WO2016076384A1 - 有機エレクトロルミネッセンス素子 - Google Patents
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Definitions
- the present invention relates to an organic electroluminescence device, and more particularly to an organic electroluminescence device (hereinafter abbreviated as an organic EL device) using a specific arylamine compound and a specific pyrimidine derivative.
- Organic EL elements are brighter and have better visibility than liquid crystal elements, which are self-luminous elements, and can display clearly. For this reason, active research has been conducted on organic EL elements.
- the light emitting layer can also be produced by doping a charge transporting compound generally called a host material with a fluorescent compound, a phosphorescent compound, or a material that emits delayed fluorescence.
- a charge transporting compound generally called a host material with a fluorescent compound, a phosphorescent compound, or a material that emits delayed fluorescence.
- the selection of the organic material in the organic EL element greatly affects various characteristics such as efficiency and durability of the element.
- the light injected from both electrodes is recombined in the light emitting layer to obtain light emission, but it is important how efficiently both holes and electrons are transferred to the light emitting layer. It is necessary to make the device excellent in carrier balance.
- the probability of recombination of holes and electrons is improved by improving the hole injection property and blocking the electrons injected from the cathode, and further excitons generated in the light emitting layer. By confining, high luminous efficiency can be obtained. Therefore, the role of the hole transport material is important, and there is a demand for a hole transport material that has high hole injectability, high hole mobility, high electron blocking properties, and high durability against electrons. ing.
- the heat resistance and amorphous nature of the material are important for the lifetime of the element.
- thermal decomposition occurs even at a low temperature due to heat generated when the element is driven, and the material deteriorates.
- crystallization of the thin film occurs even in a short time, and the element deteriorates. For this reason, the material used is required to have high heat resistance and good amorphous properties.
- NPD N, N′-diphenyl-N, N′-di ( ⁇ -naphthyl) benzidine
- Patent Reference 2 various aromatic amine derivatives
- NPD has a good hole transport capability, but its glass transition point (Tg), which is an index of heat resistance, is as low as 96 ° C., and device characteristics are degraded by crystallization under high temperature conditions.
- Tg glass transition point
- Patent Documents 1 and 2 there are compounds having an excellent mobility of hole mobility of 10 ⁇ 3 cm 2 / Vs or more, but the electron blocking property is not satisfactory.
- Patent Document 3 reports a highly durable aromatic amine derivative.
- the aromatic amine derivative of Patent Document 3 is used as a charge transport material for an electrophotographic photosensitive member, and an example in which it is used for an organic EL device has not been studied at all.
- An arylamine compound having a substituted carbazole structure has been proposed as a compound with improved properties such as heat resistance and hole injection properties (see Patent Documents 4 and 5).
- heat resistance and hole injection properties see Patent Documents 4 and 5.
- heat resistance and light emission efficiency have been improved, but the degree is still not sufficient, and further lower drive voltage and higher There is a need for higher luminous efficiency.
- JP-A-8-048656 Japanese Patent No. 3194657 Japanese Patent No. 4943840 JP 2006-151979 A International Publication No. 2008/62636 International Publication No. 2011/059000 International Publication No. 2003/060956 JP-A-7-126615 JP 2005-108804 A
- the object of the present invention is to provide various materials for organic EL elements having excellent hole injection / transport performance, electron injection / transport performance, electron blocking capability, stability in a thin film state, durability, etc. (1) High luminous efficiency and power efficiency, (2) Low light emission starting voltage, (3) Low practical driving voltage, (4) Especially long life An organic EL element is provided.
- the present inventors paid attention to the point that the arylamine-based material is excellent in hole injection / transport capability, thin film stability and durability.
- the inventors have a two-layer structure of the hole transport layer, and when an arylamine compound having a specific structure is selected as a material for the hole transport layer (second hole transport layer) adjacent to the light emitting layer, We have obtained knowledge that holes can be efficiently injected and transported to the light emitting layer.
- a pyrimidine derivative having a specific structure is selected as a material for the electron transport layer, electrons can be efficiently injected and transported to the light emitting layer.
- an organic electroluminescence device having at least an anode, a hole injection layer, a first hole transport layer, a second hole transport layer, a light emitting layer, an electron transport layer and a cathode in this order
- the second hole transport layer contains an arylamine compound represented by the following general formula (1)
- An organic EL device is provided in which the electron transport layer contains a pyrimidine derivative represented by the following general formula (2).
- Ar 1 to Ar 4 each represents an aromatic hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group; n represents an integer of 2 to 4.
- Ar 5 represents an aromatic hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group
- Ar 6 and Ar 7 each represent a hydrogen atom, an aromatic hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group, and Ar 6 and Ar 7 do not simultaneously become a hydrogen atom
- A represents a monovalent group represented by the following structural formula (3).
- R 1 to R 4 are each a hydrogen atom, a deuterium atom, a fluorine atom, Represents a chlorine atom, a cyano group, a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group, and R 1 to R 4 and Ar 8 may be bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring.
- the first hole transport layer is a triarylamine compound having 3 to 6 triarylamine structures in the molecule, wherein the triarylamine structure is a divalent group or a single group containing no hetero atom.
- the triarylamine compound having 3 to 6 triarylamine structures is a triarylamine compound having four triarylamine structures in a molecule represented by the following general formula (4): Where r 5 , r 6 , r 9 , r 12 , r 15 and r 16 each represents an integer from 0 to 5; r 7 , r 8 , r 10 , r 11 , r 13 and r 14 are each from 0 to 4 Represents an integer of R 5 to R 16 are each a deuterium atom, fluorine atom, chlorine atom, cyano group, nitro group, alkyl group having 1 to 6 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms, or 2 to An alkenyl group having 6 carbon atoms, an alkyloxy group having 1 to 6 carbon atoms, a cycloalkyloxy group having 5 to 10 carbon atoms, an aromatic
- L 1 to L 3 each represents a single bond or a divalent group represented by any one of the following structural formulas (B) to (G).
- n1 represents an integer of 1 to 3.
- the first hole transport layer is a triarylamine compound having two triarylamine structures in the molecule, and the triarylamine structure is a divalent group or a single bond containing no hetero atom.
- the triarylamine compound having two triarylamine structures is represented by the following general formula (5): Where r 17 , r 18 , r 21 and r 22 each represents an integer of 0 to 5; r 19 and r 20 each represents an integer of 0 to 4; R 17 to R 22 are each a deuterium atom, a fluorine atom, a chlorine atom, Cyano group, nitro group, alkyl group having 1 to 6 carbon atoms, cycloalkyl group having 5 to 10 carbon atoms, alkenyl group having 2 to 6 carbon atoms, alkyloxy group having 1 to 6 carbon atoms, and 5 to 10 carbon atoms Represents a cycloalkyloxy group, an aromatic hydrocarbon group, an aromatic heterocyclic group, a condensed polycyclic aromatic group or an aryloxy group, and when these groups are bonded to the same benzene ring, multiple bonds are formed.
- the groups may be bonded to each other through a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring, L 4 represents a single bond or a divalent group represented by the structural formulas (C) to (G).
- the pyrimidine derivative contained in the electron transport layer is represented by the following general formula (2a). In the formula, Ar 5 to Ar 7 and A represent the same meaning as described in the general formula (2). (6)
- the pyrimidine derivative contained in the electron transport layer is represented by the following general formula (2b): In the formula, Ar 5 to Ar 7 and A represent the same meaning as described in the general formula (2).
- A is a monovalent group represented by the following structural formula (3a),
- Ar 8 and R 1 to R 4 represent the meanings as described in the structural formula (3).
- the light emitting layer contains a blue light emitting dopant, (9) The blue light-emitting dopant is a pyrene derivative, (10) The light emitting layer contains an anthracene derivative, (11) The light emitting layer contains the anthracene derivative as a host material, Is preferred.
- the hole transport layer has a two-layer structure, and an arylamine compound having a specific structure and a specific structure are considered in consideration of carrier balance.
- a pyrimidine derivative having a structure was combined.
- holes and electrons can be efficiently injected and transported into the light emitting layer, and an organic EL element with high efficiency, low driving voltage, and long life can be realized.
- a triarylamine compound having a specific structure was combined as a material for the first hole transport layer, and a combination of materials with a more refined carrier balance was selected.
- an organic EL device that not only has a higher light emission efficiency and a lower driving voltage than a conventional organic EL device, but also has particularly excellent durability.
- FIG. 5 is a diagram showing the configurations of organic EL elements of element examples 1 to 6 and element comparative examples 1 to 4.
- FIG. 2 is a diagram showing the structural formulas of compounds (1-1) to (1-4) in the arylamine compound of general formula (1).
- FIG. 3 is a diagram showing the structural formulas of compounds (1-5) to (1-8) in the arylamine compound of general formula (1).
- FIG. 2 is a diagram showing the structural formulas of compounds (1-9) to (1-12) in the arylamine compound of general formula (1).
- FIG. 2 is a diagram showing the structural formulas of compounds (1-13) to (1-17) in the arylamine compound of general formula (1).
- FIG. 2 is a diagram showing the structural formulas of compounds (1-18) to (1-21) in the arylamine compound of general formula (1).
- FIG. 2 is a diagram showing the structural formulas of compounds (1-22) to (1-25) in the arylamine compound of general formula (1).
- FIG. 2 is a diagram showing the structural formulas of compounds (1-26) to (1-29) in the arylamine compound of general formula (1).
- FIG. 3 is a diagram showing the structural formulas of compounds (1-30) to (1-32) in the arylamine compound of general formula (1).
- FIG. 4 is a diagram showing the structural formulas of compounds (1-33) to (1-36) in the arylamine compound of general formula (1).
- FIG. 3 is a diagram showing the structural formulas of compounds (1-37) to (1-40) in the arylamine compound of general formula (1).
- FIG. 4 is a diagram showing the structural formulas of compounds (1-41) to (1-44) in the arylamine compound of the general formula (1).
- FIG. 5 is a diagram showing the structural formulas of compounds (2-1) to (2-5) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-6) to (2-9) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing structural formulas of compounds (2-10) to (2-13) in the pyrimidine derivative represented by the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-14) to (2-17) in the pyrimidine derivative represented by general formula (2).
- FIG. 2 is a diagram showing structural formulas of compounds (2-18) to (2-21) in the pyrimidine derivative represented by the general formula (2).
- FIG. 2 is a diagram showing the structural formulas of compounds (2-22) to (2-25) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-26) to (2-29) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing structural formulas of compounds (2-30) to (2-33) in the pyrimidine derivative represented by the general formula (2).
- FIG. 3 is a diagram showing structural formulas of compounds (2-34) to (2-37) in the pyrimidine derivative represented by the general formula (2).
- FIG. 4 is a diagram showing the structural formulas of compounds (2-38) to (2-41) in the pyrimidine derivative of the general formula (2).
- FIG. 4 is a diagram showing the structural formulas of compounds (2-42) to (2-45) in the pyrimidine derivative of the general formula (2).
- FIG. 4 is a diagram showing the structural formulas of compounds (2-46) to (2-49) in the pyrimidine derivative of the general formula (2).
- FIG. 5 is a diagram showing the structural formulas of compounds (2-50) to (2-53) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-54) to (2-57) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-58) to (2-61) in the pyrimidine derivative represented by the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-62) to (2-65) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-66) to (2-69) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-70) to (2-73) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-74) to (2-76) in the pyrimidine derivative represented by general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-77) to (2-79) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing structural formulas of compounds (2-80) to (2-82) in the pyrimidine derivative represented by the general formula (2).
- FIG. 3 is a diagram showing structural formulas of compounds (2-83) to (2-85) in the pyrimidine derivative represented by the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-86) to (2-88) in the pyrimidine derivative represented by general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-89) to (2-91) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-92) to (2-94) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-95) to (2-97) in the pyrimidine derivative of the general formula (2).
- FIG. 2 is a diagram showing structural formulas of compounds (2-98) to (2-100) in the pyrimidine derivative represented by the general formula (2).
- FIG. 2 is a diagram showing the structural formulas of compounds (2-101) to (2-104) in the pyrimidine derivative of the general formula (2).
- FIG. 2 is a diagram showing the structural formulas of compounds (2-105) to (2-107) in the pyrimidine derivative represented by the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-108) to (2-110) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-111) to (2-113) in the pyrimidine derivative of the general formula (2).
- FIG. 2 is a diagram showing the structural formulas of compounds (2-114) to (2-116) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-117) to (2-119) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-120) to (2-122) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-123) to (2-126) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-127) to (2-129) in the pyrimidine derivative of the general formula (2).
- FIG. 2 is a diagram showing the structural formulas of compounds (2-130) to (2-133) in the pyrimidine derivative represented by the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-134) to (2-137) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-138) to (2-140) in the pyrimidine derivative of the general formula (2).
- FIG. 2 is a diagram showing the structural formulas of compounds (2-141) to (2-143) in the pyrimidine derivative of the general formula (2).
