WO2010104042A1 - 含フッ素重合体及びこれを用いた有機薄膜 - Google Patents
含フッ素重合体及びこれを用いた有機薄膜 Download PDFInfo
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- WO2010104042A1 WO2010104042A1 PCT/JP2010/053805 JP2010053805W WO2010104042A1 WO 2010104042 A1 WO2010104042 A1 WO 2010104042A1 JP 2010053805 W JP2010053805 W JP 2010053805W WO 2010104042 A1 WO2010104042 A1 WO 2010104042A1
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- thin film
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- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
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Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
- C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
- C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
- C09B69/109—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing other specific dyes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
- H10K10/40—Organic transistors
- H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
- H10K10/462—Insulated gate field-effect transistors [IGFETs]
- H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1428—Side-chains containing oxygen containing acyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/146—Side-chains containing halogens
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
- C08G2261/512—Hole transport
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/90—Applications
- C08G2261/92—TFT applications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present invention relates to a fluoropolymer, an organic thin film using the same, and an organic thin film element, an organic thin film transistor, an organic solar cell, and an optical sensor provided with the organic thin film.
- Thin films containing organic materials having electric charge (electron or hole) transport properties are expected to be applied to organic thin film elements such as organic thin film transistors, organic solar cells, and optical sensors. Development of type semiconductors (showing hole transport properties) and organic n-type semiconductors (showing electron transport properties) is underway.
- a compound having a thiophene ring such as oligothiophene or polythiophene is expected to exhibit a high hole transportability because it can take a stable radical cation state.
- polythiophene having a side chain with a long chain length has a long conjugate length and can transport holes more effectively.
- polythiophene poly (3-alkylthiophene) and poly (3-alkyl-4-fluorothiophene) have been proposed (Patent Document 1, Non-Patent Document 1).
- poly (3-alkylthiophene) is excellent in solubility in organic solvents and can be formed into a large area by coating, but has a relatively low ionization potential.
- the threshold voltage and the off-current tend to change easily. Therefore, it has been difficult to operate stably over a long period of time.
- poly (3-alkyl-4-fluorothiophene) was not easily doped with oxygen, but was insufficiently soluble in organic solvents.
- the organic semiconductor material is less susceptible to oxygen doping and can be uniformly formed by coating.
- the present invention has been made in view of such circumstances, and is suitable as an organic semiconductor material, and provides a fluorine-containing polymer excellent in both stability to doping with oxygen and solubility in an organic solvent. For the purpose. Moreover, it aims at providing the organic thin film obtained using this fluoropolymer, an organic thin film element provided with this organic thin film, an organic thin-film transistor, an organic solar cell, and an optical sensor.
- the fluoropolymer of the present invention is characterized in that the structure represented by the formula (I) is contained in a repeating unit. [Wherein, R 1 and R 2 are the same or different and each represents a hydrogen atom or a monovalent group. ]
- This fluoropolymer is an organic semiconductor material that can exhibit excellent charge (hole) transportability, and has high stability against doping with oxygen and high solubility in organic solvents. Have. Although such a factor is not necessarily clear, it is estimated as follows. That is, this fluorine-containing polymer has a high conjugated property because it repeatedly has a thiophene ring in the main chain, and contains a fluorine atom with a high electron-withdrawing property in the side chain bonded to the thiophene ring. Therefore, the ionization potential as a whole compound is high. As a result, while having excellent hole transport properties, it is considered that doping with oxygen is very difficult to receive. In addition, since the side chain contains a carbonyl group next to the carbon atom to which the fluorine atom is bonded, the fluoropolymer maintains high solubility despite the introduction of the fluorine atom. It is thought that.
- the fluoropolymer of the present invention has high environmental stability such as little influence by oxygen, the organic thin film using this is also stable, and as a result, stable in the atmosphere. It is possible to form an organic thin film element capable of exhibiting the performance obtained.
- the fluorine-containing polymer of the present invention more preferably contains a structure represented by the formula (II) in the repeating unit. Among them, it is particularly preferable that the structure represented by the formula (I) and the structure represented by the formula (II) are alternately included. In addition to the structure represented by the formula (I), the fluorine-containing polymer of the present invention can exhibit the above-described effects more satisfactorily by including one or more such structures. Furthermore, the fluorine-containing polymer of the present invention includes alternately the structure represented by the formula (I) and the structure represented by the formula (II), thereby improving solubility in an organic solvent, and an organic thin film It is also excellent in electrical characteristics and stability when formed. [Wherein Ar 1 represents a divalent aromatic hydrocarbon group having 6 or more carbon atoms or a divalent heterocyclic group having 4 or more carbon atoms. ]
- Ar 1 is preferably a group represented by formula (III).
- Z 1 is more preferably a group represented by the formula (ii).
- the fluorine-containing polymer having these structures has a particularly excellent hole transport property. [Wherein R 3 and R 4 are the same or different and each represents a hydrogen atom or a monovalent group. R 3 and R 4 may be bonded to each other to form a ring.
- Z 1 is defined by the formulas (i), (ii), (iii), (iv), (v), (vi), (vii), (viii) and (ix) (hereinafter, “(i) to (ix) ) "And R 5 , R 6 , R 7 and R 8 in these formulas are the same or different and represent a hydrogen atom or a monovalent group. Indicates a substituent. R 5 and R 6 may be bonded to each other to form a ring, and the group represented by the formula (iv) may be horizontally reversed. ]
- R 1 and R 2 are the same or different and are preferably a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or a fluoroalkyl group having 1 to 20 carbon atoms.
- R 1 and R 2 are those radicals, in addition to stability to oxygen doping is further improved, it is further improved even solubility in an organic solvent.
- the present invention also provides an organic thin film containing the fluoropolymer of the present invention. Since the organic thin film of the present invention contains the above-mentioned fluoropolymer of the present invention, it has high hole transportability, excellent stability against oxygen doping, and can be formed by coating. For this reason, even a large area has uniform characteristics.
