WO2021172185A1 - Composé aromatique polycyclique fusionné - Google Patents

Composé aromatique polycyclique fusionné Download PDF

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WO2021172185A1
WO2021172185A1 PCT/JP2021/006291 JP2021006291W WO2021172185A1 WO 2021172185 A1 WO2021172185 A1 WO 2021172185A1 JP 2021006291 W JP2021006291 W JP 2021006291W WO 2021172185 A1 WO2021172185 A1 WO 2021172185A1
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polycyclic aromatic
aromatic compound
photoelectric conversion
thin film
condensed polycyclic
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PCT/JP2021/006291
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English (en)
Japanese (ja)
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駿介 堀
希望 小野寺
秀典 薬師寺
裕介 刀祢
智史 岩田
一樹 新見
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日本化薬株式会社
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Priority to CN202180016971.3A priority Critical patent/CN115151552A/zh
Priority to JP2022503325A priority patent/JPWO2021172185A1/ja
Priority to KR1020227029062A priority patent/KR20220149666A/ko
Publication of WO2021172185A1 publication Critical patent/WO2021172185A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • 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]
    • 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 novel condensed polycyclic aromatic compounds and their uses. More specifically, the present invention refers to condensed polycyclic aromatic compounds which are benzothiophene [3,2-b] [1] benzothiophene (hereinafter abbreviated as "BTBT”) derivatives, organic thin films containing the compounds, and the organic thin films.
  • BTBT benzothiophene
  • the present invention relates to an organic semiconductor device (field effect transistor, organic photoelectric conversion element).
  • Patent Document 1 shows that a BTBT derivative exhibits excellent charge mobility and its thin film has organic semiconductor properties.
  • Patent Document 2 reports a field effect transistor manufactured by a solution process using an alkyl derivative of BTBT.
  • BTBT derivatives useful as organic electronics compounds have been developed so far, but the BTBT derivatives in these documents are organic semiconductors in the heat annealing step after manufacturing the electrodes of the field effect transistor element. There was a problem that the characteristics were significantly deteriorated.
  • organic photoelectric conversion elements are expected to be applied to next-generation image sensors, and several groups have reported on them.
  • a quinacridone derivative is used for a photoelectric conversion element (Patent Document 3)
  • a photoelectric conversion element using a quinacridone derivative is applied to an imaging device
  • a diketopyrrolopyrrole derivative is used (Patent Document 3).
  • a document 5 There is a document 5).
  • the present invention has been made in view of the above-mentioned conventional problems, and an object of the present invention is a condensed polycyclic aromatic compound having excellent heat resistance in a practical process temperature range, an organic thin film containing the compound, and the organic substance.
  • An object of the present invention is to provide an organic semiconductor device having a thin film (field effect transistor, organic photoelectric conversion element).
  • R 1 and R 2 are the general formula (2) or (3).
  • n represents an integer of 0 to 2.
  • X represents an oxygen atom, a sulfur atom or a selenium atom.
  • R 3 is a hydrogen atom or a substituted or unsubstituted aromatic hydrocarbon group. Represents.
  • the substituent is represented by, and the other represents a hydrogen atom.
  • a condensed polycyclic aromatic compound having excellent heat resistance in a practical process temperature range, an organic thin film containing the compound, and an organic semiconductor device having the organic thin film (field effect transistor, organic photoelectric conversion element). ) can be provided.
  • FIG. 1 is a schematic cross-sectional view showing some examples of the structure of the field effect transistor (element) of the present invention, where A is a bottom contact-bottom gate type field effect transistor (element) and B is a top contact-bottom.
  • Gate type field effect transistor (element) C is top contact-top gate type field effect transistor (element)
  • D is top & bottom contact bottom gate type field effect transistor (element)
  • E is electrostatic induction type field effect transistor (element) Element
  • F indicates a bottom contact-top gate type field effect transistor (element).
  • FIG. 2 is an explanatory diagram for explaining a manufacturing process of a top contact-bottom gate type field effect transistor (element) as an example of one aspect of the field effect transistor (element) of the present invention, and FIGS.
  • FIG. 3 shows a cross-sectional view illustrating an embodiment of the organic photoelectric conversion element of the present invention.
  • FIG. 4 is an AFM image of an organic thin film prepared using the condensed polycyclic aromatic compound of the present invention.
  • FIG. 5 is an AFM image of an organic thin film prepared using the condensed polycyclic aromatic compound of the present invention.
  • FIG. 6 is an AFM image of an organic thin film prepared using a comparative example compound.
  • FIG. 7 is an AFM image of an organic thin film prepared using the condensed polycyclic aromatic compound of the present invention.
  • FIG. 8 is an AFM image of an organic thin film prepared using the condensed polycyclic aromatic compound of the present invention.
  • the condensed polycyclic aromatic compound of the present invention is represented by the above general formula (1).
  • one of R 1 and R 2 represents a substituent represented by the above general formula (2) or (3), and the other represents a hydrogen atom.
  • R 1 and R 2 in the formula (1) it is preferable that one of them is a substituent represented by the above general formula (2) and the other is a hydrogen atom, and R 1 is the above general formula (2). ), It is more preferable that R 2 is a hydrogen atom.
  • n represents an integer of 0 to 2, preferably 1 or 2, and more preferably 1.
  • X represents an oxygen atom, a sulfur atom or a selenium atom, an oxygen atom or a sulfur atom is preferable, and a sulfur atom is more preferable.
  • R 3 represents a hydrogen atom or a substituted or unsubstituted aromatic hydrocarbon group.
  • the aromatic hydrocarbon group represented by R 3 is a residue obtained by removing one hydrogen atom from the aromatic ring of the aromatic hydrocarbon compound, and the aromatic hydrocarbon group preferably has 5 to 20 carbon atoms. .. Specific examples include a phenyl group, a biphenyl group (1-biphenyl group, 2-biphenyl group), a naphthyl group (1-naphthyl group, 2-naphthyl group) and the like. Of these, a phenyl group is more preferable.
  • substituted or unsubstituted means “having or not having a substituent”
  • substituted or unsubstituted aromatic hydrocarbon group means an aromatic having a substituent. It means an aromatic hydrocarbon having no hydrocarbon group or substituent. The substituent is not particularly limited.
  • the condensed polycyclic aromatic compound represented by the general formula (1) can be synthesized by various conventionally known methods, and the synthesis method of the following scheme will be described as an example.
  • the compound represented by the formula (1) can be synthesized by a known method disclosed in Patent Document 6, Patent Document 7, and Non-Patent Document 1.
  • a synthesis method based on the following scheme can be mentioned.
  • a nitrostilbene derivative (A') as a raw material, a benzothienobenzothiophene skeleton (D) is formed, and the benzothienobenzothiophene skeleton (D) is reduced to obtain an amination (E).
  • Halogenation of this compound (E) yields a halide (F) (an iodide is described as an example of the halide (F) in the scheme below, but is not limited thereto).
  • the compound represented by the formula (1') (R 1 in the formula (1) is the formula (2) or the formula (3). It is possible to obtain a compound in which R 2 is a hydrogen atom as a substituent). According to the method of Patent Document 5, the compound represented by the formula (1') can be produced from the corresponding benzaldehyde derivative in one step, which is more efficient. Note that boric acid derivative (G ') R 1 in the formula (1' corresponds to R 1 in).
  • the starting material in the above scheme is changed from the nitrostilbene derivative (A') to the nitrostilbene derivative (A ′′) represented by the following formula, and the boric acid derivative (G') is represented by the following formula.
  • an acid derivative (G ′′) By changing to an acid derivative (G ′′), it is possible to obtain a compound represented by the following formula (1 ′′) (a compound in which R 1 is a hydrogen atom and R 2 is a substituent in the formula (1)). Is.
  • the reaction temperature of the above coupling reaction is usually ⁇ 10 to 200 ° C., preferably 40 to 160 ° C., and more preferably 60 to 120 ° C.
  • the reaction time is not particularly limited, but is usually 1 to 72 hours, preferably 3 to 48 hours. Depending on the type of catalyst described later, the reaction temperature can be lowered or the reaction time can be shortened.
  • the above coupling reaction is preferably carried out in an inert gas atmosphere such as an argon atmosphere, a nitrogen substitution, a dry argon atmosphere, and a dry nitrogen stream.
