WO2007069416A1

WO2007069416A1 - Organic semiconductor material, organic semiconductor film, organic semiconductor device and organic thin film transistor

Info

Publication number: WO2007069416A1
Application number: PCT/JP2006/322542
Authority: WO
Inventors: Hidekane Ozeki; Rie Katakura; Yasushi Okubo
Original assignee: Konica Minolta Holdings, Inc.
Priority date: 2005-12-13
Filing date: 2006-11-13
Publication date: 2007-06-21
Also published as: JPWO2007069416A1

Abstract

Disclosed are an organic semiconductor material, organic semiconductor film, organic semiconductor device and organic thin film transistor having high mobility and excellent durability. Specifically disclosed is an organic semiconductor material characterized by having a structure represented by the following general formula (1). (In the formula, X represents Ge or Sn; Y represents a parent nucleus having at least one heterocycle or a fullerene parent nucleus; and R1-R3 respectively represent a hydrogen atom or a substituent.)

Description

Specification

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

Technical field

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

Background art

With the widespread use of information terminals, there is an increasing need for flat panel displays as computer displays. In addition, with the progress of computerization, information that has been provided in paper media has been increasingly digitized, and electronic paper is a display media for mopile that is thin, light, and easy to carry. There is a growing need for digital paper.

[0003] Generally, in a flat display device, a display medium is formed by using elements utilizing liquid crystal, organic EL (organic electoluminescence), electrophoresis, or the like. In such display media, a technology using an active drive element (TFT element) as an image drive element has become mainstream to ensure uniformity of screen brightness, screen rewriting speed, and the like! For example, in an ordinary computer display, these TFT elements are formed on a glass substrate, and liquid crystal, organic EL elements, etc. are sealed.

Here, semiconductors such as a—Si (amorphous silicon) and p—Si (polysilicon) can be mainly used for TFT elements, and these S 泮 conductors (and metal films as required). The TFT element is manufactured by forming a multi-layered structure and sequentially forming source, drain, and gate electrodes on the substrate. The production of such TFT elements usually requires sputtering and other vacuum-based manufacturing processes.

[0005] However, in the manufacture of such a TFT element, the vacuum system manufacturing process including the vacuum chamber must be repeated many times to form each layer, resulting in extremely high equipment costs and running costs. It was huge. For example, in TFT devices, it is usually necessary to repeat the steps of vacuum deposition, dope, photolithography, development, etc. many times to form each layer. The device is formed on the substrate through several tens of steps. For the semiconductor portion that is the key to the switching operation, multiple types of semiconductor layers such as p-type and n-type are stacked. In such a conventional manufacturing method using Si semiconductors, it is not easy to change the equipment, for example, a design change of a manufacturing apparatus such as a vacuum chamber is required in response to the need for a large display screen.

[0006] In addition, since the formation of a TFT element using such a conventional Si material includes a process at a high temperature, the substrate material is limited to a material that can withstand the process temperature. Become. For this reason, in practice, glass must be used, and when the above-mentioned electronic paper or digital paper! /, And a thin display using such a conventionally known TFT element are used, the display Will be heavy and inflexible, and may be broken by the impact of a drop. These characteristics resulting from the formation of TFT elements on a glass substrate are desirable in satisfying the demand for easy-to-use thin displays for portable use as information technology advances.

[0007] On the other hand, research on organic semiconductor materials has been energetically advanced in recent years as an organic compound having a high charge transporting property. These compounds are reported in numerous papers such as organic laser oscillators as discussed in Non-Patent Document 1, etc., as well as, for example, Non-Patent Document 2, in addition to charge transport materials for organic EL devices. Applications to organic thin film transistor devices (organic TFT devices) are expected! If these organic semiconductor devices can be realized, it is possible to obtain a semiconductor that can be made into a solution by making the manufacturing process relatively low, vacuuming at a temperature, simplifying the manufacturing process by low-pressure deposition, and further improving the molecular structure appropriately. Production by printing methods including inkjet method by converting organic semiconductor solution into ink is also considered. Manufacturing using these low-temperature processes has been considered impossible for conventional Si-based semiconductor materials, but there are possibilities for devices using organic semiconductors, and therefore the above-mentioned restrictions on substrate heat resistance are relaxed. For example, a TFT element may be formed on the transparent resin substrate. If a TFT element is formed on a transparent resin substrate and the display material can be driven by the TFT element, the display will be lighter and more flexible than conventional ones, and will not crack even if dropped (or (It is difficult to break)). [0008] However, as an organic semiconductor for realizing such a TFT element, the acenes such as pentacene and tetracene have been studied so far (see, for example, Patent Document 1) and phthalocyanines including lead phthalocyanine. , Low molecular weight compounds such as perylene and its tetracarboxylic acid derivatives (see, for example, Patent Document 2), and aromatic oligomers typically represented by thiophene hexamer called oc-chenyl or sexithiophene (for example, see Patent Document 3) ), Naphthalene, anthracene and a compound in which a 5-membered aromatic heterocyclic ring is condensed symmetrically (for example, see Patent Document 4), modified oligo and polydithienopyridine (for example, see Patent Document 5), and polythiophene. Polyethylene biylene, poly-p-phenylene biylene, and other conjugated polymers A material exhibiting sufficient carrier mobility / ONZOFF ratio while maintaining sufficient solubility in a solvent that is only possible with various types of compounds (for example, see Non-Patent Documents 1 to 3) has been found. ,.

