TW200808697A - Novel fluorine-containing aromatic compounds, organic semiconductor materials, and organic thin film devices - Google Patents

Abstract

The invention provides p-conjugated compounds which each consist of a carboaromatic group and a fluorine-containing aromatic group which are bonded to each other and which exhibit excellent carrier mobility when used in organic thin film devices as the organic semiconductor material; and organic semiconductors materials made by using the p-conjugated compounds as the charge transport material. Fluorine-containing aromatic compounds represented by the general formula (1) (wherein ArF is a perfluorinated aromatic group (with the proviso that the fluorine atoms of the perfluorinated aromatic group may be replaced by perfluoroalkyl); n is an integer of 1 to 4; Q is an n-valent aromatic group derived from a structure represented by the general formula (2) by removing n hydrogen atoms (with the proviso that the hydrogen atoms of the aromatic group may be replaced by alkyl of 1 to 8 carbon atoms or fluorine-containing alkyl of 1 to 8 carbon atoms); and p is an integer of 0 to 4); and organic semiconductor materials containing the fluorine -containing aromatic compounds.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to novel fluorine-containing aromatic compounds, organic semiconductor materials and organic thin film devices which are applicable to organic thin film devices. [Prior Art] In recent years, development of organic electronic components using organic compounds as semiconductor materials has been achieved. In the application example, it is expected to be an organic EL element (organic electroluminescence element) which is expected to be a flat right-angle display, and an organic thin film solar cell which is a lightweight and flexible power source, and is used for pixel driving of a display. Thin Film Transistor (TFT) can be manufactured by a low-cost process such as printing, and an organic thin film transistor (hereinafter referred to as "organic TFT") which can be noticed in response to a flexible substrate. The organic compound is easy to process as compared with the inorganic material, and it is expected to realize a low-cost device by using an organic compound as a semiconductor material. Further, regarding a semiconductor device using an organic compound, it can be applied to a plurality of substrates including a plastic substrate because it can be mounted at a low temperature. Further, since the semiconductor material of the organic compound is soft in structure, it is expected to realize a device such as a flexible display by using a plastic substrate and a semiconductor material of an organic compound in combination. In general, in order to increase the lifetime of the organic EL element, the low driving voltage, the low threshold voltage of the organic TFT element, the switching speed, and the like, the carrier mobility of the organic semiconductor material is required to be improved. Organic semiconductor materials -6 - 200808697 Body mobility is generally low, but in recent years, the use of pentacene-based organic TFT elements has achieved a fairly amorphous mobility (> 1.0cm2 / Vs) (Reference Non-patent document i). Among the organic semiconductor materials, there is no effective method for improving the mobility of the carrier, but it is important to enhance the interaction between molecules and control the molecular arrangement. Specifically, an example in which a conjugated system is expanded by a planar structure and a condensed polycyclic compound such as pentacene having a strong intermolecular interaction by a π-stacking effect is used (refer to Non-Patent Document 1), and An example in which the electron-attracting aromatic group and the electron-donating aromatic are coexistent in the molecule, and the charge is shifted, not only the intermolecular interaction is improved, but also the molecular arrangement can be controlled (see Non-Patent Document 2). Further, in terms of a method for improving the intermolecular interaction, an interaction of a fluorine-containing aromatic group and a hydrocarbon aromatic group is known (for example, refer to Non-Patent Document 3). However, this interaction is used in the case of improving the mobility of the organic semiconductor material, and there is an example in which a fluorine atom is introduced into the pentacene skeleton, but the carrier mobility cannot be said to be sufficiently high (refer to Non-Patent Document 4). Further, the organic semiconductor material is generally a p-type semiconductor material having a hole transporting property, and an n-type semiconductor material having electron transporting properties is scarce. In particular, in terms of the characteristics of the n-type semiconductor, tetradecanoic acid dianhydride or a diimine derivative thereof, fullerene (C 6 0 ), and a copper oxyfluoride dye are known as 'gasification and Wubensi' but The carrier-carrying degree has a high degree of stability in the atmosphere, and there is a problem as a practical material for an organic thin film device. -7 - 200808697 (refer to Non-Patent Document 5). [Non-Patent Document 1] DJ Gundlach, SF Nelson, J. Jachson, Appl. Phys. Lett, (2002), 80, 2925. [Non-Patent Document 2] H. Tada, Y. Yamashita et al · Materials Research Society Symposium Proceedings, (2002), 725, 143.

[Non-Patent Document 3] G.W. Coates, J.W. Ziller, R.H.Grubbs et al.?J.Am.Chem.Soc.? (1 99 8 ), 1 20,3 64 1.

[Non-Patent Document 4] J_E. Anthony, G.G. Malliaras et al., Org. Lett., (2005), 7 (15), 3 1 63.

[Non-Patent Document 5] HE Katz, et al., Nature, (2000), 404, 478. [Disclosure] [The subject of the invention] The present invention provides, can be used as a solution to the problems of the above prior art. An organic semiconductor material, a π-conjugated compound in which a hydrocarbon aromatic group and a fluorine-containing aromatic group are combined, and an organic semiconductor material excellent in carrier mobility and the like using the π-conjugated compound as a charge transport material. Further, the present invention has an object of providing a high performance organic thin film device containing the above organic semiconductor material. [Means for Solving the Problem] -8-200808697 As a result of efforts to achieve this goal, the inventors have found that a specific fluorine-containing aromatic compound is used as an organic thin film device of an organic semiconductor material, and has n-type semiconductor characteristics and height. The carrier mobility is completed to complete the present invention. That is, the present invention is mainly directed to the following (i) to (vii). (i) a fluorine-containing aromatic compound characterized by the following formula (1): [Chemical Formula 1]

Q

(1)

ArF is a perfluoroaromatic group (however, the fluorine atom in the perfluoroaromatic group may be substituted by a perfluoroparent group); η is an integer of 1 to 4; and Q is represented by the following formula (2) Constructing a valence aromatic group obtained by removing η hydrogen atoms (however, the hydrogen atom in the aromatic group may be substituted by an alkyl group having 1 to 8 carbon atoms or a fluorine-containing alkyl group having 1 to 8 carbon atoms); ? For the 〇~4 integer. Mi

