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    • 专利摘要:
    PURPOSE: Provided is an organic electroluminescent device (hereunder abbreviated to organic EL device). More specifically, it comprises a dipyridylthiophene derivative. CONSTITUTION: The organic electroluminescent device is characterized by comprising a dipyridylthiophene derivative represented by the following general formula(1): where X is S or SO2, R5 and R6 each independently represent a hydrogen atom, an alkyl group of 1-6 carbons, an alkenyl group of 2-6 carbons, an alkoxy group of 1-6 carbons, an aryloxy group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, with the proviso that when R5 and R6 each independently represent an alkenyl, alkoxy, aryl or heterocyclic group they may be bonded together but not into a benzo condensed ring, and A1 and A2 are independently represented by the following formula(2) or (3): where R1-R4 and R7-R10 each independently represent a hydrogen atom, an alkyl group of 1-6 carbons, an alkenyl group of 2-6 carbons, an alkoxy group of 1-6 carbons, an aryloxy group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, with the proviso that when they are each independently an alkenyl, alkoxy, aryl or heterocyclic group and are adjacent, they may be bonded together.
    公开号:KR20020019879A
    申请号:KR1020010050562
    申请日:2001-08-22
    公开日:2002-03-13
    发明作者:야마다히로시；우치다마나부；나카노다카하루；후루카와겐지
    申请人:고토 기치；칫소가부시키가이샤；
    IPC主号:
    专利说明:

    Organic electroluminescent device comprising dipyridylthiophene derivative
    [1] The present invention relates to an organic electroluminescent device (hereinafter abbreviated as "organic EL device"). More specifically, the present invention relates to an organic EL device comprising a dipyridylthiophene derivative.
    [2] Recently, attention has been focused on organic EL devices as next-generation full color flat panel displays, which has led to their active research and development. The organic EL device is an injection type EL device in which a light emitting layer is sandwiched between two electrodes, where recombination and subsequent light emission thereof occur by injection of electrons and holes into the organic light emitting layer. The materials used are low molecular weight materials and polymeric materials, which are known to provide organic EL devices with high brightness.
    [3] There are two types of such organic EL devices. One is obtained by doping the charge transport layer with a fluorescent dye, as disclosed in CW Tang et al. (J. Appl. Phys., 65, 3610 (1989)), and the other only the fluorescent dye itself (See, eg, the device described in Jpn. J. Appl. Phys. 27, L269 (1988)).
    [4] Devices using fluorescent dyes as light emitting layers are classified into three types. The first form has three layers sandwiching the light emitting layer between the electron transporting layer and the hole transporting layer, the second form has two layers in which the hole transporting layer and the light emitting layer are laminated together, and the third form has the electron transporting layer and the light emitting layer together It has two layers stacked. Such a multilayer structure is known to enhance the luminous efficiency of an organic EL device.
    [5] Known hole transport materials used in organic EL devices include many different materials that are predominantly triphenylamine derivatives, although some materials are known that can be used as electron transport materials. Moreover, the electron transporting material present is charged compared to known hole transporting materials (e.g., N, N'-di (1-naphthyl) -N, N'-diphenyl-4,4'-diaminobiphenyl). When the carrying capacity is low and used in organic EL devices, they limit the performance of the EL device and make it impossible to achieve satisfactory device characteristics.
    [6] Specific examples of such electron transport materials include known metal complexes of auxin derivatives (see Japanese Patent Application Laid-Open No. 59-194393 and the like) and 2- (4-biphenylyl) -5- (4-3) Tertiary butylphenyl) -1,3,4-oxadiazole (PBD). The former can drive the organic EL device at a relatively low voltage, but it is still unsuitable, and the light emission itself is green, so it is difficult to achieve emission of blue light. The above-mentioned organic EL device (Jpn. J. Appl. Phys. 27, L269 (1988)) is an example of using the latter as the electron transporting layer. However, since the instability of the thin film, including the tendency of crystallization, has been pointed out as a problem, compounds having multiple oxadiazole rings have been developed (see Journal of the Chemical Society of Japan, 11, 1540 (1991), Japanese Laid-Open Patent Publication). Japanese Patent Laid-Open No. 6-145658, Japanese Patent Laid-Open No. 6-92947, Japanese Patent Laid-Open No. 5-152027, Japanese Patent Laid-Open No. 5-202011, Japanese Laid Open Patent Publication No. Hei 6-136359, etc.). Nevertheless, these compounds also exhibit inadequate properties such as high drive voltages in practical use. Quinoxaline derivatives have been reported as additional compounds (Japanese Patent Laid-Open No. 6-207169). Dimerization increases the molecular weight and thus enhances the stability of the thin film, but such dimers are unsuitable for practical use since still high drive voltages are required. Silacyclopentadiene derivatives have also been reported (see Japanese Patent Application Laid-Open No. 9-87616 and the like). They can drive organic EL devices at relatively low voltages, but are also insufficient in practical use. Dibenzoxazolylthiophene derivatives have been reported as thiophene ring-containing compounds (see, for example, JP-A-5-343184, JP-A-11-345686 and the like). However, although thin film stability has been improved by the introduction of substituents, the drive voltage is too high to be suitable for practical use.