[0009] Recently, it has been reported that a single crystal of rubrene, which is highly soluble and acene, has very high mobility (see Non-Patent Document 4). Crystals are produced by vapor phase epitaxy, and films cast by solution casting are amorphous, and sufficient mobility is not obtained.

[0010] In addition, a compound in which a functional group is added to pentacene, which is a compound having high carrier mobility by vacuum deposition, is disclosed, and it has been reported that relatively good carrier mobility can be obtained by solution coating. (For example, refer to Patent Document 6.) ₀

However, acene-based compounds such as rubrene and pentacene are easily oxidized by air and converted into an oxidant called endperoxide, which greatly deteriorates the performance as a field effect transistor. It is known that there are still problems to be solved regarding the storage stability in solution and the stability of the coating film! /

[0012] With regard to the stability over time of such an organic semiconductor element, for example, in JP-A 2003-292588, US Patent Application Publication No. 2003Z136958, 2003Z160230, 2003Z164495, “The use of polymer TFTs in integrated circuit logic elements for microelectronics greatly improves their mechanical durability and extends their useful life.

[0013] However, many of the semiconductor polythiophenes are acidicly doped with ambient oxygen. It is considered unstable when exposed to air because the conductivity increases. As a result, the off-state currents of these device-powered devices increase, and therefore the current on-zoff ratio decreases. Therefore, many of these materials must be taken with great care to eliminate environmental oxygen and eliminate or minimize environmental oxygen during material processing and device fabrication. This precautionary measure raises the cost of manufacturing, and the appeal of certain polymer TFTs as an alternative to amorphous silicon technology, especially for large area devices, is diminished. These and other disadvantages are avoided or minimized in embodiments of the present invention. Therefore, there is a demand for an electronic device having a strong resistance to oxygen, a relatively high current ONZOFF ratio, '' and the organic semiconductor material will deteriorate over time! To prevent it much! The problem has become a major issue for practical application.

[0014] As an example of an acene compound that is relatively stable against oxidation, it has been reported that some compounds in which the 6th and 13th positions of pentacene are substituted with silylethyl groups have good coating film stability. is the degree that (for example, non-patent document 5, 6 and Patent Document 7.) ₀

[0015] However, in these reports, there is only a qualitative description that the stability to acid and soot has been improved, and the stability that can still withstand practical use is obtained. ,.

[0016] Further, by substituting a part of the pentacene nucleus of a compound in which the 6th and 13th positions of pentacene are substituted with a silylethyl group with an electron-withdrawing group such as a halogen atom or a cyano group, the acid of the compound is reduced. Some attempts have been made to increase the reduction potential (see, for example, Non-Patent Document 7), but organic semiconductor materials that combine high mobility and device durability have not yet been obtained. ,is the current situation.

Patent Document 1: Japanese Patent Laid-Open No. 5-55568

Patent Document 2: JP-A-5-190877

Patent Document 3: JP-A-8-264805

Patent Document 4: JP-A-11-195790

Patent Document 5: Japanese Patent Laid-Open No. 2003-155289

Patent Document 6: Pamphlet of International Publication No. 03Z016599

Patent Document 7: U.S. Pat.No. 6690029B1 Non-patent literature 1: Science magazine 289 卷, 599 pages (2000) Non-patent literature 2: Nature magazine 403 卷, 521 pages (2000)

Non-patent literature 3: Advanced Material magazine, 2002, 2nd

¾ Y

No., page 99

Non-Patent Document 4: Sci R Xe Ince, vol. 303 (2004), p. 1644

1

Non-Patent Document 5: Org. Lett., Vol. 4 (2002), p. 15

Non-Patent Document 6: J. Am. Chem. Soc., Vol. 127 (2005), p. 4986

Non-Patent Document 7: Org. Lett., Vol. 7 (2005), p. 3163

Disclosure of the invention

Problems to be solved by the invention

[0017] An object of the present invention is an organic semiconductor material that is manufactured by a simple process, has good characteristics as a transistor, is stable against oxygen in the air, and sufficiently suppresses deterioration over time. Organic semiconductor films, organic semiconductor devices and organic thin film transistors.

Means for solving the problem

[0018] The above object of the present invention has been achieved by the following configurations 1 to 7.