- FIG. 2 is a diagram showing the structural formulas of compounds (2-144) to (2-147) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-148) to (2-150) in the pyrimidine derivative represented by the general formula (2).
- FIG. 2 is a diagram showing the structural formulas of compounds (2-151) to (2-154) in the pyrimidine derivative of the general formula (2).
- FIG. 2 is a diagram showing the structural formulas of compounds (2-155) to (2-157) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-158) to (2-161) in the pyrimidine derivative represented by the general formula (2).
- FIG. 2 is a diagram showing the structural formulas of compounds (2-162) to (2-165) in pyrimidine derivatives represented by general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-166) to (2-168) in the pyrimidine derivative of the general formula (2).
- FIG. 2 is a diagram showing the structural formulas of compounds (2-169) to (2-172) in pyrimidine derivatives of general formula (2).
- FIG. 2 is a diagram showing the structural formulas of compounds (2-173) to (2-176) in the pyrimidine derivative of the general formula (2).
- FIG. 2 is a diagram showing the structural formulas of compounds (2-177) to (2-180) in the pyrimidine derivative represented by the general formula (2).
- FIG. 2 is a diagram showing the structural formulas of compounds (2-181) to (2-184) in the pyrimidine derivative of the general formula (2).
- FIG. 2 is a diagram showing the structural formulas of compounds (2-185) to (2-188) in the pyrimidine derivative of the general formula (2).
- FIG. 2 is a diagram showing the structural formulas of compounds (2-189) to (2-192) in the pyrimidine derivative of the general formula (2).
- FIG. 4 is a diagram showing the structural formulas of compounds (2-193) to (2-196) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-197) to (2-200) in the pyrimidine derivative represented by the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-201) to (2-204) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-205) to (2-208) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-209) to (2-212) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-213) to (2-216) in the pyrimidine derivative of the general formula (2).
- FIG. 4 is a diagram showing the structural formulas of compounds (2-217) to (2-220) in the pyrimidine derivative represented by the general formula (2).
- FIG. 2 is a diagram showing the structural formulas of compounds (2-221) to (2-223) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-224) to (2-227) in the pyrimidine derivative of the general formula (2).
- FIG. 2 is a diagram showing the structural formulas of compounds (2-228) to (2-231) in the pyrimidine derivative represented by the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-232) to (2-235) in the pyrimidine derivative of the general formula (2).
- FIG. 2 is a diagram showing the structural formulas of compounds (2-236) to (2-239) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-240) to (2-243) in the pyrimidine derivative of the general formula (2).
- FIG. 3 is a diagram showing the structural formulas of compounds (2-244) to (2-247) in the pyrimidine derivative of the general formula (2).
- FIG. 2 is a diagram showing the structural formulas of compounds (2-248) to (2-252) in the pyrimidine derivative of the general formula (2).
- FIG. 2 is a diagram showing the structural formulas of compounds (2-253) to (2-256) in the pyrimidine derivative represented by general formula (2).
- FIG. 4 is a diagram showing the structural formulas of compounds (2-257) to (2-260) in the pyrimidine derivative represented by the general formula (2).
- FIG. 2 is a diagram showing the structural formulas of compounds (2-261) to (2-264) in the pyrimidine derivative of the general formula (2).
- FIG. 4 is a diagram showing the structural formulas of compounds (4-1) to (4-4) in the triarylamine compound of the general formula (4).
- FIG. 5 is a diagram showing the structural formulas of compounds (4-5) to (4-7) in the triarylamine compound of general formula (4).
- FIG. 4 is a diagram showing the structural formulas of compounds (4-8) to (4-11) in the triarylamine compound of the general formula (4).
- FIG. 4 is a diagram showing the structural formulas of compounds (4-12) to (4-15) in the triarylamine compound of general formula (4).
- FIG. 4 is a diagram showing the structural formulas of compounds (4-16) to (4-17) in the triarylamine compound of general formula (4).
- FIG. 3 is a diagram showing the structural formulas of compounds (4′-1) to (4′-2) in triarylamine compounds other than the general formula (4).
- FIG. 4 is a diagram showing the structural formulas of compounds (5-1) to (5-4) in the triarylamine compound of the general formula (5).
- FIG. 5 is a diagram showing the structural formulas of compounds (5-5) to (5-7) in the triarylamine compound of the general formula (5).
- FIG. 5 is a diagram showing the structural formulas of compounds (5-8) to (5-10) in the triarylamine compound of the general formula (5).
- FIG. 5 is a diagram showing the structural formulas of compounds (5-11) to (5-14) in the triarylamine compound of the general formula (5).
- FIG. 5 is a diagram showing the structural formulas of compounds (5-15) to (5-18) in the triarylamine compound of the general formula (5).
- FIG. 2 is a diagram showing the structural formulas of compounds (5-19) to (5-22) in the triarylamine compound of general formula (5).
- FIG. 3 is a diagram showing a structural formula of a compound (5-23) in the triarylamine compound of the general formula (5).
- FIG. 3 is a diagram showing the structural formulas of compounds (5′-1) to (5′-2) in triarylamine compounds other than the general formula (5).
- the organic EL device of the present invention has at least an anode, a hole injection layer, a first hole transport layer, a second hole transport layer, and a light emitting layer on a transparent substrate such as a glass substrate or a plastic substrate (for example, a polyethylene terephthalate substrate).
- the electron transport layer and the cathode have a basic structure formed in this order.
- the layer structure can take various forms, for example, an electron blocking layer is provided between the second hole transport layer and the light emitting layer, A hole blocking layer may be provided between the electron transport layers, or an electron injection layer may be provided between the electron transport layer and the cathode.
- FIG. 1 shows a layer structure adopted in an element example to be described later.
- an anode 2 a hole injection layer 3, a first hole transport layer 4, a first layer are formed on a transparent substrate 1.
- the second hole transport layer 5 contains an arylamine compound represented by the general formula (1)
- the electron transport layer 7 has the general formula ( It has an important feature in that it contains a pyrimidine derivative represented by 2).
- the arylamine compound represented by the general formula (1) and the pyrimidine derivative represented by the general formula (2) will be described.
- Such an arylamine compound has a high glass transition point Tg (for example, 100 ° C. or more), as will be understood from Examples described later, and therefore, the thin film state is stable and the heat resistance is excellent.
- Tg glass transition point
- it has a high work function as compared with the work function (about 5.4 eV) of a general hole transport material, and therefore, it has excellent hole transportability, and the hole mobility is high. It is large and has good hole injection characteristics. Furthermore, it has excellent electron blocking properties.
- n represents an integer of 2 to 4, and preferably represents an integer of 2 or 3 from the viewpoint of hole transport capability.
- Ar 1 to Ar 4 each represents an aromatic hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group.
- aromatic hydrocarbon group, aromatic heterocyclic group or condensed polycyclic aromatic group represented by Ar 1 to Ar 4 include phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthracenyl group, phenanthrenyl.
- Ar 1 to Ar 4 are preferably present independently of each other, but Ar 1 and Ar 2 or Ar 3 and Ar 4 are each bonded via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom. They may be bonded to each other to form a ring.
- the aromatic heterocyclic group represented by Ar 1 ⁇ Ar 4 sulfur-containing aromatic heterocyclic group, for example a thienyl group, benzothienyl group, benzothiazolyl group, dibenzothienyl group, oxygen-containing aromatic heterocyclic group such as furyl A pyrrolyl group, a benzofuranyl group, a benzooxazolyl group, a dibenzofuranyl group; or an N-substituted carbazolyl group having a substituent selected from the aromatic hydrocarbon groups and condensed polycyclic aromatic groups exemplified above. preferable.
- the above aromatic hydrocarbon group, aromatic heterocyclic group or condensed polycyclic aromatic group may have a substituent.
- substituents include the following groups in addition to a deuterium atom, a cyano group, and a nitro group.
- Halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, iodine atoms
- Alkyl groups having 1 to 6 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert- Butyl, n-pentyl, isopentyl, neopentyl, n- A hexyl group
- An alkyloxy group having 1 to 6 carbon atoms such as a methyloxy group, an ethyloxy group, a propyloxy group
- An alkenyl group such as a vinyl group, an allyl
- substituents may further have the substituents exemplified above. These substituents may exist independently of each other, but are bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring. Also good.
- the arylamine compound represented by the general formula (1) can be synthesized by a method known per se such as Suzuki coupling.
- the produced arylamine compound is purified by column chromatography, adsorption purification using silica gel, activated carbon, activated clay, etc., recrystallization or crystallization using a solvent, and finally purified by sublimation purification. .
- the compound can be identified by NMR analysis.
- glass transition point (Tg) and work function can be measured.
- the glass transition point (Tg) is an indicator of the stability of the thin film state.
- the glass transition point (Tg) can be determined by a high-sensitivity differential scanning calorimeter (manufactured by Bruker AXS, DSC3100S) using powder.
- Work function is an indicator of hole transportability.
- the work function can be obtained by preparing a 100 nm thin film on an ITO substrate and using an ionization potential measuring apparatus (Sumitomo Heavy Industries, Ltd., PYS-202).
- Ar 1 to Ar 4 are preferably an aromatic hydrocarbon group, an oxygen-containing aromatic heterocyclic group or a condensed polycyclic aromatic group, and include a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group, a phenanthrenyl group, a fluorenyl group, a dibenzo group.
- a furanyl group is more preferred.
- Ar 1 and Ar 2 are preferably different groups, or Ar 3 and Ar 4 are preferably different groups, more preferably Ar 1 and Ar 2 are different groups, and Ar 3 and Ar 4 are different groups. preferable.
- the bonding mode of the phenylene group in the general formula (1) from the viewpoint of the stability of the thin film that affects the device lifetime, not all bonds are 1,4-bonds, but 1,4-bonds. Further, it is preferable that 1,2-bond or 1,3-bond are mixed.
- FIGS. 2 to 12 Specific examples of preferable compounds among the arylamine compounds represented by the general formula (1) are shown in FIGS. 2 to 12, and the arylamine compounds represented by the general formula (1) include these compounds. It is not limited. Note that D in the structural formula represents deuterium.
- Such a pyrimidine derivative is excellent in electron injection ability and transport ability, and is a preferred compound as a material for the electron transport layer.
- Ar 5 represents an aromatic hydrocarbon group, an aromatic heterocyclic group or a condensed polycyclic aromatic group
- Ar 6 and Ar 7 represent a hydrogen atom, an aromatic hydrocarbon group, Represents an aromatic heterocyclic group or a condensed polycyclic aromatic group.
- Ar 6 and Ar 7 do not become a hydrogen atom at the same time.
- aromatic hydrocarbon group, aromatic heterocyclic group or condensed polycyclic aromatic group represented by Ar 5 to Ar 7 include a phenyl group, a biphenylyl group, a terphenylyl group, a tetrakisphenyl group, a styryl group, Naphthyl, anthracenyl, acenaphthenyl, phenanthrenyl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthenyl, triphenylenyl, spirobifluorenyl, furyl, thienyl, benzofuranyl, benzothienyl And groups such as a group, a dibenzofuranyl group, and a dibenzothienyl group.
- the aromatic hydrocarbon group, aromatic heterocyclic group or condensed polycyclic aromatic group represented by Ar 5 to Ar 7 may have a substituent.
- substituent In addition to the deuterium atom, cyano group and nitro group, the following groups can be mentioned.
- Halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, iodine atoms; Alkyl groups having 1 to 6 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert- Butyl, n-pentyl, isopentyl, neopentyl, n- A hexyl group; An alkyloxy group having 1 to 6 carbon atoms, such as a methyloxy group, an ethyloxy group, a propyloxy group; An alkenyl group, such as a vinyl group, an allyl group; An aryloxy group such as a phenyloxy group, a tolyloxy group; Arylalkyloxy groups such as benzyloxy group, phenethyloxy group; An aromatic hydrocarbon group or a condensed poly
- substituents may further have the substituents exemplified above. These substituents may be present independently of each other, but are bonded to each other via a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring. In addition, these substituents and Ar 5 , Ar 6 or Ar 7 to which the substituents are bonded are bonded to each other via an oxygen atom, a sulfur atom or a substituted or unsubstituted methylene group to form a ring. You may do it.
- A represents a monovalent group represented by the following structural formula (3).
- Ar 8 represents an aromatic heterocyclic group.
- Specific examples of the aromatic heterocyclic group represented by Ar 8 include triazinyl group, pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, thienyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group.
- the aromatic heterocyclic group represented by Ar 8 may have a substituent.
- the aromatic hydrocarbon group represented by Ar 5 to Ar 7 in the general formula (2), the aromatic heterocyclic group, or the condensed polycyclic aromatic group may have a substituent.
- the same thing can be given.
- the aspect which a substituent can take is also the same.
- the phenyl group and Ar 8 may be present independently of each other, but via a substituted or unsubstituted methylene group, as in exemplified compounds 2-248 and 2-249 described later. They may combine with each other to form a ring.