  • catalysts for the coupling reaction using the halide (F) include tri-tert-butylphosphine, triadamantylphosphine, 1,3-bis (2,4,6-trimethylphenyl) imidazolidinium chloride, and 1,3-bis (2).
  • a palladium-based catalyst is preferable.
  • Pd (dppf) Cl 2, Pd (PPh 3) 2 Cl 2, Pd (PPh 3) 4 are more preferable, Pd (PPh 3) 4 is more preferred.
  • a plurality of types of these catalysts may be mixed and used, or other catalysts may be mixed and used with these catalysts.
  • the amount of these catalysts used in the coupling reaction is preferably 0.001 to 0.500 mol, more preferably 0.001 to 0.200 mol, and even more preferably 0.001 to 0.200 mol, based on 1 mol of the halide (F). Is 0.001 to 0.100 mol, most preferably 0.001 to 0.050 mol.
  • a basic compound for the coupling reaction using the halide (F) includes hydroxides such as lithium hydroxide, barium hydroxide, sodium hydroxide and potassium hydroxide; lithium carbonate, lithium hydrogencarbonate, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate and the like.
  • Carbonates such as cesium carbonate; Acetates such as lithium acetate, sodium acetate and potassium acetate; Phosphates such as trisodium phosphate and tripotassium phosphate; Alcoxides; metal hydrides such as sodium hydride and potassium hydroxide; organic bases such as pyridine, picolin, lutidine, triethylamine, tributylamine, diisopropylethylamine and N, N-dicyclohexylmethylamine, and phosphates.
  • hydroxide is preferable, and trisodium phosphate, tripotassium phosphate, sodium hydroxide, and potassium hydroxide are more preferable.
  • These basic compounds may be used alone or in combination of two or more. The amount of these basic compounds used in the coupling reaction is preferably 1 to 100 mol, more preferably 1 to 10 mol, based on 1 mol of the halide (F).
  • the above coupling reaction may be carried out in a solvent.
  • Any solvent can be used as long as it can dissolve a required raw material, a halide (F) or a boric acid derivative, and a catalyst, a basic compound, an alkali metal salt, etc., which are used as necessary.
  • the solvent include aromatic compounds such as chlorobenzene, o-dichlorobenzene, bromobenzene, nitrobenzene, toluene and xylene; saturated aliphatic hydrocarbons such as n-hexane, n-heptan and n-pentane; cyclohexane.
  • Cycloheptane, cyclopentane and other alicyclic hydrocarbons n-propyl bromide, n-butyl chloride, n-butyl bromide, dichloromethane, dibromomethane, dichloropropane, dibromopropane, dichlorobutane, chloroform, bromoform, tetrachloride
  • Saturated aliphatic halogenated hydrocarbons such as carbon, carbon tetrabromide, trichloroethane, tetrachloroethane and pentachloroethane;
  • cyclic halogenated hydrocarbons such as chlorocyclohexane, chlorocyclopentane and bromocyclopentane; ethyl acetate, propyl acetate, Esters such as butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionat
  • the method for purifying the condensed polycyclic aromatic compound represented by the general formula (1) is not particularly limited, and known methods such as recrystallization, column chromatography, and vacuum sublimation purification can be adopted. Moreover, these methods can be combined as needed.
  • condensed polycyclic aromatic compound of the present invention represented by the general formula (1) in which R 3 in the formulas (2) and (3) is an aromatic hydrocarbon group include the above No.
  • examples thereof include compounds in which the furan ring or thiophene ring of the compounds represented by 1 to 36 is substituted with an aromatic hydrocarbon group such as a phenyl group, a biphenyl group and a naphthyl group.
  • the place of substitution is not particularly limited, but for example, the substituent is bonded to the carbon atom next to the S atom, Se atom, and O atom at both ends of the condensed polycyclic aromatic compound of the present invention. There are cases.
  • the organic thin film of the present invention contains a condensed polycyclic aromatic compound represented by the formula (1).
  • the film thickness of the organic thin film varies depending on the application, but is usually 1 nm to 1 ⁇ m, preferably 5 nm to 500 nm, and more preferably 10 nm to 300 nm.
  • Examples of the method for forming the organic thin film include a dry process such as a thin film deposition method and various solution processes, but it is preferable to form the organic thin film by a solution process.
  • Examples of the solution process include spin coating method, drop casting method, dip coating method, spray method, flexo printing, letterpress printing method such as resin letterpress printing, offset printing method, dry offset printing method, and flat plate printing method such as pad printing method.
  • Recessed printing method such as gravure printing method, screen printing method, copy printing method, stencil printing method such as lingraph printing method, inkjet printing method, micro contact printing method, etc., and a method in which a plurality of these methods are combined can be mentioned. ..
  • the field effect transistor of the present invention controls the current flowing between two electrodes (source electrode and drain electrode) provided in contact with the organic thin film of the present invention by a voltage applied to another electrode called a gate electrode. It is a thing.
  • a structure in which the gate electrode is insulated with an insulating film is generally used.
  • a structure in which a metal oxide film is used as an insulating film is called a MOS structure, and a structure in which a gate electrode is formed via a Schottky barrier (that is, a MES structure) is also known.
  • the MIS structure is often used.
  • 1 is a source electrode
  • 2 is an organic thin film (semiconductor layer)
  • 3 is a drain electrode
  • 4 is an insulator layer
  • 5 is a gate electrode
  • 6 is a substrate.
  • a to D and F are called horizontal transistors because current flows in the direction parallel to the substrate.
  • A is called a bottom contact bottom gate structure
  • B is called a top contact bottom gate structure.
  • C is provided with a source electrode, a drain electrode, and an insulator layer on a semiconductor, and a gate electrode is formed on the source electrode, a drain electrode, and an insulator layer, which is called a top contact top gate structure.
  • D has a structure called a top & bottom contact bottom gate type transistor.
  • F has a bottom contact top gate structure.
  • E is a schematic diagram of a transistor having a vertical structure, that is, a static induction transistor (SIT).
  • SIT static induction transistor
  • the substrate is not shown in E in FIG. 1, a substrate is usually provided outside the source electrode or drain electrode represented by 1 and 3 in FIG. 1E.
  • the substrate 6 needs to be able to hold each layer formed on the substrate 6 without peeling.
  • insulating materials such as resin plates, films, paper, glass, quartz, and ceramics; insulating layers formed by coating on conductive substrates such as metals and alloys; materials made up of various combinations of resins and inorganic materials, etc.
  • the resin film that can be used include polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, polyamide, polyimide, polycarbonate, cellulose triacetate, and polyetherimide.
  • the thickness of the substrate is usually 1 ⁇ m to 10 mm, preferably 5 ⁇ m to 5 mm.
  • a conductive material is used for the source electrode 1, the drain electrode 3, and the gate electrode 5.
  • metals such as platinum, gold, silver, aluminum, chromium, tungsten, tantalum, nickel, cobalt, copper, iron, lead, tin, titanium, indium, palladium, molybdenum, magnesium, calcium, barium, lithium, potassium and sodium.
  • conductive oxides such as InO 2 , ZnO 2 , SnO 2 , ITO
  • conductive polymer compounds such as polyaniline, polypyrrole, polythiophene, polyacetylene, polyparaphenylene vinylene, polydiaacetylene; silicon, germanium, Semiconductors such as gallium arsenic; carbon materials such as carbon black, fullerene, carbon nanotubes, graphite and graphene can be used. Further, the conductive polymer compound and the semiconductor may be doped.
  • the dopant examples include inorganic acids such as hydrochloric acid and sulfuric acid; organic acids having acidic functional groups such as sulfonic acid; Lewis acids such as PF 5 , AsF 5 , FeCl 3 ; halogen atoms such as iodine; lithium, sodium and potassium. Such as metal atoms and the like. Boron, phosphorus, arsenic and the like are also widely used as dopants for inorganic semiconductors such as silicon.
  • a conductive composite material in which carbon black, metal particles, etc. are dispersed in the above-mentioned dopant is also used.
  • the source electrode 1 and the drain electrode 3 that come into direct contact with the semiconductor it is important to select an appropriate work function or surface treatment in order to reduce the contact resistance.
  • the distance between the source electrode and the drain electrode is an important factor that determines the characteristics of the device, and an appropriate channel length is required. If the channel length is short, the amount of current that can be taken out increases, but short-channel effects such as the influence of contact resistance may occur, and the semiconductor characteristics may deteriorate.
  • the channel length is usually 0.01 to 300 ⁇ m, preferably 0.1 to 100 ⁇ m.