- the present invention includes a source electrode and a drain electrode, an organic semiconductor layer serving as a current path between them, and a gate electrode that controls the amount of current passing through the current path.
- An organic thin film transistor comprising an organic thin film is provided.
- the organic semiconductor layer is made of the organic thin film of the present invention, it can exhibit high mobility and has high environmental stability.
- this invention provides an organic solar cell and an optical sensor provided with the organic thin film of the said invention. Since these organic thin film elements also include the organic thin film of the present invention, the charge transport required for the operation of each element can be obtained well, exhibit excellent characteristics, and have high environmental stability. Become.
- a fluorine-containing polymer that is suitable as an organic semiconductor material and that is excellent in both stability to doping with oxygen and solubility in an organic solvent.
- organic thin films obtained by using such fluorine-containing polymers and having high hole transportability and high environmental stability such as high durability against oxygen doping, as well as organic thin film elements, organic thin film transistors, organic thin films A solar cell and an optical sensor can be provided.
- the fluoropolymer of this embodiment has a structure represented by the formula (I) in its repeating unit.
- the repeating unit constituting the fluoropolymer may have only the structure represented by the formula (I), and may further include other structures as described later.
- Such a fluorine-containing polymer has a thiophene ring structure in the main chain repeatedly, so that the conjugation flatness between these rings is good and the interaction between molecules is strong, and it is bonded to the thiophene ring. Since it has an ⁇ -fluoroketone structure (—C ( ⁇ O) —C (F) ⁇ ) as a side chain, the ionization potential is increased and resistance to oxygen doping is improved.
- this fluoropolymer has the side chain of the specific structure mentioned above, since it is excellent also in the solubility to an organic solvent, it can form a homogeneous thin film as a solution state, and this is excellent. Organic thin films having high performance and organic thin film elements using the same can be manufactured.
- R 1 and R 2 are the same or different and are a hydrogen atom or a monovalent group, but a fluorine atom, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group having 1 to 20 carbon atoms, An alkoxy group having 1 to 20 carbon atoms or a fluoroalkoxy group having 1 to 20 carbon atoms is preferable, and a fluorine atom, an alkyl group having 1 to 20 carbon atoms, or a fluoroalkyl group having 1 to 20 carbon atoms is more preferable.
- one of R 1 and R 2 is a fluorine atom and the other is a fluoroalkyl group having 1 to 12 carbon atoms.
- a linear or branched saturated or unsaturated hydrocarbon group (particularly a group consisting of a low molecular chain), a monovalent group having 3 to 60 carbon atoms.
- Cyclic group (monocyclic or condensed ring, carbocyclic or heterocyclic ring, saturated or unsaturated ring, may have a substituent), hydroxyl group, alkoxy group, alkanoyloxy group, amino Group, oxyamino group, alkylamino group, dialkylamino group, alkanoylamino group, cyano group, nitro group, sulfo group, alkyl group substituted by halogen atom, alkoxysulfonyl group (Alkoxy group may be substituted by halogen atom) Alkylsulfonyl group (the alkyl group may be substituted with a halogen atom), sulfamoyl group, alkylsulfam
- Examples of the saturated hydrocarbon group include a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms is preferable.
- Examples of the alkyl group include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, 3-methylbutyl group, pentyl group, hexyl group and 2-ethylhexyl.
- Group heptyl group, octyl group, nonyl group, decyl group, lauryl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, and cyclododecyl group.
- group containing an alkyl group in the structure for example, an alkoxy group, an alkylamino group, and an alkoxycarbonyl group
- alkyl group in the structure include those having the same group as described above as the alkyl group.
- Examples of the unsaturated hydrocarbon group include a vinyl group, 1-propenyl group, allyl group, propargyl group, isopropenyl group, 1-butenyl group and 2-butenyl group.
- alkanoyl group examples include formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group and isovaleryl group.
- group containing an alkanoyl group in the structure examples include those having the same group as described above as the alkanoyl group. Note that an alkanoyl group having 1 carbon atom refers to a formyl group, and the same applies to a group containing an alkanoyl group in its structure.
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- the fluorine-containing polymer of this embodiment further has one or more structures represented by the formula (II) in the repeating unit. It is preferable because resistance to water and solubility in solvents are improved.
- Ar 1 in Formula (II) is a divalent aromatic hydrocarbon group having 6 or more carbon atoms or a divalent heterocyclic group having 4 or more carbon atoms, and these may further have a substituent.
- the divalent aromatic hydrocarbon group means a group consisting of the remaining atomic group obtained by removing two hydrogen atoms from a benzene ring or condensed ring, preferably a group having 6 to 60 carbon atoms, More preferred are groups of ⁇ 20. This carbon number does not include the carbon number of the substituent.
- the condensed ring include naphthalene ring, anthracene ring, tetracene ring, pentacene ring, pyrene ring, perylene ring, and fluorene ring.
- the divalent aromatic hydrocarbon group is preferably a group consisting of the remaining atomic group obtained by removing two hydrogen atoms from a benzene ring, pentacene ring, pyrene ring or fluorene ring.
- examples of the substituent that the divalent aromatic hydrocarbon group may have include a halogen atom, a saturated or unsaturated hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, a monovalent heterocyclic group, An amino group, a nitro group, and a cyano group are mentioned.
- the divalent heterocyclic group means a group consisting of the remaining atomic group obtained by removing two hydrogen atoms from a heterocyclic compound, preferably a group having 4 to 60 carbon atoms, and a group having 4 to 20 carbon atoms. Is more preferable.
- the heterocyclic compound is an organic compound having a cyclic structure, and the elements constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, boron, and silicon in the ring. The thing included in.
- Examples of such a divalent heterocyclic group include groups composed of the remaining atomic groups obtained by removing two hydrogen atoms from thiophene, thienothiophene, dithienothiophene, thiazole, pyrrole, pyridine, and pyrimidine. Of these, a group composed of the remaining atomic group obtained by removing two hydrogen atoms from thiophene, thienothiophene, or thiazole is preferable.
