WO2018103745A1 - 咔唑类化合物及其应用 - Google Patents

咔唑类化合物及其应用 Download PDF

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WO2018103745A1
WO2018103745A1 PCT/CN2017/115309 CN2017115309W WO2018103745A1 WO 2018103745 A1 WO2018103745 A1 WO 2018103745A1 CN 2017115309 W CN2017115309 W CN 2017115309W WO 2018103745 A1 WO2018103745 A1 WO 2018103745A1
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group
organic
carbazole compound
carbon atoms
carbazole
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PCT/CN2017/115309
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English (en)
French (fr)
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潘君友
胡光
杨曦
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广州华睿光电材料有限公司
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Priority to CN201780059447.8A priority Critical patent/CN109790163B/zh
Publication of WO2018103745A1 publication Critical patent/WO2018103745A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to the field of electronics, and in particular to a carbazole compound and its use.
  • organic semiconductor materials Due to the diversity of molecular structure design, relatively low manufacturing cost, and superior optoelectronic performance, organic semiconductor materials have great potential applications in many optoelectronic devices, such as organic light-emitting diodes (OLEDs) and organic photovoltaic cells (OPVs). Airport Effect Transistor (OFET), etc. Especially since the double-layer OLED structure was reported by Deng Qingyun et al. (C.W. Tang and S.A. Van Slyke, Appl. Phys. Lett., 1987, 51, 913), organic semiconductor materials have been rapidly developed in the field of flat panel display and illumination.
  • the organic thin film light-emitting element must satisfy an improvement in luminous efficiency, a reduction in driving voltage, and an improvement in durability.
  • an improvement in luminous efficiency a reduction in driving voltage
  • an improvement in durability a reduction in durability
  • carbazole organic semiconductor materials have a wide range of applications in optoelectronic devices due to their superior optoelectronic properties, redox properties, and stability.
  • aromatic group or the aromatic hetero group of the fused ring structure such as fluoranthene, fluorene, fluorene, phenanthrene, phenanthroline, benzofluoranthene, etc., generally has good carrier transport due to the planar structure of the molecule. Performance and photoelectric response.
  • the currently reported carbazoles or organic semiconductor materials having a fused ring structure have certain limitations in carrier transport capability, stability, and lifetime of photovoltaic devices.
  • CN 104350627 A discloses compounds in which a carbazole group substituted with a nitrogen atom on a benzene ring is bonded to a fused ring group containing benzofluoranthene. Such compounds are used as electron transport layers for blue OLED devices, resulting in lower voltages and longer lifetimes. However, the electron transport materials of the fused ring carbazole system have not been further studied.
  • CN 104768926 A discloses compounds in which triphenylamine is attached to a fused ring group. Such compounds are used as electron transport layers for blue OLED devices, resulting in lower voltages and longer lifetimes. However, often compared with triphenylamines, carbazole as a kind of transport material unit with more conjugates, its effect on the performance and lifetime of the device combined with the design of fused ring structure has not been further compared and studied.
  • Ar 1 is a fused aryl group having a ring number of 13 to 60 or a fused heteroaryl group having a ring number of 13 to 60;
  • Ar 2 and Ar 3 are each independently selected from an aryl group having 6 to 60 carbon atoms, a heteroaryl group having 3 to 60 carbon atoms, a fused aryl group having 7 to 60 carbon atoms, and a carbon atom number of a heterocyclic aryl group of 4 to 60 or one of a combination group formed by at least two of the above groups being bonded to each other, and at least one of the Ar 2 and the Ar 3 includes a heteroaryl group having an N atom;
  • R 1 is selected from the group consisting of H, D, F, CN, NO 2 , CF 3 , alkenyl, alkynyl, amine, acyl, amide, cyano, isocyano, alkoxy, hydroxy, carbonyl, sulfone, An alkyl group having 1 to 60 carbon atoms, a cycloalkyl group having 3 to 60 carbon atoms, an aryl group having 6 to 60 carbon atoms, a heteroaryl group having 3 to 60 carbon atoms, and a carbon number of a thick aryl group of 7 to 60, a fused heteroaryl group having 4 to 60 carbon atoms, and one of a combination group in which at least two of the above groups are bonded to each other, and at least the L 2 and L 3 a heteroaryl group having an N atom;
  • n is an integer from 0 to 20;
  • p and q are each independently selected from one of integers from 0 to 4, and p and q are not 0 at the same time.
  • the above carbazole compound is advantageous in achieving better carrier transport, photoelectric response and energy level matching by directly connecting the nitrogen atom of the carbazole to the condensed or fused heteroaryl group of the planar structure, thereby improving the compound.