[0019] 1. An organic semiconductor material having a structure represented by the following general formula (1):

[0020] [Chemical 1]

R ₃

[In the formula, X represents Ge or Sn. Y represents a mother nucleus or fullerene mother nucleus having at least one heterocycle. R to R each represents a hydrogen atom or a substituent. ]

I 3

2. The organic semiconductor material according to I, wherein the organic semiconductor material has at least two partial structures obtained by removing Y from the structure represented by the general formula (I). [0022] 3. The organic semiconductor material as described in 1 or 2 above, wherein the structure represented by the general formula (1) is represented by the following general formula (2).

[0023] [Chemical formula 2] General formula (2)

[Wherein, X represents Ge or Sn. R to R each represents a hydrogen atom or a substituent, and Z

4 9 1

-Z represents an aromatic heterocyclic group. nl and n2 represent an integer of 0 to 3. ]

2

4. Said R ~ R ί represents an alkyl group or a cycloalkyl group,

1 9

The organic semiconductor material according to any one of 1 to 3.

[0025] 5. An organic semiconductor film comprising the organic semiconductor material according to any one of 1 to 4 above.

[0026] 6. An organic semiconductor device using the organic semiconductor material according to any one of 1 to 4 above.

[0027] 7. An organic thin film transistor, wherein the organic semiconductor material according to any one of 1 to 4 is used for a semiconductor layer.

The invention's effect

[0028] According to the present invention, an organic semiconductor material that is manufactured by a simple process, has good characteristics as a transistor, and further suppresses deterioration over time, an organic semiconductor film using the organic semiconductor material, an organic semiconductor device, and an organic thin film transistor are provided. Could be provided. Brief Description of Drawings

[0029] FIG. 1 is a diagram showing a configuration example of an organic thin film transistor of the present invention.

FIG. 2 is an example of a schematic equivalent circuit diagram of the organic thin film transistor sheet of the present invention.

FIG. 3 is a schematic view showing an example of an organic EL element having a sealing structure.

FIG. 4 is a schematic diagram showing an example of a substrate having TFTs used in an organic EL element.

[0030] 1 Organic semiconductor layer

2 Source electrode

3 Drain electrode

4 Gate electrode

5 Insulation layer

6 Support

7 Gate bus line

8 Sourcenos line

10 Organic thin film transistor sheet

11 Organic thin-film transistors

12 Output element

13 Storage capacitor

14 Vertical drive circuit

15 Horizontal drive circuit

101, 201 substrate

102 organic EL devices

102a, 202 anode

102b OLED layer

102c, 204 cathode

103 Sealing film

205 Drive element

206 Hole transport layer 207 Light emitting layer

208 Electron transport layer

601 board

602 TFT

BEST MODE FOR CARRYING OUT THE INVENTION

In the organic semiconductor material of the present invention, an organic semiconductor material useful for thin film transistor applications is obtained by using a compound having a structure defined in any one of claims 1 to 7. be able to. In addition, the organic semiconductor film, organic semiconductor device, and organic thin film transistor (hereinafter, also referred to as organic TFT) of the present invention manufactured using the organic semiconductor material have excellent carrier mobility and good ONZOFF characteristics. It was found to be highly durable while exhibiting transistor characteristics.

Hereinafter, details of each component according to the present invention will be described.

[0033] With regard to the above problems, the researchers of the present invention studied further improvement with reference to the above-mentioned known information, and as a result, the acene compound substituted with a silylethynyl group appeared to be substituted with an alkyl group, an aryl group, or the like. It was confirmed that it has improved oxygen stability compared to nacene compounds.

[0034] As an effect of substitution with a silylethynyl group, V in Non-Patent Document 5 described above, an aromatic ring in a crystal can be obtained by introducing a large substituent such as a silylethyl group into the peri-position of pentacene. However, when a crystal that only has a “Face to Face” structure was produced, a stable thin film was obtained only with a specific size of substituent that resulted in a stable crystal structure.

[0035] According to Non-Patent Document 6, “the introduction of the silylethyl group has made it possible to deepen the HOMO level by 300 mV or more with respect to the unsubstituted aromatic ring, so that stability against acid (oxygen) is obtained. There is a description of "Isn't it?"

[0036] Further, as described in Non-Patent Document 7, by substituting the pentacene mother nucleus with an electron-withdrawing group, the acid-reduction potential is deepened, and acid-acid stability is imparted. It has been known.

[0037] As described above, the stability of the acene-based compound such as pentacene with respect to acid is improved. In order to achieve this, it is presumed that both three-dimensional factors, not just electronic factors, are involved.

[0038] Based on these findings, the researchers of the present invention substituted the end of the ethynyl group with various metals. When Ge and Sn were used, the crystallinity was better than when Si was used. It was discovered that the stability of the acid was greatly improved.

[0039] Further, by adjusting the length and size of substituents such as alkyl groups bonded to Ge and Sn, it is possible to use only anthradithiophene, for example, polythiophene, oligothiophene, phthalocyanine, fullerene, etc. As a result, the present invention was completed by confirming that the solubility was drastically improved and the crystallinity and acidity stability were also good.

[0040] << Organic semiconductor material >>

The organic semiconductor material of the present invention will be described.

