WO2023048118A1 - 化合物および有機エレクトロルミネッセンス素子 - Google Patents

化合物および有機エレクトロルミネッセンス素子 Download PDF

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WO2023048118A1
WO2023048118A1 PCT/JP2022/034920 JP2022034920W WO2023048118A1 WO 2023048118 A1 WO2023048118 A1 WO 2023048118A1 JP 2022034920 W JP2022034920 W JP 2022034920W WO 2023048118 A1 WO2023048118 A1 WO 2023048118A1
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幸喜 加瀬
絵里子 千葉
炳善 梁
文チャン 黄
雄太 平山
秀一 林
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Hodogaya Chemical Co Ltd
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Priority to CN202280051936.XA priority Critical patent/CN117715901A/zh
Priority to US18/681,888 priority patent/US20240360358A1/en
Priority to JP2023549688A priority patent/JPWO2023048118A1/ja
Priority to KR1020247004063A priority patent/KR20240067230A/ko
Priority to EP22872872.1A priority patent/EP4406947A4/en
Publication of WO2023048118A1 publication Critical patent/WO2023048118A1/ja
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Definitions

  • the present invention provides compounds suitable for self-luminous electronic devices suitable for various display devices, particularly compounds suitable for organic electroluminescence devices (hereinafter abbreviated as organic EL devices), and organic EL devices, electronic devices or It relates to electronic devices.
  • organic EL devices organic electroluminescence devices
  • organic EL elements are self-luminous elements, they are brighter than liquid crystal elements, have excellent visibility, and are capable of displaying clear images, which has led to active research.
  • the effect of the capping layer in the light-emitting device of the top emission structure is that the current efficiency of the light-emitting device using Ir(ppy) 3 as the light-emitting material was 38 cd/A without the capping layer. In the light-emitting element using ZnSe with a thickness of 60 nm, the efficiency was improved to 64 cd/A, which is about 1.7 times. In addition, it is shown that the maximum transmittance of the semi-transparent electrode and the capping layer does not always coincide with the maximum efficiency, and that the maximum light extraction efficiency is determined by the interference effect. (For example, see Non-Patent Document 3).
  • Alq 3 tris(8-hydroxyquinoline)aluminum
  • Alq 3 is a green light-emitting material or electron
  • organic EL material that is commonly used as a transport material
  • it has a weak absorption around 450 nm, which is used for blue light emitting materials. There is also the problem of reduced efficiency.
  • the material for the capping layer should have a high refractive index, a low extinction coefficient, and excellent stability and durability of the thin film. Good materials are in demand.
  • An object of the present invention is to provide a compound having a high refractive index and a low extinction coefficient in the wavelength range of 450 nm to 750 nm, which is suitable as a material for the capping layer of an organic EL device.
  • Another object of the present invention is to provide an organic EL device in which light extraction efficiency is improved by using the compound.
  • the physical properties of a compound suitable for the capping layer of an organic EL device include (1) a high refractive index, (2) a low extinction coefficient, (3) the possibility of vapor deposition, and (4) a thin film. (5) high glass transition temperature;
  • the physical properties of the organic EL element to be provided in the present invention are (1) high light extraction efficiency, (2) no decrease in color purity, and (3) no change over time. It can transmit light, and (4) it has a long life.
  • the present inventors optimized the molecular design by focusing on the fact that the compound with a carbazole skeleton is excellent in the stability and durability of the thin film. A material with high refractive index and low extinction coefficient was developed in the range. Moreover, as a result of producing an organic EL device using the compound and diligently evaluating the characteristics of the device, the present invention was completed because the conventional problems could be solved.
  • A represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group
  • B and C which may be the same or different, represent an unsubstituted naphthyl group, an unsubstituted quinolyl group, an unsubstituted benzofuranyl group, or an unsubstituted benzothienyl group
  • L may be the same or different from each other and are a single bond, a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent aromatic heterocyclic group, or a substituted or unsubstituted represents a divalent condensed polycyclic aromatic group.
  • B and C in the general formulas (3) and (4), which may be the same or different, are a 2-naphthyl group, a 3-quinolyl group, a 2-benzofuranyl group, or a 2-benzothienyl group; A compound according to 2).