  • Photoelectric properties and stability which in turn enable photovoltaic devices including the compound to have higher stability, higher luminous efficiency, and longer lifetime devices. It has been verified by experiments that the difference in energy level between HOMO and LUMO of the material including the above carbazole compound is small, indicating that the stability of the above carbazole compound is good, and the ⁇ E ST of the above carbazole compound is small, indicating that the above hydrazine is included.
  • the device life of the azole compound material is long, and the device lifetime of the organic light emitting diode including the above carbazole compound is more than twice that of the organic light emitting diode not including the above carbazole compound, and includes the above carbazole.
  • the luminous efficiency of the organic light-emitting diode of the compound-like compound is at least 47.2% higher than that of the organic light-emitting diode not including the above-mentioned carbazole compound.
  • the above carbazole compounds can be used to prepare electronic devices having higher stability, higher luminous efficiency, and longer lifetime.
  • the aryl group means a hydrocarbon group containing at least one aromatic ring unless otherwise specified.
  • Heteroaryl refers to an aromatic hydrocarbon group containing at least one hetero atom.
  • the hetero atom may be, for example, O, N or S.
  • the aryl or heteroaryl group includes not only a group having an aromatic ring or a heteroaryl ring, but also a group having a non-aromatic ring, such as a pyridyl group, a thienyl group, a pyrrolyl group, a pyrazolyl group, Groups such as triazolyl, imidazolyl, oxazolyl, oxadiazolyl, thiazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl or carbene are also considered to be aryl or hetero Aryl.
  • a non-aromatic ring such as a pyridyl group, a thienyl group, a pyrrolyl group, a pyrazolyl group
  • Groups such as triazolyl, imidazolyl, oxazolyl, oxadiazolyl,
  • the aryl or heteroaryl group may further include a group in which at least two aromatic rings or heteroaromatic rings are bonded by a non-aromatic ring group, wherein the number of non-H atoms in the non-aromatic ring group is less than 10 %. In one embodiment, the number of non-H atoms in the non-aromatic ring group is less than 5%. In one embodiment, the non-aromatic ring group is a C atom, an N atom or an O atom.
  • the aryl group is a phenyl group, a biphenyl group, a terphenyl group, a tolyl group, a chlorophenyl group or a derivative of the above group.
  • Heteroaryl is pyridinyl, thienyl, pyrrolyl, pyrazolyl, triazolyl, imidazolyl, oxazolyl, oxadiazolyl, thiazolyl, Tetrazolyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, carbene or a derivative of the above group.
  • a fused aryl group refers to an aryl group having two or more rings, and wherein two adjacent rings share two carbon atoms (ie, a fused ring).
  • a fused heteroaryl group refers to a fused aryl group containing at least one hetero atom.
  • the hetero atom may be, for example, N, O or S.
  • the fused or fused heteroaryl group includes not only a group having an aromatic ring or a heteroaromatic ring, but also a group composed of at least two aromatic rings or heteroaryl rings bonded by a non-aromatic ring group.
  • a group wherein the number of non-H atoms in the non-aromatic ring group is less than 10%.
  • the number of non-H atoms in the non-aromatic ring group is less than 5%.
  • the non-aromatic ring group is a C atom, an N atom or an O atom.
  • the 9,9'-spirobifluorenyl, 9,9-diarylsulfonyl, triarylamine, and diaryl ether are also considered to be fused or fused heteroaryl.
  • the fused aryl group is a naphthyl group, an anthracenyl group, a fluorenyl group, a phenanthryl group, a benzophenanyl group, a perylene group, a tetraphenylene group, a fluorenyl group, a benzofluorenyl group, a fluorenyl group, a fluorenyl group or a derivative of the above group.
  • the fused heteroaryl group is a benzofuranyl group, a benzothienyl group, a fluorenyl group, a carbazolyl group, a pyrroloimidazolyl group, a pyrrolopyrrolyl group, a thienopyrrolidinyl group, a thienothiophenyl group, a furopyrrolyl group, a furan Furanyl, thienofuranyl, benzoisoxazolyl, benzisothiazolyl, benzimidazolyl, quinolyl, isoquinolyl, o-naphthylnaphthyl, quinoxalinyl, phenanthryl, Berridinyl, quinazolinyl, quinazolinone groups and derivatives of the above groups.