(2) (ii) The fluorine-containing aromatic compound of (i), wherein η is 2. (iii) the fluorine-containing aromatic compound of (ii), wherein the perfluoro aromatic group selected from the group consisting of ArF-based perfluorophenyl, perfluoronaphthyl' and perfluorobiphenyl, P is 〇 Or 1. (iv) The fluorine-containing aromatic compound of (iii), wherein p is 〇-9-200808697, and the bonding position of Q-C tri-C-ArF in Q is 2 and 6 positions. (v) A fluorine-containing aromatic compound of (iii), wherein p is 1, and the bonding position of -C=C-ArF in Q is 2 and 6 or 9 and 10 is Vi(Vi) such as The fluorine-containing aromatic compound of the formula (1), wherein the fluorine-containing aromatic compound represented by the formula (1) is a compound represented by the following formula (1 1 ), and a compound represented by the following formula (12), The compound represented by the formula (13) is selected from the group consisting of a compound represented by the following formula (14), a compound represented by the following formula (15), and a compound represented by the following formula (16). Compound. -10- 200808697 [化3]

(vii) An organic semiconductor material characterized by containing a fluorine-containing aromatic compound according to any one of (i) to (vi). (viii) an organic thin film device comprising an organic thin film device having a gate electrode, a gate insulating layer, an organic semiconductor layer, a source electrode and a drain electrode organic thin film transistor on a substrate, characterized in that the organic semiconductor device The layer contains the fluorine-containing aromatic compound of any one of (i) to (vi). (ix) An organic thin film device comprising an organic compound layer having an organic compound layer of one or more layers of an anode 11 - 200808697 ' on a substrate, and an organic EL element of a cathode, characterized by the organic compound The layer contains the fluorine-containing aromatic compound of any one of (i) to (vi). [Effect of the Invention] The fluorine-containing aromatic compound of the present invention and the organic semiconductor material of the present invention have high carrier mobility when used as a charge transporting material, and have high-performance organic TFTs, organic EL elements, and the like because of electron transport properties. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail by way of representative examples. First, the fluorine-containing aromatic compound of the present invention will be described. The fluorine-containing aromatic compound of the present invention is a compound represented by the following formula (1). In the present specification, the "compound represented by the formula (1)" or the like is represented by "compound (1)" or the like. (1) In the compound (1), ArF is a perfluoroaromatic group. Here, the "perfluoro aromatic group" means a hydrogen atom in which all of the aromatic monovalent hydrocarbon groups are replaced by a fluorine atom. However, the fluorine atom in the perfluoroaromatic group may be substituted by a perfluoroalkyl group. In this case, the perfluoroalkyl group has a carbon number of 1 to 8, and a linear or branched alkyl group of 1 to 4 is preferred. ArF is preferably selected from the group consisting of unsubstituted perfluorophenyl, unsubstituted perfluoronaphthyl and unsubstituted perfluorobiphenyl (--12-200808697 C6F4C6F5). More preferably, it is an unsubstituted perfluorophenyl group or an unsubstituted perfluoronaphthyl group. In the compound (1), η is an integer of from 1 to 4. n is preferably 1 or 2, and more preferably 2. In the compound (1), Q is an η-valent aromatic group obtained by removing η hydrogen atoms from the structure represented by the following formula (2). However, the hydrogen atom in the aromatic group is preferably 1 to 8 carbon atoms, preferably 1 to 4 alkyl groups or 1 to 8 carbon atoms, and preferably 1 to 4 fluorine-containing alkyl groups. . [Chemical 5]

Here, Ρ is an integer of 〇~4. Ρ is 0 or 1 is better. In the Q aspect, η is 2, and ρ is 0 or 1. Further, η is 2, ρ is 〇 or 1, and the hydrogen atom in the aromatic group is preferably unsubstituted. In the compound (1), the molecules in the crystal structure are preferably arranged in a regular arrangement. Therefore, it is preferable that the molecular symmetry is high, and from the viewpoint of molecular symmetry, the binding position of -C^C-ArF in Q, η When 2, ρ is 〇, 2 and 6 are preferred; further, η is 2, and ρ is 1, preferably 2 and 6 or 9 and 10 are preferred. Further, in the case of the compound (1), a compound represented by the following formula (11), a compound represented by the following formula (1 2 ), a compound represented by the following formula (1 3 ), and the following formula (14) The compound shown by the formula, the compound represented by the following formula (15), and the compound represented by the following formula (16) are preferably selected from the group consisting of -13 to 200808697. [Chemical 6]

The method for producing the compound (1) is not particularly limited. It can be produced by the following method. For example, in the case where n is 1 in the compound (1), it can be produced by the following method (1) or (2). (1) A method of performing a coupling reaction with an ethynyl compound having an active proton as shown in the following formula (a) or (b): QC^C-H+ L-ArF QC = C-ArF+ HL (a) -14 - 200808697 or QL + H-CEC-ArF QC Tri-C-ArF+HL (b) Here, ArF&Q has the same meaning as in the above formula (1), and 1> is a leaving group. The leaving group L is a halogen atom such as a chlorine atom, a bromine atom or an iodine atom. The catalyst for the coupling reaction is preferably a transition metal of palladium, copper, platinum, nickel or the like, a salt thereof or a complex thereof. The catalyst may be used alone or in combination of two or more. In the case of mixing two or more kinds of examples, a palladium catalyst having a valence of tetrakis(triphenylphosphine)palladium (iridium) or the like is mixed with a transition metal salt such as copper bromide or copper iodide. Alternatively, a lithium halide salt such as lithium bromide or lithium iodide may be used in the above catalyst. Further, in terms of the solvent of the above coupling reaction, it is preferred to capture the formed HL, and a solvent of an amine is generally used. Specifically, for example, triethylamine, diisopropylamine, pyrrolidine, acridine, acridine or the like can be used. Alternatively, these may be mixed with other solvents. In this case, other aprotic solvents such as benzene, toluene or tetrahydrofuran are preferably used. The reaction temperature of the reaction is preferably carried out at 30 to 150 °C. Among them, it is preferred to carry out heating at a temperature of 70 to 100 °C. The compound of the formula Q-C = C-H in the formula (a) can be produced by the following method. QL + —+ HL (c) Q«C = CC(CH3)2〇H->QC = CH + 0= C(CH3)2 (d) -15- 200808697 Here, ArF, Q and L are each It has the same meaning as in the above formula (a). The reaction represented by the reaction formula (c) is a coupling reaction, and can be carried out under the same conditions as the coupling reaction represented by the above formula (a) or (b). The reaction represented by the reaction formula (d) is a reaction for forming an ethynyl group via deacetation, and is usually carried out under basic conditions. The base to be used may be potassium hydroxide, sodium hydroxide, calcium hydroxide, potassium carbonate or sodium carbonate, and potassium hydroxide or sodium hydroxide is preferred from the viewpoint of alkali strength. Further, the reaction is preferably carried out by rapidly removing the produced acetone from the system, and it is preferred to carry out the heating under reduced pressure. The reaction pressure is preferably in the range of 0.01 to 0.5 Pa, more preferably in the range of 0.3 to 0.5 Pa. The reaction temperature is preferably carried out at 30 to 200 ° C, and heating at 100 to 150 ° C is preferred. The compound represented by the formula H-CEC-ArF in the reaction formula (b) can also be produced in the same manner. (2) A method of using a nucleophilic substitution reaction accompanying detachment of a fluorine atom as shown in the following formula:

Q-C = C- M~l· F-Ar^ —> Q-C III C-ArF+ MF Here, 八 and Q are the same as those in the above formula (1), and Μ represents a monovalent metal. For the one-valent metal ruthenium, lithium, potassium, sodium, or the like can be used. The nucleophilic substitution reaction is preferably carried out at a low temperature in an aprotic polar solvent. The reaction temperature is preferably -80 to 10 ° C, more preferably -16 to 200808697 2 0 ° C to 5 ° C. In the solvent aspect of the reaction, it is preferred to use an aprotic polar solvent. Specifically, for example, diethyl ether, t-butyl methyl ether, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl hydrazine is used. Next, an organic semiconductor material according to the present invention and an organic thin film device of the present invention will be described. The organic semiconductor material of the present invention is an organic semiconductor material containing the above compound (1). The organic semiconductor material of the present invention may be a compound (1). For example, it may be mixed with other organic semiconductor materials, or may contain various kinds of dopants. In the case of a dopant, for example, when used as a light-emitting layer of an organic EL device, coumarin, quinacridone, Rubrene, a diphenylethylene derivative, a fluorescent dye, or the like can be used. Next, an organic thin film device according to the present invention will be described. The organic thin film device of the present invention is an organic thin film device using the organic semiconductor material of the present invention. That is, the organic thin film device of the present invention is an organic thin film device containing the compound (1). Specifically, the organic thin film device of the present invention has at least one organic layer, and at least one of the organic layers contains the above compound (1). The organic thin film device of the present invention can be in various forms, but one of the suitable types is an organic TFT. More specifically, an organic thin film device comprising an organic TFT having a gate electrode, a gate insulating layer, an organic semiconductor layer, a source electrode, and a germanium electrode on the substrate, for example, the organic thin film 4J containing the compound (1) -+· pyt device. -17- 200808697 Compound (1) achieves large intermolecular interaction and high carrier mobility by interaction of a perfluoroaromatic group represented by ArF with a hydrocarbon aromatic group represented by Q. The organic semiconductor layer (organic active layer) of the TFT is effective. Further, the compound (1) has an electron accepting property and electron transporting property by the electron affinity of the fluorine-containing aromatic group, and can be used as an n-type semiconductor. The substrate is not particularly limited, and may be composed of a conventional composition. In terms of substrates, such as glass (eg, quartz glass), tantalum, ceramics, plastics. In terms of plastics, for example, polyethylene phthalate, polyethylene naphthalene, polycarbonate, and the like are widely used as resin substrates. It is preferable that the resin substrate is formed by laminating a gas barrier film for reducing gas permeability such as oxygen or water vapor. The gate electrode is not particularly limited and, for example, may be constituted by a known one. For the gate electrode, for example, gold, platinum, chromium, tungsten, giant, nickel, copper, aluminum, silver, magnesium, calcium, etc., alloys thereof, polyfluorene, amorphous germanium, graphite, indium tin oxide ( Hereinafter, it is referred to as "ΙΤΟ"), a material such as zinc oxide or a conductive polymer. The gate insulating layer is not particularly limited. For example, it can be constituted by a known one. For the gate insulating layer, SiO 2 , Si 3 N 4 , SiON, Al 2 〇 3 ' Ta 205, amorphous ruthenium, polyimide resin, polyvinyl phenol resin, parylene resin, polymethyl methacrylate resin, fluorine can be used. Resin (PTFE ' PFA, PETFE, PCTFE, CYTOP (registered trademark), etc.) and other materials. -18- 200808697 The organic semiconductor layer is not particularly limited as long as it contains the layer of the compound (1). For example, a layer composed only of the compound (1) may be used, and a layer containing a substance other than the compound (1) may be used. Any of the source electrode and the ruthenium electrode is not particularly limited, and may be, for example, a known one. For the source electrode and the yttrium electrode, either of them can be used in gold, white gold, chrome, crane 'group ^ 錬 'copper ' brocade, silver 'table' or the alloy of the temple or the temple of the temple, poly 矽, amorphous 矽, graphite, ITO, zinc oxide, conductive polymers and other materials. The organic TFT has a structure in which the gate layer, the gate insulating layer, the organic semiconductor layer, the source electrode, and the germanium electrode are sequentially arranged from the substrate side (1); the gate electrode and the gate insulating layer are provided from the substrate side. The source electrode, the germanium electrode, and the organic semiconductor layer are sequentially configured (2); and have an organic semiconductor layer, a source electrode, a germanium electrode, a gate insulating layer, and a gate electrode in the order of the substrate (3): and have a slave substrate Any one of the source electrode and the ytterbium electrode, the organic semiconductor layer, the gate insulating layer, and the gate electrode may be formed in the order of (4). The machine has a layered limit and the method of the semi-conductor has a layer-edge absolute gate, and the pole-electrical gate is based on the condition of the electric source. 8 Ann source system and, the state of the structure 〇 method f [f of the layer 澧 SHn semi-finished machine has a layer source edge to touch the bottom of the gate, the pole of the electric layer gate sequence will be 0 pole power and 极 极 极The gate of the sluice gate or the square gate of the sluice gate or the method of the smashing of the sluice gate rf and the pole power source method are not formed by the method of forming the -19-200808697, and any one of them can be used as described above. The material is formed by a known film production method such as a vacuum evaporation method, an electron beam evaporation method, an RF sputtering method, a spin coating method, or a printing method. The method for forming the organic semiconductor layer is not particularly limited. It is formed by using a known method for producing a film such as the above-mentioned compound (1) by a vacuum evaporation method, a spin coating method, an inkjet method, or the like. The compound (1) has a chemical structure in which a perfluoroaromatic group represented by ArF and a hydrocarbon aromatic group represented by Q are arranged to some extent, and a perfluoroaromatic group and a hydrocarbon aromatic The interaction of the base has a crystal structure in which a perfluoroaromatic group and a hydrocarbon aromatic group are alternately stacked and laminated. Therefore, if the intermolecular interaction is large, the π electron orbitals between the molecules can be expected to have high carrier mobility by overlapping. Therefore, this material is used for an organic semiconductor layer (also referred to as an "organic active layer") of an organic TFT (electrical effect transistor), and a large electrical boundary effect mobility characteristic can be realized. The organic thin film of the present invention is formed of an organic TFT. The use of the device is not particularly limited, and is suitable as a TFT for flexible display driving using a plastic substrate. In general, it is difficult to fabricate a TFT made of an inorganic material on a plastic substrate. However, in the production process of the organic thin film device of the present invention made of an organic TFT, a vacuum evaporation method, a spin coating method, an inkjet method, a printing method, and the like are used as described above, and a plastic process is not used because of a high-temperature process. A TFT for driving a pixel is formed on the substrate. In particular, the compound (1) used in the present invention is soluble in a general-purpose organic solvent such as chloroform or tetrahydrofuran, and is suitable for use in a low-cost process such as a spin coating method, an inkjet method, or a printing method, in the case of -20-200808697. The production of paper-based (flexible) displays such as inexpensive. One of other applications of the organic thin film device containing the compound (1) of the present invention is, for example, an organic EL device. Specifically, an organic thin film device comprising an organic EL layer having an anode, an organic compound layer having one or more layers, and a cathode, wherein the organic compound layer is an organic thin film device substrate containing the compound (1), The anode and the cathode are not particularly limited, and any of them may be a conventionally known configuration. The substrate is not particularly limited, and, for example, it can be constituted by a conventionally known one. For the substrate, for example, a transparent material such as glass or plastic is used as one of the applicable types. Further, in the case where the cathode has permeability and the cathode side emits light, a material other than the transparent material such as ruthenium may be used. The anode is not particularly limited, and, for example, it can be constituted by a conventionally known one. Specifically, a material that transmits light is used. More specifically, IT ◦, indium oxide, tin oxide, indium oxide, and zinc oxide are preferred. Or a film of a metal such as gold, platinum, silver or magnesium alloy; or a polymer organic material such as polyaniline, polythiophene, polypyrrole or a derivative thereof. The cathode is not particularly limited, and, for example, it can be constituted by a conventionally known one. Specifically, an alkali metal such as Li, K or Na having a low work function; an alkaline earth metal such as Mg or Ca is suitably used from the viewpoint of electron injectability. Further, a halide of an alkali metal such as LiF, LiCl, KF, KC1, NaF or NaCl is preferable to a metal such as A1 which can be set thereon. -21 - 200808697 The organic compound layer has a structure of one or more layers, and the layer constitution thereof is not particularly limited, and it can be constituted by a conventionally known one. For example, a one-layer structure formed by the light-emitting layer from the anode side to the cathode side; a two-layer structure formed by the hole transport layer/light-emitting layer; a two-layer structure formed by the light-emitting layer/electron transport layer; and a hole transport layer Three-layer structure formed by the light-emitting layer/electron transport layer; four-layer structure formed by the hole injection layer/hole transport layer/light-emitting layer/electron injection layer; hole injection layer/hole transport layer/light-emitting layer/ The 5-layer structure formed by the electron transport layer/electron injection layer is typical. As described above, the organic compound layer contains the above compound (1). In the organic compound layer, at least one of the layers used in the above various layer constitutions may contain the compound (1). For example, in the case of the above five-layer structure, at least one layer of the compound (1) selected from the group consisting of the hole injection layer, the hole transport layer, the light-emitting layer, the electron transport layer, and the electron injection layer may be used. In the organic compound layer, one type or two or more types of the above compound (1) can be used. Further, in the organic compound layer, a light-emitting organic compound other than the compound (1) can be used. The luminescent organic compound other than the compound (1) is not particularly limited, and, for example, those conventionally known can be used. The organic compound layer may be composed of at least one layer containing the compound (1), and each layer may be conventionally known. Hereinafter, an example in which the organic compound layer has a five-layer structure will be described. However, the invention is not limited thereto. The material constituting the hole injection layer or the hole transport layer includes a titanium cyanine dye derivative, a naphthalocyanine dye derivative, a porphyrin derivative, an aromatic tertiary amine derivative, diphenylethylene, and polyvinylcarbazole. , polythiophene, polyaniline, etc.-22- 200808697 It is preferred that the conductive polymer material has a high electron supply property or a compound containing a substituent. In particular, in terms of the material constituting the hole injection layer, a compound having a small ionization potential which is easily injected by the anode hole is preferable. Further, in terms of the material constituting the hole transport layer, a compound having the same level as the ionization potential of the light-emitting layer is preferred. a luminescent material or a host material of the luminescent layer, such as a metal complex of a quinoline metal complex, an aminoquinoline metal complex, a benzoquinoline metal complex, etc.; Condensed polycyclic compounds such as benzene, halobenzene, caves, and Perylene. Further, coumarin, quinacridone, rubrene, diphenylethylene derivative, fluorescent pigment or the like may be slightly doped in the light-emitting layer. In terms of materials constituting the electron transport layer or the electron injecting layer, specifically, for example, there are abominine sitting, three sitting, phenanthrene, Bathocuproine, porphyrin complex,

