the ONZOFF ratio is ^10-5 or more, which means it has little deterioration over time and is high! / It can be seen that when combined with durability.

[0125] Among the organic semiconductor elements of the present invention, silyl groups or The organic TFT element 8, which uses an acaenyl compound with a very sterically large substituent such as a siloxy group, has excellent durability with a mobility of ^10_2 even after durability tests. It had By using such substituents, even if the mother nucleus is a very large acene mother nucleus such as heptacene, it exhibits sufficient durability. It was confirmed that a semiconductor device was obtained.

[0126] Example 2

《Fabrication of organic EL device》

The organic EL device was manufactured by referring to the method described in Nature, volume 395, pages 151-154, and a top emission type organic EL device having a sealing structure as shown in FIG. 3 was manufactured. In FIG. 3, 101 is a substrate, 102a is an anode, 102b is an organic EL layer (specifically, includes an electron transport layer, a light emitting layer, a hole transport layer, etc.), 102c is a cathode, and 102a is an anode. A light emitting element 102 is formed by an organic EL layer 102b and a cathode 102c. 103 indicates a sealing film. Note that the organic EL device of the present invention may be either a bottom emission type or a top emission type.

[0127] By combining the organic EL device of the present invention and the organic thin film transistor of the present invention (here, the organic thin film transistor of the present invention is used as a switching transistor, a driving transistor, etc.), an active matrix type light emitting device can be produced. In that case, for example, as shown in FIG. 4, an example is an embodiment in which a substrate in which a TFT 602 (or an organic thin film transistor 602) is formed on a glass substrate 601 is used. Here, for the manufacturing method of TFT602, a known TFT manufacturing method can be referred to. Of course, the TFT may be a conventionally known top gate type TFT or a bottom gate type TFT.

[0128] The organic EL device produced above showed good light emission characteristics in various light emission forms such as monochromatic, full color, and white.

Claims

Scope of Claims An organic semiconductor material characterized by containing a compound represented by the following general formula (1).

[Convert 1] One

(In the formula, L represents a divalent linking group, Y and Z are an aromatic hydrocarbon ring or an aromatic

1 1 1

1

represents a heteroaryl group, and the alkyl group, cycloalkyl group, aralkyl group, aryl group, and heteroaryl group further form a group bonded via an oxygen, sulfur, nitrogen, or silicon atom, respectively. You may. m represents an integer from 1 to 5, and nl represents an integer from 0 to 3. ) [2] As set forth in claim 1, wherein the L is a group having an ethynyl group.

1

Organic semiconductor materials.

[3] The organic compound according to claim 1 or claim 2, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2). semiconductor material.

[Case 2]

—General formula (2)

(In the formula, Y and Z represent an aromatic hydrocarbon ring or an aromatic heterocycle. R is an aromatic represents a kyl group, a cycloalkyl group, an aralkyl group, an aryl group, or a heteroaryl group, and the alkyl group, the cycloalkyl group, the aralkyl group, the aryl group, and the heteroaryl group each further include oxygen, sulfur, A group bonded via a nitrogen or silicon atom may also be formed. m represents an integer from 1 to 5, and n2 represents an integer from 1 to 2. )

[4] The above R force tertiary alkyl group, tertiary alkyloxy group, alkylsilyl group, alkylsilyl group

2

4. The organic semiconductor material according to claim 3, which represents an xy group or an (alkylsilyl)alkyl group.

[5] An organic semiconductor material characterized by containing a compound represented by the following general formula (3).

[C3]

-

(In the formula, Y and Z represent an aromatic hydrocarbon ring or an aromatic heterocycle, and L is a single bond.

3 3 3

3 5

represents an aryl group, an aryl group or an alkylsiloxy group. n3 represents an integer from 1 to 2. )

[6] According to claim 5, wherein Z represents a benzene ring, and n3 is 2.

3

organic semiconductor materials.

[7] An organic semiconductor film comprising the organic semiconductor material according to any one of claims 1 to 6.

[8] The organic semiconductor material according to any one of claims 1 to 6.

8. The organic semiconductor film according to claim 7, wherein the organic semiconductor film is formed by dissolving in an organic solvent, applying the obtained solution, and drying.

[9] An organic semiconductor device characterized by using the organic semiconductor material according to any one of claims 1 to 6. An organic thin film transistor characterized in that the organic semiconductor material according to any one of claims 1 to 6 is used for a semiconductor layer.