- the divalent heterocyclic group may have a substituent, in which case the carbon number of the divalent heterocyclic group does not include the carbon number of the substituent.
- substituents examples include a halogen atom, a saturated or unsaturated hydrocarbon group, an aryl group, an alkoxy group, an aryloxy group, a monovalent heterocyclic group, an amino group, a nitro group, and a cyano group.
- Ar 1 is preferably a group consisting of the remaining atomic group obtained by removing two hydrogen atoms from a condensed ring or a thiophene ring.
- the structure represented by the formula (I) has a thiophene ring
- the structure represented by the formula (II) has a condensed ring or a thiophene ring, thereby further improving the planarity of the ⁇ -conjugated structure.
- the molecule easily takes a ⁇ - ⁇ stack structure, and the charge transport property is further improved.
- a ⁇ -conjugated structure including a thiophene ring can reduce the interplanar spacing of the ⁇ - ⁇ stack structure and is further excellent in the effect of improving the charge transport property. Therefore, Ar 1 is a hydrogen atom from the thiophene ring. A group consisting of the remaining atomic groups excluding two is particularly preferred. In addition, Ar 1 preferably has a substituent from the viewpoint of improving solubility in an organic solvent and maintaining good ⁇ -conjugated planarity.
- R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are the same or different and are a hydrogen atom or a monovalent group.
- the same groups as those shown as 1 and R 2 can be mentioned.
- Z 1 is any one of groups represented by formulas (i) to (ix), and is represented by any one of formulas (ii), (iii), (v), (viii) and (ix).
- the group represented by formula (ii), (iii) and (v) is more preferred, and the group represented by formula (ii) is particularly preferred.
- the group represented by formula (III) includes a thiophene ring (where Z 1 is a group of formula (ii)), a furan ring (where Z 1 is a group of formula (iii)), and a pyrrole ring (Z 1 Is a group of the formula (v)), in particular those having a thiophene ring can exhibit characteristic electrical properties for the reasons as described above, and may exhibit new electrical properties that have not been seen before. I can expect.
- the fluorine-containing polymer of this embodiment may have the structure represented by the formula (I) in the repeating unit, but the structure represented by the formula (I) and the formula (II) (preferably the formula It is preferable to have in a repeating unit combining with the structure represented by (III).
- the fluoropolymer may contain two or more types of structures represented by the formula (I) in the repeating unit, or a structure represented by the formula (II) (preferably the formula (III)). 2 or more types may be included.
- the structure represented by the formula (I) and the structure represented by the formula (II) are preferably based on 100 mol of the former.
- the latter is preferably contained at a ratio of 10 to 1000 mol, more preferably at a ratio of 25 to 400 mol of the latter with respect to 100 mol of the former, and 50 to 200 mol of the latter with respect to 100 mol of the former. More preferably, it is contained in a ratio.
- fluoropolymer compounds represented by the formulas (IV) to (IX) are suitable.
- These fluorine-containing polymers have particularly excellent charge transport properties, are highly stable against oxygen doping, and have excellent solubility.
- R 1 and R 2 are as defined above.
- Ar 11 , Ar 12 and Ar 13 are the same or different and are the same as Ar 1 described above, and groups suitable as these groups are also the same as those for Ar 1 .
- m is an integer of 1-6.
- n and p are the same or different and are integers of 1 to 6, and n + p is preferably 6 or less.
- q and r are the same or different, and are an integer of 1 to 10, preferably an integer of 1 to 6, and more preferably an integer of 1 to 3.
- k represents the degree of polymerization and is preferably an integer of 2 to 500.
- the terminal group of the fluoropolymer is not particularly limited. However, when the fluoropolymer is used as the organic thin film, if the polymerization active group remains as it is at the terminal, the characteristics and durability when the organic thin film element is formed may be lowered. Therefore, when the terminal group is a polymerization active group, it may be protected with a stable group.
- the terminal group includes a hydrogen atom, a fluorine atom, an alkyl group, an alkoxy group, an acyl group, an aminoketo group, an aryl group, and a monovalent heterocyclic group (a part or all of the hydrogen atoms bonded to these groups are fluorine atoms). And a group having an ⁇ -fluoroketone structure, other electron donating groups and electron withdrawing groups.
- a fluoroalkyl group, a fluoroalkoxy group, a fluoroaryl group, a group having an ⁇ -fluoroketone structure, or an electron withdrawing group other than these is preferred, and all the hydrogen atoms are fluorine atoms
- Particularly preferred is a group substituted with, for example, a perfluoroalkyl group, a perfluoroalkoxy group or a perfluorophenyl group.
- a terminal group what has a conjugated bond continuous with the conjugated structure of the principal chain of a fluoropolymer is also preferable.
- a group having a conjugated structure bonded to an aryl group or heterocyclic group in the main chain via a carbon-carbon bond can be mentioned.
- Suitable fluoropolymers include compounds represented by formulas (1) to (9).
- R 1 , R 2 , R 3 , R 4 , k, q and r are all as defined above.
- R 9 and R 10 are the same or different and are a hydrogen atom or a monovalent group, and examples of the monovalent group include the same groups as those described above for R 1 and R 2 .
- R 15 and R 16 are the same or different and are any of the terminal groups described above, and are preferably a phenyl group.
- R 17 , R 18 , R 19 and R 20 are the same or different and each represents a hydrogen atom or a monovalent group, preferably an alkyl group, an alkoxy group or an aryl group, and more preferably an alkyl group.
- the groups represented by the same symbol may be the same or different. However, from the viewpoint of facilitating the production of the fluoropolymer, it is preferable that a plurality of groups having the same symbol are the same group.
- k can be appropriately set according to the method for forming the organic thin film using the fluoropolymer.
- k is preferably an integer of 3 to 500, more preferably an integer of 6 to 300, and an integer of 20 to 200. Is more preferable.
- the polystyrene-equivalent number average molecular weight of the fluoropolymer is preferably 1 ⁇ 10 3 to 1 ⁇ 10 7 , and 1 ⁇ 10 4 to 1 ⁇ 10 6 is more preferable.