Perylene, a tetracarboxylic acid, or a derivative thereof, but not limited thereto, the layers may be composed of two or more layers. The organic EL element has a structure in which an organic compound layer having a structure of one or more layers and a cathode are provided on the substrate side, and an organic compound layer having a structure of one or more layers, and an organic compound layer having a structure of one or more layers from the substrate side. The composition of the anode. The method for producing the organic EL device is not particularly limited, and is, for example, a method in which an anode, an organic compound layer, and a cathode are laminated on a substrate, and a method in which a cathode, an organic compound layer, and an anode are sequentially laminated on a substrate. -23- 200808697 The method for forming the anode and the cathode is not particularly limited, and any one may be used, for example, using the above materials, vacuum evaporation, electron beam evaporation, RF sputtering, spin coating, It is formed by a known film production method such as an inkjet method, a printing method, or a spray method. The method for forming the organic compound layer is not particularly limited, and a method for producing a film containing the above compound (1), such as a vacuum evaporation method, a spin coating method, or a printing method, using the above compound (1) To form. Further, regarding the layer containing the above compound (1), for example, a vacuum evaporation method, an electron beam evaporation method, an RF sputtering method, a spin coating method, an inkjet method, a printing method, or a spray method using the above materials. It is formed by a well-known film production method. In general, in an organic EL device, when a voltage is applied between an anode and a cathode, 'the hole from the anode is injected into the light-emitting layer through the hole injection layer and the hole transport layer', and the cathode is injected through the electron injection layer and the electron transport layer. Light-emitting layer. Thereby, the holes and the electrons are recombined in the light-emitting layer, and at this time, the luminescent organic compound molecules contained in the light-emitting layer are excited by the generated energy to generate an exciton. Then, the generated excitons generate a luminescence phenomenon in the ground state deactivation process. Conventionally, when an organic EL device is put into practical use, it is an important issue to reduce the driving voltage and improve the quantum efficiency of luminescence. In order to solve this problem, it is desired to efficiently take out holes and inject them into the light-emitting layer, and the cathode efficiently extracts electrons into the light-emitting layer, and the holes and electrons are transported to the light-emitting layer without loss and efficiency. In the present invention, since the compound (1) has excellent conductivity of electrons and electrons, the hole injection layer for the organic EL element, the hole injection layer and the electron transport layer are effective at least one layer. In the white light layer, both the hole and the electron are injected, and the light-emitting layer is also suitable for recombination. Further, by using a compound having a high carrier mobility (1 EL element hole injection layer, a hole transport layer, an electron injection layer, and at least one layer of the light-emitting layer, the hole and the electron can have a light-emitting layer. The organic film of the present invention which is formed by driving the organic EL element is not particularly limited. For example, it is suitable for an organic EL display device of an organic EL display device, and has an organic number of pixels. In the case of a passive organic EL device, a portion of the organic compound layer containing the light-emitting layer between the plaque-like anode wiring and the intersection of the ridge-like arrangement and the anode wiring is typically held as a light-emitting element. The pixels are formed, and the pixels are in a matrix, and the elements used for switching in the organic EL element are arranged in a matrix, which can be an active organic EL. In the organic thin film device of the present invention, as described above For the electrical device, the substrate of the optical device such as the organic EL element, and the plastic substrate can be used. The plastic used as the substrate is heat-resistant, dimensionally safe, and electrically insulating. Workability, low air permeability and low suction are preferred. In terms of plastics, there is polyethylene terephthalate 丨 transport layer, electricity 7. Also, because of the necessity of f, it is used for organic layer, electronic transmission ~ Inefficient injection pressure is reduced. : Setting, its purpose 〇 The cathode wiring structure in which the EL elements are placed in an alternating configuration is arranged in an intersecting manner. Machine TFT combination buys components. For crystals, etc. In addition to glass substrates, the resistance to moisture is excellent, polynaphthalene • 25- 200808697, polystyrene, polycarbonate, polyacrylate, polyimine and so on. In the organic thin film device of the present invention, it is preferable to have a moisture-proof layer (gas barrier layer) on the surface on the electrode side of the substrate and on the reverse side or both surfaces of the electrode. The material constituting the moisture-proof layer has inorganic substances such as cerium nitride and cerium oxide. The moisture-proof layer can be formed by a known film forming method such as RF sputtering. Further, the organic thin film device of the present invention may have a hard coat layer or a primer layer as necessary. The organic thin flü apparatus of the present invention may have various aspects other than the above-described organic TFT and organic EL. For example, an organic thin film solar cell is another suitable type of organic thin film device characterized by containing the compound (1) of the present invention. The organic thin film device of the present invention is not particularly limited in use, and can be used for a display device (display), a display element, a backlight, an optical communication, an electronic photo, an illumination source, a recording light source, an exposure light source, a reading light source, a logo, a billboard, A wide range of uses such as decoration and batteries. [Embodiment] [Examples] The present invention will be specifically described by the following examples. However, the invention is not limited thereto. 1. Synthesis of Intermediates (1) Synthesis of 2,6-diacetylynylnaphthalene as an intermediate for the synthesis of the compounds (1 1 ) and (12) described later, -26-200808697 by the following formula (A) and B) Synthesis of 2,6-diethynylnaphthalene. [Chemistry 7]