  • L in the general formulas (3) and (4), which may be the same or different, is a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, or a substituted or unsubstituted
  • the condensed polycyclic aromatic group” includes the "aromatic hydrocarbon group", “aromatic heterocyclic group” or A divalent group obtained by removing one hydrogen atom from the group exemplified as the "condensed polycyclic aromatic group” can be mentioned.
  • a in the general formulas (1) to (4) is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted quinolyl group.
  • a substituted or unsubstituted benzofuranyl group a substituted or unsubstituted benzothienyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted benzoxazolyl group, or a substituted Alternatively, it is preferably an unsubstituted benzothiazolyl group.
  • B and C in the general formulas (1) to (4) may be the same or different, substituted or unsubstituted naphthyl group, substituted or unsubstituted quinolyl group, or substituted or An unsubstituted benzofuranyl group is preferred.
  • the compound represented by the general formula (1) is preferably a compound represented by the general formula (3)
  • the compound represented by the general formula (2) is a compound represented by the general formula (4) It is preferably a compound represented by.
  • the thickness of the capping layer is preferably in the range of 30 nm to 120 nm, more preferably in the range of 40 nm to 80 nm.
  • the compounds represented by the general formulas (1) and (2) of the present invention have (1) a high refractive index in the wavelength range of 450 nm to 750 nm, (2) a low extinction coefficient, and (3) vapor deposition. and (4) it is stable in a thin film state and (5) it has high heat resistance. A significantly improved organic EL device is obtained.
  • FIG. 1 shows the structures of compounds (1-1) to (1-12) as examples of the compounds of the present invention.
  • FIG. 1 shows the structures of compounds (1-13) to (1-24) as examples of the compounds of the present invention.
  • FIG. 1 shows the structures of compounds (1-25) to (1-36) as examples of the compounds of the present invention.
  • FIG. 1 shows the structures of compounds (1-37) to (1-48) as examples of the compounds of the present invention.
  • FIG. 1 shows the structures of compounds (1-49) to (1-57) as examples of the compounds of the present invention.
  • FIG. 1 shows the structures of compounds (1-58) to (1-66) as examples of the compounds of the present invention.
  • FIG. 1 shows the structures of compounds (1-67) to (1-75) as examples of the compounds of the present invention.
  • FIG. 1 shows the structures of compounds (1-1) to (1-12) as examples of the compounds of the present invention.
  • FIG. 1 shows the structures of compounds (1-13) to (1-24) as examples of the compounds of the present invention.
  • FIG. 1 shows the structures of compounds
  • carbazole compounds represented by the general formulas (1) and (2) are novel compounds
  • the compounds can be synthesized, for example, by a coupling reaction using a known copper catalyst or palladium catalyst. (For example, see Non-Patent Document 4 and Non-Patent Document 5).
  • FIGS. 1 to 10 specific examples of preferred compounds are shown in FIGS. 1 to 10, but are not limited to these compounds.
  • Purification of the compounds represented by the general formulas (1) and (2) is not particularly limited, and purification by column chromatography, adsorption purification by silica gel, activated carbon, activated clay, etc., recrystallization purification method using a solvent, or crystallization.
  • a known method used for purification of organic compounds such as a purification method and a sublimation purification method, can be used, and the compound can be identified by NMR analysis.
  • As physical properties it is preferable to measure the melting point, glass transition point (Tg), and refractive index.
  • the melting point is an index of vapor deposition properties
  • the glass transition point (Tg) is an index of the stability of the thin film state
  • the refractive index is an index of improvement in light extraction efficiency.
  • the melting point and glass transition point (Tg) can be measured using powder with a high-sensitivity differential scanning calorimeter (DSC3100SA, manufactured by Bruker AXS).
  • the refractive index and extinction coefficient can be measured by preparing a thin film of 80 nm on a silicon substrate and using a spectrometer (F10-RT-UV, manufactured by Filmetrics).