- the fluorine-containing polymer is prepared by preparing a raw material compound having a structure represented by the formula (I) and a raw material compound having a structure represented by the formula (II) as necessary, and reacting them. It can be manufactured by forming.
- Examples of the raw material compound having a structure represented by the formula (I) include a compound represented by the formula (X).
- Examples of the raw material compound having a structure represented by the formula (II) include those represented by the formula (XI). Compounds.
- a fluorine-containing polymer is obtained by reacting these raw material compounds in combination as necessary.
- a fluorine-containing polymer containing a combination of a plurality of structures represented by formula (II) in a repeating structure, such as formula (VI), (VII), (VIII) or (IX) A plurality of raw material compounds represented by the formula (XI) may be used.
- a raw material compound (intermediate raw material compound) having a certain structure is produced in advance by reacting only a part of the raw material compounds, and then this is converted to other raw material compounds. And may be further reacted to obtain a fluoropolymer.
- Examples of such intermediate raw material compounds include compounds represented by formulas (XII), (XIII), and (XIV).
- R 1 , R 2 , Ar 1 , Ar 11 , Ar 12 , n, m and p are all as defined above.
- W 1 and W 2 are the same or different and are reactive groups, and are halogen atoms, alkyl sulfonate groups, aryl sulfonate groups, aryl alkyl sulfonate groups, alkyl stannyl groups, aryl stannyl groups, aryl alkyl stannyl groups, boron Acid ester residues, sulfonium methyl groups, phosphonium methyl groups, phosphonate methyl groups, monohalogenated methyl groups, boric acid residues (ie, groups represented by —B (OH) 2 ), formyl groups, vinyl groups, and the like. Can be mentioned. Examples of the boric acid ester residue include groups represented by formulas (100a) to (100f).
- W 1 and W 2 are the same or different and are a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an arylalkyl sulfonate group, an alkylstannyl group, or a borate ester residue. Or it is preferable that it is a boric acid residue.
- a method using a Wittig reaction a method using a Heck reaction, a method using a Horner-Wadsworth-Emmons reaction, a method using a Knoevenagel reaction, a method using a Suzuki coupling reaction, a method using a Grignard reaction, and a Stille reaction are used.
- the method and the method using a Ni (0) catalyst are preferable because the structure of the fluoropolymer is easily controlled.
- a method using a Suzuki coupling reaction, a method using a Grignard reaction, a method using a Stille reaction, and a method using a Ni (0) catalyst make it easy to obtain raw materials suitable for these reactions and simplify the reaction operation. It is preferable because it is possible.
- the raw material compound can be dissolved in an organic solvent and further reacted using an alkali or an appropriate catalyst. In this case, it is preferable to perform the reaction at a melting point or more and a boiling point or less of the organic solvent.
- the organic solvent varies depending on the raw material compound used and the reaction, it is generally preferable to use an organic solvent that has been sufficiently deoxygenated to suppress side reactions, thereby allowing the reaction to proceed under an inert atmosphere. It is preferable. From the same viewpoint, the organic solvent is preferably subjected to a dehydration treatment (however, this is not the case in the case of a reaction in a two-phase system with water such as the Suzuki coupling reaction). What is necessary is just to select an alkali and a suitable catalyst according to reaction. As the alkali and catalyst, those which are sufficiently dissolved in the solvent used in the reaction are preferable.
- the raw material compound before the reaction is preferably purified by a method such as distillation, sublimation purification, and recrystallization.
- the obtained fluoropolymer is preferably subjected to purification treatment such as reprecipitation purification and fractionation by chromatography.
- Solvents used in the reaction include saturated hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene and xylene, carbon tetrachloride, chloroform, dichloromethane, chlorobutane, bromobutane and chloropentane.
- Halogenated saturated hydrocarbons such as bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene, methanol, ethanol, propanol, isopropanol, butanol, t -Alcohols such as butyl alcohol, carboxylic acids such as formic acid, acetic acid, propionic acid, dimethyl ether, diethyl ether, methyl-t-butyl ether, tetra Dorofuran, tetrahydropyran, dioxane and the like, hydrochloric acid, hydrobromic acid, hydrofluoric acid, sulfuric acid, and inorganic acids such as nitric acid is. These solvents may be used alone or in combination of two or more.
- the fluoropolymer can be obtained by quenching with water, extracting with an organic solvent, and distilling off the solvent.
- the product can be isolated and purified by a method such as fractionation by chromatography or recrystallization.
- Organic thin film contains the above-mentioned fluoropolymer.
- the thickness of the organic thin film is preferably 1 nm to 100 ⁇ m, more preferably 2 nm to 1000 nm, further preferably 5 nm to 500 nm, and particularly preferably 20 nm to 200 nm.
- the organic thin film may contain one kind of fluorine-containing polymer alone, or may contain two or more kinds of fluorine-containing polymers.
- the organic thin film may contain an electron transporting material and a hole transporting material in addition to the fluorinated polymer in order to enhance the electron transporting property or hole transporting property.
- hole transport materials include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triaryldiamine derivatives, oligothiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, and aromatic amines in side chains or main chains.
- hole transport materials include polysiloxane derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyarylene vinylene and derivatives thereof, and polythienylene vinylene and derivatives thereof.
- Electron transport materials include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyano Examples include ethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, polyfluorene and derivatives thereof, and fullerenes such as C60 and derivatives thereof.
- the organic thin film may contain a charge generating material in order to generate a charge by light absorbed in the organic thin film.
- charge generation materials include azo compounds and derivatives thereof, diazo compounds and derivatives thereof, metal-free phthalocyanine compounds and derivatives thereof, metal phthalocyanine compounds and derivatives thereof, perylene compounds and derivatives thereof, polycyclic quinone compounds and derivatives thereof, squarylium compounds And derivatives thereof, azulenium compounds and derivatives thereof, thiapyrylium compounds and derivatives thereof, and fullerenes such as C60 and derivatives thereof.
- the organic thin film may contain other materials necessary for developing various functions.