    [7] As mentioned above, the electron transporting material used in the conventional organic EL device does not meet the conventional demand for high performance by a full color flat panel display, so that the superior material has a lower voltage and more It is required to achieve high efficiency.
    [8] The present invention has been accomplished in view of these problems in the prior art, and an object thereof is to provide a low voltage, high efficiency organic EL device.
    [9] As a result of intensive research to solve the above-mentioned problems associated with the conventional organic EL device, the present inventors have found that high performance electron transport capable of providing a low voltage, high efficiency organic EL device when a specific dipyridylthiophene derivative is used. It has been found that the material, the present invention has been completed accordingly.
    [10] The present invention has the following configuration.
    [11] A first aspect of the invention is an organic electroluminescent device characterized in that it comprises a dipyridylthiophene derivative of formula (1).
    [12]
    [13] In Formula 1 above,
    [14] X is S or SO 2 ,
    [15] R 5 and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group, a substituted or unsubstituted aryl group, or a substitution Heterocyclic group, unsubstituted or substituted, provided that when R 5 and R 6 are each independently alkenyl, alkoxy, aryl, or heterocyclic groups, they may be bonded together, but not with a benzo condensed ring,
    [16] A 1 and A 2 are independently a group of formula (2) or a group of formula (3).
    [17]
    [18]
    [19] In Formulas 2 and 3 above
    [20] R 1 to R 4 and R 7 to R 10 are each independently a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, an aryloxy group, substituted or substituted Unsubstituted aryl groups or substituted or unsubstituted heterocyclic groups provided that they are each independently alkenyl, alkoxy, aryl or heterocyclic groups, and when adjacent, they may be bonded together.
    [21] According to a preferred embodiment of the invention, in formula (1) A 1 and A 2 are both groups of formula (2).
    [22] According to another preferred embodiment of the invention, in formula (1) A 1 and A 2 are both groups of formula (3).
    [23] According to another preferred embodiment of the invention, in formula (1) A 1 is a group of formula (2), A 2 is a group of formula (3).
    [24] Another preferred embodiment of the present invention is an organic electroluminescent device wherein the dipyridylthiophene derivative of formula 1 is contained in an electron transporting layer.
    [25] Another preferred embodiment of the present invention is an organic electroluminescent device in which the dipyridylthiophene derivative of formula 1 is contained in the light emitting layer.
    [26] A second aspect of the invention is an electron transporting material comprising a dipyridylthiophene derivative of formula (1).
    [27] A third aspect of the invention is a luminescent material comprising a dipyridylthiophene derivative of formula (1).
    [28] The present invention will now be described in more detail. In Formulas 1, 2 and 3, X is S or SO 2 , and R 1 to R 10 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and having 1 to 6 carbon atoms. An alkoxy group, an aryloxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
    [29] Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary-butyl, tert-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl May be mentioned. As examples of alkenyl groups, mention may be made of vinyl, allyl, 1-propenyl, 1,3-butadienyl, 2-pentenyl and 2-hexenyl, and as examples of alkoxy groups, methoxy, ethoxy And propoxy; mention may be made of phenyloxy and naphthyloxy as examples of aryloxy groups. As examples of aryl groups, mention may be made of phenyl and naphthyl, and as examples of heterocyclic groups, mention may be made of thiophene, benzoxazole, benzothiazole, pyridine, quinoline and phenanthroline.
    [30] When R 1 to R 10 are each independently alkenyl, alkoxy, aryl or heterocyclic groups, they may be bonded together, but R 5 and R 6 are not bonded to the benzo condensed ring.
    [31] Of the compounds of formula 1, some have a plurality of R 1 to R 4 groups or a plurality of R 7 to R 10 groups, but in this case each R 1 to R 4 or each R 7 to R 10 is independent As atoms or groups mentioned above.
    [32] The following may be mentioned as specific examples of dipyridylthiophene derivatives used in the present invention.