The specific synthesis method of 2,6-diacetylynylnaphthalene is as follows. Add 20.15 g of 2,6-dibromonaphthalene, 2.0 g of tetrakis(triphenylphosphine)palladium (G) and 1 · 14 g to a four-necked flask equipped with a thermoelectric thermometer and a mechanical stirrer of 3 〇〇mL. Triphenylphosphine, the system was filled with nitrogen. Next, 60 mL of triethylamine was added. Further, 015 g of copper bromide (1) and 0.59 g of lithium bromide were dissolved in 15 mL of tetrahydrofuran (hereinafter referred to as "THF"), and 23.9 g of 2-methylbut-3-yn-2-ol was further added thereto. . Next, the system was heated to 90 to 9 5 ° C and stirred for 2 to 3 hours. Next, after cooling the reaction system to room temperature, 200 mL of 0.5 mol/L hydrochloric acid was added, and the precipitated solid was collected by filtration. The recovered solid was washed with water, washed with toluene, washed with methanol, and dried under vacuum at 50 ° C for 2 hours to obtain a nearly pure 4,4'-(naphthalene-2,6-di 1) bis (2-methylbut-3-yn-2-ol) 16.0 g (yield: 77%) (refer to the above formula (A)). The product thus obtained was transferred to a four-necked flask equipped with a thermoelectric thermometer and a mechanical stirrer in a volume of 300 mL, and 29.8 g of mobile sarcophagus and 13.4 g of pulverized potassium hydroxide were added thereto and stirred and dispersed. Next, the system was depressurized to 0·23 Pa, and then heated at 1 〇 〇~1 3 〇 °C to continue heating and stirring until foaming due to acetone generation was not performed. Then, 100 mL: -27-200808697 methyl chloride and 10 mL of water were added, and after stirring, the insoluble solid was removed by filtration. The crude product is extracted with dichloromethane, and concentrated to obtain a mixture with mobile sarcophagus, which is purified by column chromatography to obtain 7.3 g of near-purified 2,6-diacetylynylnaphthalene (yield: 86%). (Refer to equation (B) above). Further, 2,6-diethynylnaphthalene was identified by 1H-NMR analysis. The results of the analysis are shown below.