  • the width (channel width) between the source electrode and the drain electrode is usually 10 to 5000 ⁇ m, preferably 40 to 2000 ⁇ m. In addition, it is possible to form a longer channel width by making the electrode structure a comb-shaped structure, and it is necessary to make this channel width an appropriate length depending on the required current amount and device structure. be.
  • the structure (shape) of each of the source electrode and the drain electrode will be explained.
  • the structures of the source electrode and the drain electrode may be the same or different.
  • each electrode In the case of a bottom contact structure, it is generally preferable to prepare each electrode by a lithography method and to form each electrode in a rectangular parallelepiped. Recently, the printing accuracy of various printing methods has been improved, and it has become possible to manufacture electrodes with high accuracy by using techniques such as inkjet printing, gravure printing, and screen printing. In the case of a top contact structure having electrodes on a semiconductor, vapor deposition can be performed using a shadow mask or the like. It has become possible to directly print and form an electrode pattern using a technique such as inkjet.
  • the length of the electrode is the same as the channel width described above.
  • the width of the electrode is not particularly specified, but it is preferably short in order to reduce the area of the device within the range in which the electrical characteristics can be stabilized.
  • the width of the electrode is usually 0.1 to 1000 ⁇ m, preferably 0.5 to 100 ⁇ m.
  • the thickness of the electrode is usually 0.1 to 1000 nm, preferably 1 to 500 nm, and more preferably 5 to 200 nm. Wiring is connected to each of the electrodes 1, 3 and 5, but the wiring is also made of almost the same material as the electrodes.
  • a material having an insulating property is used.
  • Polymers such as resins and copolymers combining these; metal oxides such as silicon oxide, aluminum oxide, titanium oxide and tantalum oxide; strong dielectric metal oxides such as SrTIO 3 and BaTIO 3 ; silicon nitride, aluminum nitride and the like.
  • Dioxides such as nitrides, sulfides, and fluorides; or polymers in which particles of these dielectrics are dispersed can be used.
  • the insulator layer one having high electrical insulation characteristics can be preferably used in order to reduce the leakage current. As a result, the film thickness can be reduced, the insulation capacity can be increased, and the current that can be taken out increases. Further, in order to improve the mobility of the semiconductor, it is preferable that the surface energy of the surface of the insulator layer is lowered and the film is smooth without unevenness. Therefore, a self-assembled monolayer or a two-layer insulator layer may be formed.
  • the film thickness of the insulator layer 4 varies depending on the material, but is usually 0.1 nm to 100 ⁇ m, preferably 0.5 nm to 50 ⁇ m, and more preferably 1 nm to 10 ⁇ m.
  • the condensed polycyclic aromatic compound of the present invention is used as the material of the semiconductor layer 2.
  • the organic semiconductor film can be formed into the semiconductor layer 2 by a method similar to the method for forming the organic thin film shown above.
  • a plurality of layers may be formed for the semiconductor layer 2 (organic thin film), but a single layer structure is more preferable.
  • the film thickness of the semiconductor layer 2 is preferably as thin as long as it does not lose the necessary functions. In horizontal field-effect transistors as shown in A, B, and D, the characteristics of the device do not depend on the film thickness if the film thickness is equal to or greater than the specified value, but the leakage current increases as the film thickness increases. be.
  • the film thickness of the semiconductor layer 2 for exhibiting the required function is usually 1 nm to 1 ⁇ m, preferably 5 nm to 500 nm, and more preferably 10 nm to 300 nm.
  • another layer can be provided between the substrate layer and the insulating film layer, between the insulating film layer and the semiconductor layer, and on the outer surface of the device as needed.
  • a protective layer is formed directly on the semiconductor layer 2 or through another layer, the influence of outside air such as humidity can be reduced.
  • the electrical characteristics can be stabilized, such as increasing the on / off ratio of the field effect transistor.
  • the material of the protective layer is not particularly limited, and is, for example, a film made of an epoxy resin, an acrylic resin such as polymethylmethacrylate, and various resins such as polyurethane, polyimide, polyvinyl alcohol, fluororesin, and polyolefin; silicon oxide, aluminum oxide, and nitrided.
  • Inorganic oxide films such as silicon; and films made of dielectrics such as nitride films are preferably used, and in particular, resins (polymers) having low oxygen and moisture permeability and water absorption are preferable.
  • Gas barrier protective materials developed for organic EL displays can also be used.
  • the film thickness of the protective layer can be selected as desired depending on the purpose, but is usually 100 nm to 1 mm.
  • the characteristics as a field effect transistor by performing surface modification or surface treatment on the substrate or insulator layer on which the organic thin film is laminated in advance. For example, by adjusting the degree of hydrophilicity / hydrophobicity of the substrate surface, the film quality and film forming property of the film formed on the substrate surface can be improved.
  • the characteristics of organic semiconductor materials may change significantly depending on the state of the film such as the orientation of molecules. Therefore, by surface-treating the substrate, the insulator layer, etc., the molecular orientation of the interface portion with the organic thin film formed thereafter is controlled, or the trap portion on the substrate or the insulator layer is reduced. , It is considered that the characteristics such as carrier mobility are improved.
  • the trap site refers to a functional group such as a hydroxyl group existing on the untreated substrate, and when such a functional group is present, electrons are attracted to the functional group, and as a result, the carrier mobility is lowered. Therefore, reducing the trap portion is often effective for improving characteristics such as carrier mobility.
  • Examples of the surface treatment for improving the characteristics as described above include self-assembling monolayer treatment with hexamethyldisilazane, octyltrichlorosilane, octadecyltrichlorosilane, etc., surface treatment with polymers, hydrochloric acid, sulfuric acid, acetic acid, etc. Acid treatment with sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, etc., ozone treatment, fluorination treatment, plasma treatment with oxygen, argon, etc., Langmuir Brodget film formation treatment, and other insulators. And semiconductor thin film formation treatment, mechanical treatment, electrical treatment such as corona discharge, rubbing treatment using fibers and the like, and a combination of these can also be performed.
  • each layer such as a substrate layer and an insulating film layer or an insulating film layer and a semiconductor layer (organic thin film)
  • the above-mentioned vacuum process and solution process can be appropriately adopted.
  • the field-effect transistor of the present invention is manufactured by providing various necessary layers and electrodes on the substrate 6 (see FIG. 2 (1)).
  • the substrate the one described above can be used. It is also possible to perform the above-mentioned surface treatment on this substrate.
  • the thickness of the substrate 6 is preferably thin as long as it does not interfere with the required functions. Although it depends on the material, it is usually 1 ⁇ m to 10 mm, preferably 5 ⁇ m to 5 mm. Further, if necessary, the substrate can be provided with the function of an electrode.
  • the gate electrode 5 is formed on the substrate 6 (see FIG. 2 (2)).
  • the electrode material the one described above is used.
  • a method for forming the electrode film various methods can be used, and for example, a vacuum vapor deposition method, a sputtering method, a coating method, a thermal transfer method, a printing method, a sol-gel method and the like are adopted. It is preferable to perform patterning as necessary so as to obtain a desired shape at the time of film formation or after film formation.
  • Various methods can be used as the patterning method, and examples thereof include a photolithography method in which patterning and etching of a photoresist are combined.
  • a vapor deposition method using a shadow mask, a sputtering method, an inkjet printing method, a printing method such as screen printing, offset printing, and letterpress printing, a soft lithography method such as a microcontact printing method, and a method in which a plurality of these methods are combined are used. It can also be used and patterned.
  • the film thickness of the gate electrode 5 varies depending on the material, but is usually 0.1 nm to 10 ⁇ m, preferably 0.5 nm to 5 ⁇ m, and more preferably 1 nm to 3 ⁇ m. Further, when the gate electrode and the substrate are also used, the film thickness may be larger than the above.
  • An insulator layer 4 is formed on the gate electrode 5 (see FIG. 2 (3)).
  • the material of the insulator layer 4 the material described above is used.
  • Various methods can be used to form the insulator layer 4. For example, application methods such as spin coating, spray coating, dip coating, casting, bar coating, blade coating, screen printing, offset printing, printing methods such as inkjet, vacuum deposition method, molecular beam epitaxial growth method, ion cluster beam method, ion play. Examples thereof include a dry process method such as a ting method, a sputtering method, an atmospheric pressure plasma method, and a CVD method.