    [33] 2,3,4,5-tetra (2-pyridyl) thiophene,
    [34] 2,5-di (3-pyridyl) -3,4-di (2-pyridyl) thiophene,
    [35] 2- (2-pyridyl) -3,4-di (2-pyridyl) -5- (3-pyridyl) thiophene,
    [36] 2,5-di (2-pyridyl) -3,4-diphenylthiophene,
    [37] 2,5-di (3-pyridyl) -3,4-diphenylthiophene,
    [38] 2,5-bis (6- (2-pyridyl) -2-pyridyl) -3,4-diphenylthiophene,
    [39] 2,5-bis (6- (2-pyridyl) -3-pyridyl) -3,4-diphenylthiophene,
    [40] 2- (6- (2-pyridyl) -2-pyridyl) -3,4-diphenyl-5- (6- (2-pyridyl) -3-pyridyl) thiophene,
    [41] 2,5-bis (6- (2-benzoxazolyl) -2-pyridyl) -3,4-diphenylthiophene,
    [42] 2,5-bis (6- (2-benzoxazolyl) -3-pyridyl) -3,4-diphenylthiophene,
    [43] 2- (6- (2-benzoxazolyl) -2-pyridyl) -3,4-diphenyl-5- (6- (benzoxazolyl) -3-pyridyl) thiophene,
    [44] 2,5-bis (6- (2-benzothiazolyl) -2-pyridyl) -3,4-diphenylthiophene,
    [45] 2,5-bis (6- (2-benzothiazolyl) -3-pyridyl) -3,4-diphenylthiophene,
    [46] 2- (6- (2-benzothiazolyl) -2-pyridyl) -3,4-diphenyl-5- (6- (benzothiazolyl) -3-pyridyl) thiophene,
    [47] 2,5-bis (6- (3-quinolyl) -2-pyridyl) -3,4-diphenylthiophene,
    [48] 2,5-bis (6- (3-quinolyl) -3-pyridyl) -3,4-diphenylthiophene,
    [49] 2- (6- (2-quinolyl) -2-pyridyl) -3,4-diphenyl-5- (6-quinolyl) -3-pyridyl) thiophene,
    [50] 2,5-di (2-quinolyl) -3,4-diphenylthiophene,
    [51] 2,5-di (3-quinolyl) -3,4-diphenylthiophene,
    [52] 2,5-di (4-isoquinolyl) -3,4-diphenylthiophene,
    [53] 2,5-di (2- (1,10-phenanthryl))-3,4-diphenylthiophene,
    [54] 2,5-di (3- (1,10-phenanthryl))-3,4-diphenylthiophene,
    [55] 2,5-di (2-pyridyl) -3,4-dimethylthiophene,
    [56] 2,5-di (3-pyridyl) -3,4-dimethylthiophene,
    [57] 2,5-bis (6- (2-pyridyl) -2-pyridyl) -3,4-di-tert-butylthiophene,
    [58] 2,5-bis (6- (2-pyridyl) -3-pyridyl) -3,4-di-tert-butylthiophene,
    [59] 2,5-bis (6- (2-pyridyl) -2-pyridyl) -3,4-di (2-pyridyl) thiophene,
    [60] 2,5-bis (6- (2-pyridyl) -3-pyridyl) -3,4-di (2-pyridyl) thiophene,
    [61] 2,5-bis (6- (2-pyridyl) -2-pyridyl) -3,4-ethylenedioxythiophene,
    [62] 2,5-bis (6- (2-pyridyl) -3-pyridyl) -3,4-ethylenedioxythiophene,
    [63] 2- (6- (2-pyridyl) -2-pyridyl) -3,4-ethylenedioxy-5- (6- (2-pyridyl) -3-pyridyl) thiophene,
    [64] 2,5-bis (6- (2-pyridyl) -2-pyridyl) -3,4-trimethylenethiophene,
    [65] 2,5-bis (6- (2-pyridyl) -3-pyridyl) -3,4-trimethylenethiophene,
    [66] 2- (6- (2-pyridyl) -2-pyridyl) -3,4-trimethylene-5- (6- (2-pyridyl) -3-pyridyl) thiophene,
    [67] 2,2 ', 5,5'-tetra (2-pyridyl) -3,3'-bithiophene,
    [68] 2,2 ', 5,5'-tetra (3-quinolyl) -3,3'-bithiophene,
    [69] 2,3,4,5-tetra (2-pyridyl) thiophene-1,1-dioxide,
    [70] 2,3,4,5-tetra (3-pyridyl) thiophene-1,1-dioxide,
    [71] 2,5-bis (6- (2-pyridyl) -2-pyridyl) -3,4-diphenylthiophene-1,1-dioxide,
    [72] 2,5-bis (6- (2-pyridyl) -3-pyridyl) -3,4-diphenylthiophene-1,1-dioxide,
    [73] 2- (6- (2-pyridyl) -2-pyridyl) -3,4-diphenyl-5- (6- (2-pyridyl) -3-pyridyl) thiophene-1,1-dioxide ,
    [74] 2,5-bis (6- (2-pyridyl) -2-pyridyl) -3,4-ethylenedioxythiophene-1,1-dioxide,
    [75] 2,5-bis (6- (2-pyridyl) -3-pyridyl) -3,4-ethylenedioxythiophene-1,1-dioxide,
    [76] 2,5-bis (6- (2-pyridyl) -2-pyridyl) -3,4-trimethylenethiophene-1,1-dioxide and
    [77] 2,5-bis (6- (2-pyridyl) -3-pyridyl) -3,4-trimethylenethiophene-1,1-dioxide.
    [78] These compounds are known methods, for example, the methods described in J. Am. Chem. Soc., 116, 1880 (1994), J. Am. Chem. Soc., 121, 9744 (1999), the method described in J. Am. Chem. Soc., 92, 7610 (1970) or the methods described in the synthetic examples herein. Can be.
    [79] These dipyridylthiophene derivatives are suitable as materials for forming an electron transporting layer in which the organic EL device of the present invention can operate with low voltage and high efficiency. This is due to the excellent electron transporting properties of the dipyridylthiophene derivatives of the formulas (1) and (2) used in the present invention. Moreover, since the dipyridylthiophene derivatives themselves are luminescent, they are also suitable as luminescent materials for organic EL devices.
    [80] Although various forms of the structure of the organic EL device of the present invention can be mentioned, the basic structure has an organic layer containing a dipyridylthiophene derivative sandwiched between a pair of electrodes (anode and cathode), and in some cases, different A hole transport layer, light emitting layer or electron transport layer form of material may be combined with the dipyridylthiophene derivative layer. When used as an electron transporting layer, different materials can be mixed and used to further enhance the function.