iH-NMR (3 00·4 ΜΗζ, solvent: CDC13, benchmark: TMS) δ (ppm); 3.18 (s, 2H), 7.53 (d, 2H), 7.74 (d, 2H), 7.98 (s, 2H) ( 2) Synthesis of 2,6-diethynyl fluorene For the synthesis of the compounds (1 3 ) and (1 4 ) described later, 2,6- is synthesized by the following formulas (C) and (D). Diacetylene hydrazine. [化8]

The specific synthesis method of 2,6-diacetylenyl hydrazine is as follows. After adding k〇g2,6-dibromofluorene, 94 mg of tetrakis(triphenylphosphine)palladium (ruthenium) and 57 mg of triphenylphosphine in a three-necked flask equipped with a thermoelectric thermometer and a magnetic stirrer of 50 mL. , the system is filled with nitrogen. Next, 2 mL of triethylamine was added. Further, 12 mg of copper (I) bromide and 25 mg of lithium bromide were added to 〇.75 mL of THF, and then 2-methylbut-3-yn-2-ol of -28-200808697 l.〇g was added thereto. Next, the system was heated to 90 to 95 ° C and stirred for 3 to 4 hours. Next, after cooling the reaction system to room temperature, 40 mL of 0.5 mol / L hydrochloric acid was added, and the precipitated solid was collected by filtration. The recovered solids were washed with water, washed with toluene, washed with methanol, and dried under vacuum at 50 ° C for 2 hours to obtain a nearly pure 4,4 ^ (蒽-2,6 - 2 Base) bis(2·methylbut-3-yn-2-ol) 0.9 g (yield: 85%) (refer to the above formula (C)). In the thus obtained product, 〇·8 g was transferred to a 20 OmL four-necked flask having a thermoelectric pair thermometer and a mechanical stirrer, and 2.2 g of flowing paraffin and 0.7 g of pulverized potassium hydroxide were further added thereto, stirred and dispersed. . Next, the system was depressurized to 〇. 23 Pa, and then heated at 100 to 130 ° C, and the heating and stirring were continued until the foaming due to the generation of acetone did not occur. Then, 40 mL of dichloromethane and 40 mL of water were added and stirred, and the insoluble solid was removed by filtration. The crude product was extracted with dichloromethane and chloroform, and concentrated to give a mixture with a liquid paraffin, which was purified by column chromatography to obtain a nearly pure 2,6-diethynyl ruthenium.45 g (yield: 87) % ) (Refer to equation (D) above). Further, 2,6-diethynyl fluorene was determined by 111 analysis. The results of the analysis are shown below. iH-NMR (3 00.4MHz, solvent: CDC13, benchmark: TMS) δ (ppm); 3.22 ( s ^ 2H ) , 7.48 ( d, 2H ) , 7.95 ( d, 2H ), 8. 19 ( s, 2H ) , 8.35 ( s, 2H ) 2 . Synthesis of fluorine-containing aromatic compound -29- 200808697 (Example 1 ): Compound (11 ) (1) Synthesis of compound (11) The device has a capacity of thermoelectric pair thermometer and mechanical mixer In a 30 mL four-necked flask, 1.7 g of 2,6-diacetylynylnaphthalene, 0.5 g of tetrakis(triphenylphosphine)palladium (ruthenium) and ruthenium (9 g of copper bromide (I)) were added, and the system was purged with nitrogen. . Next, 35 mL of toluene and 4.5 mL of triethylamine were added. Further, 7.3 g of bromopentafluorobenzene was added thereto. Next, the system was heated to 90 to 95 ° C and stirred for 3 to 4 hours. Next, after cooling the reaction system to room temperature, after adding 10 mL of 0.5 m 〇l / L hydrochloric acid, the precipitated solid was collected by filtration. The recovered solid was washed with water, washed with toluene, washed with methanol, and dried under vacuum at 60 ° C for 2 hours to obtain an almost pure compound (1 1 ) 4.1 g (yield: 87). %). (2) Purification of the compound (i) by sublimation purification at 250 ° C under the reduced pressure of 2.5 × 10 0 - 4 to 6. 〇 xl (T4Pa under reduced pressure in the compound (1 1 ) obtained above. Pure white crystals 1.8 g. This white crystal was judged to be 2,6-bis(pentafluorophenylethynyl)naphthalene (compound (1 1 )) by 19F-NmR and 1H-NMR analysis. .

19F-NMR (282.7ΜΗζ, solvent: C D C 13, reference: C F C13 ) δ (ppm) ; -136.34 (4F) , -152.70 (2F) , -162.14 (4F )

W-NMR (3〇〇·4ΜΗζ, dissolved! J: CDC13, benchmark: TMS) δ (ppm); 7.64 (d, 2H), 7.84 (d, 2H), 8.11 (s, 2H -30- 200808697 ( Example 2): Compound (1 2 ) (1 ) Compound (1 2 ) was synthesized in a four-necked flask equipped with a thermoelectric thermometer and a mechanical stirrer having a capacity of 300 mL, and 〇.3@2,6-diacetylene was added. Naphthalene, 0.09 § tetrakis(triphenylphosphine)palladium (ruthenium) and rhodium ruthenium bromide (I), the system was filled with nitrogen. Then, 6 mL of toluene and 〇.75 mL of triethylamine were added. Further, 1.7 g of 2-bromo heptafluoronaphthalene was added thereto. Then, the system was heated to 90 to 95 ° C and then "disturbed for 3 to 4 hours. Then, after cooling the reaction system to room temperature, '1 0 0 m L 0.5 m was added. After 1 / L hydrochloric acid, the precipitated solid was collected by filtration, and the recovered solid was washed with water, washed with toluene and washed with acetone, and dried under vacuum at 60 ° C for 2 hours to obtain a nearly pure compound. (1 2 ) 5.6 g (yield: 92%). (2) Purification of the compound (1 2 ) The decompression of l.〇g in the compound (12) obtained above at 5 ·5 χΙΟ·4 to 6.0×10 −4 Pa Next, after 3 5 0 °C Purification by sublimation gave 5 g of pure white crystals. This white crystals were confirmed to be 2,6-bis((heptafluoronaphthalen-2-yl)ethynyl)naphthalene (compound(s) by 19F-NMR and 1H-NMR. 1 2 )). The results of the analysis are shown below.