  • a method of forming an oxide film on a metal by a thermal oxidation method such as a sol-gel method, alumite on aluminum, or silicon oxide on silicon is adopted.
  • a predetermined surface treatment may be applied to the insulator layer in order to favorably orient the molecules of the compounds constituting the semiconductor at the interface between the two layers.
  • the surface treatment method the same method as the surface treatment of the substrate can be used.
  • the film thickness of the insulator layer 4 is preferably as thin as possible because the amount of electricity taken out can be increased by increasing its electric capacity.
  • the film is thin as long as its function is not impaired. It is usually 0.1 nm to 100 ⁇ m, preferably 0.5 nm to 50 ⁇ m, and more preferably 5 nm to 10 ⁇ m.
  • a coating method such as a dip coating method, a die coater method, a roll coater method, a bar coater method, and a spin coating method, a forming method by a solution process such as an inkjet method, a screen printing method, an offset printing method, and a microcontact printing method.
  • a solution process such as an inkjet method, a screen printing method, an offset printing method, and a microcontact printing method.
  • the method of forming an organic thin film by a solution process will be described.
  • the organic semiconductor composition is applied to a substrate (insulator layer, exposed portion of source electrode and drain electrode).
  • the coating method includes spin coating method, drop casting method, dip coating method, spray method, flexo printing, letterpress printing method such as resin letterpress printing, offset printing method, dry offset printing method, and flat plate printing method such as pad printing method.
  • Recessed printing method such as gravure printing method, silk screen printing method, copy printing method, stencil printing method such as lingraph printing method, inkjet printing method, micro contact printing method, etc. Will be printed.
  • a Langmuir project method in which a monomolecular film of an organic thin film prepared by dropping the above composition on the water surface is transferred to a substrate and laminated, and two liquid crystal or melted materials are used. It is also possible to adopt a method of sandwiching between substrates and introducing them between substrates by capillarity.
  • the environment such as the temperature of the substrate and composition at the time of film formation is also important, and the characteristics of the field effect transistor may change depending on the temperature of the substrate and composition, so it is preferable to carefully select the temperature of the substrate and composition. ..
  • the substrate temperature is usually 0 to 200 ° C, preferably 10 to 120 ° C, and more preferably 15 to 100 ° C. Care must be taken as it largely depends on the solvent in the composition used.
  • the film thickness of the organic thin film produced by this method is preferably thin as long as the function is not impaired. There is a concern that the leakage current will increase as the film thickness increases.
  • the film thickness of the organic thin film is usually 1 nm to 1 ⁇ m, preferably 5 nm to 500 nm, and more preferably 10 nm to 300 nm.
  • the characteristics of the organic thin film thus formed can be further improved by post-treatment.
  • heat treatment improves and stabilizes the characteristics of organic semiconductors because the distortion in the film generated during film formation is alleviated, pinholes are reduced, and the arrangement and orientation in the film can be controlled. Can be achieved.
  • the field effect transistor of the present invention is manufactured, it is effective to perform this heat treatment in order to improve the characteristics.
  • the heat treatment is performed by heating the substrate after forming the organic thin film.
  • the temperature of the heat treatment is not particularly limited, but is usually about 180 ° C. from room temperature, preferably 40 to 160 ° C., and more preferably 45 to 150 ° C.
  • the heat treatment time at this time is not particularly limited, but is usually about 10 seconds to 24 hours, preferably about 30 seconds to 3 hours.
  • the atmosphere at that time may be in the atmosphere, but it may also be in an inert atmosphere such as nitrogen or argon.
  • the film shape can be controlled by solvent vapor.
  • an oxidizing or reducing gas such as oxygen or hydrogen or an oxidizing or reducing liquid induces a change in characteristics due to oxidation or reduction. You can also do it. This can be used, for example, for the purpose of increasing or decreasing the carrier density in the membrane.
  • the characteristics of the organic thin film can be changed by adding a trace amount of elements, atomic groups, molecules, and polymers to the organic thin film.
  • acids such as oxygen, hydrogen, hydrochloric acid, sulfuric acid, sulfonic acid ; Lewis acids such as PF 5 , AsF 5 , FeCl 3 ; halogen atoms such as iodine; metal atoms such as sodium and potassium; tetrathiafluvalene (TTF) and Donor compounds such as phthalocyanine can be doped.
  • acids such as oxygen, hydrogen, hydrochloric acid, sulfuric acid, sulfonic acid ; Lewis acids such as PF 5 , AsF 5 , FeCl 3 ; halogen atoms such as iodine; metal atoms such as sodium and potassium; tetrathiafluvalene (TTF) and Donor compounds such as phthalocyanine
  • TTF tetrathiafluvalene
  • Donor compounds such as phthal
  • dopings can be added at the time of synthesizing the organic semiconductor compound, added to the organic semiconductor composition, added in the step of forming the organic thin film, or the like, even if it is not after the production of the organic thin film.
  • the material used for doping is added to the material that forms the organic thin film during vapor deposition and co-deposited, or the organic thin film is mixed with the surrounding atmosphere when the organic thin film is produced (the organic thin film is formed in an environment where the doping material is present). It is also possible to accelerate the ions in a vacuum and cause them to collide with the membrane for doping.
  • the effects of these dopings include changes in electrical conductivity due to an increase or decrease in carrier density, changes in carrier polarity (p-type, n-type), changes in Fermi levels, and the like.
  • the source electrode 1 and the drain electrode 3 can be formed in the same manner as in the case of the gate electrode 5 (see FIG. 2 (5)). Further, various additives and the like can be used to reduce the contact resistance with the organic thin film.
  • Forming the protective layer 7 on the organic thin film has the advantages that the influence of the outside air can be minimized and the electrical characteristics of the field effect transistor can be stabilized (see FIG. 2 (6)).
  • the above-mentioned material is used as the material of the protective layer.
  • the film thickness of the protective layer 7 can be any film thickness depending on the purpose, but is usually 100 nm to 1 mm.
  • the protective layer is made of resin
  • a method of applying a resin solution and then drying to form a resin film for example, a method of applying a resin solution and then drying to form a resin film; a resin monomer is applied or vapor-deposited. Examples thereof include a method of polymerizing later. Crosslinking may be performed after the film formation.
  • a forming method by a vacuum process such as a sputtering method or a vapor deposition method
  • a forming method by a solution process such as a sol-gel method
  • a protective layer can be provided as needed between each layer as well as on the organic thin film. These layers may help stabilize the electrical properties of field effect transistors.
  • the field effect transistor can also be used as a digital device such as a memory circuit device, a signal driver circuit device, a signal processing circuit device, or an analog device. Further, by combining these, it becomes possible to manufacture a display, an IC card, an IC tag, and the like. Further, since the field effect transistor can change its characteristics by an external stimulus such as a chemical substance, it can also be used as a sensor.
  • the material for an organic photoelectric conversion element of the present invention contains a condensed polycyclic aromatic compound represented by the above formula (1).
  • the content of the compound represented by the formula (1) in the material for an organic photoelectric conversion element of the present invention is not particularly limited as long as the performance required in the application using the material for an organic photoelectric conversion element is exhibited, but is usually limited. Is 50% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more.
  • the material for an organic photoelectric conversion element of the present invention includes a compound other than the compound represented by the formula (1) (for example, a material for an organic photoelectric conversion element other than the compound represented by the formula (1)), an additive and the like. It may be used together.
  • the compounds and additives that can be used in combination are not particularly limited as long as the performance required in the application using the material for the organic photoelectric conversion element is exhibited.
  • the organic photoelectric conversion element of the present invention has the organic thin film of the present invention.
  • An organic photoelectric conversion element is an element in which a photoelectric conversion unit (film) is arranged between a pair of electrode films facing each other, and light is incident on the photoelectric conversion unit from above the electrode films.
  • the photoelectric conversion unit generates electrons and holes in response to the incident light, and a semiconductor reads out a signal corresponding to the electric charge to indicate the amount of incident light according to the absorption wavelength of the photoelectric conversion film unit.
  • a transistor for reading may be connected to the electrode film on the side where light is not incident.
  • organic photoelectric conversion element arranged closer to the light source does not shield (transmit) the absorption wavelength of the organic photoelectric conversion element arranged behind the organic photoelectric conversion element when viewed from the light source side
  • a plurality of organic photoelectric conversion elements may be used. It may be used by laminating.
  • the organic photoelectric conversion element of the present invention uses an organic thin film containing a condensed polycyclic aromatic compound represented by the above formula (1) as a constituent material of the photoelectric conversion unit.