    [81] Concrete structures include (1) anode / hole transport layer / dipyridylthiophene derivative layer / cathode, (2) anode / hole transport layer / light emitting layer / dipyridylthiophene derivative layer / cathode and (3) anode / hole transport layer Mention may be made of multilayer structures such as / dipyridylthiophene derivative layers / electron transporting layers / cathodes.
    [82] The organic EL device of the present invention having the above-mentioned structure is preferably supported on a substrate. The substrate may be one having mechanical strength, thermal stability and transparency, of which glass, transparent plastic film, or the like may be used. The positive electrode material for the organic EL device of the present invention may be a metal, an alloy, a conductive compound or a mixture thereof whose work function exceeds 4 eV. Specifically, mention may be made of metals such as Au and conductive transparent materials such as CuI, indium tin oxide (hereinafter abbreviated as "ITO"), SnO 2 and ZnO.
    [83] The negative electrode material may be a metal, alloy, conductive compound or mixture thereof having a work function of less than 4 eV. Specifically, aluminum, calcium, magnesium, lithium, magnesium alloy or aluminum alloy and the like may be mentioned, wherein the alloy includes aluminum / lithium fluoride, aluminum / lithium, magnesium / silver, magnesium / indium and the like. In order to achieve efficient light emission of the organic EL device, at least one electrode preferably has a light transmittance of 10% or more. The sheet resistance of the electrode is preferably several hundred k / It is as follows. The film thickness depends on the nature of the electrode material, but is usually selected in the range of 10 nm to 1 μm, preferably 10 to 400 nm. Such an electrode can be manufactured using the above-mentioned electrode material to form a thin film by a method such as vapor deposition or sputtering.
    [84] As another hole transporting material used in the organic EL device of the present invention, a material commonly used as a hole charge transporting material for a photoconductive material in the prior art or well-known used in the hole injection layer and the hole transporting layer of an organic EL device Material may be selected. Examples include carbazole derivatives (N-phenylcarbazole, polyalkylenecarbazoles, etc.), triarylamine derivatives [TPD, polymers having aromatic tertiary amines as main chain or side chain, 1,1-bis (4-di- p-tolylaminophenyl) cyclohexane, N, N'-diphenyl-N, N'-dinaphthyl-4,4'-diaminobiphenyl, 4,4 ', 4 "-tris {N- (3 -Methylphenyl) -N-phenylamino} triphenylamine, the compounds described in J. Chem. Soc. Chem. Comm., 2175 (1996), Japanese Patent Application Laid-Open No. 57-144558 Japanese Unexamined Patent Application Publication No. 61-62038, Japanese Unexamined Patent Application Publication No. 61-124949, Japanese Unexamined Patent Application Publication No. 61-134354, Japanese Unexamined Patent Application Publication No. 61-62038 134355, Japanese Patent Laid-Open No. 61-112164, Japanese Patent Laid-Open No. 4-308688, Japanese Patent Laid-Open No. 6-312979, Japanese Patent Laid-Open No. 6-267658, Japanese Patent Laid-Open No. 7-90256, Japanese Patent Laid-Open No. 7-97355, Japanese Laid-Open Patent Japanese Patent Laid-Open No. 6-1972, Japanese Patent Laid-Open No. 7-126226, Japanese Patent Laid-Open No. 7-126615, Japanese Patent Laid-Open No. 7-331238, Japan Starburst described in the compounds described in JP-A-8-100172 and JP-A-8-48656 (see Adv. Mater., 6, 677 (1994)). Amine derivatives, etc.], stilbene derivatives (compounds described in Preprints of 72nd National Meeting of the Chemical Society of Japan (II), p.1392, 2PB098, etc.), phthalocyanine derivatives (nonmetals, copper phthalocyanine, etc.) And polysilanes and the like can be mentioned.
    [85] There is no particular limitation on other electron transporting materials used in the organic EL device of the present invention, and the electron injection layer and the electron transporting layer of the material or organic EL device which are commonly used as electron transporting compounds for the photoconductive material in the prior art in use. Well-known materials for use can be selected. Preferred examples of electron transport compounds include diphenylquinone derivatives (compounds described in the Journal of the Society of Electrophotography of Japan, 30 (3), 266 (1991), etc.), perylene derivatives (see references : Compounds described in J. Appl. Phys., 27, 269 (1988), etc.), oxadiazole derivatives (see Jpn. J. Appl. Phys., 27, L713 (1988), Appl. Phys Compounds described in Lett., 55, 1489 (1989), etc.), thiophene derivatives (compounds described in JP-A-4-212286, etc.), triazole derivatives (see Jpn Compounds described in J. Appl. Phys., 32, L917 (1993)), thiadiazole derivatives (compounds described in Polymer Preprints, Japan, 43, (III), Pla007, etc.) , Metal complexes of auxin derivatives (compounds described in the Technical Report of the Institute of Electronics, Information and Communication Engineers, 92 (311), 43 (1992)), and polymers of quinoxaline derivatives (see Jpn J. Appl. Phys., 33, L250 (1994), etc.), phenanthroline derivatives (compounds described in Polymer Preprints, Japan, 43, 14J07, etc.) and silacyclopenta Diene derivatives (compounds described in JP-A-9-87616, etc.) may be mentioned.