  • Ar 1 is a fused aryl group having a ring number of 13 to 60 or a fused heteroaryl group having a ring number of 13 to 60;
  • Ar 2 and Ar 3 are each independently selected from an aryl group having 6 to 60 carbon atoms, a heteroaryl group having 3 to 60 carbon atoms, a fused aryl group having 7 to 60 carbon atoms, and a carbon atom number of a fused aromatic group of 4 to 60 or one of a combination of at least two of the above groups, and at least one of Ar 2 and Ar 3 contains a heteroaryl group having an N atom;
  • R 1 is selected from the group consisting of H, D, F, CN, NO 2 , CF 3 , alkenyl, alkynyl, amine, acyl, amide, cyano, isocyano, alkoxy, hydroxy, carbonyl, sulfone, An alkyl group having 1 to 60 carbon atoms, a cycloalkyl group having 3 to 60 carbon atoms, an aryl group having 6 to 60 carbon atoms, a heteroaryl group having 3 to 60 carbon atoms, and a carbon number of a thick aryl group of 7 to 60, a fused heteroaryl group having 4 to 60 carbon atoms, and one of a combination group in which at least two of the above groups are bonded to each other;
  • n is an integer from 0 to 20;
  • p and q are each independently selected from one of integers from 0 to 4, and p and q are not 0 at the same time.
  • Ar 1 is a fused aryl group having 13 to 50 ring atoms or a fused heteroaryl group having 13 to 50 ring atoms.
  • Ar 1 is a fused aryl group having 13 to 40 ring atoms or a fused heteroaryl group having 13 to 40 ring atoms.
  • Ar 1 is a fused aryl group having 13 to 30 ring atoms or a fused heteroaryl group having 13 to 30 ring atoms.
  • Ar 1 is a fused aryl group having 13 to 20 ring atoms or a fused heteroaryl group having 13 to 20 ring atoms.
  • Ar 1 is a fused heteroaryl group, and the hetero atom of Ar 1 is Si, N, P, O, S or Ge.
  • Ar 1 is a fused heteroaryl group, and the hetero atom of Ar 1 is Si, N, P, O or S.
  • Ar 1 is a fused heteroaryl group and the hetero atom of Ar 1 is N, O or S.
  • Ar 1 is a fused ring group having 3 to 20 ring atoms.
  • Ar 1 is a three-membered ring group, a four-membered ring group, a five-membered ring group or a six-membered ring group.
  • Ar 1 is a fused ring group having 3 to 10 ring atoms.
  • Ar 1 is a fused ring group having 3 to 5 ring atoms.
  • the structural formula of Ar 1 is selected from one of the following structural formulae:
  • X 1 is CR 2 or N;
  • -R 2 , -R 3 , -R 4 , -R 5 , -R 6 and -R 7 are each independently selected from the group consisting of a single bond, -H, -D, -F, -CN, -NO 2 , -CF 3 , Alkenyl, alkynyl, amine, acyl, amide, cyano, isocyano, alkoxy, hydroxy, carbonyl, sulfone, alkyl having from 1 to 60, carbon number from 3 to 60 a cycloalkyl group, an aryl group having 6 to 60 carbon atoms, a heteroaryl group having 3 to 60 carbon atoms, a condensed aryl group having 7 to 60 carbon atoms, and a heteropoly group having 4 to 60 carbon atoms.
  • Y 1 is selected from one of CR 3 -R 4 and O.
  • -R 2 , -R 3 , -R 4 , -R 5 , -R 6 and -R 7 are each independently selected from substituted alkyl groups having 1 to 60 carbon atoms, substituted carbons. a cycloalkyl group having 3 to 60 atoms, a substituted aryl group having 6 to 60 carbon atoms, a substituted heteroaryl group having 3 to 60 carbon atoms, and a substituted fused aromatic group having 7 to 60 carbon atoms.
  • a heterocyclic aryl group having 4 to 60 carbon atoms and a substituted carbon atom are each independently selected from substituted alkyl groups having 1 to 60 carbon atoms, substituted carbons.
  • a cycloalkyl group having 3 to 60 atoms a substituted aryl group having 6 to 60 carbon atoms
  • a substituted heteroaryl group having 3 to 60 carbon atoms a substituted fused aromatic group having 7 to 60 carbon atoms.
  • -R 2 , -R 3 , -R 4 , -R 5 , -R 6 and -R 7 are each independently selected from the group consisting of a single bond, -H, -D, -F, -CN, - NO 2 , -CF 3 , alkenyl, alkynyl, amino, acyl, amide, cyano, isocyano, alkoxy, hydroxy, carbonyl, sulfone, alkyl having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, a condensed aromatic group having 7 to 30 carbon atoms, and a carbon number It is one of 4 to 30 fused heteroaryl groups and a combination group formed by at least two of the above groups being bonded to each other.