  • the photoelectric conversion unit is one or a plurality of types selected from the group consisting of a photoelectric conversion layer, an electron transport layer, a hole transport layer, an electron block layer, a hole block layer, a crystallization prevention layer, an interlayer contact improvement layer, and the like. It often consists of an organic thin film layer other than the photoelectric conversion layer.
  • the condensed polycyclic aromatic compound of the present invention is preferably used as an organic thin film layer of a photoelectric conversion layer, but in addition to the above organic thin film layers (particularly, an electron transport layer, a hole transport layer, an electron block layer, and holes). It can also be used as a block layer).
  • the electron block layer and the hole block layer are also represented as a carrier block layer.
  • a photoelectric conversion layer it may be composed of only the condensed polycyclic aromatic compound of the present invention, but may contain an organic semiconductor material in addition to the condensed polycyclic aromatic compound of the present invention.
  • These organic thin film layers may have a laminated structure, but may include an organic thin film formed by co-depositing a material, and at the same time, a co-deposited film, a single film, or another co-deposited film is formed in a plurality of layers. , It may be an organic thin film that functions.
  • the electrode film used in the organic photoelectric conversion element of the present invention is positive when the photoelectric conversion layer included in the photoelectric conversion unit described later has hole transportability or when the organic thin film layer other than the photoelectric conversion layer has hole transportability.
  • a hole transport layer it plays a role of extracting holes from the photoelectric conversion layer and other organic thin film layers and collecting them, and the photoelectric conversion layer included in the photoelectric conversion unit has electron transportability.
  • the organic thin film layer is an electron transporting layer having electron transporting properties, it plays a role of extracting electrons from the photoelectric conversion layer and other organic thin film layers and discharging them.
  • the material that can be used as the electrode film is not particularly limited as long as it has a certain degree of conductivity, but the adhesion to the adjacent photoelectric conversion layer and other organic thin film layers, electron affinity, ionization potential, stability, etc. It is preferable to select in consideration of.
  • Materials that can be used as the electrode film include conductive metal oxides such as tin oxide (NESA), indium oxide, indium tin oxide (ITO) and indium zinc oxide (IZO); gold, silver, platinum, chromium and aluminum.
  • Metals such as iron, cobalt, nickel and tungsten; inorganic conductive substances such as copper iodide and copper sulfide; conductive polymers such as polythiophene, polypyrrole and polyaniline; carbon and the like. If necessary, a plurality of these materials may be mixed and used, or a plurality of these materials may be laminated in two or more layers.
  • the conductivity of the material used for the electrode film is not particularly limited as long as it does not interfere with the light reception of the organic photoelectric conversion element more than necessary, but it is preferably as high as possible from the viewpoint of the signal strength of the organic photoelectric conversion element and the power consumption.
  • an ITO film having a sheet resistance value of 300 ⁇ / ⁇ or less functions sufficiently as an electrode film, but a commercially available substrate having an ITO film having a conductivity of several ⁇ / ⁇ is also available. Therefore, it is desirable to use a substrate having such high conductivity.
  • the thickness of the ITO film (electrode film) can be arbitrarily selected in consideration of conductivity, but is usually about 5 to 500 nm, preferably about 10 to 300 nm.
  • Examples of the method for forming a film such as ITO include a conventionally known vapor deposition method, electron beam method, sputtering method, chemical reaction method, coating method and the like.
  • the ITO film provided on the substrate may be subjected to UV-ozone treatment, plasma treatment, or the like, if necessary.
  • the transparent electrode film used for at least one of the electrode films on the side where light is incident ITO, IZO, SnO 2 , ATO (antimony-doped tin oxide), ZnO, AZO (Al-doped zinc oxide) , GZO (gallium-doped zinc oxide), TiO 2 and FTO (fluorinated tin oxide) and the like.
  • the transmittance of light incident through the transparent electrode film at the absorption peak wavelength of the photoelectric conversion layer is preferably 60% or more, more preferably 80% or more, and particularly preferably 95% or more. ..
  • the electrode film used between the photoelectric conversion layers (this is an electrode film other than the pair of electrode films described above) is the respective photoelectric conversion. It is necessary to transmit light having a wavelength other than the light detected by the layer, and it is preferable to use a material that transmits 90% or more of the incident light, and a material that transmits 95% or more of the light is used for the electrode film. Is more preferable.
  • the electrode film is plasma-free.
  • plasma-free means that plasma is not generated when the electrode film is formed, or the distance from the plasma generation source to the substrate is 2 cm or more, preferably 10 cm or more, more preferably 20 cm or more, and reaches the substrate. It means a state in which the plasma is reduced.
  • Examples of devices that do not generate plasma during film formation of the electrode film include electron beam vapor deposition devices (EB thin film deposition devices) and pulse laser vapor deposition devices.
  • EB thin film deposition devices electron beam vapor deposition devices
  • pulse laser vapor deposition devices pulse laser vapor deposition devices.
  • the method of forming a transparent electrode film using an EB vapor deposition apparatus is referred to as an EB vapor deposition method
  • the method of forming a transparent electrode film using a pulse laser vapor deposition apparatus is referred to as a pulse laser vapor deposition method.
  • an opposed target type sputtering device As a device that can realize a state in which plasma can be reduced during film formation, for example, an opposed target type sputtering device, an arc plasma vapor deposition device, or the like can be considered.
  • the transparent conductive film When the transparent conductive film is used as an electrode film (for example, the first conductive film), a DC short circuit or an increase in leakage current may occur.
  • One of the causes is that fine cracks generated in the photoelectric conversion layer are covered with a dense film such as TCO (Transient Conductive Oxide), and the conduction between the transparent conductive film and the electrode film on the opposite side is increased. it is conceivable that. Therefore, when a material having a relatively inferior film quality such as Al is used for the electrode, the leakage current is unlikely to increase.
  • TCO Transient Conductive Oxide
  • the sheet resistance of the conductive film in the organic photoelectric conversion element for an optical sensor of the present embodiment is usually 100 to 10000 ⁇ / ⁇ , and the degree of freedom in film thickness is large. Further, the thinner the transparent conductive film, the smaller the amount of light absorbed, and generally the higher the light transmittance. When the light transmittance is high, the amount of light absorbed by the photoelectric conversion layer is increased and the photoelectric conversion ability is improved, which is very preferable.
  • the photoelectric conversion unit included in the organic photoelectric conversion element of the present invention may include an organic thin film layer other than the photoelectric conversion layer and the photoelectric conversion layer.
  • An organic semiconductor film is generally used for the photoelectric conversion layer constituting the photoelectric conversion unit, but the organic semiconductor film may be one layer or a plurality of layers, and in the case of one layer, a P-type organic semiconductor film, An N-type organic semiconductor film or a mixed film thereof (bulk heterostructure) is used.
  • a plurality of layers there are about 2 to 10 layers, which is a structure in which any one of a P-type organic semiconductor film, an N-type organic semiconductor film, or a mixed film (bulk heterostructure) thereof is laminated, and the layers are layers.
  • a buffer layer may be inserted in.
  • the thickness of the photoelectric conversion layer is usually 50 to 500 nm.
  • the organic semiconductor film of the photoelectric conversion layer has a triarylamine compound, a benzidine compound, a pyrazoline compound, a styrylamine compound, a hydrazone compound, a triphenylmethane compound, a carbazole compound, a polysilane compound, a thiophene compound, and a phthalocyanine, depending on the wavelength band to be absorbed.
  • the condensed polycyclic aromatic compound of the present invention When used as the photoelectric conversion layer, it is preferable to have a HOMO level shallower than the HOMO (Highest Occupied Molecular Orbital) level of the organic semiconductor to be combined described above. This makes it possible to improve the photoelectric conversion efficiency in addition to suppressing the generation of dark current.
  • HOMO Highest Occupied Molecular Orbital
  • the organic thin film layer other than the photoelectric conversion layer constituting the photoelectric conversion unit is a layer other than the photoelectric conversion layer, for example, an electron transport layer, a hole transport layer, an electron block layer, and a hole block. It is also used as a layer, a crystallization prevention layer, an interlayer contact improvement layer, and the like.
  • an element that efficiently converts even weak light energy into an electric signal can be obtained. Therefore, it is preferable.