[0041] << Compound with structure represented by general formula (1) >>

The organic semiconductor material of the present invention has a structure represented by the following general formula (1).

[0042] The partial structures excluding Y from the structure represented by the general formula (1) are each a germylethynyl group.

Represents a stannylenyl group.

In general formula (1), Y represents a mother nucleus having at least one heterocycle or a fullerene mother nucleus. Here, the heterocycle may be a single ring or may be contained in a condensed ring, and the heterocycle is preferably an aromatic heterocycle.

In the general formula (1), examples of the substituent represented by R to R include an alkyl group.

13

(For example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, etc.), cycloalkyl group ( For example, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (for example, bur group, allyl group, etc.), alkyl group (for example, ethul group, propargyl group, etc.), aromatic hydrocarbon group (aromatic group) Also referred to as carbocyclic group, aryl group, etc. For example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthyl group, fluorenyl group, phenanthryl group Group, indenyl group, pyrenyl group, bif ヱ -ryl group, etc.), aromatic heterocyclic group (for example, furyl group, chenyl group, pyridyl group, pyridazyl group, pyrimidinyl group, pyrazyl group, triazinyl group, imidazolyl group) Group, pyrazolyl group, thiazolyl group, quinazolinyl group, phthalazinyl group, etc.), heterocyclic group (eg, pyrrolidyl group, imidazolidyl group, morpholyl group, oxazolidyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, propyloxy group) , Pentyloxy, hexyloxy, octyloxy, dodecyloxy, etc.), cycloalkoxy (eg, cyclopentyloxy, cyclohexyloxy, etc.), aryloxy (eg, phenoxy, naphthyloxy, etc.), alkylthio Groups (e.g. methylthio, ethyl Group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), cycloalkylthio group (eg, cyclopentylthio group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.) Etc.), alkoxy carbo yl groups (eg methyloxy carbo yl group, ethyloxy carbonyl group, butyloxy carbonyl group, octyloxy carbonyl group, dodecyloxy carbonyl group, etc.), arylo A xycarbonyl group (for example, a phenylcarboxyl group, a naphthyloxycarboxyl group, etc.), a sulfamoyl group (for example, an aminosulfol group, a methylaminosulfol group, a dimethylaminosulfol group, a butyrate) Ruaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfo Group, O-lipped Le aminosulfonyl - group, dodecyl aminosulfonyl - group, Hue - Ruaminosuruho

Group, naphthylaminosulfol group, 2-pyridylaminosulfol group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbon group, pentylcarbonyl group, cyclohexylcarboxyl group). Group, octylcarbol group, 2-ethylhexylcarbol group, dodecylcarpol group, phenolcarol group, naphthylcarbol group, pyridylcarbol group, etc.), acyloxy group (for example, acetylyloxy group) , Ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group (for example, methylcarbolamino group, ethylcarbo- group) Luamino group, dimethyl carbolumino group, propyl carbolumino group, pentyl carbolumino group, cyclohexyl Lucacarbomino group, 2-ethylhexylcarbolumino group, octylcarbolumino group, dodecy Rucarbo-amino group, phenyl-carboamino group, naphthyl-carbolamino group, etc., strong rubamoyl group (for example, amino-carboro group, methylaminocarbolo group, dimethylaminocarbole group, propylaminocarbole group) Group, pentylaminocarbol group, cyclohexaminocarbol group, octylaminocarbol group, 2-ethylhexylaminomino group, dodecylaminocarbol group, phenol Ruaminocarbol group, naphthylaminocarbole group, 2-pyridylaminocarbol group, etc., ureido group (for example, methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecyl group) Ureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group), sulfier group For example, methylsulfyl group, ethylsulfyl group, butylsulfyl group, cyclohexylsulfuryl group, 2-ethylhexylsulfyl group, dodecylsulfuryl group, phenylsulfyl group, naphthylsulfuryl group, 2-pyridylsulfeyl group, etc.), alkylsulfol groups (for example, methylsulfol group, ethylsulfol group, butylsulfol group, cyclohexylsulfol group, 2-ethylhexylsulfol group, Dodecylsulfol group, etc.), arylsulfol group (eg, phenylsulfol group, naphthylsulfol group, 2-pyridylsulfol group, etc.), amino group (eg, amino group, ethylamino group, Dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, arlino group, A tyramino group, a 2-pyridylamino group, etc.), a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a fluorinated hydrocarbon group (for example, a fluoromethyl group, a trifluoromethyl group, a pentafluoroethyl group, a pentafluoro group) For example, a triphenylsilyl group, a triisopropylpropyl group, a triphenylsilyl group, a ferroethyl group, etc.). Among these, the substituent is preferably an alkyl group. These substituents may be further substituted with the above substituents V, or a plurality may be bonded to each other to form a ring! / ,.