    [86] The electron transporting layer of the organic EL device of the present invention is composed of a monolayer comprising a dipyridylthiophene compound and / or one or more of the above-mentioned compounds according to the present invention, or a multilayer laminate comprising different types of compounds. Can be done. The electron transport layer can also be prepared by dispersing the dipyridylthiophene compound according to the invention in a polymeric material.
    [87] Other luminescent materials that can be used in the luminescent layer for the organic EL device of the present invention include solar fluorescent materials, fluorescent brighteners, laser dyes, organic scintillants and literature (see the Polymer Functional Material Series, "Photofunctional Materials", ed. By Well-known luminescent materials such as various fluorescence assay reagents described in Society of Polymer Science, Japan, Kyoritsu Publishing, (1991), P236). Specifically, polycyclic condensation compounds (eg anthracene, phenanthrene, pyrene, chrysene, perylene, coronene, rubrene and quinacridone), oligophenylene compounds (eg quarterphenyl), flashes for liquid scintillation Agent (e.g., 1,4-bis (2-methylstyryl) benzene, 1,4-bis (4-methylstyryl) benzene, 1,4-bis (4-phenyl-5-oxazolyl) benzene, 1 , 4-bis (5-phenyl-2-oxazolyl) benzene, 2,5-bis (5-tert-butyl-2-benzoxazolyl) thiophene, 1,4-diphenyl-1,3-butadiene , 1,6-diphenyl-1,3,5-hexatriene and 1,1,4,4-tetraphenyl-1,3-butadiene), described in Japanese Unexamined Patent Publication No. 63-264692 Metal complexes of auxin derivatives, coumarin dyes, dicyanomethylenepyran dyes, dicyanomethylenethiopyran dyes, polymethine dyes, oxobenzanthracene dyes, xanthene dyes, carbostyryl dyes and perylene dyes, German Patent No. 2,534,713 Oxazine compounds described in, Preprints of the 40th Annual Meetin g of the Japan Society of Applied Physics, 1146 (1993)), a spiro compound described in Japanese Unexamined Patent Application Publication No. 7-278537, and Japanese Unexamined Patent Application Publication No. 4-363891. Preferred are the oxadiazole compounds described in. The well known phosphors described in the literature ("Organic EL materials and displays", CMC, p. 170) can also be used in the light emitting layer of the organic EL device of the present invention. Specifically, indium complexes (compounds described in Appl. Phys. Lett., 75, 4 (1999), etc.), platinum complexes (see Nature, 395, 151 (1998)). Compounds, etc.) and europium complexes (compounds described in Jpn. J. Appl. Phys., 34, 1883 (1995), and the like).
    [88] Each layer constituting the organic EL device of the present invention can be formed by producing a thin film using a material for each layer by well known methods (e.g., vapor deposition, spin coating or casting, etc.). The film thickness of each layer formed by this method is not particularly limited and may be appropriately selected depending on the nature of the material, but is usually selected in the range of 2 to 5000 nm. In terms of easily obtaining a homogeneous film and suppressing the formation of pinholes, vapor deposition is preferably used as a method of forming a thin film of dipyridylthiophene derivative alone. When deposition is used to form a thin film, the deposition conditions vary depending on the form of the dipyridylthiophene derivative, the crystallinity and related structures desired for the molecular accumulation film, etc., but in most cases, the bait heating temperature of 50 to 400 ° C. (boat heating temperature), a vacuum degree of 10 -6 to 10 -3 Pa, a deposition rate of 0.01 to 50 nm / sec, a substrate temperature of -150 to +300 ℃ and a film thickness in the range of 5 nm to 5 ㎛ It is preferable.
    [89] A method for producing an organic EL device comprising the above-mentioned anode / hole transporting layer / light emitting layer / dipyridylthiophene derivative / cathode structure is one example of a method for producing an organic EL device using the dipyridylthiophene derivative according to the present invention. As will now be explained. A positive electrode was prepared by forming a thin film composed of a positive electrode material on a suitable substrate by vapor deposition so that the film thickness was 1 탆 or less, preferably 10 to 200 nm. 1 μm or less, the light emitting layer is formed on the hole transporting layer so as to have a film thickness of 1 μm or less, and a thin film of dipyridylthiophene derivative is formed on the light emitting layer to prepare an electron transporting layer. The intended organic EL device is obtained by forming a thin film so as to have a film thickness of 1 m or less by vapor deposition to produce a cathode. For the manufacture of the organic EL device, the forming order can be reversed to form the cathode, the electron transporting layer, the light emitting layer, the hole transporting layer and the anode.
    [90] When a direct current voltage is applied to the organic EL device obtained by this method, the applied polarity can be + for the anode and-for the cathode, and an application voltage of about 2 to 40 V is applied to the transparent or translucent electrode surface ( Light emission is allowed from either the positive or negative electrode or both sides). The organic EL device also emits light upon application of an alternating voltage. The applied exchange may have any desired wave shape.
    [91] Example
    [92] The invention will now be described in more detail by way of examples.