- R 1 to R 4 are each a hydrogen atom, a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group, or an aromatic heterocyclic group. Or represents a condensed polycyclic aromatic group.
- R 1 to R 4 and the aforementioned Ar 8 may exist independently of each other, but are bonded to each other through a single bond, a substituted or unsubstituted methylene group, an oxygen atom or a sulfur atom to form a ring. You may do it.
- the alkyl group having 1 to 6 carbon atoms represented by R 1 to R 4 may be linear or branched, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl. Group, 2-methylpropyl group, t-butyl group, n-pentyl group, 3-methylbutyl group, tert-pentyl group, n-hexyl group, iso-hexyl group, tert-hexyl group and the like.
- aromatic hydrocarbon group, aromatic heterocyclic group or condensed polycyclic aromatic group represented by R 1 to R 4 include a phenyl group, a biphenylyl group, a terphenylyl group, a tetrakisphenyl group, a styryl group, Naphtyl group, Anthracenyl group, Acenaphthenyl group, Phenanthrenyl group, Fluorenyl group, Indenyl group, Pyrenyl group, Perylenyl group, Fluoranthenyl group, Triphenylenyl group, Spirobifluorenyl group, Triazinyl group, Pyridyl group, Pyrimidinyl group, Furyl group , Pyrrolyl group, thienyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group, benzoxazolyl
- the aromatic hydrocarbon group, aromatic heterocyclic group or condensed polycyclic aromatic group represented by R 1 to R 4 may have a substituent.
- the aromatic hydrocarbon group represented by Ar 5 to Ar 7 in the general formula (2), the aromatic heterocyclic group, or the condensed polycyclic aromatic group may have a substituent.
- the same thing can be given.
- the aspect which a substituent can take is also the same.
- the following embodiments 1) to 14) are preferable.
- This pyrimidine derivative is represented by the following general formula (2a).
- Ar 5 to Ar 7 and A have the same meanings as described in the general formula (2).
- This pyrimidine derivative is represented by the following general formula (2b).
- Ar 5 to Ar 7 and A have the same meanings as described in the general formula (2).
- A is a monovalent group represented by the following structural formula (3a). This embodiment is preferable from the viewpoint of thin film stability.
- Ar 8 and R 1 to R 4 have the same meanings as described in the structural formula (3).
- A is a monovalent group represented by the following structural formula (3b).
- Ar 8 and R 1 to R 4 have the same meanings as described in the structural formula (3).
- Ar 5 represents an aromatic hydrocarbon group or a condensed polycyclic aromatic group
- Ar 6 and Ar 7 each represent a hydrogen atom, an aromatic hydrocarbon group, or a condensed polycyclic aromatic group.
- Ar 6 is a phenyl group having a substituent.
- Ar 6 is a phenyl group having a substituent, and the substituent is a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted condensed polycyclic aromatic group.
- Ar 6 is a phenyl group having a substituent, and the substituent is a substituted or unsubstituted aromatic hydrocarbon group.
- Ar 6 is a phenyl group having a substituent, and the substituent is a substituted or unsubstituted condensed polycyclic aromatic group.
- Ar 7 is a hydrogen atom.
- Ar 5 is a phenyl group having a substituent.
- Ar 5 is a phenyl group having a substituent, and the substituent is a substituted or unsubstituted condensed polycyclic aromatic group.
- Ar 5 is a substituted or unsubstituted condensed polycyclic aromatic group.
- Ar 5 is an unsubstituted phenyl group.
- Ar 5 in the general formula (2) includes a phenyl group; a biphenylyl group; a naphthyl group; an anthracenyl group; an acenaphthenyl group; a phenanthrenyl group; a fluorenyl group; an indenyl group; a pyrenyl group; a perylenyl group; a fluoranthenyl group; Spirobifluorenyl group; oxygen-containing aromatic heterocyclic group such as furyl group, benzofuranyl group, dibenzofuranyl group; or sulfur-containing aromatic heterocyclic group such as thienyl group, benzothienyl group, dibenzothienyl group; , Phenyl group, biphenylyl group, naphthyl group, phenanthrenyl group, fluorenyl group, pyrenyl group, fluoranthenyl group, triphenylenyl group, spirobifluorenyl
- the phenyl group preferably has a substituted or unsubstituted condensed polycyclic aromatic group or a phenyl group as a substituent, and includes a naphthyl group, a phenanthrenyl group, a pyrenyl group, a fluoranthenyl group, a triphenylenyl group, More preferably, it has a spirobifluorenyl group or a phenyl group as a substituent. Furthermore, it is also preferable that the substituent which the phenyl group has and the phenyl group are bonded to each other via an oxygen atom or a sulfur atom to form a ring.
- Ar 6 includes a phenyl group having a substituent; a substituted or unsubstituted spirobifluorenyl group; an oxygen-containing aromatic heterocyclic group such as a furyl group, a benzofuranyl group, a dibenzofuranyl group; or a sulfur-containing aromatic complex. Ring groups such as thienyl, benzothienyl, dibenzothienyl are preferred.
- the substituent of the phenyl group includes an aromatic hydrocarbon group such as a phenyl group, a biphenylyl group, and a terphenyl group; a condensed polycyclic aromatic group such as a naphthyl group, an acenaphthenyl group, a phenanthrenyl group, a fluorenyl group, and an indenyl group.
- Ar 7 includes a hydrogen atom; a substituted phenyl group; a substituted or unsubstituted spirobifluorenyl group; an oxygen-containing aromatic heterocyclic group such as a furyl group, a benzofuranyl group, a dibenzofuranyl group; or a sulfur-containing group.
- Aromatic heterocyclic groups such as thienyl, benzothienyl, dibenzothienyl are preferred.
- the substituent of the phenyl group includes an aromatic hydrocarbon group such as a phenyl group, a biphenylyl group, and a terphenyl group; a condensed polycyclic aromatic group such as a naphthyl group, an acenaphthenyl group, a phenanthrenyl group, a fluorenyl group, and an indenyl group.
- Ar 8 includes a nitrogen-containing aromatic heterocyclic group such as triazinyl group, pyridyl group, pyrimidinyl group, pyrrolyl group, quinolyl group, isoquinolyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalinyl group, Benzimidazolyl, pyrazolyl, azafluorenyl, diazafluorenyl, naphthyridinyl, phenanthrolinyl, acridinyl, carbolinyl, azaspirobifluorenyl, diazaspirobifluorenyl are preferred, Triazinyl group, pyridyl group, pyrimidinyl group, quinolyl group, isoquinolyl group, indolyl group, quinoxalinyl group, azafluorenyl group, diazafluorenyl group, benzoimidazoly
- Ar 5 and Ar 6 may be the same, but are preferably not the same from the viewpoint of the stability of the thin film.
- the embodiment in which Ar 5 and Ar 6 are the same group includes an embodiment having different substituents and an embodiment having substituents at different positions.
- Ar 6 and Ar 7 may be the same group, but may be easily crystallized by improving the symmetry of the whole molecule. From the viewpoint of thin film stability, Ar 6 And Ar 7 are preferably different groups. Moreover, it is preferable that one of Ar 6 and Ar 7 is a hydrogen atom.
- FIGS. 13 to 83 Specific examples of preferred compounds among the pyrimidine derivatives represented by the general formula (2) are shown in FIGS. 13 to 83, but such pyrimidine derivatives are not limited to these compounds.
- Compounds 2-1 to 2-49, 2-66 to 2-99, 2-103 to 2-105, 2-107 to 2-148, 2-150 to 2-182 and 2-184 to 2-264 Corresponds to the general formula (2a).
- Compounds 2-50 to 2-65, 2-100 to 2-102, 2-106, 2-149 and 2-183 correspond to the general formula (2b).
- D in the structural formula represents deuterium.
- the pyrimidine derivative represented by the general formula (2) can be synthesized by a method known per se (see Patent Documents 6 and 7).
- the anode 2 is formed on the transparent substrate 1 by vapor deposition of an electrode material having a large work function such as ITO or gold.
- the hole injection layer 3 is provided between the anode 2 and the first hole transport layer 4.
- the hole injection layer 3 includes a known material such as a starburst type triphenylamine derivative; various triphenylamine tetramers; a porphyrin compound represented by copper phthalocyanine; an acceptor property such as hexacyanoazatriphenylene. Heterocyclic compounds; coating-type polymer materials; and the like can be used.
- an arylamine compound represented by the general formula (1), a triarylamine compound represented by the following general formula (4), or a triarylamine compound represented by the following general formula (5) is used. You can also.
- the materials used for the above-described hole injection layer are P-doped with trisbromophenylamine hexachloroantimony, a radialene derivative (see International Publication No. 2014/009310), or a benzidine derivative such as TPD.
- a polymer compound having a structure in its partial structure can also be used in combination.
- the hole injection layer 3 can be obtained.
- each layer described below can be obtained by forming 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 transport layer exists between the hole injection layer 3 and the light emitting layer 6.
- this hole transport layer is composed of the first hole transport layer 4 and the second hole transport layer 5. It has a two-layer structure.
- a known hole transport material can be used for the first hole transport layer.
- known hole transport materials include the following specific examples: Benzidine derivatives such as N, N′-diphenyl-N, N′-di (m-tolyl) benzidine (TPD), N, N′-diphenyl-N, N′-di ( ⁇ -naphthyl) benzidine (NPD), N, N, N ′, N′-tetrabiphenylylbenzidine; 1,1-bis [4- (di-4-tolylamino) phenyl] cyclohexane (TAPC);
- Various triarylamine trimers and tetramers for example, triarylamine compounds having 3 to 6 triarylamine structures in the molecule, wherein the triarylamine structure does not contain a heteroatom Or a triarylamine compound linked by a single bond, A triarylamine compound having two triarylamine structures
- a triarylamine compound having 3 to 6 triarylamine structures in the molecule wherein the triarylamine structures are linked by a divalent group or a single bond not containing a hetero atom.
- a triarylamine compound (hereinafter sometimes abbreviated as a triarylamine compound having 3 to 6 triarylamine structures); a triarylamine compound having two triarylamine structures in the molecule, , A triarylamine compound in which the triarylamine structures are linked by a divalent group or a single bond that does not contain a hetero atom (hereinafter sometimes abbreviated as a triarylamine compound having two triarylamine structures). .); Is preferably used.
- the triarylamine compound having 3 to 6 triarylamine structures is preferably a triarylamine compound represented by the following general formula (4). This is because, in addition to the hole transportability, the film has excellent thin film stability and heat resistance, and is easy to synthesize.
- a triarylamine compound represented by the following general formula (5) is preferable. This is because, in addition to the hole transportability, the film has excellent thin film stability and heat resistance, and is easy to synthesize.
- the materials used for the first hole transport layer are P-doped with trisbromophenylamine hexachloroantimony, a radicalene derivative (see International Publication No. 2014/009310), or a benzidine derivative such as TPD.
- a polymer compound having a structure in its partial structure can also be used in combination.
- the compound used for forming the first hole transport layer 4 is different from the compound used for forming the second hole transport layer 5 described later.
- an arylamine compound corresponding to the general formula (1) may be used for the first hole transport layer 4 as long as the above condition is satisfied.
- the above materials may be used alone for film formation, or may be mixed with other materials for film formation.
- a stacked structure of layers formed independently, mixed layers formed, or mixed with a single layer formed may be employed.
- a triarylamine compound represented by the general formula (4) A triarylamine compound represented by the general formula (4);
- the triarylamine compound represented by the general formula (4) has four triarylamine structures.
- r 5 to r 16 represent the number of substituents R 5 to R 16 bonded to the aromatic ring.
- r 5 , r 6 , r 9 , r 12 , r 15 and r 16 each represent an integer from 0 to 5, and r 7 , r 8 , r 10 , r 11 , r 13 and r 14 are respectively Represents an integer of 0-4.
- r 5 , r 6 , r 9 , r 12 , r 15 , r 16 are integers of 2 to 5, or r 7 , r 8 , r 10 , r 11 , r 13 , r 14 are 2 to
- it is an integer of 4 it means that a plurality of R 5 to R 16 are bonded to the same aromatic ring (benzene ring).
- the plurality of substituents may be present independently of each other, but may be a single bond, a substituted or unsubstituted methylene group, oxygen A ring may be formed by bonding to each other via an atom or a sulfur atom.
- a plurality of substituents may be bonded to form a naphthalene ring as in the exemplified compound 4-8 described later.
- the groups R 5 to R 16 substituted on the aromatic ring are each a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 5 to 10 carbon atoms.
- An aromatic group or an aryloxy group is represented.
- the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 2 to 6 carbon atoms, and the alkyloxy group having 1 to 6 carbon atoms may be linear or branched.
- alkyl group having 1 to 6 carbon atoms, the cycloalkyl group having 5 to 10 carbon atoms, or the alkenyl group having 2 to 6 carbon atoms represented by R 5 to R 16 include a methyl group, an ethyl group, and n -Propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl Group, vinyl group, allyl group, isopropenyl group, 2-butenyl group and the like.