The compound having the structure represented by the general formula (1) is not particularly limited, but is a compound containing a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted aromatic heterocycle. Is preferred. For example, aromatic hydrocarbon rings include benzene ring, biphenyl ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, tali Sen ring, naphthacene ring, triphenylene ring, o-terphel ring, m-terphel ring, p terphel ring, acenaphthene ring, coronene ring, fluorene ring, fluoranthrene ring, naphthacene ring, pentacene ring Perylene ring, pentaphen ring, picene ring, pyrene ring, pyranthrene ring, anthraanthrene ring, and the like. Aromatic heterocycles include furan ring, thiophene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, benzimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring. , Benzimidazole ring, benzothiazole ring, benzoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, force rubazole ring, carboline ring, and at least one carbon atom of the hydrocarbon ring constituting the carboline ring is a nitrogen atom A ring that is substituted!

[0046] <Compound with structure represented by general formula (2)>

Among the compounds having the structure represented by the general formula (1), a compound having a structure represented by the general formula (2) is more preferable.

In the general formula (2), the substituents represented by R to R in the general formula (1)

4 9 1

It is synonymous with the substituent respectively represented by -R.

Three

[0048] In the general formula (2), examples of the aromatic heterocycle represented by Z to Z include a furan ring,

1 2

Thiophene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, triazine ring, benzoimidazole ring, oxadiazole ring, triazole ring, imidazole ring, pyrazole ring, thiazole ring, indole ring, benzimidazole ring, benzothiazole ring, benzothiazole ring Examples include a ring in which at least one carbon atom of a hydrocarbon ring constituting a zoxazole ring, quinoxaline ring, quinazoline ring, phthalazine ring, force rubazole ring, force ruporin ring, or carboline ring is further substituted with a nitrogen atom. . Of these, a thiophene ring is preferred. These aromatic heterocycles may be unsubstituted or have a substituent.

In general formula (1), those having the same meanings as the substituents represented by R to R can be mentioned. n

13

1 and n2 are preferably both forces nl and n2 representing an integer of 0 to 3.

[0049] Specific examples of the compound having the structure represented by the general formula (1) and the compound having the structure represented by the general formula (2) relating to the organic semiconductor material of the present invention are shown below. Is not limited to these.

S005

[2S00]

ひ S meta 900Zdf / e :) d 9 690 / 00Z OAV [9 ^] [seoo]

ひ S meta 900Zdf / e :) d 91- 9 690 / 00Z OAV [00]

ひ S meta 900Zdf / e :) d 9 V 9 690 / 00Z OAV

[8 ^] [eeoo]

9 690 / 00Z OAV

[6 ^] [9S00]

ε

9 690 / M 00 OAV [οτ ^] [zeoo]

ひ S meta 900Zdf / e :) d 61 · 9 690 / 00Z OAV

[π¾] [8S00]

ひ S meta 900Zdf / e :) d 03 9 690 / 00Z OAV

[0059] [Chemical 12]

The precursor which may contain a precursor of a compound having the structure represented by the general formula (1) relating to the organic semiconductor material of the present invention is defined by energy application or chemical treatment.

A compound intended to produce the compound of the present invention. For example, an aromatic ring ( A force that includes a compound in which a part of an aromatic hydrocarbon ring or aromatic heterocycle is oxidized with oxygen is not limited thereto.

[0061] An example of the synthesis of the compound having the structure represented by the general formula (1) relating to the organic semiconductor material of the present invention is shown below, but the present invention is not limited thereto.

<< Synthesis Example 1: Synthesis of Compound 19 >>

Exemplified compound 19 was synthesized according to the following scheme.

[0063] [Chemical 13]

(Synthesis of Compound 19)

Raw material 1 Intermediate 1

5.4 mmol of raw material 1 (synthetic method is described in Tetrahedron. Vol. 28, 1972, pp4591) is dissolved in 40 ml of dehydrated THF, and 4.3 mmol of n-BuLi is added at -70 ° C, and at -70 ° C. 2 o'clock Stir for a while to produce Intermediate 1. Furthermore, the raw material 2 (the synthesis method is described in J. Org. Chem., Vo 1.57, No23, 1992, 6193) at 70 ° C was adjusted to 0.887 mol and returned to room temperature. Add 15 ml of SnCl · 2Η and 2 ml of HC1 aqueous solution, and stir for 5 minutes at room temperature to complete the reaction.

twenty two

Finished.

[0065] Thereafter, 600 ml of hexane is added, washed with distilled water and saturated saline, the organic layer is adsorbed onto a silica gel column as it is, the solvent is removed, and column chromatography is performed with hexane as a developing solvent. The raw material was removed. Further, the hexane solution obtained by column chromatography was concentrated and then recrystallized three times with hexane to obtain Compound 19 in a yield of 32%. The molecular structure of the obtained compound 19 was measured by NMR (nuclear magnetic resonance spectrum) and mass spectrum, and confirmed to be consistent with the target product. Furthermore, it was confirmed that the purity was 99% or more from the result of HPLC (high performance liquid chromatography) measurement.

[0066] Other similar compounds were synthesized in the same manner.