    [93] Synthesis Example 1
    [94] Synthesis of 2,5-bis (6- (2-pyridyl) -2-pyridyl) -3,4-diphenylthiophene (hereinafter abbreviated as "BPPDPT")
    [95] 3.5 g of 3,4-diphenylthiophene and 60 ml of tetrahydrofuran were placed in a flask, and cooled to -30 ° C under an argon atmosphere, and then 11 ml of an n-butyllithium / n-hexane solution at a concentration of 1.5 mol / l was added. Add it down. The mixture is stirred at −30 ° C. for 2 hours, after which 4.1 g of zinc chloride / tetramethylethylenediamine complex is added, the temperature is raised to room temperature. After stirring for 30 minutes, 3.8 g of 2-bromo-6- (2-pyridyl) pyridine and 0.52 g of palladium chloride / bistriphenylphosphine complex are added and the mixture is stirred at reflux for 2 hours. After the reaction was completed, the product was cooled to room temperature, purified water was added, the organic layer was extracted, and the concentrate obtained using an evaporator was purified by recrystallization to give 2- (6- (2-pyridyl) -2-. 4.5 g of pyridyl) -3,4-diphenylthiophene are obtained. 3.3 g of 2- (6- (2-pyridyl) -2-pyridyl) -3,4-diphenylthiophene and 80 ml of tetrahydrofuran were added to the flask, and after cooling to -30 DEG C under an argon atmosphere, 6.2 ml of an n-butyllithium / n-hexane solution at a concentration of 1.5 mol / l was added dropwise. The mixture is stirred at −30 ° C. for 2 hours, after which 2.4 g of zinc chloride / tetramethylethylenediamine complex is added, the temperature is raised to room temperature. After stirring for 30 minutes, 2.2 g of 2-bromo-6- (2-pyridyl) pyridine and 0.30 g of palladium chloride / bistriphenylphosphine complex are added and the mixture is stirred at reflux for 2 hours. After the reaction was completed, the product was cooled to room temperature, purified water was added, and the organic layer was extracted. The organic layer is concentrated using an evaporator and purified by column chromatography and recrystallization to give 1.1 g of BPPDPT.
    [96] 1 H-NMR (CDCl 3 ) δ = 8.6-8.7 (m, 2H), 8.4-8.5 (m, 2H), 8.2-8.3 (dd, 2H), 7.8-7.9 (m, 2H), 7.5-7.6 (t , 2H), 7.3-7.4 (m, 2H), 7.2-7.3 (m, 6H), 7.1-7.2 (m, 4H), 6.8-6.9 (dd, 2H).
    [97] Example 1
    [98] An ITO deposited 25 mm x 75 mm x 1.1 mm glass panel having a thickness of 50 nm (Tokyo Sanyo Vacuum Industries Co., Ltd.) is used as the transparent support substrate. The transparent support substrate was fixed to a substrate holder of a commercial deposition apparatus (Sinku Kiko Co., Ltd.), and N, N'-dinaphthyl-N, N'-diphenyl-4,4'-diamino Molybdenum Deposition Bow, containing biphenyl (hereinafter abbreviated as "NPD"), Molybdenum Deposition Bow, containing 9-dimethyrylborylanthracene (hereinafter abbreviated as "DMBA"), Molybdenum containing BPPDPT A deposition boat, a molybdenum deposition boat containing lithium fluoride, and a tungsten deposition boat containing aluminum are placed thereon. The pressure in the vacuum vessel was reduced to 1 × 10 −3 Pa, and the NPD containing deposition boat was heated to 50 nm film thickness for the deposition of NPD to form a hole transport layer, and then the DMBA containing deposition boat was deposited with a 30 nm film. Heated for deposition of DMBA to thickness to form a light emitting layer. The BPPDPT containing deposition boat is then heated to the deposition of BPPDPT to a film thickness of 20 nm to form an electron transport layer. The deposition rate is 0.1-0.2 nm / sec. The lithium fluoride containing deposition boat is then heated to deposit a film thickness of 0.5 nm at a deposition rate of 0.003 to 0.01 nm / sec, and then the aluminum containing deposition boat is 100 nm film at a deposition rate of 0.2 to 0.5 nm / sec. Heating to obtain a thickness to obtain an organic EL device. Using an ITO electrode as the anode and a lithium fluoride / aluminum electrode as the cathode, a direct current voltage of about 4 V was applied to produce a current flow of about 8 mA / cm 2, resulting in a luminance of 100 mA / m 2 and a light emission of about 1 lm / W. Efficiency yields blue luminescence with a wavelength of 460 nm.
    [99] Comparative Example 1
    [100] An organic EL device was obtained in the same manner as in Example 1 except for using aluminum tris (8-hydroxyquinoline) (hereinafter abbreviated as "ALQ") instead of BPPDPT. Using an ITO electrode as the anode and a lithium fluoride / aluminum electrode as the cathode, a direct current voltage of about 6 V was applied to produce a current flow of about 10 mA / cm 2, with a luminance of 100 mA / m 2 and a light emission of about 0.2 lm / W. Efficiency yields blue luminescence with a wavelength of 460 nm.
    [101] Example 2
    [102] An organic EL device was obtained in the same manner as in Example 1 except that ALQ was used instead of DMBA.