- examples of other materials include a sensitizer for sensitizing the function of generating a charge by absorbed light, a stabilizer for increasing stability, a UV absorber for absorbing UV light, and the like. .
- the organic thin film may contain a polymer compound other than the fluoropolymer as a polymer binder in order to enhance mechanical properties.
- a polymer binder those not extremely disturbing the electron transport property or hole transport property are preferable, and those having no strong absorption against visible light are preferably used.
- Such polymer binders include poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof.
- Derivatives, polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like are exemplified.
- Examples of the method for producing an organic thin film according to this embodiment include film formation using a solution in which a fluorine-containing polymer and, if necessary, an electron transport material, a hole transport material, a polymer binder, and the like are mixed in a solvent. The method of performing is mentioned. Moreover, when a fluoropolymer has sublimation property, an organic thin film can also be formed by a vacuum evaporation method.
- the solvent used for the film formation using the solution may be any solvent that dissolves the fluoropolymer and other materials, such as toluene, xylene, mesitylene, tetralin, decalin, bicyclohexyl, n-butylbenzene, sec-butyl.
- Halogenation of unsaturated hydrocarbon solvents such as benzene and tert-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, etc.
- saturated hydrocarbon solvents halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and trichlorobenzene, and ether solvents such as tetrahydrofuran and tetrahydropyran.
- the fluorinated polymer can be dissolved in these solvents in an amount of 0.1% by mass or more, preferably 0.5% by mass or more.
- film forming methods using a solution examples include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and screen printing.
- Application methods such as a flexographic printing method, an offset printing method, an ink jet printing method, a dispenser printing method, a nozzle coating method, and a capillary coating method can be used. Of these, spin coating, flexographic printing, ink jet printing, dispenser printing, nozzle coating, and capillary coating are preferred.
- the process of manufacturing an organic thin film may include the process of orienting a fluoropolymer.
- the main chain molecules or the side chain molecules are arranged in one direction, so that the charge (electron or hole) mobility may be improved.
- a method for aligning the fluoropolymer a method known as a liquid crystal alignment method can be used.
- the rubbing method, the photo-alignment method, the sharing method (shear stress application method) and the pulling coating method are simple, useful and easy to use as the alignment method, and the rubbing method and the sharing method are preferable.
- the organic thin film of the above-described embodiment includes the fluoropolymer of the above-described embodiment, the organic thin film has excellent charge (electron or hole) transportability. Therefore, this organic thin film can efficiently transport electrons or holes injected from electrodes or the like, or electric charges generated by light absorption, etc., and can be used for various electric elements (organic thin film elements) using the organic thin film. Can be applied.
- the fluoropolymer of the above embodiment also has high environmental stability, such as excellent resistance to oxygen doping, performance can be achieved even in normal air by forming a thin film using these. It is possible to produce an organic thin film element that is stable.
- examples of organic thin film elements will be described.
- the organic thin film transistor includes a source electrode and a drain electrode, an organic semiconductor layer containing the above-described fluoropolymer (that is, an active layer, the same applies hereinafter) that serves as a current path between them, and a gate electrode that controls the amount of current passing through the current path.
- the field effect type and the electrostatic induction type are exemplified.
- a field effect organic thin film transistor includes a source electrode and a drain electrode, an organic semiconductor layer containing a fluoropolymer that serves as a current path between them, a gate electrode that controls the amount of current passing through the current path, and an organic semiconductor layer and a gate electrode It is preferable to provide an insulating layer disposed between the two.
- the source electrode and the drain electrode are preferably provided in contact with the organic semiconductor layer containing the fluoropolymer, and further, the gate electrode is preferably provided with an insulating layer in contact with the organic semiconductor layer interposed therebetween.
- the static induction organic thin film transistor includes a source electrode and a drain electrode, an organic semiconductor layer containing a fluoropolymer that serves as a current path between them, and a gate electrode that controls the amount of current passing through the current path.
- Is preferably provided in the organic semiconductor layer.
- the source electrode, the drain electrode, and the gate electrode provided in the organic semiconductor layer are preferably provided in contact with the organic semiconductor layer containing the fluoropolymer.
- the structure of the gate electrode may be any structure as long as a current path flowing from the source electrode to the drain electrode is formed and the amount of current flowing through the current path can be controlled by a voltage applied to the gate electrode. It is done.
- FIG. 1 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a first embodiment.
- An organic thin film transistor 100 shown in FIG. 1 includes a substrate 1, a source electrode 5 and a drain electrode 6 formed on the substrate 1 with a predetermined interval, and a source electrode 5 and a drain electrode 6 so as to cover the substrate 1. Formed on the insulating layer 3 so as to cover the region of the insulating layer 3 formed between the source electrode 5 and the drain electrode 6, the insulating layer 3 formed on the organic semiconductor layer 2, and the insulating layer 3 between the source electrode 5 and the drain electrode 6.
- the gate electrode 4 is provided.
- FIG. 2 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a second embodiment.
- the organic thin film transistor 110 shown in FIG. 2 includes a substrate 1, a source electrode 5 formed on the substrate 1, an organic semiconductor layer 2 formed on the substrate 1 so as to cover the source electrode 5, The drain electrode 6 formed on the organic semiconductor layer 2 with a predetermined interval, the insulating layer 3 formed on the organic semiconductor layer 2 and the drain electrode 6, and the insulation between the source electrode 5 and the drain electrode 6 And a gate electrode 4 formed on the insulating layer 3 so as to cover the region of the layer 3.
- FIG. 3 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a third embodiment.
- An organic thin film transistor 120 shown in FIG. 3 includes a substrate 1, an organic semiconductor layer 2 formed on the substrate 1, a source electrode 5 and a drain electrode 6 formed on the organic semiconductor layer 2 with a predetermined interval, The insulating layer 3 formed on the organic semiconductor layer 2 so as to partially cover the source electrode 5 and the drain electrode 6, the region of the insulating layer 3 where the source electrode 5 is formed below, and the drain electrode 6 below And a gate electrode 4 formed on the insulating layer 3 so as to partially cover the formed region of the insulating layer 3.