[0067] << Organic Semiconductor Film, Organic Semiconductor Device, Organic Thin Film Transistor >>

The organic semiconductor film, organic semiconductor device, and organic thin film TFT (organic thin film transistor) of the present invention will be described.

[0068] When the organic semiconductor material of the present invention is used for a semiconductor layer of an organic semiconductor film, an organic semiconductor device, or an organic thin film transistor, an organic semiconductor device and an organic thin film transistor that are driven well can be provided. An organic thin film transistor has a source electrode and a drain electrode connected with an organic semiconductor as a semiconductor layer on a support, a top gate type having a gate electrode on the gate electrode via a gate insulating layer, and a support. First, it is roughly divided into a bottom gate type having a gate electrode and having a source electrode and a drain electrode connected by an organic semiconductor through a gate insulating layer.

[0069] In order to install the organic semiconductor material of the present invention on a semiconductor layer of an organic semiconductor film, an organic semiconductor device, or an organic thin film transistor, the organic semiconductor material can be installed on a substrate by vacuum deposition.

The solution prepared by dissolving in an appropriate solvent and adding additives as necessary is preferably placed on the substrate by cast coating, spin coating, printing, ink jet method, abrasion method or the like.

[0070] In this case, the solvent for dissolving the organic semiconductor material of the present invention dissolves the organic semiconductor material. However, there is no particular limitation as long as a solution with an appropriate concentration can be prepared. Specifically, a chain ether solvent such as dimethyl ether or diisopropyl ether, a cyclic ether solvent such as tetrahydrofuran or dioxane, Ketone solvents such as acetone methyl ketone, alkyl halide solvents such as chloroform and 1,2-dichloroethane, aromatics such as toluene, o-dichlorobenzene, nitrobenzene, and m-talezole. Solvent, N-methylpyrrolidone, disulfur carbon, and the like. Among these solvents, a solvent containing a non-halogen solvent is preferably a non-halogen solvent.

In the organic thin film transistor of the present invention, it is preferable to use the organic semiconductor material of the present invention for the semiconductor layer as described above. The semiconductor layer is preferably formed by applying a solution or dispersion containing these organic semiconductor materials. The solvent that dissolves the organic semiconductor material is preferably composed of a non-halogen solvent that is preferably a solvent containing the non-halogen solvent.

[0072] In the present invention, the material for forming the source electrode, the drain electrode, and the gate electrode is not particularly limited as long as it is a conductive material. Platinum, gold, silver, nickel, chromium, copper, iron, tin, Antimony bell, tantalum, indium, palladium, tellurium, rhenium, iridium, ano-remium, ruthenium, germanium, molybdenum, tungsten, tin oxide 'antimony, indium oxide' tin (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 monopotassium alloy, magnesium, Lithium, Anoleum, Magne Umum Z copper mixture, Magnesium Z silver mixture, Magnesium Z aluminum mixture, Magnesium Z indium mixture, Aluminum Z acid-aluminum mixture, Lithium Z aluminum mixture, etc. are used, especially platinum, gold, silver, copper Aluminum, indium, ιτο and carbon are preferred. Alternatively, known conductive polymers whose conductivity has been improved by doping or the like, for example, conductive polyarlin, conductive polypyrrole, conductive polythiophene, a complex of polyethylene dioxythiophene and polystyrene sulfonic acid, etc. are also suitably used. . Of these, those having low electrical resistance on the contact surface with the semiconductor layer are preferred. [0073] As a method for forming an electrode, a method for forming an electrode using a known photolithographic method or a lift-off method using a conductive thin film formed by a method such as vapor deposition or sputtering using the above as a raw material, aluminum, copper, or the like There is a method of etching on a metal foil using a resist by thermal transfer, ink jet or the like. Alternatively, the conductive polymer solution or dispersion, or the conductive fine particle dispersion may be directly patterned by inkjet, or may be formed from the coating film by lithography, laser abrasion, or the like. In addition, 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 relief printing, intaglio printing, planographic printing, or screen printing can also be used.

As a gate insulating layer, various insulating films can be used. In particular, an inorganic oxide film having a high relative dielectric constant is preferable. Examples of inorganic oxides include silicon oxide, aluminum oxide, tantalum oxide, titanium oxide, tin oxide, vanadium oxide, barium strontium titanate, barium zirconate titanate, lead zirconate titanate, titanate Examples include lead lanthanum, strontium titanate, barium titanate, barium magnesium fluoride, bismuth titanate, strontium bismuth titanate, strontium bismuth tantanoate, bismuth tantalate niobate, and trioxide yttrium. Among them, preferable are silicon oxide, acid aluminum, acid tantalum, and acid titanium. Inorganic nitrides such as silicon nitride and aluminum nitride can also be suitably used.

[0075] Examples of the method for forming the film include a vacuum deposition method, a molecular beam epitaxy growth method, an ion cluster beam method, a low energy ion beam method, an ion plating method, a CVD method, a sputtering method, and an atmospheric pressure plasma method. Dry process, spray coating method, spin coating method, blade coating method, dip coating method, casting method, roll coating method, bar coating method, die coating method, and other methods by patterning such as printing and inkjet Etc., and can be used depending on the material.