    [103] Using an ITO electrode as the anode and a lithium fluoride / aluminum electrode as the cathode, a direct current voltage of about 4 V was applied to produce a current flow of about 4 mA / cm 2, resulting in a luminance of about 100 mA / m 2 and about 2 lm / W. The light emission efficiency yields green light emission having a wavelength of 520 nm.
    [104] Example 3
    [105] An ITO deposited 25 mm x 75 mm x 1.1 mm glass panel having a thickness of 50 nm (Tokyo Sanyo Vacuum Industries Co., Ltd.) is used as the transparent support substrate. The transparent support substrate is fixed to a substrate holder of a commercially available deposition apparatus (Sinku Kiko Co., Ltd.), and a molybdenum deposition bow containing NPD, a molybdenum deposition bow containing BPPDPT, and a molybdenum deposition bow containing lithium fluoride And a tungsten deposition boat containing aluminum thereon. The pressure in the vacuum vessel was reduced to 1 × 10 −3 Pa, and the NPD containing deposition boat was heated to 50 nm film thickness for the deposition of NPD to form a hole transporting layer, and then the BPPDPT containing deposition boat was formed using a 50 nm film. Heated for deposition of BPPDPT to thickness to form a light emitting layer. The deposition rate is 0.1-0.2 nm / sec. The lithium fluoride containing deposition boat is then heated to deposit a film thickness of 0.5 nm at a deposition rate of 0.003 to 0.01 nm / sec, and then the aluminum containing deposition boat is 100 nm film at a deposition rate of 0.2 to 0.5 nm / sec. Heating to obtain a thickness to obtain an organic EL device. Using an ITO electrode as the anode and a lithium fluoride / aluminum electrode as the cathode, a direct current voltage of about 7 V was applied to produce a current flow of about 50 mA / cm 2 to obtain blue light emission. The emission spectrum corresponds to the emission spectrum of the BPPDPT deposited film and the emission wavelength is 430 nm.
    [106] Synthesis Example 2
    [107] Synthesis of 2,5-bis (6- (2-pyridyl) -2-pyridyl) -3,4-ethylenedioxythiophene (hereinafter abbreviated as "BPPEOT")
    [108] 0.68 g of BPPEOT is obtained in exactly the same manner as in Synthesis Example 1, except that 3,4-ethylenedioxythiophene is used instead of 3,4-diphenylthiophene.
    [109] 1 H-NMR (CDCl 3 ) δ = 8.6-8.7 (m, 4H), 8.2-8.3 (d, 2H), 8.0-8.1 (d, 2H), 7.8-7.9 (m, 2H), 7.9-8.0 (t , 2H), 7.3-7.4 (m, 2H), 4.5 (s, 4H).
    [110] Example 4
    [111] An ITO deposited 25 mm x 75 mm x 1.1 mm glass panel having a thickness of 50 nm (Tokyo Sanyo Vacuum Industries Co., Ltd.) is used as the transparent support substrate. The transparent support substrate is fixed to a substrate holder of a commercially available deposition apparatus (Shinku Kiko Co., Ltd.), NPD-containing molybdenum deposition boat, ALQ-containing molybdenum deposition boat, BPPEOT-containing molybdenum deposition boat, molybdenum containing lithium fluoride A tungsten deposition boat containing a deposition boat and aluminum is placed thereon. The pressure in the vacuum vessel was reduced to 1 x 10 -3 Pa, and the NPD containing deposition boat was heated to 50 nm film thickness for the deposition of NPD to form a hole transport layer, and then the ALQ containing deposition boat was formed with a 30 nm film. The thickness is heated to deposit ALQ to form a light emitting layer. The BPPEOT-containing deposition boat is then heated to the deposition of BPPEOT to a film thickness of 20 nm to form an electron transport layer. The deposition rate is 0.1-0.2 nm / sec. The lithium fluoride containing deposition boat is then heated to deposit a film thickness of 0.5 nm at a deposition rate of 0.003 to 0.01 nm / sec, and then the aluminum containing deposition boat is 100 nm film at a deposition rate of 0.2 to 0.5 nm / sec. Heating to obtain a thickness to obtain an organic EL device. Using an ITO electrode as the anode and a lithium fluoride / aluminum electrode as the cathode, a direct current voltage of about 3 V was applied to produce a current flow of about 4 mA / cm 2, resulting in a luminance of about 100 mA / m 2 and about 2 mA / W The light emission efficiency yields green light emission having a wavelength of 520 nm.
    [112] Synthesis Example 3
    [113] Synthesis of 2,5-bis (6- (2-pyridyl) -3-pyridyl) -3,4-diphenylthiophene (hereinafter abbreviated as "BP3PDPT")
    [114] 0.49 g of magnesium and 5 ml of tetrahydrofuran were placed in a flask, and 65 ml of tetrahydrofuran solution containing 3.9 g of 2,5-dibromo-3,4-diphenylthiophene was added dropwise at room temperature under an argon atmosphere. The mixture is heated to reflux. After stirring for 3 hours, the mixture is cooled to -78 ° C and 70 ml of tert-butyl methyl ether solution containing 2.2 ml of trimethylborate is added dropwise to raise the temperature of the mixture to room temperature. After stirring for 15 hours, the solvent was distilled off, 75 ml of toluene, 25 ml of ethanol, 4.7 g of 2- (2-pyridyl) -5-bromopyridine, 0.69 g of palladium / tetrakistriphenylphosphine complex and sodium carbonate After adding 4.2 g, the mixture is stirred at reflux for 6 hours. After the reaction was completed, the product was cooled to room temperature, purified water was added, and the organic layer was extracted. The organic layer is concentrated using an evaporator and purified by column chromatography and recrystallization to give 0.78 g of BP3PDPT.