  • the electron transport layer plays a role of transporting electrons generated in the photoelectric conversion layer to the electrode film and a role of blocking holes from moving from the electrode film of the electron transport destination to the photoelectric conversion layer.
  • the hole transport layer plays a role of transporting generated holes from the photoelectric conversion layer to the electrode film and a role of blocking the movement of electrons from the electrode film of the hole transport destination to the photoelectric conversion layer.
  • the electron block layer plays a role of hindering the movement of electrons from the electrode film to the photoelectric conversion layer, preventing recombination in the photoelectric conversion layer, and reducing dark current.
  • the hole block layer has a function of hindering the movement of holes from the electrode film to the photoelectric conversion layer, preventing recombination in the photoelectric conversion layer, and reducing dark current.
  • the hole block layer is formed by laminating or mixing a hole blocking substance alone or two or more kinds.
  • the hole-blocking substance is not limited as long as it is a compound capable of preventing holes from flowing out from the electrode to the outside of the device.
  • Examples of the compound that can be used for the hole blocking layer include phenanthroline derivatives such as vasophenanthroline and vasocuproin, silol derivatives, quinolinol derivative metal complexes, oxaziazole derivatives, oxazole derivatives, and quinoline derivatives.
  • phenanthroline derivatives such as vasophenanthroline and vasocuproin
  • silol derivatives such as vasophenanthroline and vasocuproin
  • silol derivatives such as vasophenanthroline and vasocuproin
  • silol derivatives such as vasophenanthroline and vasocuproin
  • silol derivatives such as vasoph
  • FIG. 3 shows a typical element structure of the organic photoelectric conversion element of the present invention, but the present invention is not limited to this structure.
  • 1 is an insulating layer
  • 2 is one electrode film
  • 3 is an electron block layer
  • 4 is a photoelectric conversion layer
  • 5 is a hole block layer
  • 6 is the other electrode film
  • 7 is an insulating group.
  • the transistor for reading is not shown in the figure, it suffices if it is connected to the electrode film of 2 or 6, and if the photoelectric conversion layer 4 is transparent, the side opposite to the side on which the light is incident is opposite. It may be formed on the outside of the electrode film of. Light is incident on the photoelectric conversion element from either the upper part or the lower part unless the components other than the photoelectric conversion layer 4 extremely prevent the light of the main absorption wavelength of the photoelectric conversion layer from being incident. But it may be.
  • reaction temperature is the internal temperature in the reaction system unless otherwise specified.
  • EI-MS was measured using ISQ7000 manufactured by Thermo Scientific
  • thermal analysis measurement was performed using TGA / DSC1 manufactured by Metertredo
  • nuclear magnetic resonance (NMR) was measured using JNM-EC400 manufactured by JEOL Ltd. ..
  • the mobility of the field effect transistor was evaluated using B1500 or 4155C, which is a mobility evaluation semiconductor parameter manufactured by Agilent.
  • the surface of the organic thin film was observed using an atomic force microscope (AFM) AFM5400L manufactured by Hitachi High-Technology.
  • AFM atomic force microscope
  • the current and voltage application measurement of the organic photoelectric conversion element in the examples was performed using a semiconductor parameter analyzer 4200-SCS (manufactured by Keithley Instruments).
  • the light-dark ratio in the examples means a current obtained by dividing the current when light irradiation is performed by the current in a dark place.
  • Example 1 Synthesis of condensed polycyclic aromatic compound represented by No. 5 of Specific Example
  • Step 1 Synthesis of 2- (benzo [1,2-b: 5,4-b'] dithiophene-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane THF (140 parts) was mixed with benzo [1,2-b: 5,4-b'] dithiophene (5.0 parts) synthesized by a known method, and 2.8 M normal butyl at ⁇ 75 ° C. under a nitrogen atmosphere. Lithium (10.4 parts) was added and the mixture was stirred for 1 hour.
  • pinacol isopropoxyboronic acid (5.8 parts) was added at ⁇ 75 ° C., and the mixture was stirred for 30 minutes, heated to 20 ° C., and then stirred for another 2 hours.
  • the obtained reaction solution was quenched with water (100 parts) and separated and extracted with chloroform.
  • the obtained organic layer was dried over sodium sulfate, and the solvent was distilled off under reduced pressure.
  • the obtained solid was purified by a silica gel column (developing solvent: toluene) and recrystallized in toluene to obtain 2- (benzo [1,2-b: 5,4-b'] dithiophene-2-. Il) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (3.6 parts, yield 45%) was obtained.
  • Step 2 2,7-Bis (benzo [1,2-b: 5,4-b'] dithiophen-2-yl) [1] benzothioeno [3,2-b] [1] synthesis of benzothiophene DMF (300 parts), water (12 parts), 2,7-diiodo [1] benzothiophene [3,2-b] [1] benzothiophene (1.9 parts) synthesized by the method described in Patent No. 4945757. , 2- (Benzo [1,2-b: 5,4-b'] dithiophene-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane obtained in step 1.
  • Example 2 Synthesis of condensed polycyclic aromatic compound represented by No. 14 of Specific Example
  • Step 3 Synthesis of 2- (benzo [1,2-b: 4,5-b'] dithiophene-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane THF (140 parts) was mixed with benzo [1,2-b: 4,5-b'] dithiophene (5.0 parts) synthesized by a known method, and 2.8 M normal butyl at ⁇ 75 ° C. under a nitrogen atmosphere. Lithium (10.4 parts) was added and the mixture was stirred for 1 hour.
  • pinacol isopropoxyboronic acid (5.8 parts) was added at ⁇ 75 ° C., and the mixture was stirred for 30 minutes, heated to 20 ° C., and then stirred for another 2 hours.
  • the obtained reaction solution was quenched with water (100 parts) and separated and extracted with chloroform.
  • the obtained organic layer was dried over sodium sulfate, and the solvent was distilled off under reduced pressure.
  • the obtained solid was purified by a silica gel column (developing solvent: toluene) and recrystallized in toluene to obtain 2- (benzo [1,2-b: 4,5-b'] dithiophene-2-yl. ) -4,4,5,5-Tetramethyl-1,3,2-dioxaborolane (3.6 parts, yield 45%) was obtained.
  • Step 4 2,7-Bis (benzo [1,2-b: 4,5-b'] dithiophen-2-yl) [1] benzothioenoe [3,2-b] [1] synthesis of benzothiophene DMF (300 parts), water (12 parts), 2,7-diiodo [1] benzothiophene [3,2-b] [1] benzothiophene (1.9 parts) synthesized by the method described in Patent No. 4945757.
  • Example 3 (Preparation of Field Effect Transistor of the Present Invention) No. 1 of the specific example obtained in Example 1 was placed on an n-doped silicon wafer with a Si thermal oxide film surface-treated with 1,1,1,3,3,3-hexamethyldisilazane.
  • the condensed polycyclic aromatic compound represented by 5 was formed into a 100 nm film by resistance heating vacuum deposition.
  • Au was vacuum-deposited on the organic thin film obtained above using a shadow mask to prepare a source electrode and a drain electrode having a channel length of 20 to 200 ⁇ m and a channel width of 2000 ⁇ m, respectively, to prepare the top contact type of the present invention.
  • a field effect transistor (FET) element 1 (configuration shown in FIG. 1B) was made.
  • the thermal oxide film in the n-doped silicon wafer with the thermal oxide film has the function of an insulating layer, and the n-doped silicon wafer also has the functions of the substrate and the gate electrode.
  • Example 4 (Preparation of Field Effect Transistor of the Present Invention) No. of the specific example obtained in Example 1.
  • the condensed aromatic compound represented by No. 5 was used in Example No. 2 obtained in Example 2.
  • the field effect transistor (FET) element 2 of the present invention was produced by a method according to Example 3 except that the compound was changed to the compound represented by 14.
  • Example 1 Manufacturing of Field Effect Transistor for Comparison No. of the specific example obtained in Example 1.
  • the method according to Example 3 was used except that the condensed polycyclic aromatic compound represented by 5 was changed to the compound represented by the following formula (x) synthesized by the method described in JP-A-2018-014474.
  • a field effect transistor (FET) element 3 for comparison was manufactured.
  • Ci is determined by the dielectric constant of the SiO 2 insulating film used
  • Z and L are determined by the device structure of the organic transistor device
  • Id and Vg are determined when measuring the current value of the field effect transistor device
  • Vt is determined by Id and Vg. Can be done.