  • -R 2 , -R 3 , -R 4 , -R 5 , -R 6 and -R 7 are each independently selected from substituted alkyl groups having 1 to 30 carbon atoms, substituted carbons. a cycloalkyl group having 3 to 30 atoms, a substituted aryl group having 6 to 30 carbon atoms, a substituted heteroaryl group having 3 to 30 carbon atoms, and a substituted fused aromatic group having 7 to 30 carbon atoms The group and the substituted carbon have at least one of 4 to 30 fused aromatic groups.
  • -R 2 , -R 3 , -R 4 , -R 5 , -R 6 and -R 7 are each capable of forming a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a single ring.
  • -R 2 is capable of forming a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aromatic group with -R 3 , -R 4 , -R 5 , -R 6 or -R 7 .
  • -R 7 is capable of forming a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aromatic group with -R 2 , -R 3 , -R 4 , -R 5 or -R 6 .
  • -R 3 and -R 4 can form a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aryl group or a polycyclic aryl group with each other.
  • -R 5 and -R 6 can form a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aryl group or a polycyclic aryl group with each other.
  • Ar 1 is selected from the group consisting of fluorenyl, fluoranthenyl, phenanthryl, benzophenanyl, perylene, tetraphenyl, anthracenyl, benzofluorenyl, fluorenyl, fluorenyl One of oxazolyl, dibenzofuranyl and dibenzothiophenyl.
  • the structural formula of Ar 1 is selected from one of the following structural formulae:
  • the structural formula of the heteroaryl group having an N atom is selected from one of the following structural formulae:
  • X 2 is CR 8 or N, and the heteroaryl group of the formula N atoms having at least one of X 2 is N;
  • -R 8 , -R 9 , -R 10 , -R 11 , -R 12 and -R 13 are each independently selected from the group consisting of a single bond, -H, -D, -F, -CN, -NO 2 , -CF 3 , Alkenyl, alkynyl, amine, acyl, amide, cyano, isocyano, alkoxy, hydroxy, carbonyl, sulfone, alkyl having from 1 to 60, carbon number from 3 to 60 a cycloalkyl group, a carbon number of 6 to 60 aryl groups, a carbon number of 3 to 60 heteroaryl groups, a aryl group having 7 to 60 carbon atoms, and a fused heteroaryl group having 4 to 60 carbon atoms. And one of the combination groups formed by at least two of the above groups being bonded to each other.
  • -R 8 , -R 9 , -R 10 , -R 11 , -R 12 and -R 13 are each independently selected from alkyl groups each independently selected from substituted carbon atoms having from 1 to 60 carbon atoms. a substituted cycloalkyl group having 3 to 60 carbon atoms, an substituted aryl group having 6 to 60 carbon atoms, a substituted heteroaryl group having 3 to 60 carbon atoms, and a substituted carbon atom of 7 to 60. A thick aryl group of 60 and one of the substituted heteroaryl groups having 4 to 60 carbon atoms.
  • -R 8 , -R 9 , -R 10 , -R 11 , -R 12 and -R 13 are each independently selected from the group consisting of a single bond, -H, -D, -F, -CN, - NO 2 , -CF 3 , alkenyl, alkynyl, amino, acyl, amide, cyano, isocyano, alkoxy, hydroxy, carbonyl, sulfone, alkyl having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, 6 to 30 aryl groups, 3 to 30 heteroaryl groups, 7 to 30 carbon atoms, and 4 carbon atoms a fused aromatic aryl group of ⁇ 30 and one of the combination groups formed by at least two of the above groups being bonded to each other.
  • -R 8 , -R 9 , -R 10 , -R 11 , -R 12 and -R 13 are each independently selected from alkyl groups each independently selected from substituted carbon atoms having from 1 to 30 carbon atoms. a substituted cycloalkyl group having 3 to 30 carbon atoms, an substituted aryl group having 6 to 30 carbon atoms, a substituted heteroaryl group having 3 to 30 carbon atoms, and a substituted carbon atom of 7 to 30. A thick aryl group of 30 and one of the substituted heteroaryl groups having 4 to 30 carbon atoms.
  • -R 8 , -R 9 , -R 10 , -R 11 , -R 12 and -R 13 are each capable of forming a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a single ring.
  • -R 8 is capable of forming a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aromatic group with -R 9 , -R 10 , -R 11 , -R 12 or -R 13 A aryl group or a polycyclic group.