    [115] 1 H-NMR (CDCl 3 ) δ = 8.6-8.7 (m, 4H), 8.3-8.4 (d, 2H), 8.2-8.3 (d, 2H), 7.7-7.9 (m, 2H), 7.5-7.7 (dd , 2H), 7.2-7.4 (m, 2H), 7.1-7.2 (m, 6H), 6.9-7.1 (m, 4H).
    [116] Example 5
    [117] An organic EL device was obtained in the same manner as in Example 4 except that PB3PDPT was used instead of BPPEOT. Using an ITO electrode as the anode and a lithium fluoride / aluminum electrode as the cathode, a direct current voltage of about 3 V was applied to produce a current flow of about 5 mA / cm 2, resulting in a luminance of about 100 mA / m 2 and about 2 mA / W The light emission efficiency yields green light emission having a wavelength of 520 nm.
    [118] Example 6
    [119] An organic EL device was obtained in the same manner as in Example 3 except that PB3PDPT was used instead of BPPDPT. Using an ITO electrode as the anode and a lithium fluoride / aluminum electrode as the cathode, a direct current voltage of about 6 V was applied to produce a current flow of about 50 mA / cm 2 to obtain blue light emission. The emission spectrum is consistent with the emission spectrum of the BP3PDPT deposited film and the emission wavelength is 455 nm.
    [120] As described above, the dipyridylthiophene derivatives of the present invention have excellent electron transporting properties, and their use as electron transporting materials or light emitting materials for organic EL devices can provide organic EL devices having low voltage and high efficiency. Can be. That is, the organic EL device according to the present invention using the dipyridylthiophene derivative as the organic layer exhibits low operating voltage, high efficiency and satisfactory full color characteristics. Therefore, the organic EL device of the present invention can be used to manufacture high efficiency display devices (e.g., full color displays).
    权利要求:
    Claims (8)
    [1" claim-type="Currently amended] An organic electroluminescent device comprising a dipyridylthiophene derivative of formula (1).
    Formula 1

    In Formula 1 above,
    X is S or SO 2 ,
    R 5 and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group, a substituted or unsubstituted aryl group, or a substitution Heterocyclic group, unsubstituted or substituted, provided that when R 5 and R 6 are each independently alkenyl, alkoxy, aryl, or heterocyclic groups, they may be bonded together, but not by a benzo condensed ring,
    A 1 and A 2 are independently a group of formula (2) or a group of formula (3).
    Formula 2

    Formula 3

    In Chemical Formulas 2 and 3 above,
    R 1 to R 4 and R 7 to R 10 are each independently a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, an alkenyl group of 2 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, an aryloxy group, substituted or substituted Unsubstituted aryl groups or substituted or unsubstituted heterocyclic groups provided that they are each independently alkenyl, alkoxy, aryl or heterocyclic groups, and when adjacent, they may be bonded together.
    [2" claim-type="Currently amended] The organic electroluminescent device according to claim 1, wherein in Formula 1, A 1 and A 2 are both groups of Formula 2. 6.
    [3" claim-type="Currently amended] The organic electroluminescent device according to claim 1, wherein in Formula 1, A 1 and A 2 are both groups of Formula 3.
    [4" claim-type="Currently amended] The organic electroluminescent device according to claim 1, wherein in Formula 1, A 1 is a group of Formula 2, and A 2 is a group of Formula 3.
    [5" claim-type="Currently amended] The organic electroluminescent device according to claim 1, wherein the dipyridylthiophene derivative of Formula 1 is contained in the electron transporting layer.
    [6" claim-type="Currently amended] The organic electroluminescent device according to claim 1, wherein the dipyridylthiophene derivative of formula (1) is contained in the light emitting layer.
    [7" claim-type="Currently amended] An electron transport material comprising a dipyridylthiophene derivative of formula (I).
    [8" claim-type="Currently amended] A light emitting material comprising a dipyridylthiophene derivative of formula (1).
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    同族专利:
    公开号 | 公开日
    DE60100187T2|2004-04-01|
    EP1186605B1|2003-04-16|
    KR100806059B1|2008-02-21|
    DE60100187D1|2003-05-22|
    EP1186605A1|2002-03-13|
    US20020034658A1|2002-03-21|
    US6696182B2|2004-02-24|
    JP2002158093A|2002-05-31|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-09-07|Priority to JP2000271608
    2000-09-07|Priority to JPJP-P-2000-00271608
    2001-08-22|Application filed by 고토 기치, 칫소가부시키가이샤
    2002-03-13|Publication of KR20020019879A
    2008-02-21|Application granted
    2008-02-21|Publication of KR100806059B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP2000271608|2000-09-07|
    JPJP-P-2000-00271608|2000-09-07|
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