[0076] The wet process includes a method of applying and drying a liquid in which fine particles of inorganic oxide are dispersed in an arbitrary organic solvent or water using a dispersion aid such as a surfactant as necessary, or an oxide precursor. A so-called sol-gel method in which a solution of a body, for example, an alkoxide body is applied and dried is used. Among these, the atmospheric pressure plasma method and the sol-gel method are preferable.

[0077] A method for forming an insulating film by plasma film formation under atmospheric pressure is atmospheric pressure or atmospheric pressure. A process in which a discharge is performed under a nearby pressure, a reactive gas is plasma-excited, and a thin film is formed on the substrate. The method is described in JP-A-11-61406, JP-A-11-133205, JP2000- No. 121804, No. 2000-147209, No. 2000-185362, etc. (hereinafter also referred to as atmospheric pressure plasma method). As a result, a highly functional thin film can be formed with high productivity.

[0078] Further, as the organic compound film, polyimide, polyamide, polyester, polyacrylate, photo-radical polymerization system, photopower thione polymerization system photocurable resin, or a copolymer containing an acrylonitrile component, polybutanol, Polybulal alcohol, novolac resin, cyanoethyl pullulan and the like can also be used. The wet process is preferred as a method for forming the organic compound film. An inorganic oxide film and an organic oxide film can be laminated and used together. The film thickness of these insulating films is generally 5011111 to 3111, preferably 100 nm to l μm.

[0079] The support is composed 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), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyethylene-sulfuride, polyarylate, polyimide, polycarbonate ( PC), cellulose triacetate (TAC), and cellulose acetate propionate (CAP). Thus, by using a plastic film, it is possible to reduce the weight as compared with the case of using a glass substrate, to improve portability, and to improve resistance to impact.

Hereinafter, an organic thin film transistor using an organic semiconductor film formed using the organic semiconductor material of the present invention will be described.

FIG. 1 is a diagram showing a configuration example of an organic thin film transistor of the present invention. In FIG. 2 (a), a source electrode 2 and a drain electrode 3 are formed on a support 6 with a metal foil or the like, an organic semiconductor layer 1 made of the organic semiconductor material of the present invention is formed between the two electrodes, and the organic semiconductor layer 1 is formed thereon. An insulating layer 5 is formed, and further a gate electrode 4 is formed thereon to form an organic thin film transistor. (B) shows the organic semiconductor layer 1 formed between the electrodes in (a). The electrode is formed so as to cover the entire surface of the electrode and the support. (C) shows that the organic semiconductor layer 1 is first formed on the support 6 by using a coating method or the like, and then the source electrode 2, the drain electrode 3, the insulating layer 5, and the gate electrode 4 are formed.

[0082] In FIG. 6D, after forming the gate electrode 4 with a metal foil or the like on the support 6, the insulating layer 5 is formed, and the source electrode 2 and the drain electrode 3 are formed with the metal foil or the like thereon. Then, an organic semiconductor layer 1 formed of the organic semiconductor material of the present invention is formed between the electrodes. Other configurations such as shown in (e) and (f) of FIG.

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

The organic thin film transistor sheet 10 has a large number of organic thin film transistors 11 arranged in a matrix. 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 12 is, for example, a liquid crystal, an electrophoretic element or the like, and constitutes a pixel in the display device. The pixel electrode may be used as the input electrode of the photosensor. In the illustrated example, the liquid crystal is shown as an output element in an equivalent circuit having resistance and capacitor power. 13 is a storage capacitor, 14 is a vertical drive circuit, and 15 is a horizontal drive circuit. Example

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto. In addition, the structures of Comparative Compounds 1 to 5 used in Examples are shown below.

[0086] [Chemical 14]

Comparative compound (1)

Example 1

<< Production of Organic TFT (Organic Thin Film Transistor) Element 2 >>: Comparative Example

A 2000 A thick thermal oxide film was formed on a Si wafer with a specific resistance of 0.01 Ω'cm as the gate electrode to form a gate insulating layer, and then surface treatment with octadecyltrichlorosilane was performed. Apply a solution of Comparative Compound (2) with a mouth-opening solution using an applicator and dry naturally to form a cast film (thickness 50 nm), and then at 50 ° C for 30 minutes in a nitrogen atmosphere. Heat treatment was applied.

[0088] Furthermore, 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 element 1 having a source electrode and a drain electrode having a width of 100 m, a thickness of 200 nm, a channel width W = 3 mm, and a channel length L = 20 μm was produced.

[0089] << Preparation of organic TFT elements 1, 3-5 >>: Comparative example

Organic TFT elements 1 and 3 to 5 were produced in the same manner except that the comparative compound (2) was changed to comparative compounds (1) and (3) to (5), respectively, in the production of the organic TFT element 2.