  • one organic layer can serve multiple roles, for example, a structure that serves as both a hole injection layer and a hole transport layer, a structure that serves as both a hole transport layer and an electron blocking layer, It is also possible to employ a structure that serves both as a hole-blocking layer and an electron-transporting layer, a structure that serves as both an electron-transporting layer and an electron-injecting layer, and the like. In addition, it is also possible to have a structure in which two or more organic layers having the same function are stacked, such as a structure in which two hole transport layers are stacked, a structure in which two light emitting layers are stacked, and a structure in which two electron transport layers are stacked. A laminated structure, a structure in which two capping layers are laminated, and the like are also possible.
  • the total thickness of each layer of the organic EL element is preferably about 200 nm to 750 nm, more preferably about 350 nm to 600 nm.
  • the film thickness of the capping layer is, for example, preferably 30 nm to 120 nm, more preferably 40 nm to 80 nm. In this case, good light extraction efficiency can be obtained.
  • the thickness of the capping layer can be appropriately changed according to the type of light-emitting material used in the light-emitting element, the thickness of the organic EL element other than the capping layer, and the like.
  • Electrode materials with a large work function such as ITO and gold, are used for the anode of organic EL elements.
  • an arylamine compound having a structure in which three or more triphenylamine structures are linked in the molecule by a single bond or a divalent group containing no heteroatom for example, a starburst type triphenylamine compound.
  • Materials such as phenylamine derivatives and various triphenylamine tetramers, porphyrin compounds typified by copper phthalocyanine, acceptor heterocyclic compounds such as hexacyanoazatriphenylene, and coating-type polymer materials can be used.
  • Thin films of these materials can be formed by known methods such as a spin coating method and an ink jet method in addition to the vapor deposition method.
  • N,N'-diphenyl-N,N'-di(m-tolyl)benzidine (hereinafter abbreviated as TPD) or N,N'-diphenyl-N,N'- benzidine derivatives such as di( ⁇ -naphthyl)benzidine, N,N,N',N'-tetrabiphenylylbenzidine, 1,1-bis[4-(di-4-tolylamino)phenyl]cyclohexane, especially in the molecule
  • the hole injection layer or the hole transport layer may be formed by P-doping a material normally used for the layer with trisbromophenylamine hexachloroantimony, a radialene derivative (see, for example, Patent Document 3), or the like. , TPD, etc., having a structure of a benzidine derivative in its partial structure, or the like can be used.
  • an electron blocking layer on the organic EL element.
  • the electron blocking layer 4,4′,4′′-tri(N-carbazolyl)triphenylamine (hereinafter abbreviated as TCTA), 9,9-bis[4-(carbazol-9-yl)phenyl] Carbazole derivatives such as fluorene, 1,3-bis(carbazol-9-yl)benzene (hereinafter abbreviated as mCP), 2,2-bis(4-carbazol-9-yl-phenyl)adamantane, 9-[4- (Carbazol-9-yl)phenyl]-9-[4-(triphenylsilyl)phenyl]-9H-fluorene
  • TCTA 4,4′,4′′-tri(N-carbazolyl)triphenylamine
  • mCP 1,3-bis(carbazol-9-yl)benzene
  • mCP 1,3-bis(carbazol-9-yl)benzene
  • Thin films of these materials can be formed by known methods such as a spin coating method and an ink jet method in addition to the vapor deposition method.
  • the light-emitting layer of an organic EL device can be used as the light-emitting layer of an organic EL device.
  • the light-emitting layer may be composed of a host material and a dopant material, and an anthracene derivative is preferably used as the host material.
  • a compound, a heterocyclic compound having a carbazole ring as a condensed ring partial structure, a carbazole derivative, a thiazole derivative, a benzimidazole derivative, a polydialkylfluorene derivative, and the like can be used.
  • the dopant material quinacridone, coumarin, rubrene, perylene and their derivatives, benzopyran derivatives, rhodamine derivatives, aminostyryl derivatives and the like can be used, and green light-emitting materials are particularly preferred. These may be deposited alone, or may be used as a single layer deposited by mixing with other materials, layers deposited alone, layers deposited by mixing, or A laminated structure of a layer formed independently and a layer formed by mixing may be employed.