- alkyloxy group having 1 to 6 carbon atoms or the cycloalkyloxy group having 5 to 10 carbon atoms represented by R 5 to R 16 include methyloxy group, ethyloxy group, n-propyloxy group, isopropyl Oxy group, n-butyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, 1-adamantyloxy group, 2 -Adamantyloxy group and the like.
- the aromatic hydrocarbon group, aromatic heterocyclic group or condensed polycyclic aromatic group represented by R 5 to R 16 is an aromatic carbon group represented by Ar 1 to Ar 4 in the general formula (1). Examples thereof are the same as those described for the hydrogen group, aromatic heterocyclic group or condensed polycyclic aromatic group.
- aryloxy group represented by R 5 to R 16 include a phenyloxy group, a biphenylyloxy group, a terphenylyloxy group, a naphthyloxy group, an anthracenyloxy group, and a phenanthrenyloxy group. Fluorenyloxy group, indenyloxy group, pyrenyloxy group, perylenyloxy group and the like.
- the cycloalkyloxy group, aromatic hydrocarbon group, aromatic heterocyclic group, condensed polycyclic aromatic group or aryloxy group of ⁇ 10 may have a substituent.
- the aromatic hydrocarbon group represented by Ar 1 to Ar 4 in the general formula (1), the aromatic heterocyclic group, or the condensed polycyclic aromatic group may have a substituent. The same thing is given. The aspect which a substituent can take is also the same.
- L 1 to L 3 are bridging groups that connect two triarylamine skeletons, and each is represented by a single bond or any one of the following structural formulas (B) to (G) Represents a divalent group.
- the divalent group represented by the following structural formulas (B) to (G) may be unsubstituted, but may be substituted with deuterium as in the exemplified compound 4-17 described later.
- n1 represents an integer of 1 to 3.
- the triarylamine compounds represented by the general formula (4) are those compounds. It is not limited to. Note that D in the structural formula represents deuterium.
- FIG. 89 shows a specific example of a preferable compound other than the triarylamine compound represented by the general formula (4) among the triarylamine compounds having 3 to 6 triarylamine structures.
- the triarylamine compound having 3 to 6 structures is not limited to these compounds.
- the triarylamine compound represented by the general formula (5) has two triarylamine structures.
- r 18 to r 22 represent the number of groups R 18 to R 22 bonded to the aromatic ring.
- r 17 , r 18 , r 21 and r 22 each represents an integer of 0 to 5
- r 19 and r 20 each represents an integer of 0 to 4.
- r 17 to r 22 are 0 means that R 17 to R 22 are not present on the aromatic ring, that is, the aromatic ring is substituted with a group represented by R 17 to R 22. It means not being done.
- the same aromatic ring (benzene ring) Means that a plurality of R 18 to R 22 are bonded to each other.
- the multiple bonded groups may be present independently of each other, but may be a single bond, a substituted or unsubstituted methylene group, oxygen They may be bonded to each other via an atom or a sulfur atom to form a ring.
- a plurality of substituents may be bonded to form a naphthalene ring as in the exemplified compound 5-13 described later.
- the substituents R 17 to R 22 bonded to the aromatic ring are each a deuterium atom, a fluorine atom, a chlorine atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 5 to 10 carbon atoms.
- the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 2 to 6 carbon atoms, and the alkyloxy group having 1 to 6 carbon atoms may be linear or branched.
- Examples of the alkyl group having 1 to 6 carbon atoms, the cycloalkyl group having 5 to 10 carbon atoms, or the alkenyl group having 2 to 6 carbon atoms represented by R 17 to R 22 include R 5 to R 5 in the general formula (4). Examples thereof include those similar to those shown for the alkyl group having 1 to 6 carbon atoms, the cycloalkyl group having 5 to 10 carbon atoms or the alkenyl group having 2 to 6 carbon atoms represented by R 16 . The aspect which these groups can take is also the same.
- Examples of the alkyloxy group having 1 to 6 carbon atoms or the cycloalkyloxy group having 5 to 10 carbon atoms represented by R 17 to R 22 include carbons represented by R 5 to R 16 in the general formula (4). Examples thereof are the same as those shown for the alkyloxy group having 1 to 6 carbon atoms or the cycloalkyloxy group having 5 to 10 carbon atoms. The aspect which these groups can take is also the same.
- Examples of the aromatic hydrocarbon group, aromatic heterocyclic group or condensed polycyclic aromatic group represented by R 17 to R 22 include aromatic carbon groups represented by Ar 1 to Ar 4 in the general formula (1). Examples thereof are the same as those described for the hydrogen group, aromatic heterocyclic group or condensed polycyclic aromatic group.
- Examples of the aryloxy group represented by R 17 to R 22 include the same groups as those shown for the aryloxy group represented by R 5 to R 16 in the general formula (4).
- the aspect which these groups can take is also the same.
- the cycloalkyloxy group, aromatic hydrocarbon group, aromatic heterocyclic group, condensed polycyclic aromatic group or aryloxy group of ⁇ 10 may have a substituent.
- the aromatic hydrocarbon group represented by Ar 1 to Ar 4 in the general formula (1), the aromatic heterocyclic group, or the condensed polycyclic aromatic group may have a substituent. The same thing is given. The aspect which a substituent can take is also the same.
- L 4 is a bridging group that connects two triarylamine structures, and represents a single bond or a divalent group represented by any one of the structural formulas (C) to (G). .
- the triarylamine compounds represented by the general formula (5) are those compounds. It is not limited to. Note that D in the structural formula represents deuterium.
- a preferred specific example of a compound other than the triarylamine compound represented by the general formula (5) among the triarylamine compounds having two triarylamine structures is shown in FIG.
- the triarylamine compound having two is not limited to these compounds.
- a triarylamine compound having 3 to 6 triarylamine structures and a triarylamine compound having two triarylamine structures can be synthesized by a method known per se (Patent Document 1, 8 and 9).
- the obtained compound is purified by column chromatography, adsorption purification by silica gel, activated carbon, activated clay, etc., recrystallization or crystallization by a solvent. And finally purified by a sublimation purification method.
- the second hole transport layer 5 on the light emitting layer 6 side is formed using the arylamine compound represented by the general formula (1). Since the arylamine compound represented by the general formula (1) exhibits a high electron blocking property in addition to the hole transporting property, the second hole transport layer 5 has both a hole transporting property and an electron blocking property. Are better. Accordingly, by making the second hole transport layer 5 adjacent to the light emitting layer 6 as shown in FIG. 1, the carrier balance in the light emitting layer 6 can be kept higher, which contributes to the improvement of the characteristics of the organic EL element. be able to.
- the second hole transport layer 5 may be a single layer, but is a stack of layers formed by mixing single layers, layers formed by mixing, or layers formed by mixing with a single layer. It is good also as a structure.
- the light emitting layer 6 is formed on the second hole transport layer 5.
- the light-emitting layer 6 includes a known light-emitting material, for example, metal complexes of quinolinol derivatives including Alq 3 ; various metal complexes; anthracene derivatives; bisstyrylbenzene derivatives; pyrene derivatives; oxazole derivatives; Etc. can be used.
- a host material an anthracene derivative is preferably used.
- a heterocyclic compound having an indole ring as a partial structure of the condensed ring, A heterocyclic compound having a carbazole ring as a partial structure of a condensed ring, A carbazole derivative, Thiazole derivatives, Benzimidazole derivatives, Polydialkylfluorene derivatives and the like can be used.
- Blue light emitting dopants such as pyrene derivatives; An amine derivative having a fluorene ring as a partial structure of the condensed ring;
- quinacridone, coumarin, rubrene, perylene, and derivatives thereof; benzopyran derivatives; indenophenanthrene derivatives; rhodamine derivatives; aminostyryl derivatives; and the like can also be used.
- the light emitting layer 6 may be a single layer, but may have a stacked structure of layers formed independently, mixed layers formed, or mixed with a single formed layer.
- a phosphorescent emitter As the phosphorescent emitter, a phosphorescent emitter of a metal complex such as iridium or platinum can be used. For example, a green phosphorescent emitter such as Ir (ppy) 3 ; a blue phosphorescent emitter such as FIrpic or FIr 6 A red phosphorescent emitter such as Btp 2 Ir (acac);
- CBP 4,4'-di (N-carbazolyl) biphenyl
- CBP a carbazole derivative such as TCTA, mCP, or the like
- TCTA TCTA
- mCP mCP
- an electron transporting host material p-bis (triphenylsilyl) benzene (UGH2); 2,2 ′, 2 ′′-(1,3,5-phenylene) -tris (1-phenyl-1H-benzimidazole) ) (TPBI);
- TPBI p-bis (triphenylsilyl) benzene
- TPBI p-bis (triphenylsilyl) benzene
- TPBI 1,3,5-phenylene
- the doping of the phosphorescent light-emitting material into the host material is preferably performed by co-evaporation in the range of 1 to 30 weight percent with respect to the entire light-emitting layer in order to avoid concentration quenching.
- a material that emits delayed fluorescence for example, a CDCB derivative such as PIC-TRZ, CC2TA, PXZ-TRZ, 4CzIPN can be used.
- the electron transport layer 7 is formed on the light emitting layer 6.
- the electron transport layer 7 is formed using a pyrimidine derivative represented by the general formula (2).
- the electron transport layer 7 includes metal complexes of quinolinol derivatives including Alq 3 and BAlq; various metal complexes; triazole derivatives; triazine derivatives; oxadiazole derivatives; pyridine derivatives; pyrimidine derivatives; Derivatives, thiadiazole derivatives, anthracene derivatives, carbodiimide derivatives, quinoxaline derivatives, pyridoindole derivatives, phenanthroline derivatives, silole derivatives, and the like.
- the electron transport layer 7 may be a single layer, but may have a laminated structure of layers formed independently, mixed layers formed, or mixed with a single formed layer. .
- an electrode material having a low work function such as aluminum or an alloy having a lower work function such as a magnesium silver alloy, a magnesium indium alloy, or an aluminum magnesium alloy is used as the electrode material. .
- the organic EL device of the present invention may have an electron blocking layer between the second hole transport layer 5 and the light emitting layer 6.
- the organic EL device of the present invention may have a hole blocking layer between the light emitting layer 6 and the electron transport layer 7.
- a hole blocking layer in addition to metal complexes of phenanthroline derivatives such as bathocuproine (BCP), quinolinol derivatives such as aluminum (III) bis (2-methyl-8-quinolinato) -4-phenylphenolate (BAlq), Various kinds of rare earth complexes, triazole derivatives, triazine derivatives, oxadiazole derivatives, and other compounds having a hole blocking action can be used. These materials may also serve as the material for the electron transport layer. These materials may be used alone for film formation, or may be mixed with other materials for film formation.
- the hole blocking layer may be a single layer, or may be a laminated structure of layers formed independently, mixed layers, or mixed with a single layer. .
- the organic EL device of the present invention may have an electron injection layer 8 between the electron transport layer 7 and the cathode 9.
- alkali metal salts such as lithium fluoride and cesium fluoride
- alkaline earth metal salts such as magnesium fluoride
- metal oxides such as aluminum oxide; and the like can be used. This can be omitted in the preferred selection of the cathode.
- Tetrakis (triphenylphosphine) palladium (1.1 g) was added and heated, followed by stirring at 72 ° C. for 10 hours. Cool to room temperature and add 60 ml of methanol. The precipitated solid was collected by filtration and washed with 100 ml of a mixed solution of methanol / water (5/1, v / v), and then 100 ml of 1,2-dichlorobenzene was added and dissolved by heating. Insoluble matter was removed by filtration, and the mixture was allowed to cool, and 200 ml of methanol was added. The precipitated crude product was collected by filtration. The crude product was reflux washed with 100 ml of methanol.
- Tetrakis (triphenylphosphine) palladium (1.0 g) was added and heated, followed by stirring at 72 ° C. for 18 hours. Cool to room temperature and add 60 ml of methanol. The precipitated solid was collected by filtration and washed with 100 ml of a mixed solution of methanol / water (5/1, v / v), and then 100 ml of 1,2-dichlorobenzene was added and dissolved by heating. Insoluble matter was removed by filtration, and the mixture was allowed to cool, and 200 ml of methanol was added. The precipitated crude product was collected by filtration. The crude product was reflux washed with 100 ml of methanol.
- Synthesis Example 8 (Compound 1-23) 129 ° C Synthesis Example 9 (Compound 1-24) 113 ° C.
- Synthesis Example 10 (Compound 1-25) 126 ° C.
- Synthesis Example 11 (Compound 1-26) 131 ° C Synthesis Example 12 (Compound 1-27) 121 ° C Synthesis Example 13 (Compound 1-28) 113 ° C Synthesis Example 14 (Compound 1-38) 117 ° C
- the arylamine compound represented by the general formula (1) has a glass transition point of 100 ° C. or higher, that is, the thin film state was stable.