  • -R 13 is capable of forming a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aromatic group with -R 8 , -R 9 , -R 10 , -R 11 or -R 12 .
  • -R 9 and -R 10 can form a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aryl group or a polycyclic aryl group with each other.
  • -R 11 and -R 12 can form a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aryl group or a polycyclic aryl group with each other.
  • the structural formula of the heteroaryl group having an N atom is selected from one of the following structural formulae:
  • Ar 2 and Ar 3 each independently comprise one of the following structural formulas or a combination of at least two of the following structural formulas:
  • n1 is an integer of 1 to 4.
  • At least one of L 2 and L 3 is a heteroaryl group having at least one N atom.
  • n is an integer from 0 to 20.
  • n is an integer from 0 to 10.
  • n is an integer from 0 to 5.
  • n is an integer from 0 to 3.
  • p and q are each independently selected from one of integers from 0 to 4, and p and q are not simultaneously 0.
  • p and q are each independently selected from one of integers from 0 to 3, and p and q are not 0 at the same time.
  • p and q are each independently selected from one of integers from 0 to 2, and p and q are not 0 at the same time.
  • p and q are each independently selected from one of integers from 0 to 1, and p and q are not 0 at the same time.
  • the carbazole compound has an electron mobility of greater than or equal to 10 -5 cm 2 ⁇ V -1 ⁇ S -1 .
  • the above carbazole compound has a high electron mobility, so that the smaller the power consumption and the larger the current carrying capacity when passing the same current.
  • the carbazole compound has an electron mobility of greater than or equal to 10 -4 cm 2 ⁇ V -1 ⁇ S -1 .
  • the carbazole compound has an electron mobility of greater than or equal to 10 -3 cm 2 ⁇ V -1 ⁇ S -1 .
  • the carbazole compound has a glass transition temperature greater than or equal to 100 °C.
  • the higher glass transition temperature makes the carbazole compound have better stability and better performance, which is beneficial to the wide application of the carbazole compound.
  • the carbazole compound has a glass transition temperature greater than or equal to 110 °C.
  • the carbazole compound has a glass transition temperature greater than or equal to 120 °C.
  • the carbazole compound has a glass transition temperature greater than or equal to 140 °C.
  • the lowest unoccupied orbital energy level (LUMO) of the carbazole compound is less than or equal to -2.7 eV.
  • the carbazole compound has a LUMO of less than or equal to -2.8 eV.
  • the carbazole compound has a LUMO of less than or equal to -2.9 eV.
  • the carbazole compound has a LUMO of less than or equal to -3.0 eV.
  • the highest occupied orbital level (HOMO) of the carbazole compound is less than or equal to -5.6 eV. In one embodiment, the carbazole compound has a HOMO of less than or equal to -5.65 eV.
  • the carbazole compound has a HOMO of less than or equal to -5.7 eV.
  • the oxazole compound has a triplet energy level (T 1 ) greater than or equal to 1.7 eV.
  • T 1 carbazole-based compound is greater than or equal to 1.9eV.
  • the carbazole-based compound is greater than or equal to T 1 of 2.15eV.
  • the carbazole-based compound T 1 of greater than or equal to 2.4eV.
  • the lowest unoccupied orbital level and the highest occupied orbital level can be measured by photoelectric effect, such as XPS (X-ray photoelectron spectroscopy) and UPS (UV photoelectron spectroscopy),
  • the CV cyclic voltammetry
  • DFT density functional theory
  • the triplet energy level T 1 can be measured by low temperature time resolved luminescence spectroscopy or by quantum simulation, for example by Time-dependent DFT simulation calculation or by commercial software Gaussian 03W (Gaussian Inc.). Simulation calculation. Among them, the specific simulation method can be found in WO2011141110.
  • the absolute values of HOMO, LUMO and T 1 depend on the measurement method, calculation method or evaluation method used. Therefore, reasonable and meaningful comparisons should be made using the same measurement method and the same evaluation method.
  • the energy level values determined by different methods should be calibrated against each other.
  • the values of HOMO, LUMO, and T 1 are simulations based on Time-dependent DFT, but do not affect the application of other measurement methods or calculation methods.
  • the carbazole compound can be applied to an electronic device as an electron transporting material (ETM), an electron injecting material (EIM), a hole blocking material (HBM), and a host material.
  • ETM electron transporting material
  • EIM electron injecting material
  • HBM hole blocking material
  • 10% to 40% of H in the carbazole compound is substituted with deuterium.