  • a phosphorescent emitter As the phosphorescent emitter, a phosphorescent emitter of a metal complex such as iridium or platinum can be used. Green phosphorescent emitters such as Ir(ppy) 3 , blue phosphorescent emitters such as FIrpic and FIr6, and red phosphorescent emitters such as Btp2Ir (acac) are used. is particularly preferred.
  • Green phosphorescent emitters such as Ir(ppy) 3
  • blue phosphorescent emitters such as FIrpic and FIr6, and red phosphorescent emitters such as Btp2Ir (acac) are used. is particularly preferred.
  • Btp2Ir acac
  • the host material at this time 4,4′-di(N-carbazolyl)biphenyl and carbazole derivatives such as TCTA and mCP can be used as host materials having hole injection/transport properties.
  • Non-Patent Document 6 materials that emit delayed fluorescence, such as CDCB derivatives such as PIC-TRZ, CC2TA, PXZ-TRZ, and 4CzIPN, as light-emitting materials.
  • CDCB derivatives such as PIC-TRZ, CC2TA, PXZ-TRZ, and 4CzIPN
  • These materials can be used to form a thin film by a known method such as a spin coating method or an inkjet method in addition to the vapor deposition method.
  • a hole blocking layer on the organic EL element.
  • metal complexes of phenanthroline derivatives such as bathocuproine, and quinolinol derivatives such as aluminum (III) bis(2-methyl-8-quinolinato)-4-phenylphenolate (hereinafter abbreviated as BAlq)
  • BAlq quinolinol derivatives
  • Compounds having a hole-blocking action can be used, such as various rare earth complexes, triazole derivatives, triazine derivatives, pyrimidine derivatives, oxadiazole derivatives, and benzazole derivatives. These materials may also serve as materials for the electron transport layer.
  • Thin films of these materials can be formed by known methods such as a spin coating method and an ink jet method in addition to the vapor deposition method.
  • the electron injection layer or electron transport layer it is possible to use a material that is N-doped with a metal such as cesium to a material normally used for the layer.
  • Electrode materials with a low work function such as aluminum, alloys with a lower work function such as magnesium-silver alloys, magnesium-calcium alloys, magnesium-indium alloys, aluminum-magnesium alloys, ITO, IZO, etc., are used as cathodes of organic EL devices. Used as an electrode material.
  • Example 20 The melting points and glass transition points of the compounds obtained in Examples 1 to 19 were measured with a high-sensitivity differential scanning calorimeter (DSC3100SA, manufactured by Bruker AXS). Table 1 shows the results.
  • Example 21 Using the compound represented by the general formula (1) or (2) obtained in Examples 1 to 19, a deposited film having a thickness of 80 nm was prepared on a silicon substrate, and a spectrometer (F10, manufactured by Filmetrics Co., Ltd.) -RT-UV) was used to measure the refractive index n and the extinction coefficient k at wavelengths of 450 nm and 750 nm. For comparison, Alq 3 and comparative compound (2-1) having the following structural formula were also measured (see, for example, Patent Document 4). Table 2 summarizes the measured results.
  • the compound of the present invention has a refractive index equal to or higher than that of Alq 3 and the comparative compound (2-1) at wavelengths between 450 nm and 750 nm. By using it as a constituent material of the capping layer, an improvement in light extraction efficiency in the organic EL device can be expected.
  • Example 22 An organic EL device was produced using the compound (1-1) obtained in Example 1, and its characteristics were evaluated. As shown in FIG. 11, the organic EL device comprises a glass substrate 1 on which a reflective ITO electrode is formed in advance as a metal anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 5 and an electron transport layer. A layer 6, an electron injection layer 7, a cathode 8, and a capping layer 9 were deposited in this order.
  • a glass substrate 1 on which ITO with a film thickness of 50 nm, a silver alloy reflective film with a film thickness of 100 nm, and an ITO film with a film thickness of 5 nm are formed in this order was subjected to ultrasonic cleaning in isopropyl alcohol for 20 minutes. Drying was performed for 10 minutes on a hot plate heated to 250°C. Then, after performing UV ozone treatment for 2 minutes, this ITO-attached glass substrate was mounted in a vacuum deposition machine, and the pressure was reduced to 0.001 Pa or less.