- ⁇ Measurement of work function> Using the arylamine compound represented by the general formula (1), a deposited film having a film thickness of 100 nm is formed on the ITO substrate, and the work is performed by an ionization potential measuring apparatus (Sumitomo Heavy Industries, Ltd., PYS-202). The function was measured.
- the arylamine compound represented by the general formula (1) exhibits a suitable energy level as compared with a work function of 5.4 eV possessed by a general hole transport material such as NPD or TPD. It had a hole transport capability.
- a hole injection layer 3, a first hole transport layer 4, a second hole transport layer 5, and a light emitting layer are formed on a glass substrate 1 on which an ITO electrode is previously formed as a transparent anode 2.
- an ITO electrode is previously formed as a transparent anode 2.
- the electron carrying layer 7, the electron injection layer 8, and the cathode (aluminum electrode) 9 were vapor-deposited in order, and the organic EL element was produced.
- a glass substrate 1 on which an ITO film having a thickness of 150 nm was formed was prepared.
- the glass substrate 1 was ultrasonically cleaned in isopropyl alcohol for 20 minutes. Subsequently, it dried for 10 minutes on the hotplate heated at 200 degreeC. Then, after performing UV ozone treatment for 15 minutes, this glass substrate with ITO was attached in a vacuum evaporation machine, and pressure was reduced to 0.001 Pa or less. Subsequently, a compound 6 having the following structural formula was formed to a film thickness of 5 nm as a hole injection layer 3 so as to cover the transparent anode 2.
- a compound 5-1 having the following structural formula was formed as a first hole transport layer 4 so as to have a film thickness of 60 nm.
- the compound 1-11 of Synthesis Example 3 was formed as the second hole transport layer 5 so as to have a film thickness of 5 nm.
- Original vapor deposition was performed to form a film thickness of 30 nm.
- lithium fluoride was formed as the electron injection layer 8 so as to have a film thickness of 1 nm.
- aluminum was deposited to 100 nm to form the cathode 9.
- the light emission characteristic when a DC voltage was applied at normal temperature in the atmosphere was measured. The results are shown in Table 1.
- the element lifetime was measured using the organic EL elements produced in the element examples 1 to 6 and the element comparative examples 1 to 4. The results are shown in Table 1.
- the element lifetime corresponds to 95% of the emission brightness of 1900 cd / m 2 (when the initial brightness is 100%) when the constant current drive is performed with the emission brightness (initial brightness) at the start of light emission being 2000 cd / m 2 : It was measured as the time to decay to 95% decay.
- the light emission efficiency is 7.95 cd / A in the device comparative example 1, whereas In the device examples 1 and 2, the high efficiency was 8.49 to 8.94 cd / A.
- the power efficiency was 6.65 lm / W in the device comparative example 1, whereas the device examples 1 and 2 had high efficiency of 6.94 to 7.30 lm / W.
- the device life was 83 hours in the device comparative example 1, whereas in the device examples 1 and 2, the life was greatly increased to 161 to 201 hours.
- the light emission efficiency is 7.96 cd / A in device comparative example 2, whereas in device examples 3 and 4 All of 8.38 to 8.82 cd / A were highly efficient.
- the power efficiency was 6.78 lm / W in the device comparative example 2, whereas the device examples 3 and 4 had high efficiency of 6.92 to 7.28 lm / W.
- the device life was 87 hours in the device comparative example 2, whereas in the device examples 3 and 4, the life was increased to 140 to 143 hours.
- the power efficiency was 6.54 lm / W in the device comparative example 3, whereas the device examples 5 and 6 had high efficiency of 6.84 to 7.13 lm / W.
- the element lifetime was 88 hours in the element comparative example 3, whereas in the element examples 5 and 6, the lifetime was greatly increased to 148 to 185 hours.
- the present invention combines an arylamine compound having a specific structure with a pyrimidine derivative having a specific structure so that holes and electrons can be efficiently injected and transported into the light emitting layer, and thus an organic EL having a high light emission efficiency and a long lifetime.
- the device is realized. Furthermore, by combining a triarylamine compound having a specific structure as a material for the first hole transport layer with respect to this combination, a combination of materials with a more refined carrier balance is obtained, and holes are emitted to the light emitting layer.
- Organic EL elements that can be injected and transported more efficiently have been realized. Therefore, according to the present invention, an organic EL element having higher luminous efficiency and longer life than that of a conventional organic EL element is realized.
- the organic EL device of the present invention has improved luminous efficiency and greatly improved durability. For example, it can be applied to household appliances and lighting applications.
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Abstract
Description
また、特許文献1および2に記載の芳香族アミン誘導体の中には、正孔の移動度が10-3cm2/Vs以上と優れた移動度を有する化合物もあるが、電子阻止性が不十分であるため、電子の一部が発光層を通り抜けてしまい、発光効率の向上が期待できない。よって、さらなる高効率化のため、より電子阻止性が高く、薄膜がより安定で耐熱性の高い材料が求められている。
更に、特許文献3には、耐久性の高い芳香族アミン誘導体が報告されている。しかし、特許文献3の芳香族アミン誘導体は、電子写真感光体の電荷輸送材料として用いられるものであり、有機EL素子に用いた例については全く検討されていない。
本発明者らは、正孔輸送層を二層構成とし、且つ、特定の構造を有するアリールアミン化合物を発光層に隣接する正孔輸送層(第二正孔輸送層)の材料として選択すると、発光層へ正孔を効率良く注入・輸送できるという知見を得た。更に、特定の構造を有するピリミジン誘導体を電子輸送層の材料として選択すると、発光層へ電子を効率良く注入・輸送できるという知見も得た。
そして、かかるアリールアミン化合物とピリミジン誘導体の組み合わせに対して更に種々の材料を組み合わせ、キャリアバランスが精緻化された材料の組み合わせを検討し、素子の特性評価を鋭意行った。その結果、本発明を完成するに至った。
前記第二正孔輸送層が、下記一般式(1)で表されるアリールアミン化合物を含有し、
前記電子輸送層が、下記一般式(2)で表されるピリミジン誘導体を含有することを特徴とする有機EL素子が提供される。
Ar1~Ar4は、それぞれ、芳香族炭化水素基、芳香族複素環基ま
たは縮合多環芳香族基を表し、
nは2~4の整数を表す。
Ar5は、芳香族炭化水素基、芳香族複素環基または縮合多環芳香族
基を表し、
Ar6、Ar7は、それぞれ、水素原子、芳香族炭化水素基、芳香族
複素環基または縮合多環芳香族基を表し、Ar6とAr7は同時に水素
原子となることはなく、
Aは、下記構造式(3)で示される1価基を表す。
Ar8は、芳香族複素環基を表し、
R1~R4は、それぞれ、水素原子、重水素原子、フッ素原子、
塩素原子、シアノ基、トリフルオロメチル基、炭素数1~6のア
ルキル基、芳香族炭化水素基、芳香族複素環基または縮合多環芳
香族基を表し、R1~R4とAr8が単結合、置換もしくは無置換
のメチレン基、酸素原子または硫黄原子を介して互いに結合して
