# US 10,312,447 B2 · Organic semiconductor element, manufacturing method thereof, compound, organic semiconductor composition, organic semiconductor film, and manufacturing method thereof

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- Number: US 10,312,447 B2
- Document ID: US10312447B2
- Status: Granted
- Kind: B2
- Application number: 15/696,194
- Filed: 2017-09-06
- Published: 2018-01-04
- Granted: 2019-06-04
- Earliest claimed: 2015-03-16
- Assignees: FUJIFILM Corporation
- Applicants: Fujifilm Corporation
- Inventors: Tetsu Kitamura; Yosuke Yamamoto; Fumiko Tamakuni; Yuta Shigenoi; Takashi Goto; Tetsuya Watanabe
- Web page: https://patentgrep.com/patent/US10312447B2

## CPC

- C08G 61/126: {with a five-membered ring containing one sulfur atom in the ring}
- C08L 65/00: Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C08L7/00 - C08L57/00, C08L61/00 take precedence); Compositions of derivatives of such polymers
- C09D 165/00: Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C09D107/00 - C09D157/00, C09D161/00 take precedence); Coating compositions based on derivatives of such polymers
- H10D 30/67: Thin-film transistors [TFT] {(Stacked nanowire, nanosheet or nanoribbon FETs H10D30/501)}
- H10K 85/111: {comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene}
- H10K 85/113: {Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene}
- H10K 85/151: {Copolymers}
- C08G 2261/124: alternating
- C08G 2261/1412: Saturated aliphatic units
- C08G 2261/1424: containing ether groups, including alkoxy
- C08G 2261/314: Condensed aromatic systems, e.g. perylene, anthracene or pyrene
- C08G 2261/3222: containing one or more oxygen atoms as the only heteroatom, e.g. furan
- C08G 2261/3223: containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
- C08G 2261/3225: containing one or more Se atoms as the only heteroatom
- C08G 2261/3241: containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
- C08G 2261/3243: containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
- C08G 2261/3245: containing nitrogen and oxygen as heteroatoms
- C08G 2261/3246: containing nitrogen and sulfur as heteroatoms
- C08G 2261/334: containing heteroatoms
- C08G 2261/344: containing heteroatoms
- C08G 2261/414: Stille reactions
- C08G 2261/512: Hole transport
- C08G 2261/514: Electron transport
- C08G 2261/59: Stability
- C08G 2261/592: against heat
- H10K 10/40: Organic transistors
- H10K 10/466: {Lateral bottom-gate IGFETs comprising only a single gate}
- H10K 10/471: {the gate dielectric comprising only organic materials}
- H10K 10/488: {the channel region comprising a layer of composite material having interpenetrating or embedded materials, e.g. a mixture of donor and acceptor moieties, that form a bulk heterojunction}
- H10K 71/12: using liquid deposition, e.g. spin coating
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES

## Abstract

Objects of the present invention are to provide an organic semiconductor element in which carrier mobility is high, variation of mobility is suppressed, and temporal stability under high temperature and high humidity is excellent, and a manufacturing method thereof, to provide a novel compound suitable for an organic semiconductor, and to provide an organic semiconductor film in which mobility is high, variation of mobility is suppressed, and temporal stability under high temperature and high humidity is excellent, a manufacturing method thereof, and an organic semiconductor composition that can suitably form the organic semiconductor film. The organic semiconductor element according to the present invention is an organic semiconductor layer containing a compound having a constitutional repeating unit represented by Formula 1 and having a molecular weight of 2,000 or greater. D-A (1)