  • 10% of the H in the oxazole compound is replaced by deuterium.
  • 20% of the H in the oxazole compound is replaced by deuterium.
  • 30% of the H in the oxazole compound is replaced by deuterium.
  • 40% of the H in the oxazole compound is replaced by deuterium.
  • the carbazole compound is a small molecule compound, ie, a molecule that is not a polymer, oligomer, dendrimer or copolymer.
  • the carbazole compound has a molar mass of from 700 g/mol to 3000 g/mol.
  • the carbazole compound has a molar mass of less than or equal to 3000 g/mol.
  • the carbazole compound has a molar mass of less than or equal to 2000 g/mol.
  • the carbazole compound has a molar mass of less than or equal to 1500 grams per mole.
  • the carbazole compound has a molar mass of less than or equal to 1000 grams per mole.
  • the molar mass of the carbazole compound is less than or equal to 1000 g/mol, so that the carbazole compound can be used as a raw material of the vapor-deposited OLED.
  • the carbazole compound has a molar mass of less than or equal to 900 grams per mole.
  • the carbazole compound has a molar mass of less than or equal to 850 grams per mole.
  • the carbazole compound has a molar mass of less than or equal to 800 grams per mole.
  • the carbazole compound has a molar mass of less than or equal to 700 grams per mole.
  • the carbazole compound has a molar mass greater than or equal to 700 grams per mole.
  • the molar mass of the carbazole compound is greater than or equal to 700 g/mol, so that the carbazole compound can be used as a raw material for a printed OLED.
  • the carbazole compound has a molar mass greater than or equal to 800 grams per mole.
  • the carbazole compound has a molar mass greater than or equal to 900 grams per mole.
  • the carbazole compound has a molar mass greater than or equal to 1000 grams per mole.
  • the carbazole compound has a molar mass greater than or equal to 1100 grams per mole.
  • the carbazole compound can be dissolved in toluene, chlorobenzene or xylene.
  • the carbazole compound has a solubility in toluene of greater than or equal to 10 mg/mL at 25 °C.
  • the high solubility of the carbazole compound in toluene makes the compound more widely used.
  • the carbazole compound has a solubility in toluene of greater than or equal to 15 mg/mL at 25 °C.
  • the carbazole compound has a solubility in toluene of greater than or equal to 20 mg/mL at 25 °C.
  • the structural formula of the carbazole compound is selected from one of the following structural formulae:
  • one structural formula represents a carbazole compound, and the interlacing between adjacent structural formulas is only a problem of document typesetting, and has no other meaning.
  • the above carbazole compound is advantageous in achieving better carrier transport, photoelectric response, and energy level matching by directly connecting the nitrogen atom of the carbazole to the condensed or fused heteroaryl group of the planar structure.
  • the photoelectric properties and stability of the compound enable photovoltaic devices including the compound to have higher stability, higher luminous efficiency, and longer lifetime devices. It has been verified by experiments that the difference in energy level between HOMO and LUMO of the material including the above carbazole compound is small, indicating that the stability of the above carbazole compound is good, and the ⁇ E ST of the above carbazole compound is small, indicating that the above hydrazine is included.
  • the device life of the azole compound material is long, and the device lifetime of the organic light emitting diode including the above carbazole compound is more than twice that of the organic light emitting diode not including the above carbazole compound, and includes the above carbazole.
  • the luminous efficiency of the organic light-emitting diode of the compound-like compound is at least 47.2% higher than that of the organic light-emitting diode not including the above-mentioned carbazole compound.
  • the above carbazole compounds can be used to prepare electronic devices having higher stability, higher luminous efficiency, and longer lifetime.
  • the Tg (glass transition temperature) of the above carbazole compound is greater than or equal to 100 ° C, so that the stability of the carbazole compound is good, and the use property is good, which is advantageous for the broad range of the carbazole compound. application.
  • the above carbazole compound can be used as an electron transporting material (ETM), an electron injecting material (EIM), a hole blocking material (HBM), and a host material (Host) in an electronic device.
  • ETM electron transporting material
  • EIM electron injecting material
  • HBM hole blocking material
  • Host host material
  • the carbazole-based polymer of one embodiment includes a repeating unit formed of the above carbazole compound.
  • the carbazole polymer is a homopolymer, ie the polymer consists of only one
  • the repeating unit is polymerized; that is, the carbazole polymer includes only the repeating unit formed by the above carbazole compound.
  • the carbazole polymer is a copolymer, that is, the polymer is polymerized from two or more repeating units.