環を形成していてもよい。
(1)前記第一正孔輸送層が、分子中にトリアリールアミン構造を3~6個有するトリアリールアミン化合物であって、該トリアリールアミン構造が、ヘテロ原子を含まない2価基または単結合で連結しているトリアリールアミン化合物を含有すること、
(2)前記トリアリールアミン構造を3~6個有するトリアリールアミン化合物が、下記一般式(4)で表される、分子中にトリアリールアミン構造を4個有するトリアリールアミン化合物であること、
r5、r6、r9、r12、r15およびr16は、それぞれ、0~5の
整数を表し、
r7、r8、r10、r11、r13およびr14は、それぞれ、0~4
の整数を表し、
R5~R16は、それぞれ、重水素原子、フッ素原子、塩素原子、シ
アノ基、ニトロ基、炭素数1~6のアルキル基、炭素数5~10のシ
クロアルキル基、炭素数2~6のアルケニル基、炭素数1~6のアル
キルオキシ基、炭素数5~10のシクロアルキルオキシ基、芳香族炭
化水素基、芳香族複素環基、縮合多環芳香族基またはアリールオキシ
基を表し、これらの基が同一のベンゼン環に複数結合する場合、複数
結合している基は、単結合、置換もしくは無置換のメチレン基、酸素
原子または硫黄原子を介して互いに結合して環を形成してもよく、
L1~L3は、それぞれ、単結合または下記構造式(B)~(G)の
いずれかで示される2価基を表す、
(4)前記トリアリールアミン構造を2個有するトリアリールアミン化合物が、下記一般式(5)で表されること、
r17、r18、r21及びr22は、それぞれ、0~5の整数を表し、
r19およびr20は、それぞれ、0~4の整数を表し、
R17~R22は、それぞれ、重水素原子、フッ素原子、塩素原子、
シアノ基、ニトロ基、炭素数1~6のアルキル基、炭素数5~10の
シクロアルキル基、炭素数2~6のアルケニル基、炭素数1~6のア
ルキルオキシ基、炭素数5~10のシクロアルキルオキシ基、芳香族
炭化水素基、芳香族複素環基、縮合多環芳香族基またはアリールオキ
シ基を表し、これらの基が同一のベンゼン環に複数結合する場合、複
数結合している基は、単結合、置換もしくは無置換のメチレン基、酸
素原子または硫黄原子を介して互いに結合して環を形成してもよく、
L4は、単結合または前記構造式(C)~(G)で示される2価基を
表す、
(5)前記電子輸送層が含有するピリミジン誘導体が、下記一般式(2a)で表されること、
の意味を表す、
(6)前記電子輸送層が含有するピリミジン誘導体が、下記一般式(2b)で表されること、
の意味を表す、
(7)前記一般式(2)において、Aが下記構造式(3a)で示される1価基であること、
の意味を表す、
(8)前記発光層が、青色発光性ドーパントを含有すること、
(9)前記青色発光性ドーパントが、ピレン誘導体であること、
(10)前記発光層が、アントラセン誘導体を含有すること、
(11)前記発光層が、前記アントラセン誘導体をホスト材料として含有すること、
が好適である。
更に上記の材料の組み合わせに対し、特定の構造を有するトリアリールアミン化合物を第一正孔輸送層の材料として組み合わせ、キャリアバランスがより精緻化された材料の組み合わせを選択した。その結果、発光層へ正孔をより効率良く注入・輸送できるようになり、高効率、低駆動電圧であって、より長寿命の有機EL素子を実現することができた。即ち、本発明によれば、従来の有機EL素子より高発光効率且つ低駆動電圧であるだけでなく、特に耐久性に優れた有機EL素子が提供される。
ハロゲン原子、例えばフッ素原子、塩素原子、臭素原子、ヨウ素原
子;
炭素数1~6のアルキル基、例えばメチル基、エチル基、n-プロ
ピル基、イソプロピル基、n-ブチル基、イソブチル基、tert-
ブチル基、n-ペンチル基、イソペンチル基、ネオペンチル基、n-
ヘキシル基;
炭素数1~6のアルキルオキシ基、例えばメチルオキシ基、エチル
オキシ基、プロピルオキシ基;
アルケニル基、例えばビニル基、アリル基;
アリールオキシ基、例えばフェニルオキシ基、トリルオキシ基;
アリールアルキルオキシ基、例えばベンジルオキシ基、フェネチル
オキシ基;
芳香族炭化水素基もしくは縮合多環芳香族基、例えばフェニル基、
ビフェニリル基、ターフェニリル基、ナフチル基、アントラセニル基
、フェナントレニル基、フルオレニル基、インデニル基、ピレニル基
、ペリレニル基、フルオランテニル基、トリフェニレニル基;
芳香族複素環基、例えばピリジル基、フリル基、チエニル基、ピロ
リル基、キノリル基、イソキノリル基、ベンゾフラニル基、ベンゾチ
エニル基、インドリル基、カルバゾリル基、ベンゾオキサゾリル基、
ベンゾチアゾリル基、キノキサリニル基、ベンゾイミダゾリル基、ピ
ラゾリル基、ジベンゾフラニル基、ジベンゾチエニル基、カルボリニ
ル基;
アリールビニル基、例えばスチリル基、ナフチルビニル基;
アシル基、例えばアセチル基、ベンゾイル基;
尚、炭素数1~6のアルキル基および炭素数1~6のアルキルオキシ基は直鎖状であっても分枝状であってもよい。これらの置換基は、さらに上記で例示した置換基を有していてもよい。また、これらの置換基同士は、互いに独立して存在していてもよいが、単結合、置換もしくは無置換のメチレン基、酸素原子または硫黄原子を介して互いに結合して環を形成していてもよい。
1,1’:3’,1’’:3’’,1’’’-クォーターフェニル
ジアミン、
1,1’:3’,1’’:2’’,1’’’:3’’’,1’’
’’-キンクフェニルジアミン、
1,1’:3’,1’’:3’’,1’’’:3’’’,1’’’
’-キンクフェニルジアミン、
1,1’:2’,1’’:2’’,1’’’-クォーターフェニル
ジアミン、
1,1’:3’,1’’:4’’,1’’’-クォーターフェニル
ジアミン、
1,1’:4’,1’’:2’’,1’’’:4’’’,1’’’
’-キンクフェニルジアミン、
1,1’:2’,1’’:3’’,1’’’:2’’’,1’’’
’-キンクフェニルジアミン、
1,1’:4’,1’’:3’’,1’’’:4’’’,1’’’
’-キンクフェニルジアミン、
1,1’:2’,1’’:2’’,1’’’:2’’’,1’’’
’-キンクフェニルジアミン
重水素原子、シアノ基、ニトロ基の他に以下の基が挙げられる。
ハロゲン原子、例えばフッ素原子、塩素原子、臭素原子、ヨウ素原
子;
炭素数1~6のアルキル基、例えばメチル基、エチル基、n-プロ
ピル基、イソプロピル基、n-ブチル基、イソブチル基、tert-
ブチル基、n-ペンチル基、イソペンチル基、ネオペンチル基、n-
ヘキシル基;
炭素数1~6のアルキルオキシ基、例えばメチルオキシ基、エチル
オキシ基、プロピルオキシ基;
アルケニル基、例えばビニル基、アリル基;
アリールオキシ基、例えばフェニルオキシ基、トリルオキシ基;
アリールアルキルオキシ基、例えばベンジルオキシ基、フェネチル
オキシ基;
芳香族炭化水素基もしくは縮合多環芳香族基、例えばフェニル基、
ビフェニリル基、ターフェニリル基、ナフチル基、アントラセニル基
、フェナントレニル基、フルオレニル基、インデニル基、ピレニル基
、ペリレニル基、フルオランテニル基、トリフェニレニル基、スピロ
ビフルオレニル基;
芳香族複素環基、例えばピリジル基、チエニル基、フリル基、ピロ
リル基、キノリル基、イソキノリル基、ベンゾフラニル基、ベンゾチ
エニル基、インドリル基、カルバゾリル基、ベンゾオキサゾリル基、
ベンゾチアゾリル基、キノキサリニル基、ベンゾイミダゾリル基、ピ
ラゾリル基、ジベンゾフラニル基、ジベンゾチエニル基、アザフルオ
レニル基、ジアザフルオレニル基、カルボリニル基、アザスピロビフ
ルオレニル基、ジアザスピロビフルオレニル基;
アリールビニル基、例えばスチリル基、ナフチルビニル基;
アシル基、例えばアセチル基、ベンゾイル基;
尚、炭素数1~6のアルキル基および炭素数1~6のアルキルオキシ基は、直鎖状であっても分枝状であってもよい。これらの置換基は、さらに上記で例示した置換基を有していてもよい。また、これらの置換基同士は、互いに独立して存在していてもよいが、単結合、置換もしくは無置換のメチレン基、酸素原子または硫黄原子を介して互いに結合して環を形成していてもよく、また、これらの置換基と当該置換基が結合しているAr5、Ar6またはAr7が酸素原子、硫黄原子または置換もしくは無置換のメチレン基を介して互いに結合して環を形成していてもよい。
1)かかるピリミジン誘導体が、下記一般式(2a)で表される。
2)かかるピリミジン誘導体が、下記一般式(2b)で表される。
3)Aが、下記構造式(3a)で示される1価基である。尚、この態様は、薄膜安定性の観点から好ましい。
4)Aが、下記構造式(3b)で示される1価基である。
5)Ar5は、芳香族炭化水素基または縮合多環芳香族基を表し、Ar6、Ar7は、それぞれ、水素原子、芳香族炭化水素基または縮合多環芳香族基を表す。
6)Ar6が、置換基を有するフェニル基である。
7)Ar6が、置換基を有するフェニル基であり、該置換基が、置換もしくは無置換の芳香族炭化水素基または置換もしくは無置換の縮合多環芳香族基である。
8)Ar6が、置換基を有するフェニル基であり、該置換基が、置換もしくは無置換の芳香族炭化水素基である。
9)Ar6が、置換基を有するフェニル基であり、該置換基が、置換もしくは無置換の縮合多環芳香族基である。
10)Ar7が、水素原子である。
11)Ar5が、置換基を有するフェニル基である。
12)Ar5が、置換基を有するフェニル基であり、該置換基が、置換もしくは無置換の縮合多環芳香族基である。
13)Ar5が、置換もしくは無置換の縮合多環芳香族基である。
14)Ar5が、無置換のフェニル基である。
この場合のフェニル基の置換基としては、芳香族炭化水素基、例えばフェニル基、ビフェニリル基、ターフェニル基;縮合多環芳香族基、例えばナフチル基、アセナフテニル基、フェナントレニル基、フルオレニル基、インデニル基、ピレニル基、ペリレニル基、フルオランテニル基、トリフェニレニル基、スピロビフルオレニル基;含酸素芳香族複素環基、例えばフリル基、ベンゾフラニル基、ジベンゾフラニル基;または含硫黄芳香族複素環基、例えばチエニル基、ベンゾチエニル基、ジベンゾチエニル基;が好ましく、フェニル基、ナフチル基、フェナントレニル基、フルオレニル基、ピレニル基、フルオランテニル基、トリフェニレニル基、スピロビフルオレニル基、ジベンゾフラニル基、ジベンゾチエニル基がより好ましい。更に、フェニル基が有する置換基とフェニル基とが酸素原子または硫黄原子を介して互いに結合して環を形成することも好ましい。
陽極2は、ITOや金のような仕事関数の大きな電極材料の蒸着により、透明基板1上に形成される。
正孔注入層3は、上記の陽極2と第一正孔輸送層4との間に設けられる。正孔注入層3には、公知の材料、例えば、スターバースト型のトリフェニルアミン誘導体;種々のトリフェニルアミン4量体;銅フタロシアニンに代表されるポルフィリン化合物;ヘキサシアノアザトリフェニレンのようなアクセプター性の複素環化合物;塗布型の高分子材料;などを用いることができる。あるいは、前記一般式(1)で表されるアリールアミン化合物、後述の一般式(4)で表されるトリアリールアミン化合物または後述の一般式(5)で表されるトリアリールアミン化合物を用いることもできる。
正孔注入層3と発光層6との間には正孔輸送層が存在するが、本発明では、この正孔輸送層が、第一正孔輸送層4と第二正孔輸送層5の2層構造となっている。
本発明の有機EL素子において、第一正孔輸送層には、公知の正孔輸送材料を使用することができる。公知の正孔輸送材料としては、以下の具体例;
ベンジジン誘導体、例えば
N,N’-ジフェニル-N,N’-ジ(m-トリル)ベンジジン
(TPD)、
N,N’-ジフェニル-N,N’-ジ(α-ナフチル)ベンジジ
ン(NPD)、
N,N,N’,N’-テトラビフェニリルベンジジン;
1,1-ビス[4-(ジ-4-トリルアミノ)フェニル]シクロヘ
キサン(TAPC);
種々のトリアリールアミン3量体および4量体、例えば
分子中にトリアリールアミン構造を3~6個有するトリアリール
アミン化合物であって、該トリアリールアミン構造が、ヘテロ原子
を含まない2価基または単結合で連結しているトリアリールアミン
化合物、
分子中にトリアリールアミン構造を2個有するトリアリールアミ
ン化合物であって、該トリアリールアミン構造が、ヘテロ原子を含
まない2価基または単結合で連結しているトリアリールアミン化合
物;
を挙げることができる。
トリアリールアミン構造を3~6個有するトリアリールアミン化合物としては、後述の一般式(4)で表されるトリアリールアミン化合物が好ましい。正孔輸送性に加え、薄膜安定性や耐熱性に優れており、更に合成が容易だからである。
トリアリールアミン構造を2個有するトリアリールアミン化合物としては、後述の一般式(5)で表されるトリアリールアミン化合物が好ましい。正孔輸送性に加え、薄膜安定性や耐熱性に優れており、更に合成が容易だからである。
既に述べた通り、本発明において発光層6側の第二正孔輸送層5は、前記一般式(1)で表されるアリールアミン化合物を用いて形成される。かかる一般式(1)で表されるアリールアミン化合物は、正孔輸送性に加え、高い電子阻止性を示すため、第二正孔輸送層5は、正孔輸送性と電子阻止性の両方に優れている。従って、図1のように、第二正孔輸送層5を発光層6に隣接させることにより、発光層6でのキャリアバランスをより高く保持することができ、有機EL素子の特性向上に貢献することができる。
発光層6は、前記第二正孔輸送層5の上に形成される。発光層6には、公知の発光材料、例えば、Alq3をはじめとするキノリノール誘導体の金属錯体;各種の金属錯体;アントラセン誘導体;ビススチリルベンゼン誘導体;ピレン誘導体;オキサゾール誘導体;ポリパラフェニレンビニレン誘導体;などを用いることができる。
インドール環を縮合環の部分構造として有する複素環化合物、
カルバゾール環を縮合環の部分構造として有する複素環化合物、
カルバゾール誘導体、
チアゾール誘導体、
ベンズイミダゾール誘導体、
ポリジアルキルフルオレン誘導体
などを用いることができる。またドーパント材料としては、
ピレン誘導体などの青色発光性ドーパント;
フルオレン環を縮合環の部分構造として有するアミン誘導体;
が好ましく用いられるが、そのほか、キナクリドン、クマリン、ルブレン、ペリレン、およびそれらの誘導体;ベンゾピラン誘導体;インデノフェナントレン誘導体;ローダミン誘導体;アミノスチリル誘導体;などを用いることもできる。