- FIG. 4 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a fourth embodiment.
- 4 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom.
- FIG. 5 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a fifth embodiment.
- An organic thin film transistor 140 shown in FIG. 5 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom.
- FIG. 6 is a schematic cross-sectional view of an organic thin film transistor (field effect organic thin film transistor) according to a sixth embodiment.
- An organic thin film transistor 150 shown in FIG. 6 includes a substrate 1, a gate electrode 4 formed on the substrate 1, an insulating layer 3 formed on the substrate 1 so as to cover the gate electrode 4, and the gate electrode 4 at the bottom.
- An organic semiconductor layer 2 formed so as to cover the region of the insulating layer 3 formed on the substrate, a source electrode 5 formed on the insulating layer 3 so as to partially cover the region of the organic semiconductor layer 2, and an organic semiconductor A source electrode 5 and a drain electrode 6 formed on the insulating layer 3 at a predetermined interval so as to partially cover the region of the layer 2 are provided.
- FIG. 7 is a schematic cross-sectional view of an organic thin film transistor (static induction organic thin film transistor) according to a seventh embodiment.
- the organic thin film transistor 160 shown in FIG. 7 has a predetermined interval on the substrate 1, the source electrode 5 formed on the substrate 1, the organic semiconductor layer 2 formed on the source electrode 5, and the organic semiconductor layer 2.
- the organic semiconductor layer 2 and / or the organic semiconductor layer 2a contain the fluoropolymer of the above-described embodiment, and the source electrode 5 and the drain electrode 6 It becomes a current passage (channel).
- the gate electrode 4 controls the amount of current passing through the current path (channel) in the organic semiconductor layer 2 and / or the organic semiconductor layer 2a by applying a voltage.
- Such a field effect organic thin film transistor can be manufactured by a known method, for example, a method described in JP-A-5-110069.
- the electrostatic induction organic thin film transistor can be produced by a known method, for example, a method described in JP-A-2004-006476.
- the substrate 1 it is sufficient that the characteristics as an organic thin film transistor are not hindered, and a glass substrate, a flexible film substrate, or a plastic substrate can be used.
- the organic thin film that becomes the organic semiconductor layer 2 can be formed by using the method for producing an organic thin film by solution coating using the fluoropolymer as described above. Thereby, even if the thin organic semiconductor layer 2 having a relatively large area is formed, uniform characteristics can be obtained.
- a material having high electrical insulation may be used, and a known material can be used.
- a known material can be used.
- SiOx, SiNx, Ta2O5, polyimide, polyvinyl alcohol, polyvinylphenol, organic glass, and a photoresist are mentioned. From the viewpoint of lowering the voltage, a material having a high dielectric constant is preferable.
- the surface of the insulating layer 3 is treated with a surface treatment agent such as a silane coupling agent in order to improve the interface characteristics between the insulating layer 3 and the organic semiconductor layer 2. It is also possible to form the organic semiconductor layer 2 after surface modification.
- a surface treatment agent such as a silane coupling agent
- the surface treatment agent include silylamine compounds such as long-chain alkylchlorosilanes, long-chain alkylalkoxysilanes, fluorinated alkylchlorosilanes, fluorinated alkylalkoxysilanes, and hexamethyldisilazane.
- the surface of the insulating layer may be treated with ozone UV or O 2 plasma.
- a protective film can be formed on the organic thin film transistor in order to protect the element.
- an organic thin-film transistor is interrupted
- the influence from the process of forming the display device driven on an organic thin-film transistor with a protective film can be reduced.
- Examples of the method for forming the protective film include a method of covering with a UV curable resin, a thermosetting resin or an inorganic SiONx film.
- a method of covering with a UV curable resin, a thermosetting resin or an inorganic SiONx film In order to effectively cut off from the atmosphere, it is preferable to perform the steps from the preparation of the organic thin film transistor to the formation of the protective film without exposure to the atmosphere (for example, in a dry nitrogen atmosphere or in a vacuum).
- FIG. 8 is a schematic cross-sectional view of the solar cell according to the embodiment.
- a solar cell 200 shown in FIG. 8 is an organic semiconductor composed of a substrate 1, a first electrode 7a formed on the substrate 1, and an organic thin film containing a fluoropolymer formed on the first electrode 7a.
- the layer 2 and the second electrode 7b formed on the organic semiconductor layer 2 are provided.
- a transparent or translucent electrode is used for one of the first electrode 7a and the second electrode 7b.
- an electrode material metals such as aluminum, gold, silver, copper, alkali metal, alkaline earth metal, and their translucent films and transparent conductive films can be used.
- each electrode is preferably selected so that the difference in work function is large.
- a charge generating agent, a sensitizer and the like can be added and used in order to increase photosensitivity.
- the substrate 1 a silicon substrate, a glass substrate, a plastic substrate, or the like can be used.
- FIG. 9 is a schematic cross-sectional view of the photosensor according to the first embodiment.
- An optical sensor 300 shown in FIG. 9 includes an organic semiconductor composed of a substrate 1, a first electrode 7a formed on the substrate 1, and an organic thin film containing a fluoropolymer formed on the first electrode 7a.
- a layer 2, a charge generation layer 8 formed on the organic semiconductor layer 2, and a second electrode 7 b formed on the charge generation layer 8 are provided.
- FIG. 10 is a schematic cross-sectional view of an optical sensor according to the second embodiment.
- An optical sensor 310 illustrated in FIG. 10 is formed on the substrate 1, the first electrode 7a formed on the substrate 1, the charge generation layer 8 formed on the first electrode 7a, and the charge generation layer 8.
- the organic semiconductor layer 2 which consists of an organic thin film containing the made fluoropolymer, and the 2nd electrode 7b formed on the organic semiconductor layer 2 are provided.
- FIG. 11 is a schematic cross-sectional view of an optical sensor according to the third embodiment.