  • Three field-effect transistor elements are respectively produced on one substrate by the method according to Examples 3 and 4 and Comparative Example 1, and after heating at 120 ° C. for 30 minutes under atmospheric pressure, the above method
  • the carrier mobility ⁇ was measured in.
  • the field-effect transistor elements 1 to 3 used for measuring the carrier mobility ⁇ after heating at 120 ° C. are heated under atmospheric pressure at 150 ° C. for 30 minutes, and then carrier transfer is performed by the above method.
  • the mobility ⁇ was measured.
  • the field-effect transistor elements 1 to 3 subjected to the measurement of the carrier mobility ⁇ after heating at 150 ° C. are heated under atmospheric pressure at 180 ° C. for 30 minutes, and then the carriers are subjected to the above method.
  • the mobility ⁇ was measured.
  • the criteria for determining heat resistance are as follows.
  • the average roughness (Ra) of the thin film was calculated using an AFM analysis program. The results are shown in Table 2. Further, the surface state of the organic thin film for calculating the average roughness used above was observed by AFM (scanning range: 1 ⁇ m). Specific example No. The AFM of the organic thin film containing the condensed polycyclic aromatic compound represented by No. 5 is shown in FIG. The AFM of the organic thin film containing the condensed polycyclic aromatic compound represented by 14 is shown in FIG. 5, and the AFM of the organic thin film containing the compound represented by the formula (x) is shown in FIG.
  • the field-effect transistor of the present invention has better heat resistance than the comparative field-effect transistor.
  • No. 5 and No. The organic thin film containing the condensed polycyclic aromatic compound of the present invention represented by 14 has a smaller change in average roughness before and after the heating test than the organic thin film containing the compound represented by the comparative formula (x). Recognize. This includes the image observed by the AFM of the organic thin film containing the condensed polycyclic aromatic compound of the present invention shown in FIGS. 4 and 5 and the compound represented by the comparative formula (x) shown in FIG. It is clear from the comparison with the image observed by AFM of the organic thin film.
  • Example 5 (Preparation and evaluation of an organic photoelectric conversion element of the compound represented by No. 5 of the specific example obtained in Example 1)
  • ITO transparent conductive glass manufactured by Geomatec Co., Ltd., ITO film thickness 150 nm.
  • the condensed polycyclic aromatic compound represented by 5 was formed into a film having a film thickness of 90 nm by resistance heating vacuum deposition.
  • aluminum was vacuum-deposited at 100 nm as an electrode to produce the organic photoelectric conversion element of the present invention.
  • As an electrode of ITO and aluminum by applying a voltage of 5V, contrast ratio when an emission light wavelength was 460nm of light irradiation was 4.4 ⁇ 10 5.
  • Comparative Example 2 (Preparation and evaluation of organic photoelectric conversion element for comparison) No. of the specific example obtained in Example 1. Comparison was performed by a method according to Example 4 except that the condensed polycyclic aromatic compound represented by 5 was changed to a compound represented by the formula (x) synthesized by the method described in JP-A-2018-014474. An organic photoelectric conversion element for use was prepared and evaluated. Contrast ratio was 3.8 ⁇ 10 4.
  • Example 6 Synthesis of condensed polycyclic aromatic compound represented by No. 13 of Specific Example (Step 5) Synthesis of intermediate compound represented by the following formula a Benzo [1,2-b: 5,4-b'] difuran (0.84 part) synthesized in THF (30 parts) by a known method.
  • 1.6 M normal butyllithium 2.5 parts was added at ⁇ 75 ° C. under a nitrogen atmosphere, and the mixture was stirred for 1 hour.
  • carbon tetrabromide (1.9 parts) was added at ⁇ 75 ° C., and the mixture was stirred for 10 minutes, heated to 20 ° C., and then stirred for another 30 minutes.
  • the obtained reaction solution was quenched with water (30 parts) and separated and extracted with ethyl acetate.
  • the obtained organic layer was dried over sodium sulfate, and the solvent was distilled off under reduced pressure.
  • the obtained solid was purified by a silica gel column (developing solvent: hexane) to obtain an intermediate compound represented by the following formula a (1.1 parts, yield 87%).
  • Step 6 No. of a specific example. Synthesis of condensed polycyclic aromatic compound represented by 13 Water (2 parts) in DMF (48 parts), compound represented by the following formula b synthesized by a known method (0.66 parts), in step 5. The obtained intermediate compound represented by the formula a (0.96 parts), tripotassium phosphate (1.1 parts), and tetrakis (triphenylphosphine) palladium (0.09 parts) are mixed to create a nitrogen atmosphere. Below, it was stirred at 80 ° C. for 6 hours. After cooling the obtained reaction solution to room temperature, water (50 parts) was added and the solid content was filtered and separated. The obtained solid content was washed with acetone, dried, and then sublimated and purified to obtain No. 1 of the above specific example. A compound represented by No. 13 (0.24 part, yield 32%) was obtained.
  • Example 7 Synthesis of condensed polycyclic aromatic compound in which a phenyl group is substituted on both terminal furan rings of No. 13 of Specific Example.
  • Step 7 Synthesis of intermediate compound represented by the following formula c
  • THF 40 parts
  • the intermediate compound (1.5 parts) represented by the formula a obtained in step 5 and phenylboronic acid (0 parts) are added.
  • .94 parts and 2M aqueous potassium carbonate solution (20 parts) were mixed and stirred under a nitrogen atmosphere. Tetrakis (triphenylphosphine) palladium (0.37 part) was added thereto, the temperature was raised to the reflux temperature, and the mixture was stirred for 3 hours.
  • Tetrakis (triphenylphosphine) palladium (0.37 part) was added thereto, the temperature was raised to the reflux temperature, and the mixture was stirred for 3 hours.
  • Step 8 Synthesis of Intermediate Compound Represented by Formula D below
  • the intermediate compound represented by Formula c (1.1 parts) obtained in Step 7 is mixed with THF (24 parts) under a nitrogen atmosphere.
  • 1.6 M normal butyllithium (2.1 parts) was added at ⁇ 75 ° C., and the mixture was stirred for 1 hour.
  • carbon tetrabromide (1.7 parts) was added at ⁇ 75 ° C. and stirred for 10 minutes, the temperature was raised to 20 ° C., and the mixture was further stirred for 30 minutes.
  • the resulting reaction was quenched with water (30 parts) and extracted twice with ethyl acetate (30 parts).
  • the obtained organic layer was dried over sodium sulfate, and the solvent was distilled off under reduced pressure.
  • the obtained solid was purified by a silica gel column (developing solvent: chloroform) to obtain an intermediate compound represented by the following formula d (0.99 parts, yield 64%).
  • Step 9 The following formula No. Synthesis of condensed polycyclic aromatic compound represented by 13-Ph Water (2 parts) in DMF (54 parts), compound represented by the following formula b synthesized by a known method (0.53 parts), step.
  • the intermediate compound (0.85 part), tripotassium phosphate (1.7 part), and tetrakis (triphenylphosphine) palladium (0.16 part) obtained by the formula d obtained in 8 were mixed and mixed.
  • the mixture was stirred at 80 ° C. for 5 hours in a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, water (50 parts) was added and the solid content was filtered and separated. The obtained solid content was washed with acetone, dried, and then sublimated and purified to obtain the following formula No.
  • a compound represented by 13-Ph (0.33 parts, yield 44%) was obtained.
  • Example 8 Synthesis of a condensed polycyclic aromatic compound in which a phenyl group is substituted on both terminal thiophene rings of No. 14 of Specific Example
  • Step 10 Synthesis of intermediate compound represented by the following formula f
  • THF 40 parts
  • the intermediate compound 2.0 parts represented by the formula e obtained by the same method as in step 3 and iodobenzene.
  • 1.6 parts and 2M aqueous potassium carbonate solution (20 parts) were mixed and stirred under a nitrogen atmosphere. Tetrakis (triphenylphosphine) palladium (0.37 part) was added thereto, the temperature was raised to the reflux temperature, and the mixture was stirred for 3 hours.
  • Step 11 Synthesis of Intermediate Compound Represented by Formula g below
  • An intermediate compound represented by Formula f (1.2 parts, 4.51 mmol) obtained in Step 10 was mixed with THF (45 parts).
  • 1.6 M normal butyllithium (2.0 parts) was added at ⁇ 75 ° C. under a nitrogen atmosphere, and the mixture was stirred for 1 hour.