電子輸送層7は、発光層6の上に形成される。電子輸送層7は、前記一般式(2)で表されるピリミジン誘導体を用いて形成される。
本発明の有機EL素子の陰極9として、アルミニウムのような仕事関数の低い電極材料や、マグネシウム銀合金、マグネシウムインジウム合金、アルミニウムマグネシウム合金のような、より仕事関数の低い合金が電極材料として用いられる。
(電子阻止層)
本発明の有機EL素子は、第二正孔輸送層5と発光層6の間に電子阻止層を有してもよい。電子阻止層には、
前記一般式(1)で表されるアリールアミン化合物;
前記一般式(4)で表されるトリアリールアミン化合物;
前記一般式(5)で表されるトリアリールアミン化合物;
カルバゾール誘導体、例えば
4,4’,4’’-トリ(N-カルバゾリル)トリフェニルアミン(
TCTA)、
9,9-ビス[4-(カルバゾール-9-イル)フェニル]フル
オレン、
1,3-ビス(カルバゾール-9-イル)ベンゼン(mCP)、
2,2-ビス(4-カルバゾール-9-イルフェニル)アダマン
タン(Ad-Cz);
トリフェニルシリル基とトリアリールアミン構造を有する化合物、
例えば
9-[4-(カルバゾール-9-イル)フェニル]-9-[4-
(トリフェニルシリル)フェニル]-9H-フルオレン;
などの電子阻止作用を有する化合物を用いることができる。これらの材料は、単独で成膜に供してもよいが、他の材料とともに混合して成膜に供してもよい。電子阻止層は、単層でもよいが、単独で成膜した層同士、混合して成膜した層同士、または単独で成膜した層と混合して成膜した層の積層構造としてもよい。
本発明の有機EL素子は、発光層6と電子輸送層7の間に正孔阻止層を有してもよい。正孔阻止層には、バソクプロイン(BCP)などのフェナントロリン誘導体や、アルミニウム(III)ビス(2-メチル-8-キノリナート)-4-フェニルフェノレート(BAlq)などのキノリノール誘導体の金属錯体の他、各種の希土類錯体、トリアゾール誘導体、トリアジン誘導体、オキサジアゾール誘導体など、正孔阻止作用を有する化合物を用いることができる。これらの材料は電子輸送層の材料を兼ねてもよい。これらの材料は、単独で成膜に供してもよいが、他の材料とともに混合して成膜に供してもよい。正孔阻止層は、単層でもよいが、単独で成膜した層同士、混合して成膜した層同士、または単独で成膜した層と混合して成膜した層の積層構造としてもよい。
本発明の有機EL素子は、電子輸送層7と陰極9の間に電子注入層8を有してもよい。電子注入層には、フッ化リチウム、フッ化セシウムなどのアルカリ金属塩;フッ化マグネシウムなどのアルカリ土類金属塩;酸化アルミニウムなどの金属酸化物;などを用いることができるが、電子輸送層と陰極の好ましい選択においては、これを省略することができる。
4,4’’’-ビス{(ビフェニル-4-イル)-フェニルアミノ}-(1,1’:4’,1’’:4’’,1’’’-クォーターフェニル)の合成;
窒素置換した反応容器に、
N-フェニル-N-{4-(4,4,5,5-テトラメチル-1
,3,2-ジオキサボロラン-2-イル)フェニル}-(1,1’
-ビフェニル-4-イル)アミン 18.2g、
4,4’-ジヨードビフェニル 7.5g、
2M炭酸カリウム水溶液 46ml、
トルエン 60mlおよび
エタノール 15ml
を加え、1時間窒素ガスを通気した。テトラキス(トリフェニルホスフィン)パラジウム1.1gを加えて加熱し、72℃で10時間撹拌した。室温まで冷却し、メタノール60mlを加えた。析出する固体をろ過によって採取し、メタノール/水(5/1、v/v)の混合溶液100mlで洗浄した後、1,2-ジクロロベンゼン100mlを加え、加熱溶解させた。不溶物をろ過によって除去した後、放冷し、メタノール200mlを加えた。析出した粗製物をろ過によって採取した。粗製物についてメタノール100mlを用いた還流洗浄を行った。その結果、4,4’’’-ビス{(ビフェニル-4-イル)-フェニルアミノ}-(1,1’:4’,1’’:4’’,1’’’-クォーターフェニル)(化合物1-1)の薄黄色粉体11.8g(収率81%)を得た。
δ(ppm)=7.66-7.77(8H)
7.50-7.64(12H)
7.42-7.50(4H)
7.28-7.38(6H)
7.20-7.26(12H)
7.08(2H)
4,4’’’’-ビス{(ビフェニル-4-イル)-フェニルアミノ}-(1,1’:4’,1’’:4’’,1’’’:4’’’,1’’’’-キンクフェニル)の合成;
窒素置換した反応容器に、
N-フェニル-N-{4-(4,4,5,5-テトラメチル-1
,3,2-ジオキサボロラン-2-イル)フェニル}-(1,1’
-ビフェニル-4-イル)アミン 16.3g、
4,4’-ジヨードターフェニル 8.0g、
2M炭酸カリウム水溶液 41ml、
トルエン 64mlおよび
エタノール 16ml
を加え、1時間窒素ガスを通気した。テトラキス(トリフェニルホスフィン)パラジウム1.0gを加えて加熱し、72℃で18時間撹拌した。室温まで冷却し、メタノール60mlを加えた。析出する固体をろ過によって採取し、メタノール/水(5/1、v/v)の混合溶液100mlで洗浄した後、1,2-ジクロロベンゼン100mlを加え、加熱溶解させた。不溶物をろ過によって除去した後、放冷し、メタノール200mlを加えた。析出した粗製物をろ過によって採取した。粗製物についてメタノール100mlを用いた還流洗浄を行った。その結果、4,4’’’’-ビス{(ビフェニル-4-イル)-フェニルアミノ}-(1,1’:4’,1’’:4’’,1’’’:4’’’,1’’’’-キンクフェニル)(化合物1-13)の薄黄色粉体9.8g(収率66%)を得た。
δ(ppm)=7.66-7.80(12H)
7.50-7.64(12H)
7.42-7.50(4H)
7.28-7.38(6H)
7.20-7.26(12H)
7.08(2H)
4,4’’’-ビス{(ビフェニル-4-イル)-フェニルアミノ}-(1,1’:3’,1’’:3’’,1’’’-クォーターフェニル)の合成;
合成例1において、
4,4’-ジヨードビフェニル
に代えて、
3,3’-ジブロモビフェニル
を用い、同様の条件で反応を行った。その結果、4,4’’’-ビス{(ビフェニル-4-イル)-フェニルアミノ}-(1,1’:3’,1’’:3’’,1’’’-クォーターフェニル)(化合物1-11)の薄黄色粉体16.2g(収率91%)を得た。
δ(ppm)=7.87(2H)
7.48-7.66(18H)
7.39-7.48(4H)
7.29-7.39(6H)
7.18-7.26(12H)
7.08(2H)
4,4’’’’-ビス{(ビフェニル-4-イル)-フェニルアミノ}-(1,1’:3’,1’’:2’’,1’’’:3’’’,1’’’’-キンクフェニル)の合成;
合成例1において、
4,4’-ジヨードビフェニル
に代えて、
3,3’’-ジブロモ(1,1’:2’,1’’-ターフェニル)
を用い、同様の条件で反応を行った。その結果、4,4’’’’-ビス{(ビフェニル-4-イル)-フェニルアミノ}-(1,1’:3’,1’’:2’’,1’’’:3’’’,1’’’’-キンクフェニル)(化合物1-15)の薄黄色粉体17.0g(収率92%)を得た。
δ(ppm)=7.00-7.62(48H)
4,4’’’’-ビス{(ビフェニル-4-イル)-フェニルアミノ}-(1,1’:3’,1’’:3’’,1’’’:3’’’,1’’’’-キンクフェニル)の合成;
合成例1において、
4,4’-ジヨードビフェニル
に代えて、
3,3’’-ジブロモ(1,1’:3’,1’’-ターフェニル)
を用い、同様の条件で反応を行った。その結果、4,4’’’’-ビス{(ビフェニル-4-イル)-フェニルアミノ}-(1,1’:3’,1’’:3’’,1’’’:3’’’,1’’’’-キンクフェニル)(化合物1-17)の薄黄色粉体10.5g(収率57%)を得た。
δ(ppm)=7.93(1H)
7.87(2H)
7.40-7.72(24H)
7.16-7.38(18H)
7.09(3H)
4,4’’’-ビス{(ビフェニル-4-イル)-フェニルアミノ}-(1,1’:2’,1’’:2’’,1’’’-クォーターフェニル)の合成;
合成例1において、
4,4’-ジヨードビフェニル
に代えて、
2,2’-ジブロモビフェニル
を用い、同様の条件で反応を行った。その結果、4,4’’’-ビス{(ビフェニル-4-イル)-フェニルアミノ}-(1,1’:2’,1’’:2’’,1’’’-クォーターフェニル)(化合物1-21)の薄黄色粉体9.0g(収率83%)を得た。
δ(ppm)=7.45-7.54(6H)
7.23-7.45(16H)
7.13-7.22(4H)
7.05-7.13(8H)
6.94(2H)
6.82(4H)
6.62(4H)
4,4’’’-ビス{(ナフタレン-1-イル)-フェニルアミノ}-(1,1’:3’,1’’:3’’,1’’’-クォーターフェニル)の合成;
合成例1において、
4,4’-ジヨードビフェニル
に代えて、
3,3’-ジブロモビフェニル
を用い、
N-フェニル-N-{4-(4,4,5,5-テトラメチル-1
,3,2-ジオキサボロラン-2-イル)フェニル}-(1,1’
-ビフェニル-4-イル)アミン
に代えて、
N-フェニル-N-{4-(4,4,5,5-テトラメチル-1
,3,2-ジオキサボロラン-2-イル)フェニル}-(ナフタレ
ン-1-イル)アミン
を用い、同様の条件で反応を行った。その結果、4,4’’’-ビス{(ナフタレン-1-イル)-フェニルアミノ}-(1,1’:3’,1’’:3’’,1’’’-クォーターフェニル)(化合物1-22)の薄黄色粉体4.00g(収率26%)を得た。
δ(ppm)=7.99(2H)
7.92(2H)
7.78-7.85(4H)
7.35-7.61(18H)
7.19-7.28(4H)
7.06-7.15(8H)
6.98(2H)
4,4’’’’-ビス{(ビフェニル-4-イル)-フェニルアミノ}-(1,1’:4’,1’’:2’’,1’’’:4’’’,1’’’’-キンクフェニル)の合成;
合成例1において、
4,4’-ジヨードビフェニル
に代えて、
4,4’’-ジブロモ(1,1’:2’,1’’-ターフェニル)
を用い、同様の条件で反応を行った。その結果、4,4’’’’-ビス{(ビフェニル-4-イル)-フェニルアミノ}-(1,1’:4’,1’’:2’’,1’’’:4’’’,1’’’’-キンクフェニル)(化合物1-23)の薄黄色粉体13.8g(収率62%)を得た。
δ(ppm)=7.60(4H)
7.03-7.56(44H)
4,4’’’’-ビス{(ビフェニル-4-イル)-フェニルアミノ}-(1,1’:2’,1’’:3’’,1’’’:2’’’,1’’’’-キンクフェニル)の合成;
合成例1において、
4,4’-ジヨードビフェニル
に代えて、
2,2’’-ジブロモ(1,1’:3’,1’’-ターフェニル)
を用い、同様の条件で反応を行った。その結果、4,4’’’’-ビス{(ビフェニル-4-イル)-フェニルアミノ}-(1,1’:2’,1’’:3’’,1’’’:2’’’,1’’’’-キンクフェニル)(化合物1-24)の薄黄色粉体9.7g(収率69%)を得た。
δ(ppm)=7.30-7.56(20H)
6.91-7.24(28H)
4,4’’’’-ビス{(ビフェニル-4-イル)-フェニルアミノ}-(1,1’:4’,1’’:3’’,1’’’:4’’’,1’’’’-キンクフェニル)の合成;
合成例1において、
4,4’-ジヨードビフェニル
に代えて、
4,4’’-ジブロモ(1,1’:3’,1’’-ターフェニル)
を用い、同様の条件で反応を行った。その結果、4,4’’’’-ビス{(ビフェニル-4-イル)-フェニルアミノ}-(1,1’:4’,1’’:3’’,1’’’:4’’’,1’’’’-キンクフェニル)(化合物1-25)の薄黄色粉体16.5g(収率74%)を得た。
δ(ppm)=7.93(1H)
7.06-7.80(47H)
4,4’’’’-ビス{(ジベンゾフラン-1-イル)-フェニルアミノ}-(1,1’:4’,1’’:2’’,1’’’:4’’’,1’’’’-キンクフェニル)の合成;
合成例8において、
N-フェニル-N-{4-(4,4,5,5-テトラメチル-1
,3,2-ジオキサボロラン-2-イル)フェニル}-(1,1’
-ビフェニル-4-イル)アミン
に代えて、
N-フェニル-N-{4-(4,4,5,5-テトラメチル-1
,3,2-ジオキサボロラン-2-イル)フェニル}-(ジベンゾ
フラン-1-イル)アミン
を用い、同様の条件で反応を行った。その結果、4,4’’’’-ビス{(ジベンゾフラン-1-イル)-フェニルアミノ}-(1,1’:4’,1’’:2’’,1’’’:4’’’,1’’’’-キンクフェニル)(化合物1-26)の薄黄色粉体14.0g(収率61%)を得た。
δ(ppm)=7.97(2H)
7.79(2H)
7.02-7.55(40H)
4,4’’’’-ビス{(ビフェニル-4-イル)-フェニルアミノ}-(1,1’:2’,1’’:2’’,1’’’:2’’’,1’’’’-キンクフェニル)の合成;
合成例1において、
4,4’-ジヨードビフェニル
に代えて、
2,2’’-ジブロモ(1,1’:2’,1’’-ターフェニル)
を用い、同様の条件で反応を行った。その結果、4,4’’’’-ビス{(ビフェニル-4-イル)-フェニルアミノ}-(1,1’:2’,1’’:2’’,1’’’:2’’’,1’’’’-キンクフェニル)(化合物1-27)の薄黄色粉体8.5g(収率61%)を得た。
δ(ppm)=7.62(4H)
6.78-7.57(36H)
6.53(4H)
6.46(2H)
6.38(2H)
4,4’’’-ビス{(ビフェニル-4-イル)-d5-フェニルアミノ}-(1,1’:3’,1’’:3’’,1’’’-クォーターフェニル)の合成;
合成例1において、
4,4’-ジヨードビフェニル
に代えて、
3,3’-ジブロモビフェニル
を用い、
N-フェニル-N-{4-(4,4,5,5-テトラメチル-1
,3,2-ジオキサボロラン-2-イル)フェニル}-(1,1’
-ビフェニル-4-イル)アミン
に代えて、
N-(フェニル-d5)-N-{4-(4,4,5,5-テトラメ
チル-1,3,2-ジオキサボロラン-2-イル)フェニル}-(
1,1’-ビフェニル-4-イル)アミン