- An optical sensor 320 shown in FIG. 11 is an organic semiconductor composed of a substrate 1, a first electrode 7a formed on the substrate 1, and an organic thin film containing a fluoropolymer formed on the first electrode 7a.
- the layer 2 and the second electrode 7b formed on the organic semiconductor layer 2 are provided.
- a transparent or translucent electrode is used as one of the first electrode 7a and the second electrode 7b.
- the charge generation layer 8 is a layer that absorbs light and generates charges.
- an electrode material metals such as aluminum, gold, silver, copper, alkali metal, alkaline earth metal, and their translucent films and transparent conductive films can be used.
- organic semiconductor layer 2 organic thin film
- a carrier generating agent, a sensitizer and the like can be added and used in order to increase photosensitivity.
- the base material 1 a silicon substrate, a glass substrate, a plastic substrate, etc. can be used as the base material 1.
- the nuclear magnetic resonance (NMR) spectrum is obtained using the product name JMN-270 (270 MHz at 1 H measurement) manufactured by JEOL (JEOL Ltd.) or the product name JMNLA-600 (600 MHz at 19 F measurement) manufactured by the same company. It was measured. Chemical shifts are expressed in parts per million (ppm). Tetramethylsilane (TMS) was used for the internal standard of 0 ppm.
- the coupling constant (J) is shown in hertz (Hz), and the abbreviations s, d, t, q, m, and br are a single line, a double line, a triple line, and a triplet, respectively. , quartet, multiplet, and wide line.
- MS mass spectrometry
- EI electron ionization
- DI direct sample introduction
- GCMS-QP5050A product name
- Silicagel 60N 40-50 ⁇ m
- All chemical substances are reagent grade and purchased from Wako Pure Chemical Industries, Ltd., Tokyo Chemical Industry Co., Ltd., Kanto Chemical Co., Ltd., Nacalai Tesque Co., Ltd., Sigma Aldrich Japan Co., Ltd., or Daikin Chemicals Co., Ltd.
- “Cyclic voltammetry” uses the product name “CV-50W” manufactured by BAS Co., Ltd. (BAS) as the measuring device, Pt electrode manufactured by BAS as the working electrode, and Pt wire as the counter electrode. Measurement was performed using an Ag wire as an electrode. During this measurement, the sweep rate was 100 mV / sec, and the scanning potential region was ⁇ 2.8 to 1.6 V. The reduction potential and oxidation potential were measured by completely dissolving 1 ⁇ 10 ⁇ 3 mol / L of the polymer and 0.1 mol / L of tetrabutylammonium hexafluorophosphate (TBAPF6) as a supporting electrolyte in a monofluorobenzene solvent. It was.
- the resulting mixture was filtered through celite and then concentrated under reduced pressure. And it refine
- the analysis results and chemical formula of the obtained compound (A) are as follows.
- the obtained organic layer was dried over magnesium sulfate and concentrated under reduced pressure. And it refine
- purified with the silica gel column (hexane / CHCl3 4/1, volume ratio), and obtained the yellow liquid compound (B) (687 mg, yield 50%) which is a target object.
- the analysis results and chemical formula of the obtained compound (B) are as follows.
- a low resistance silicon wafer with a thermal oxide film (silicon oxide film) (having a structure to be a gate electrode / insulating layer) is immersed in ethanol, distilled water, and acetone in this order, and ultrasonic cleaning is performed. Thereafter, this silicon wafer is subjected to UV-ozone cleaning to obtain a substrate having a hydrophilic surface. This substrate is immersed in hexamethyldisilazane: chloroform at room temperature and ultrasonically washed with chloroform to obtain a surface-treated substrate.
- a coating solution in which the polymer (D) synthesized above is dissolved in chloroform is prepared.
- This solution is deposited on the surface-treated substrate by spin coating to form an organic thin film.
- a gold electrode source electrode, drain electrode
- the organic transistor characteristics of the obtained organic thin film transistor were measured by changing the gate voltage Vg and the source-drain voltage Vsd using a semiconductor parameter analyzer (trade name “4200-SCS” manufactured by Keithley), the organic transistor characteristics were good. Id-Vg characteristics of a p-type semiconductor can be obtained. Further, even when the organic thin film transistor is left in the atmosphere and measured in the same manner, the increase in off current is small and stable. Therefore, the polymer (D) is not easily doped with oxygen.