## Claims

### Claim 1

An organic semiconductor element comprising:
an organic semiconductor layer containing a compound having a constitutional repeating unit represented by Formula 1 and having a molecular weight of 2,000 or greater,
D-A (1)
in Formula 1, A represents an electron acceptor unit including a partial structure having at least one of a sp2 nitrogen atom, a carbonyl group, or a thiocarbonyl group in a ring structure, D represents an electron donor unit including a divalent aromatic heterocyclic group having at least one of an N atom, an O atom, an S atom, or an Se atom in a ring structure, or a divalent aromatic hydrocarbon group consisting of a fused ring structure having two or more rings as a partial structure, and at least one of D or A has at least one monovalent group represented by Formula 1-1,
*-L-O—R (1-1)
in Formula 1-1, L represents a linear or branched alkylene group having m carbon atoms, R represents an alkyl group not having a substituent and having n carbon atoms, 6≤m+n≤50, and * represents a bonding site to another structure,
wherein, in Formula 1, A has at least one structure selected from the group consisting of structures represented by Formulae A-1 to A-7 and A-9 to A-12, as a partial structure,
wherein in Formulae A-1 to A-7 and A-9 to A-12, each X independently represents an O atom, a S atom, a Se atom or NRA1, each Y independently represents an O atom or a S atom, each Za independently represents CRA2 or a N atom, each W independently represents C(RA2)2, NRA1, a N atom, CRA2, an O atom, a S atom, or a Se atom, each RA1 independently represents an alkyl group, a monovalent group represented by Formula 1-1, or a bonding site to another structure, s each RA2independently represents a hydrogen atom, a halogen atom, an alkyl group, or a bonding site to another structure, and each * independently represents a bonding site to another structure.

### Claim 2 (depends on 1)

The organic semiconductor element according to claim 1,
wherein, in Formula 1, D represents a structure represented by Formula D-1,
in Formula D-1, each X″ independently represents an O atom, a S atom, a Se atom, or NRD1, each Zd independently represents a N atom or CRD2, each RD1 independently represents a monovalent organic group, each RD2 independently represents a hydrogen atom or a monovalent organic group, M represents a single bond, a divalent aromatic heterocyclic group, a divalent aromatic hydrocarbon group, an alkenylene group, an alkynylene group, or a divalent group obtained by combining these, p and q each independently represent an integer of 0 to 4, and each * independently represents a bonding site to another structure.

### Claim 3 (depends on 1)

The organic semiconductor element according to claim 1,
wherein a constitutional repeating unit represented by Formula 1 is a constitutional repeating unit represented by any one of Formulae 2 to 4,
in Formulae 2 to 4, each X independently represents an O atom, a S atom, a Se atom or NRA1, each Y independently represents an O atom or a S atom, each Za independently represents CRA2 or a N atom, each RA1 independently represents an alkyl group, a monovalent group represented by Formula 1-1, or a bonding site to another structure, each RA2 independently represents a hydrogen atom, a halogen atom, an alkyl group, or a bonding site to another structure, each X′ independently represents an O atom, a S atom, a Se atom, or NRD1, each Zd independently represents a N atom or CRD2, each RD1 independently represents a monovalent organic group, each RD2 independently represents a hydrogen atom or a monovalent organic group, M represents a single bond, a divalent aromatic heterocyclic group, a divalent aromatic hydrocarbon group, an alkenylene group, an alkynylene group, or a divalent group obtained by combining these, and p and q each independently represent an integer of 0 to 4.

### Claim 4 (depends on 1)

The organic semiconductor element according to claim 1,
wherein the organic semiconductor layer further contains an insulating polymer including a constitutional unit represented by Formula I-1,
in Formula I-1, R22 to R26 each independently represent a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, or a halogen atom or may form a ring by linking two of R22 to R26 that are adjacent to each other, and R21 represents a hydrogen atom or an alkyl group.

### Claim 5 (depends on 4)

The organic semiconductor element according to claim 4, further comprising:
a gate insulating film having a surface energy of 50 to 75 mNm−1.

### Claim 6 (depends on 1)

The organic semiconductor element according to claim 1, which is an organic thin film transistor.

### Claim 7

A compound comprising:
a constitutional repeating unit represented by Formula 1,
wherein a molecular weight is 2,000 or greater,
D-A (1)
in Formula 1, A represents an electron acceptor unit having at least one structure selected from the group consisting of structures represented by Formulae A-1 to A-12, as a partial structure, D represents an electron donor unit including a divalent aromatic heterocyclic group having at least one of a N atom, an O atom, a S atom, or a Se atom in a ring structure or a divalent aromatic hydrocarbon group consisting of a fused ring structure having two or more rings, as a partial structure, and at least one of D or A has at least one monovalent group represented by Formula 1-1,
in Formulae A-1 to A-7 and A-9 to A-12, each X independently represents an O atom, a S atom, a Se atom, or NRA1, each Y independently represents an O atom or a S atom, each Za independently represents CRA2 or a N atom, each W independently represents C(RA2)2, NRA1, a N atom, CRA2, an O atom, a S atom, or a Se atom, each RA1 independently represents an alkyl group, a monovalent group represented by Formula 1-1, or a bonding site to another structure, RA2's each independently represent a hydrogen atom, a halogen atom, an alkyl group, or a bonding site to another structure, and each * independently represents a bonding site to another structure,
*-L-O—R (1-1)
in Formula 1-1, L is a linear or branched alkylene group having m carbon atoms, R is an alkyl group not having a substituent and having n carbon atoms, 6≤m+n≤50, and * represents a bonding site to another structure.