[0090] <Production of organic TFT elements 6 to 13>: The present invention

In the production of the organic TFT element 2, as an alternative to the comparative compound (2), the organic thin film transistor elements 6 to 13 were produced in the same manner except that the organic TFT material of the present invention shown in Table 1 was changed. did.

[0091] << Evaluation of carrier mobility and ONZOFF ratio >>

For each of the obtained organic TFT elements 1 to 13, the carrier mobility and the ONZOFF ratio of each element immediately after fabrication and after standing for 1 month in the air were determined.

[0092] In the present invention, the saturation region force of the I-V characteristic is also obtained for the carrier mobility, and further, the drain bias is set to 50V, the gate bias is set to 50V and OV, and the ONZOFF ratio is calculated from the ratio of the drain current value. Asked.

[0093] Table 1 shows the obtained results.

[0094] [Table 1]

Organic TFT. Immediately after fabrication After 1 month

Organic semiconductor material Mobility Mobility Remarks

0NZOFF value ON / OFF value

Element No. cra ^^ / Vsec cm ² / Vsec

1 Comparative compound 1 Cannot be formed Cannot be formed Cannot be formed Cannot be formed Comparative example

2 Comparative compound 2 9.3X10— ² 1.1 X10 ⁴ 1.3X10 ³ 4.3X10 ³ Comparative example

3Comparative Compound 3 Cannot be formed Cannot be formed Cannot be formed Cannot be formed Comparative example

4 Comparative compound 4 6.0X10— ² 3.1X10 ³ Measurement not possible Measurement impossible Comparative example

5 Comparative compound 5 2.5X10- ³ 4.8X10 ³ 5.1X10 1 ⁴ 1.0X10 ³

6 Example Compound ^{^{1 9.8X10- 3 1.3 X 10 3 5.3}} X 10- 3 7.1X10 2 invention

7 Example Compound ^{^{^{2 9.7X10- 3 1.2X10 3 5.2X10- 3 6.9X10}}} 2 invention

8 examples / choice, compound 3 9.8X10 ² 1.5X10 ⁴ 1.8X10- ² 5.3 X10 ³

9 Exemplified compounds 4 9.6X10— ² 1.6X10 ⁴ 1.7X10— ² 4.8X10 ^{3 The} present invention

10 Exemplary compounds 5 1.6X10— ¹ 3.3X10 ⁵ 7.4X10— ² 3.9X10 ⁴ Present invention

11 Exemplified compounds 6 1.3X10— ^L 3.1X10 ^C 6.8X10— ² 3.3X10 ⁴ Present invention

12 Exemplary compounds 7 3.5X10— ¹ 3.8X10 ⁵ 8.2X10 4.3X10 ^{4 The} present invention

13 Example Compound ^{^{8 3.4X10- 1 3.5X10 5 7.8X 10 3.8X10}} 4 present invention

[0095] From Table 1, the organic thin film transistor elements 6 to 13 of the present invention show excellent transistor characteristics even immediately after the production, compared with the comparative organic thin film transistor element produced using the comparative organic semiconductor material. It can also be seen that it has high durability with little deterioration with time.

[0096] Example 2

An organic EL device using an organic thin film transistor will be described as an application example of an organic thin film transistor using the organic semiconductor material of the present invention.

[0097] << Production of organic EL elements >>

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

[0098] The organic EL device of the present invention and the organic thin film transistor of the present invention (here, the organic thin film of the present invention A transistor is used as a switching transistor, a driving transistor, etc.) to produce an active matrix light-emitting element. In that case, for example, as shown in FIG. As an example, an embodiment using a substrate on which a thin film transistor 602 may be formed is used. Here, a known TFT manufacturing method can be referred to for the TFT602 manufacturing method. Of course, the TFT may be a conventionally known top gate type TFT or a bottom gate type TFT.

The organic EL device fabricated above showed good emission characteristics in various emission modes such as single color, full color, and white.

Claims

An organic semiconductor material having a structure represented by the following general formula (1):

[Chemical 1]

-General formula (1)

Y— = — X— R,

R

[Wherein X represents Ge or Sn. Y represents a mother nucleus or a fullerene mother nucleus having at least one hetero ring. R to R each represents a hydrogen atom or a substituent. ]

13

[2] The organic semiconductor material according to claim 1, wherein the structural force represented by the general formula (1) also has at least two partial structures excluding Y.

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

[Chemical 2]

[Wherein X represents Ge or Sn. R to R each represents a hydrogen atom or a substituent, and Z -Z represents an aromatic heterocyclic group. nl and n2 represent an integer of 0 to 3. ]

2

[4] The R to R force represents an alkyl group or a cycloalkyl group.

1 9

Item 5. The organic semiconductor material according to any one of Items 1 to 3.

[5] An organic semiconductor film comprising the organic semiconductor material according to any one of claims 1 to 4.

[6] An organic semiconductor device using the organic semiconductor material according to any one of claims 1 to 4.

[7] An organic thin film transistor, wherein the organic semiconductor material according to any one of claims 1 to 4 is used for a semiconductor layer.