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Abstract
Description
本実施形態の含フッ素重合体は、式(I)で表される構造を繰り返し単位に有するものである。含フッ素重合体を構成する繰り返し単位は、式(I)で表される構造のみを有していてもよく、後述するようなその他の構造を更に含んでいてもよい。このような含フッ素重合体は、主鎖にチオフェン環構造を繰り返し有することから、これらの環同士の共役平面性が良好であり、分子間の相互作用が強いことに加え、チオフェン環に結合したα-フルオロケトン構造(-C(=O)-C(F)<)を側鎖として有していることから、イオン化ポテンシャルが高くなり、酸素のドーピングに対する耐性が向上する。よって、電荷輸送性に優れるほか、酸素ドーピングに対して安定な有機半導体として利用可能である。また、この含フッ素重合体は、上述した特定構造の側鎖を有することから、有機溶剤への溶解性にも優れているため、溶液状態として均質な薄膜を形成することができ、これにより優れた性能を有する有機薄膜及びこれを用いた有機薄膜素子を製造可能である。
次に、上述したような含フッ素重合体の製造方法の好適な実施形態について説明する。
次に好適な実施形態に係る有機薄膜について説明する。有機薄膜は、上述した含フッ素重合体を含むものである。
上述した実施形態の有機薄膜は、上記実施形態の含フッ素重合体を含むことから、優れた電荷(電子又はホール)輸送性を有するものとなる。したがって、この有機薄膜は、電極等から注入された電子又はホール、或いは、光吸収により発生した電荷等を効率よく輸送できるものであり、有機薄膜を用いた各種の電気素子(有機薄膜素子)に応用することができる。また、上記実施形態の含フッ素重合体は、酸素ドーピングに対する耐性にも優れるなど、高い環境安定性も有しているため、これらを用いて薄膜を形成することで、通常の大気中においても性能が安定している有機薄膜素子を製造することができる。以下、有機薄膜素子の例についてそれぞれ説明する。
まず、好適な実施形態に係る有機薄膜トランジスタについて説明する。有機薄膜トランジスタは、ソース電極及びドレイン電極、これらの間の電流経路となり上述した含フッ素重合体を含む有機半導体層(すなわち活性層である。以下同様)、電流経路を通る電流量を制御するゲート電極を備えた構造であればよく、電界効果型、静電誘導型などが例示される。
次に、本発明の有機薄膜の太陽電池への応用を説明する。図8は、実施形態に係る太陽電池の模式断面図である。図8に示す太陽電池200は、基板1と、基板1上に形成された第1の電極7aと、第1の電極7a上に形成された含フッ素重合体を含有する有機薄膜からなる有機半導体層2と、有機半導体層2上に形成された第2の電極7bと、を備えるものである。
まず、以下の実施例及び比較例で行った測定の条件を示す。
(含フッ素重合体の製造)
<化合物(A)の合成>
加熱乾燥した蓋付き試験管に、2,3-ジブロモチオフェン(3.00g,12.4mmol)、5-トリブチルスタニル-3-ヘキシルチオフェン(4.57g,10.0mmol)、テトラキス(トリフェニルホスフィン)パラジウム(0)(290mg,0.025mmol)、トルエン(20mL)を入れた後、窒素置換し、2日間還流させた。
加熱乾燥したナスフラスコに、上記で得られた化合物(A)(785mg,2.38mmol)、及びジエチルエーテル(8mL)を入れた。窒素置換し、-78℃に冷却した後、n-ブチルリチウム(1.55Mヘキサン溶液,1.7mL,2.64mmol)を加えて反応させた。1時間後、-78℃で7H-ドデカフルオロヘプタン酸エチル(1.07g,2.86mmol)を加えて撹拌した。1時間後、水を加えて酢酸エチルで抽出した。
加熱乾燥したナスフラスコに、上記で得られた化合物(B)(147mg,0.254mmol)、及びジメチルホルムアミド(3mL)を入れた後、室温でN-ブロモスクシンイミド(110mg,0.611mmol)を加えて反応させた。16時間後、水を加えて酢酸エチルで抽出した。
加熱乾燥した蓋付き試験管に、上記で得られた化合物(C)(90mg,0.12 mmol)、ビス(トリブチル)すず(71mg,0.12mmol)、テトラキス(トリフェニルホスフィン)パラジウム(0)(14mg,0.012mmol)、及びトルエン(1mL)を入れた後、窒素置換して、7日間還流させた。
まず、熱酸化膜(シリコン酸化膜)付の低抵抗シリコンウエハー(ゲート電極/絶縁層となる構成を有する)を、エタノール、蒸留水、アセトンの順でそれぞれに浸漬させ、超音波洗浄を行う。その後、このシリコンウエハーをUV-オゾン洗浄して、表面が親水性である基板を得る。この基板を、ヘキサメチルジシラザン:クロロホルムに室温で浸漬し、クロロホルムで超音波洗浄して、表面処理された基板を得る。
Claims (10)
- 前記Z1が、式(ii)で表される基である、請求項3記載の含フッ素重合体。
- 前記R1及び前記R2が、同一又は異なり、フッ素原子、炭素数1~20のアルキル基又は炭素数1~20のフルオロアルキル基である、請求項1~4のいずれか一項に記載の含フッ素重合体。
- 請求項1~5のいずれか一項に記載の含フッ素重合体を含む、有機薄膜。
- 請求項6記載の有機薄膜を備える、有機薄膜素子。
- ソース電極及びドレイン電極と、これらの間の電流経路となる有機半導体層と、前記電流経路を通る電流量を制御するゲート電極と、を備え、
前記有機半導体層が、請求項6記載の有機薄膜からなる、有機薄膜トランジスタ。 - 請求項6記載の有機薄膜を備える、有機太陽電池。
- 請求項6記載の有機薄膜を備える、光センサ。
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EP10750795A EP2407499A1 (en) | 2009-03-11 | 2010-03-08 | Fluoropolymer and thin organic film comprising same |
CN2010800112469A CN102348738A (zh) | 2009-03-11 | 2010-03-08 | 含氟聚合物和使用其的有机薄膜 |
US13/255,669 US20120056168A1 (en) | 2009-03-11 | 2010-03-08 | Fluoropolymer and thin organic film comprising same |
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WO2012002246A1 (ja) * | 2010-07-02 | 2012-01-05 | コニカミノルタホールディングス株式会社 | 有機光電変換素子およびそれを用いた太陽電池 |
JPWO2013094456A1 (ja) * | 2011-12-22 | 2015-04-27 | コニカミノルタ株式会社 | 有機光電変換素子 |
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JP5937382B2 (ja) * | 2012-03-06 | 2016-06-22 | 国立大学法人東京工業大学 | 有機半導体用有機ヘテロ高分子及びそれを用いた半導体デバイス |
CN106226378B (zh) * | 2016-07-13 | 2019-03-12 | 电子科技大学 | 一种嵌有含氟聚合物的二氧化氮传感器及其制备方法 |
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WO2012002246A1 (ja) * | 2010-07-02 | 2012-01-05 | コニカミノルタホールディングス株式会社 | 有機光電変換素子およびそれを用いた太陽電池 |
US9634261B2 (en) | 2010-07-02 | 2017-04-25 | Konica Minolta Inc. | Organic photoelectric conversion element and solar cell using same |
JPWO2013094456A1 (ja) * | 2011-12-22 | 2015-04-27 | コニカミノルタ株式会社 | 有機光電変換素子 |
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JP2010209264A (ja) | 2010-09-24 |
US20120056168A1 (en) | 2012-03-08 |
TW201035114A (en) | 2010-10-01 |
KR20110131261A (ko) | 2011-12-06 |
CN102348738A (zh) | 2012-02-08 |
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