  • pinacol isopropoxyboronic acid (0.92 part) was added at ⁇ 75 ° C. and the mixture was stirred for 30 minutes, the temperature was raised to 20 ° C., and the mixture was further stirred for 2 hours.
  • reaction solution was quenched with a saturated aqueous solution of ammonium chloride (50 parts), and separated and extracted with ethyl acetate.
  • organic layer was dried over sodium sulfate, and the solvent was distilled off under reduced pressure.
  • the obtained solid was purified by a silica gel column (developing solvent: chloroform) to obtain a compound represented by the following formula g (0.97 part, yield 55%).
  • Step 12 The following formula No. Synthesis of condensed polycyclic aromatic compound represented by 14-Ph Water (1.6 parts) was added to DMF (43 parts), and the compound represented by the following formula h (0.43 parts) synthesized by a known method. , The intermediate compound (0.85 parts, 2.17 mmol) of the formula g obtained in step 11, tripotassium phosphate (1.4 parts), and tetrakis (triphenylphosphine) palladium (0.12). Part) was mixed, and the mixture was stirred at 90 ° C. for 6 hours under a nitrogen atmosphere. After cooling the obtained reaction solution to room temperature, water (50 parts) was added and the solid content was filtered and separated. The obtained solid content was washed with acetone, dried, and then sublimated and purified to obtain the following formula No. A compound represented by 14-Ph (0.19 part, yield 29%) was obtained.
  • Example 9 Synthesis of condensed polycyclic aromatic compound represented by No. 16 of Specific Example
  • Step 13 Synthesis of intermediate compound represented by the following formula i Naft [2,3-b: 6,7-b'] difuran (1.0 part) synthesized in THF (50 parts) by a known method.
  • 1.6 M normal butyllithium 2.2 parts
  • carbon tetrabromide 1.8 parts
  • the obtained reaction solution was quenched with water (30 parts) and separated and extracted with ethyl acetate.
  • the obtained organic layer was dried over sodium sulfate, and the solvent was distilled off under reduced pressure.
  • the obtained solid was purified by a silica gel column (developing solvent: hexane) to obtain a compound represented by the following formula i (1.0 part, yield 73%).
  • Step 14 No. of a specific example. Synthesis of condensed polycyclic aromatic compound represented by 16 Water (2 parts) in DMF (48 parts), compound represented by the following formula b synthesized by a known method (0.57 parts), in step 13. The obtained intermediate compound represented by the formula i (1.0 part), tripotassium phosphate (1.0 part) and tetrakis (triphenylphosphine) palladium (0.09 part) are mixed and subjected to a nitrogen atmosphere. , 80 ° C. for 6 hours. After cooling the obtained reaction solution to room temperature, water (50 parts) was added and the solid content was filtered and separated. The obtained solid content was washed with acetone, dried, and then sublimated and purified to obtain No. 1 of the above specific example. A compound represented by 16 (0.27 part, yield 34%) was obtained.
  • Example 10 Synthesis of condensed polycyclic aromatic compound represented by No. 17 of Specific Example
  • Step 15 Synthesis of intermediate compound represented by the following formula j Naft [2,3-b: 6,7-b'] difuran (1.5 parts) synthesized by a method known to THF (50 parts).
  • 1.6 M normal butyllithium 2.9 parts was added at ⁇ 75 ° C. under a nitrogen atmosphere, and the mixture was stirred for 1 hour.
  • carbon tetrabromide (2.3 parts) was added at ⁇ 75 ° C. and stirred for 10 minutes, the temperature was raised to 20 ° C., and the mixture was further stirred for 30 minutes.
  • the obtained reaction solution was quenched with water (30 parts) and separated and extracted with ethyl acetate.
  • the obtained organic layer was dried over sodium sulfate, and the solvent was distilled off under reduced pressure.
  • the obtained solid was purified by a silica gel column (developing solvent: hexane) to obtain an intermediate compound represented by the following formula j (1.3 parts, yield 64%).
  • Step 16 No. of a specific example. Synthesis of condensed polycyclic aromatic compound represented by 17 In DMF (48 parts), water (2 parts), a compound represented by the following formula b synthesized by a known method (0.37 parts), in step 15. The obtained intermediate compound represented by the formula j (0.7 parts), tripotassium phosphate (0.6 parts) and tetrakis (triphenylphosphine) palladium (0.05 parts) are mixed and subjected to a nitrogen atmosphere. , 80 ° C. for 6 hours. After cooling the obtained reaction solution to room temperature, water (50 parts) was added and the solid content was filtered and separated. The obtained solid content was washed with acetone, dried, and then sublimated and purified to obtain No. 1 of the above specific example. The compound represented by 17 (0.13 part, yield 24%) was obtained.
  • Example 11 (Preparation of Field Effect Transistor of the Present Invention) No. of the specific example obtained in Example 1.
  • the condensed aromatic compound represented by No. 5 was used in Example No. 6 obtained in Example 6.
  • the field effect transistor (FET) element 4 of the present invention was produced by a method according to Example 3 except that the compound was changed to the compound represented by 13.
  • Example 12 (Preparation of Field Effect Transistor of the Present Invention) No. of the specific example obtained in Example 1.
  • the condensed aromatic compound represented by No. 5 was obtained in Example 7.
  • the field effect transistor (FET) element 5 of the present invention was produced by a method according to Example 3 except that the compound was changed to the compound represented by 13-Ph.
  • Example 6 Heat resistance test of organic thin film No. of the specific example obtained in Example 6.
  • the condensed polycyclic aromatic compound represented by No. 13 and No. 1 obtained in Example 7.
  • 100 nm organic thin films were prepared on n-doped silicon wafers with oxide films.
  • the organic thin film obtained above is heated at 120 ° C. for 30 minutes under atmospheric pressure and then cooled to room temperature, then heated at 150 ° C. for 30 minutes under atmospheric pressure and then cooled to room temperature. Then, after further heating at 180 ° C.
  • the average roughness (Ra) of the thin film was calculated using an AFM analysis program. The results are shown in Table 4. Further, the surface state of the organic thin film for calculating the average roughness used above was observed by AFM (scanning range: 1 ⁇ m). Specific example No. The AFM of the organic thin film containing the condensed polycyclic aromatic compound represented by No. 13 is shown in FIG. The AFMs of organic thin films containing condensed polycyclic aromatic compounds represented by 13-Ph are shown in FIG. 8, respectively.
  • Example 13 (Preparation and evaluation of an organic photoelectric conversion element of the compound represented by No. 13 of the specific example obtained in Example 6) No. of the specific example obtained in Example 1.
  • the organic photoelectric conversion element of the present invention was prepared and evaluated by a method according to Example 5 except that the compound was changed to the compound represented by 13. Contrast ratio was 5.4 ⁇ 10 4.
  • Example 14 (Preparation and evaluation of an organic photoelectric conversion element of the compound represented by No. 13-Ph obtained in Example 7) No. of the specific example obtained in Example 1.
  • the condensed polycyclic aromatic compound represented by No. 5 was obtained in Example 7.
  • the organic photoelectric conversion element of the present invention was prepared and evaluated by the method according to Example 5 except that the compound was changed to the compound represented by 13-Ph. Contrast ratio was 5.0 ⁇ 10 4.
  • a condensed polycyclic aromatic compound having excellent heat resistance in a practical process temperature range, an organic thin film containing the compound, and an organic semiconductor device having the organic thin film (field effect transistor, organic photoelectric conversion element). ) can be provided.

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Abstract

Le but de la présente invention est de fournir : un composé aromatique polycyclique fusionné ayant une excellente résistance à la chaleur dans une plage de température de traitement pratique ; une couche mince organique contenant ledit composé ; et un dispositif semi-conducteur organique (transistor à effet de champ, élément de conversion photoélectrique organique) comprenant ladite couche mince organique. La présente invention comprend un composé aromatique polycyclique fusionné représenté par la formule générale (1) : (Dans la formule (1), concernant R1 et R2, l'un représente un atome d'hydrogène et l'autre représente un substituant représenté par la formule générale (2) ou (3) : (dans les formules (2) et (3), n représente un nombre entier de 0 à 2, X représente un atome d'oxygène, un atome de soufre ou un atome de sélénium, R3 représente un atome d'hydrogène ou un groupe hydrocarboné aromatique substitué ou non substitué)).
PCT/JP2021/006291 2020-02-28 2021-02-19 Composé aromatique polycyclique fusionné WO2021172185A1 (fr)

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