19F-NMR (282.7ΜΗζ, solvent: THF-d8, benchmark: CFC13) δ (ppm); -113.1 (2F), -134.5 (2F), -144.1 (2F), -144.6 (2F), -149.3 ( 2F) , -153.2 (2F) > -156.3 -31 - 200808697 (4F )

iH-NMR (3 00·4 ΜΗζ, solvent: THF-d8, basis: TMS) δ (ppm); 7.74 (d, 2H), 8·03 (d, 2H), 8.29 (s, 2H (Example 3) • Compound (1 3 ) (1 ) Synthesis of compound (1 3 ) Thermocouple was placed in a three-necked flask of 50 mL capacity with a magnetic stirrer, and 0.29 g of 2,6-diethynyl fluorene, 88 mg of tetra ( Triphenylphosphine)palladium(0) and 19 mg of copper (I) bromide were charged with nitrogen. Next, 6 mL of toluene and 0.75 mL of triethylamine were added. Further, 1.0 g of bromopentafluorobenzene was added thereto. Then, the system was heated to 95 ° C and stirred for 3 to 4 hours. Then, after the reaction system was cooled to room temperature, 40 mL of 0.5 mol/L hydrochloric acid was added, and the precipitated solid was collected by filtration and recovered. The order was washed with water, washed with toluene, washed with methanol, and dried under vacuum at 60 ° C for 2 hours to obtain 0.44 g of a nearly pure compound (1 3 ) (yield: 62%). 2) Purification of the compound (1 3 ) 0.3 g of the compound (13) obtained above is purified by sublimation at 350 ° C under reduced pressure of 5.5χ1〇·4~ 6.〇xl〇_4Pa. get The white crystals were as follows: 1 5 g. This white crystal was analyzed by 19F-NMR and i-NMR to obtain 2,6-bis(pentafluorophenylethynyl)naphthalene (compound (13)). -32- 200808697 The results are as follows. 19F-NMR (282.7MHz, solvent: THF-d8, benchmark: CFC13) δ (ppm); - 1 3 7.20 ( 4F ) , -153.78 (2F) , -162.95 ( 4F )

h-NMR (3 00·4 ΜΗζ, solvent: THF-d8, standard · TMS) δ (ppm); 7.59 (d, 2H), 8.12 (d, 2H), 8.40 (s, 2H), 8.58 (s, 2H) (Example 4): Compound (1 4 ) (1) Compound (14) was synthesized by placing a thermoelectric thermometer in a three-necked flask equipped with a magnetic stirrer having a capacity of 50 mL, and adding 〇.3§2,6-two Ethyl hydrazine, 7711^tetrakis(triphenylphosphine)palladium (ruthenium) and 14m copper (I) bromide were charged with nitrogen. Next, 6 mL of toluene and 0.75 mL of triethylamine were added. Further, 1.4 g of 2-bromo heptafluoronaphthalene was added thereto. In addition, the system was heated to 95 ° C and stirred for 3 to 4 hours. Next, after cooling the reaction system to room temperature, 40 mL of 0.5 mol/L hydrochloric acid was added, and the precipitated solid was collected by filtration. The solids recovered in this order were washed with water, washed with toluene and washed with acetone, and dried under vacuum at 60 ° C for 2 hours to obtain a nearly pure compound (14) 0.81 g (yield: 82%). ). (2) Purification of the compound (1 4 ) 0.5 g of the compound (14) obtained above is purified by sublimation at 400 ° C under a reduced pressure of 5·5 χ 1 (Γ4 to 6.〇xl (T4Pa). -33- 200808697 White crystal 〇.26g. This white crystal was analyzed by 19F-NMR and 1H-NMR as 2,6-bis((heptafluoronaphthalen-2-yl)ethynyl)anthracene (compound (1 4 )). The analysis results are as follows.

19F-NMR (282.7MHz, solvent: THF-d8, benchmark: CFC13) δ (ppm); -1 13.2 ( 2F ) , -134.6 (2F) , -144.1 (2F ), -144.5 ( 2F ) , -149.4 ( 2F) , -153.2 ( 2F) , -156.4 (4F )