を用い、同様の条件で反応を行った。その結果、4,4’’’-ビス{(ビフェニル-4-イル)-d5-フェニルアミノ}-(1,1’:3’,1’’:3’’,1’’’-クォーターフェニル)(化合物1-28)の薄黄色粉体8.7g(収率68%)を得た。
δ(ppm)=7.87(2H)
7.40-7.66(20H)
7.30-7.38(4H)
7.19-7.26(8H)
4,4’’’-ビス{(ビフェニル-4-イル)-フェニルアミノ}-(1,1’:3’,1’’:4’’,1’’’-クォーターフェニル)の合成;
合成例1において、
4,4’-ジヨードビフェニル
に代えて、
3,4’-ジブロモビフェニル
を用い、同様の条件で反応を行った。その結果、4,4’’’-ビス{(ビフェニル-4-イル)-フェニルアミノ}-(1,1’:3’,1’’:4’’,1’’’-クォーターフェニル)(化合物1-38)の薄黄色粉体14.0g(収率84%)を得た。
δ(ppm)=7.00-8.00(44H)
一般式(1)で表されるアリールアミン化合物について、高感度示差走査熱量計(ブルカー・エイエックスエス製、DSC3100S)によってガラス転移点を求めた。
ガラス転移点
合成例1(化合物1-1) 119℃
合成例2(化合物1-13) 124℃
合成例3(化合物1-11) 114℃
合成例4(化合物1-15) 115℃
合成例5(化合物1-17) 118℃
合成例6(化合物1-21) 111℃
合成例7(化合物1-22) 112℃
合成例8(化合物1-23) 129℃
合成例9(化合物1-24) 113℃
合成例10(化合物1-25) 126℃
合成例11(化合物1-26) 131℃
合成例12(化合物1-27) 121℃
合成例13(化合物1-28) 113℃
合成例14(化合物1-38) 117℃
一般式(1)で表されるアリールアミン化合物を用いて、ITO基板の上に膜厚100nmの蒸着膜を作製して、イオン化ポテンシャル測定装置(住友重機械工業株式会社、PYS-202)によって仕事関数を測定した。
仕事関数
合成例1(化合物1-1) 5.68eV
合成例2(化合物1-13) 5.69eV
合成例3(化合物1-11) 5.73eV
合成例4(化合物1-15) 5.74eV
合成例5(化合物1-17) 5.77eV
合成例6(化合物1-21) 5.73eV
合成例7(化合物1-22) 5.81eV
合成例8(化合物1-23) 5.71eV
合成例9(化合物1-24) 5.74eV
合成例10(化合物1-25) 5.72eV
合成例11(化合物1-26) 5.74eV
合成例12(化合物1-27) 5.73eV
合成例13(化合物1-28) 5.76eV
合成例14(化合物1-38) 5.74eV
図1に示すように、ガラス基板1上に透明陽極2としてITO電極をあらかじめ形成したものの上に、正孔注入層3、第一正孔輸送層4、第二正孔輸送層5、発光層6、電子輸送層7、電子注入層8、陰極(アルミニウム電極)9の順に蒸着して、有機EL素子を作製した。
続いて、透明陽極2を覆うように正孔注入層3として、下記構造式の化合物6を膜厚5nmとなるように形成した。
正孔注入層3の上に、第一正孔輸送層4として下記構造式の化合物5-1を膜厚60nmとなるように形成した。
第一正孔輸送層4の上に、第二正孔輸送層5として合成例3の化合物1-11を膜厚5nmとなるように形成した。
第二正孔輸送層5の上に、発光層6として下記構造式の化合物7-Aと下記構造式の化合物8-Aを、蒸着速度比が化合物7-A:化合物8-A=5:95となる蒸着速度で二元蒸着を行い、膜厚20nmとなるように形成した。
発光層6の上に、電子輸送層7として下記構造式の化合物2-92と下記構造式の化合物9を、蒸着速度比が化合物2-92:化合物9=50:50となる蒸着速度で二元蒸着を行い、膜厚30nmとなるように形成した。
電子輸送層7の上に、電子注入層8としてフッ化リチウムを膜厚1nmとなるように形成した。
最後に、アルミニウムを100nm蒸着して陰極9を形成した。
作製した有機EL素子について、大気中常温で直流電圧を印加したときの発光特性を測定した。結果を表1に示した。
素子実施例1において、第二正孔輸送層5の材料として合成例3の化合物1-11に代えて合成例14の化合物1-38を用いた点以外は、同様の条件で有機EL素子を作製した。作製した有機EL素子について、大気中常温で直流電圧を印加したときの発光特性を測定した。結果を表1に示した。
素子実施例1において、電子輸送層7の材料として化合物2-92に代えて下記構造式の化合物2-123を用いた点以外は、同様の条件で有機EL素子を作製した。作製した有機EL素子について、大気中常温で直流電圧を印加したときの発光特性を測定した。結果を表1に示した。
素子実施例3において、第二正孔輸送層5の材料として合成例3の化合物1-11に代えて合成例14の化合物1-38を用いた点以外は、同様の条件で有機EL素子を作製した。作製した有機EL素子について、大気中常温で直流電圧を印加したときの発光特性を測定した。結果を表1に示した。
素子実施例1において、電子輸送層7の材料として化合物2-92に代えて下記構造式の化合物2-124を用いた以外は、同様の条件で有機EL素子を作製した。作製した有機EL素子について、大気中常温で直流電圧を印加したときの発光特性を測定した。結果を表1に示した。
素子実施例5において、第二正孔輸送層5の材料として合成例3の化合物1-11に代えて合成例14の化合物1-38を用いた点以外は、同様の条件で有機EL素子を作製した。作製した有機EL素子について、大気中常温で直流電圧を印加したときの発光特性を測定した。結果を表1に示した。
素子実施例1において、第二正孔輸送層5の材料として合成例3の化合物1-11に代えて前記化合物5-1を用いた点以外は、同様の条件で有機EL素子を作製した。この場合、第一正孔輸送層4と第二正孔輸送層5は、一体の正孔輸送層(膜厚65nm)として機能する。作製した有機EL素子について、大気中常温で直流電圧を印加したときの発光特性を測定した。結果を表1に示した。
素子実施例3において、第二正孔輸送層5の材料として合成例3の化合物1-11に代えて前記化合物5-1を用いた点以外は、同様の条件で有機EL素子を作製した。この場合、第一正孔輸送層4と第二正孔輸送層5は、一体の正孔輸送層(膜厚65nm)として機能する。作製した有機EL素子について、大気中常温で直流電圧を印加したときの発光特性を測定した。結果を表1に示した。
素子実施例5において、第二正孔輸送層5の材料として合成例3の化合物1-11に代えて前記化合物5-1を用いた点以外は、同様の条件で有機EL素子を作製した。この場合、第一正孔輸送層4と第二正孔輸送層5は、一体の正孔輸送層(膜厚65nm)として機能する。作製した有機EL素子について、大気中常温で直流電圧を印加したときの発光特性を測定した。結果を表1に示した。
素子実施例1において、第二正孔輸送層5の材料として合成例3の化合物1-11に代えて前記化合物5-1を用いた点、および、電子輸送層7の材料として化合物2-92に代えて下記構造式の化合物ETM-1(国際公開第2003/060956号参照)を用いた以外は、同様の条件で有機EL素子を作製した。この場合、第一正孔輸送層4と第二正孔輸送層5は、一体の正孔輸送層(膜厚65nm)として機能する。作製した有機EL素子について、大気中常温で直流電圧を印加したときの発光特性を測定した。結果を表1に示した。
2 透明陽極
3 正孔注入層
4 第一正孔輸送層
5 第二正孔輸送層
6 発光層
7 電子輸送層
8 電子注入層
9 陰極
Claims (12)
- 少なくとも陽極、正孔注入層、第一正孔輸送層、第二正孔輸送層、発光層、電子輸送層および陰極をこの順に有する有機エレクトロルミネッセンス素子において、
前記第二正孔輸送層が、下記一般式(1)で表されるアリールアミン化合物を含有し、
前記電子輸送層が、下記一般式(2)で表されるピリミジン誘導体を含有することを特徴とする有機エレクトロルミネッセンス素子。
Ar1~Ar4は、それぞれ、芳香族炭化水素基、芳香族複
素環基または縮合多環芳香族基を表し、
nは2~4の整数を表す、
Ar5は、芳香族炭化水素基、芳香族複素環基または縮合
多環芳香族基を表し、
Ar6、Ar7は、それぞれ、水素原子、芳香族炭化水素基
、芳香族複素環基または縮合多環芳香族基を表し、Ar6とA
r7は同時に水素原子となることはなく、
Aは、下記構造式(3)で示される1価基を表す、
Ar8は、芳香族複素環基を表し、
R1~R4は、それぞれ、水素原子、重水素原子、フッ
素原子、塩素原子、シアノ基、トリフルオロメチル基、炭
素数1~6のアルキル基、芳香族炭化水素基、芳香族複素
環基または縮合多環芳香族基を表し、
R1~R4とAr8が単結合、置換もしくは無置換のメ
チレン基、酸素原子または硫黄原子を介して互いに結合し
て環を形成していてもよい。 - 前記第一正孔輸送層が、分子中にトリアリールアミン構造を3~6個有するトリアリールアミン化合物であって、該トリアリールアミン構造が、ヘテロ原子を含まない2価基または単結合で連結しているトリアリールアミン化合物を含有する、請求項1記載の有機エレクトロルミネッセンス素子。
- 前記トリアリールアミン構造を3~6個有するトリアリールアミン化合物が、下記一般式(4)で表される、分子中にトリアリールアミン構造を4個有するトリアリールアミン化合物である、請求項2記載の有機エレクトロルミネッセンス素子。
r5、r6、r9、r12、r15およびr16は、それぞれ、
0~5の整数を表し、
r7、r8、r10、r11、r13およびr14は、それぞれ
、0~4の整数を表し、
R5~R16は、それぞれ、重水素原子、フッ素原子、塩素
原子、シアノ基、ニトロ基、炭素数1~6のアルキル基、炭素
数5~10のシクロアルキル基、炭素数2~6のアルケニル基
、炭素数1~6のアルキルオキシ基、炭素数5~10のシクロ
アルキルオキシ基、芳香族炭化水素基、芳香族複素環基、縮合
多環芳香族基またはアリールオキシ基を表し、これらの基が同
一のベンゼン環に複数存在している場合、複数存在している基
は、単結合、置換もしくは無置換のメチレン基、酸素原子また
は硫黄原子を介して互いに結合して環を形成してもよく、
L1~L3は、それぞれ、下記構造式(B)~(G)のいず
れかで示される2価基または単結合を表す。
- 前記第一正孔輸送層が、分子中にトリアリールアミン構造を2個有するトリアリールアミン化合物であって、該トリアリールアミン構造が、ヘテロ原子を含まない2価基または単結合で連結しているトリアリールアミン化合物を含有する、請求項1記載の有機エレクトロルミネッセンス素子。
- 前記トリアリールアミン構造を2個有するトリアリールアミン化合物が、下記一般式(5)で表される、請求項4記載の有機エレクトロルミネッセンス素子。
r17、r18、r21およびr22は、それぞれ、0~5の整
数を表し、
r19およびr20は、それぞれ、0~4の整数を表し、
R17~R22は、それぞれ、重水素原子、フッ素原子、塩素
原子、シアノ基、ニトロ基、炭素数1~6のアルキル基、炭素
数5~10のシクロアルキル基、炭素数2~6のアルケニル基
、炭素数1~6のアルキルオキシ基、炭素数5~10のシクロ
アルキルオキシ基、芳香族炭化水素基、芳香族複素環基、縮合
多環芳香族基またはアリールオキシ基を表し、これらの基が同
一のベンゼン環に複数結合する場合、複数結合している基は、
単結合、置換もしくは無置換のメチレン基、酸素原子または硫
黄原子を介して互いに結合して環を形成してもよく、
L4は、下記構造式(C)~(G)のいずれかで示される2
価基または単結合を表す。
- 前記発光層が、青色発光性ドーパントを含有する、請求項1記載の有機エレクトロルミネッセンス素子。
- 前記青色発光性ドーパントが、ピレン誘導体である、請求項9記載の有機エレクトロルミネッセンス素子。
- 前記発光層が、アントラセン誘導体を含有する、請求項1記載の有機エレクトロルミネッセンス素子。
- 前記発光層が、前記アントラセン誘導体をホスト材料として含有する、請求項11記載の有機エレクトロルミネッセンス素子。
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CN115536633A (zh) * | 2017-07-20 | 2022-12-30 | 索路思高新材料有限公司 | 一种化合物及包含其的有机电致发光元件 |
JP2020527578A (ja) * | 2017-07-20 | 2020-09-10 | トゥサン ソーラス カンパニー リミテッドDoosan Solus Co., Ltd. | 有機発光化合物及びこれを用いた有機電界発光素子 |
JP7364711B2 (ja) | 2017-07-20 | 2023-10-18 | ソリュース先端素材株式会社 | 有機発光化合物及びこれを用いた有機電界発光素子 |
CN110944988A (zh) * | 2017-07-20 | 2020-03-31 | 株式会社斗山 | 有机发光化合物及包含其的有机电致发光元件 |
JP2023501280A (ja) * | 2019-10-31 | 2023-01-18 | ソールブレイン・カンパニー・リミテッド | 有機化合物、それを含む有機発光ダイオード、及び該有機発光ダイオードを含む表示装置 |
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TWI690504B (zh) | 2020-04-11 |
EP3220437B1 (en) | 2021-04-14 |
KR20170086555A (ko) | 2017-07-26 |
KR102421540B1 (ko) | 2022-07-14 |
EP3220437A1 (en) | 2017-09-20 |
CN107112427A (zh) | 2017-08-29 |
US20170317291A1 (en) | 2017-11-02 |
EP3220437A4 (en) | 2018-07-11 |
JP6703952B2 (ja) | 2020-06-03 |
US10276800B2 (en) | 2019-04-30 |
CN107112427B (zh) | 2019-09-24 |
JPWO2016076384A1 (ja) | 2017-10-05 |
TW201627271A (zh) | 2016-08-01 |
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