  • an electron acceptor (Acceptor-1) of the following structural formula and a compound (3-1) of the following structural formula are deposited at a deposition rate ratio of Acceptor-1:compound (3-1)
  • Two-source vapor deposition was performed at a vapor deposition rate of 3:97 to form a film having a thickness of 10 nm.
  • a compound (3-1) having the following structural formula was formed as a hole transport layer 4 on the hole injection layer 3 so as to have a film thickness of 140 nm.
  • a compound (3-2) of the following structural formula and a compound (3-3) of the following structural formula are deposited as a light-emitting layer 5 at a vapor deposition rate ratio of (3-2):(3- 3) Binary vapor deposition was performed at a vapor deposition rate of 5:95 to form a film having a thickness of 20 nm.
  • Lithium fluoride was formed as an electron injection layer 7 on the electron transport layer 6 so as to have a thickness of 1 nm.
  • a magnesium-silver alloy was formed as a cathode 8 so as to have a thickness of 12 nm.
  • the compound (1-1) of Example 1 was formed as a capping layer 9 so as to have a film thickness of 60 nm.
  • Table 3 summarizes the measurement results of the light emission characteristics of the fabricated organic EL device when a DC voltage was applied in the atmosphere at room temperature.
  • Example 23 to 40 An organic EL device was manufactured under the same conditions as in Example 22, except that the compound (1-1) of Example 1 was replaced with the compound (1-1) of Example 1 as the capping layer 9 and the compounds of Examples 2 to 19 were formed to a thickness of 60 nm. made.
  • Table 3 summarizes the measurement results of the light emission characteristics of the fabricated organic EL device when a DC voltage was applied in the atmosphere at room temperature.
  • Example 1 For comparison, an organic EL device was manufactured under the same conditions as in Example 22, except that the capping layer 9 was changed to the compound (1-1) of Example 1 and Alq3 was formed to a thickness of 60 nm. made. Table 3 summarizes the measurement results of the light emission characteristics of the fabricated organic EL device when a DC voltage was applied in the atmosphere at room temperature.
  • Example 2 For comparison, under the same conditions as in Example 22, except that the compound (2-1) was formed as the capping layer 9 in place of the compound (1-1) of Example 1 so as to have a thickness of 60 nm. An organic EL device was produced. Table 3 summarizes the measurement results of the light emission characteristics of the fabricated organic EL device when a DC voltage was applied in the atmosphere at room temperature.
  • the voltage, luminance, luminous efficiency and power efficiency in Table 3 are the values at a current density of 10 mA/cm 2 , and the device life is calculated by dividing the initial luminance by 100 when driving at a constant current density of 10 mA/cm 2 . %, and measured as the time required for the brightness to decay to 95%.
  • the devices of Comparative Examples 1 and 2 and the devices of Examples 22 to 40 had substantially the same driving voltage at a current density of 10 mA/cm 2 , whereas the luminance and light emission All the devices of Examples were superior to the devices of Comparative Examples in terms of efficiency, power efficiency, and device life.
  • the compound represented by the general formula (1) or (2) of the present invention is a material that can be suitably used for the capping layer, and by increasing the refractive index of the capping layer, This indicates that the light extraction efficiency can be significantly improved.
  • the compound of the present invention has a high refractive index, can significantly improve the light extraction efficiency, and is stable in a thin film state, so it is excellent as a compound suitably used for organic EL devices. Further, an organic EL device produced using the compound of the present invention can obtain high efficiency. Furthermore, when it is desired to display clear and bright images with good color purity, it is particularly preferable to use the compounds of the present invention that do not absorb in any of the blue, green and red wavelength regions. For example, it can be expected to be used for home appliances and lighting.

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  • Spectroscopy & Molecular Physics (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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WO2025084253A1 (ja) 2023-10-17 2025-04-24 保土谷化学工業株式会社 カルバゾール化合物および有機エレクトロルミネッセンス素子
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WO2025084253A1 (ja) 2023-10-17 2025-04-24 保土谷化学工業株式会社 カルバゾール化合物および有機エレクトロルミネッセンス素子
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WO2025262916A1 (ja) * 2024-06-21 2025-12-26 シャープディスプレイテクノロジー株式会社 発光素子および表示装置

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