### Claim 8 (depends on 7)

The compound according to claim 7,
wherein, in Formula 1, D is a structure represented by Formula D-1,
in Formula D-1, each X′ independently represents an O atom, a S atom, a Se atom, or NRD1, each Zd independently represents a N atom or CRD2, each RD1 independently represents a monovalent organic group, each RD2 independently represents a hydrogen atom or a monovalent organic group, M represents a single bond, a divalent aromatic heterocyclic group, a divalent aromatic hydrocarbon group, an alkenylene group, an alkynylene group, or a divalent group obtained by combining these, p and q each independently represent an integer of 0 to 4, and each * independently represents a bonding site to another structure.

### Claim 9 (depends on 7)

The compound according to claim 7,
wherein the constitutional repeating unit represented by Formula 1 is a constitutional repeating unit represented by any one of Formulae 2 to 5,
in Formulae 2 to 4, each X independently represents an O atom, a S atom, a Se atom, or NRA1, each Y independently represents an O atom or a S atom, each Za independently represents CRA2 or a N atom, each RA1 independently represents an alkyl group, a monovalent group represented by Formula 1-1, or a bonding site to another structure, each RA2 independently represents a hydrogen atom, a halogen atom, an alkyl group, or a bonding site to another structure, each X′ independently represents an O atom, a S atom, a Se atom, or NRD1, each Zd independently represents an N atom or CRD2, each RD1 independently represents a monovalent organic group, each RD2 independently represents a hydrogen atom or a monovalent organic group, M represents a single bond, a divalent aromatic heterocyclic group, a divalent aromatic hydrocarbon group, an alkenylene group, an alkynylene group, or a divalent group obtained by combining these, and p and q each independently represent an integer of 0 to 4.

### Claim 10 (depends on 7)

The compound according to claim 7, that is an organic semiconductor compound.

### Claim 11 (depends on 7)

An organic semiconductor composition comprising:
the compound according to claim 7, and
a solvent.

### Claim 12 (depends on 11)

The organic semiconductor composition according to claim 11, further comprising:
an insulating polymer including a constitutional unit represented by Formula I-1,
in Formula I-1, R22 to R26 each independently represent a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, or a halogen atom and may form a ring by linking two of R22 to R26 that are adjacent to each other, and R21 represents a hydrogen atom or an alkyl group.

### Claim 13 (depends on 7)

An organic semiconductor film comprising the compound according to claim 7.

### Claim 14 (depends on 13)

The organic semiconductor film according to claim 13, further comprising an insulating polymer including a constitutional unit represented by Formula I-1,
in Formula I-1, R22 to R26 each independently represent a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, or a halogen atom, and may form a ring by linking two of R22 to R26 that are adjacent to each other, and R21 represents a hydrogen atom or an alkyl group.

### Claim 15 (depends on 11)

A method of manufacturing an organic semiconductor film, comprising:
a coating step of coating a substrate with the organic semiconductor composition according to claim 11.

### Claim 16 (depends on 12)

A method of manufacturing an organic semiconductor film, comprising:
a coating step of coating a gate insulating film having a surface energy of 50 to 75 mNm−1 with the organic semiconductor composition according to claim 12.

### Claim 17 (depends on 11)

A method of manufacturing an organic semiconductor element, comprising:
a coating step of coating a substrate with the organic semiconductor composition according to claim 11.

### Claim 18 (depends on 12)

A method of manufacturing an organic semiconductor element, comprising:
a coating step of coating a gate insulating film having a surface energy of 50 to 75 mNm−1 with the organic semiconductor composition according to claim 12.