h-NMR (300.4MHz, solvent: THF-d8, ept.: TMS) δ (ppm); 7.60 (d, 2H), 8.11 (d, 2H), 8.41 (s, 2H ), 8.59 ( s, 2H ) 3 Evaluation of Physical Properties of Fluorinated Aromatic Compound Film (Example 5) A glass substrate having a thickness of 130 nm was fixed to a substrate holder of a vacuum evaporation machine, and the pressure was reduced to a vacuum of 1 x 1 (T6 Torr (1·33χ1 (Γ4Ρ〇. Next, This was synthesized in Synthesis Example 1, and the purified compound (11) was evaporated to a thickness of 40 nm at a vapor deposition rate of 2 nm/sec. The ionization potential of the vaporized compound (1 1 ) film was carried out. The measurement was carried out by an atmospheric photoelectron spectroscopic device (AC-3, manufactured by Rigaku Corporation) at 6.2 eV. Further, the film absorption spectrum of the compound (1 1 ) to be vaporized was measured by spectrophotometer (UV-3100). Measured by Shimadzu Corporation, the absorption maximum wavelength is 280 nm and 3 3 6 nm, and the wavelength of the absorption end of the longest wavelength side is 327 nm. 〇-34- 200808697 The characteristics, compound (1 1 The HOMO and LUMO levels of the film are required to be -6.2eV and -2.9eV, respectively. Therefore, it is expected that the film of the compound (1 1 ) has electrons. 4. Organic TFT fabrication and evaluation (Example 6) A gate electrode having a width of 5 mm and a thickness of 30 nm was formed by sputtering a gold film on a glass substrate through a photomask. The film of polychloro-p-xylene is vapor-evaporated to form a gate insulating layer (polymer insulating film). Specifically, monochloroxylene dimer (poly(p-dimethylbenzene), Japanese parylene (Japanese) under reduced pressure )))))) A two-radical monomer forms a poly-polychloro-p-xylene film having a thickness of 99 Onm. The subsequent process is carried out in a steaming machine in a glove box. On the glass substrate forming the gate insulating layer, the compound (1 2 ) is formed. The thickness of the organic semiconductor layer is formed by vaporization at a vapor deposition rate of 0.05 nm/sec to a thickness of about 40 nm. The degree of vacuum in the chamber of the evaporation apparatus is 2x1 (T4Pa or less), and then a metal mask is used on the organic semiconductor layer. Calcium is formed by vacuum evaporation to form a source The electrode and the ruthenium electrode are further formed by vaporizing silver to form a protective layer, and an organic TFT is obtained. The channel width (W) and the channel length (L) of the organic TFT are 5 mm - 35 - 200808697 and 7 5 μηι °, respectively. The graph showing the electrical characteristics of the organic TFT produced in Example 6. In Fig. 1, the horizontal axis is the 汲 voltage (V), and the vertical axis is the 汲 current (A). From Fig. 1, the compound (12) used in Example 6 is used. The fabricated organic TFT exhibits characteristics of an n-type semiconductor. As shown in Fig. 1, the variation curve of the 汲 current in each of the gate voltages has a field of saturation of the linear region (voltage proportional field) and the sorghum voltage of the low 汲 voltage. Further, the threshold voltage (Vt) of the organic TFT fabricated in Example 2 was 23V. In general, the electron mobility (μ) of the organic TFT can be calculated from the following formula (A) indicating the saturation 汲 current Id.

Id= ( W / 2L) μα ( Vg-Vt) 2 (A) where L is the length of the channel, W is the width of the channel, and Ci is the capacitance per unit area of the insulating layer ' V g is the gate voltage ' V t is Threshold voltage. The Ci of the poly-p-xylene used as the insulating layer was 2.86 x 1 (T9 F/cm 2 . The result of calculating the electron mobility (μ) by the above formula (A) 'The organic TFT fabricated in Example 6 was known to be 2.6. Xl (Electrical mobility of r4cm2/Vs) (Example 7) An organic TFT was produced using the compound (14) in the same manner as in Example 6. The organic TFT produced by the present invention showed the characteristics of the n-type semiconductor. The method was calculated as a result of calculating the degree of electron mobility (μ), and it was found that an electron mobility of 2.7×10 −4 cm 2 /Vs was obtained. (Comparative Example 1) The same method as in Example 6 except that calcium as a source and a ruthenium electrode was replaced by gold. An organic TFT was produced by using a compound (17) in which a compound (1 2 ) fluorine-substituted naphthyl group was changed to an unsubstituted naphthyl group, and the obtained organic TF T showed the characteristics of a p-type semiconductor, and was calculated in the same manner as in Example 6. As a result of the hole mobility (μ), the hole mobility of 6.4 XI 0_3 cm 2 /Vs was obtained. [Chem. 9] (17) [Industrial use possibility] The fluorine-containing aromatic compound and organic semiconductor material of the present invention 'Can be used for high performance organic XFT, organic EL Further, it can be widely used in organic thin film solar cells, display devices (displays), display elements, backlights, optical communication, electronic photographs, illumination sources, recording light sources, exposure light sources, reading light sources, signs, billboards, decorations, The use of the battery, etc., is hereby incorporated by reference in its entirety to the entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire entire Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 1] A diagram showing the electrical characteristics of the organic TFT fabricated in Example 2. -38-

Claims (1)

200808697 X. Patent Application Scope l A fluorine-containing aromatic compound characterized by the following formula (1): [Chemical 1] (1) ArF is a perfluoroaromatic group (however, the chlorine atom in the perfluoroaromatic group may be substituted by a perfluoroalkyl group); 11 is an integer of 1 to 4; and Q is represented by the following formula (2) The n-valent aromatic group obtained by removing n hydrogen atoms is shown (however, the hydrogen atom in the aromatic group may be a fluorinated alkane having a carbon number of 1 to 8 or a carbon number of 1 to 8) Base substitution);:? It is an integer from 0 to 4. [Chemical 2] (2) 2. The fluorine-containing aromatic compound of the first aspect of the patent application, wherein η is 2 〇3. The fluorine-containing aromatic compound of claim 2, wherein the ArF is a perfluorophenyl group or a perfluoro group. A perfluoroaromatic group selected from the group consisting of a naphthyl group and a perfluorobiphenyl group, and P is 〇 or 1. 4. The fluorine-containing aromatic compound of claim 3, wherein P is 0, and the bonding position of Q-C3C·A rF is 2 and 6 positions. 5. The fluorine-containing aromatic compound of claim 3, wherein P is 1, and the bonding position of Q-C tri-C-ArF is 2, 6 or 9 and -39-200808697 1 0 . 6. The fluorine-containing aromatic compound of the third aspect of the invention, wherein the fluorine-containing aromatic compound represented by the formula (1) is a compound represented by the following formula (11), and the following formula (1 2) The compound shown by the following formula (13), the compound represented by the following formula (1 4), the compound represented by the following formula (15), and the following formula (16) Compounds selected from the group of compounds. [Chemical 3] An organic semiconductor material characterized by containing a fluorine-containing aromatic compound according to any one of claims 1 to 6. An organic thin film device comprising an organic thin film device having a gate electrode, a gate insulating layer, an organic semiconductor layer, a source electrode and a drain electrode on a substrate, characterized by the organic semiconductor layer A fluorine-containing aromatic compound according to any one of claims 1 to 6. An organic thin film device comprising an organic thin film device having an anode, an organic compound layer having a structure of one or more layers, and a cathode organic EL device, wherein the organic compound layer contains the first patent application range A fluorine-containing aromatic compound of any one of the above. -41 -