  • the carbazole polymer is a copolymer obtained by polymerizing two monomers, and one of the two monomers is the above carbazole compound or a derivative thereof.
  • the other of the two monomers is an arylamine compound.
  • the carbazole polymer is a block copolymer, that is, the polymer is formed by joining two or more polymer segments having different properties.
  • One of the polymer segments is a polymer segment formed by the above carbazole compound, and the other polymer segment is an aromatic amine structure.
  • the carbazole polymer is a dendrimer.
  • a dendrimer For the structure and application of the dendrimer, see [Dendrimers and Dendrons, Wiley-VCH Verlag GmbH & Co. KGaA, 2002, Ed. George R. Newkome, Charles N. Moorefield, Fritz Vogtle.], and details are not described herein.
  • the number of repeating units of the carbazole polymer is from 10 to 1000. Of course, it should be noted that the number of repeating units can be set as needed.
  • the carbazole polymer is a conjugated polymer, ie the backbone of the polymer consists essentially of sp2 hybrid orbitals of C atoms.
  • the polymer is still considered to be a conjugated polymerization. Things.
  • the main chain of the polymer contains a group such as an aryl amine, an aryl phosphine, other heteroarmotics, and an organometallic complexes, This polymer is still considered to be a conjugated polymer.
  • the carbazole polymer is a non-conjugated polymer and the carbazole compound is located on the side chain of the polymer.
  • the above carbazole polymer includes the above carbazole compound, so that the polymer has good solubility, stability and photoelectric properties, and can be used as a hole injecting material (HIM), a hole transporting material (HTM), and an electron transporting material.
  • HIM hole injecting material
  • HTM hole transporting material
  • ETM electron injecting material
  • EIM electron blocking material
  • HBM hole blocking material
  • HOS illuminator
  • Hos host material
  • the organic electroluminescent material of the first embodiment includes at least one of the above carbazole compound and the above carbazole polymer, and an organic functional material.
  • the organic functional material is selected from the group consisting of a hole injection material (HIM), a hole transport material (HTM), an electron injection material (EIM), an electron transport material (ETM), a hole blocking material (HBM), At least one of an electron blocking material (EBM), a host material (Host), a singlet illuminant, a thermally activated delayed fluorescent luminescent material (TADF), a triplet illuminant, a host material, and an organic dye.
  • HIM hole injection material
  • HTM hole transport material
  • EIM electron injection material
  • ETM electron transport material
  • HBM hole blocking material
  • the invention further relates to a mixture comprising at least one oxazole compound or polymer according to the invention, and at least one organic functional material.
  • One of the organic functional materials described herein is a hole (also called a hole) injection or transport material (HIM/HTM), a hole blocking material (HBM), an electron injecting or transporting material (EIM/ETM), an electron blocking material.
  • HIM/HTM hole injection or transport material
  • HBM hole blocking material
  • EIM/ETM electron injecting or transporting material
  • EBM organic matrix material
  • ost singlet illuminant
  • TADF thermally activated delayed fluorescent luminescent material
  • triplet illuminant phosphorescent illuminant
  • organic dye is a luminescent metal organic complex.
  • the triplet emitter is a luminescent metal organic complex.
  • Various organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1, and WO 2011110277A1, the entire disclosure of which is hereby incorporated by reference.
  • the organic functional material may be a small molecular material or a polymeric material.
  • the carbazole compound is present in the mixture according to the invention in an amount of from 50% by weight to 99% by weight. In the mixture according to the present invention, the carbazole compound is contained in an amount of from 60% by weight to 97% by weight. In the mixture according to the present invention, the carbazole compound is contained in an amount of from 60% by weight to 95% by weight. . In the mixture according to the present invention, the carbazole compound is contained in an amount of from 70% by weight to 90% by weight.
  • the mixture according to the invention comprises a compound or polymer according to the invention and a fluorescent luminescent material (single-state illuminant).
  • the mixture according to the invention comprises a compound or polymer according to the invention and a thermally activated delayed fluorescent luminescent material (TADF).
  • TADF thermally activated delayed fluorescent luminescent material
  • the mixture according to the invention comprises a compound or polymer according to the invention, a fluorescent luminescent material and a TADF material.
  • fluorescent luminescent material or singlet illuminant (fluorescent luminescent material) and TADF material are described in some detail below (but are not limited thereto).
  • Singlet emitters tend to have longer conjugated pi-electron systems.
  • styrylamine and its derivatives disclosed in JP 2913116 B and WO 2001021729 A1
  • indenoindenes and derivatives thereof disclosed in WO 2008/006449 and WO 2007/140847.
  • the singlet emitter can be selected from the group consisting of monostyrylamine, dibasic styrylamine, ternary styrylamine, quaternary styrylamine, styrene phosphine, styrene ether, and arylamine. At least one of them.
  • a monostyrylamine refers to a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine.
  • a dibasic styrylamine refers to a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a ternary styrylamine refers to a compound comprising three unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a quaternary styrylamine refers to a compound comprising four unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine.
  • a preferred styrene is stilbene, which may be further substituted.
  • the corresponding phosphines and ethers are defined similarly to amines.
  • An arylamine or an aromatic amine refers to a compound comprising three unsubstituted or substituted aromatic ring or heterocyclic systems directly bonded to a nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably selected from the fused ring system and preferably has at least 14 aromatic ring atoms.
  • An aromatic amide refers to a compound in which a diaryl arylamine group is attached directly to the oxime, preferably at the position of 9.
  • An aromatic quinone diamine refers to a compound in which two diaryl arylamine groups are attached directly to the oxime, preferably at the 9,10 position.
  • the definitions of aromatic decylamine, aromatic guanidine diamine, aromatic thiamine and aromatic quinone diamine are similar, and the diaryl aryl group is best. Connected to the 1 or 1,6 position of the ⁇ .
  • Examples of singlet emitters based on vinylamines and arylamines are also preferred examples and can be found in the following patent documents: WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007 /115610, US 7250532 B2, DE 102005058557 A1, CN 1583691 A, JP 08053397 A, US 6251531 B1, US 2006/210830 A, EP 1957606 A1 and US 2008/0113101 A1, the entire contents of which are hereby incorporated by reference. This article is incorporated herein by reference.
  • Further preferred singlet emitters can be selected from indenoindole-amines and indenofluorene-diamines, as disclosed in WO 2006/122630, benzoindoloindole-amines and benzoindenoindole-diamines , as disclosed in WO 2008/006449, dibenzoindolo-amine and dibenzoindeno-diamine, as disclosed in WO 2007/140847.
  • polycyclic aromatic hydrocarbon compounds in particular derivatives of the following compounds: for example, 9,10-bis(2-naphthoquinone), naphthalene, tetraphenyl, xanthene, phenanthrene , ⁇ (such as 2,5,8,11-tetra-t-butyl fluorene), anthracene, phenylene such as (4,4'-bis(9-ethyl-3-carbazolevinyl)-1 , 1 '-biphenyl), indenyl hydrazine, decacycloolefin, hexacene benzene, anthracene, stilbene, aryl hydrazine (such as US20060222886), arylene vinyl (such as US5121029A, US5130603A), cyclopentane Alkene such as tetraphenylcyclopentadiene, rubrene,
  • TDF Thermally activated delayed fluorescent luminescent material
  • the thermally activated delayed fluorescent luminescent material is a third generation organic luminescent material developed after organic fluorescent materials and organic phosphorescent materials.
  • Such materials generally have a small singlet-triplet energy level difference ( ⁇ Est), and triplet excitons can be converted into singlet exciton luminescence by anti-intersystem crossing. This can make full use of the singlet excitons and triplet excitons formed under electrical excitation.
  • the quantum efficiency in the device can reach 100%.
  • TADF materials need to have a small singlet-triplet energy level difference, typically ⁇ Est ⁇ 0.3 eV for TADF materials. Further, ⁇ Est of the TADF material is ⁇ 0.2 eV. Further, ⁇ Est of the TADF material is ⁇ 0.1 eV. Further, ⁇ Est of the TADF material is ⁇ 0.05 eV. In one embodiment, the TADF material has better fluorescence quantum efficiency.
  • TADF materials can be found in the following patent documents: CN103483332(A), TW201309696(A), TW201309778(A), TW201343874(A), TW201350558(A), US20120217869(A1), WO2013133359(A1), WO2013154064(A1) , Adachi, et.al. Adv. Mater., 21, 2009, 4802, Adachi, et. al. Appl. Phys. Lett., 98, 2011, 083302, Adachi, et. al. Appl. Phys. Lett., 101, 2012, 093306, Adachi, et. al. Chem.
  • TADF luminescent materials are listed in the table below:
  • the invention relates to a composition or ink comprising a compound or polymer or mixture according to the invention, and at least one organic solvent. It should be noted that the composition and the ink in the present embodiment have the same meanings. Further, the present invention provides a film prepared from a solution comprising a compound or polymer according to the present invention.
  • the viscosity and surface tension of the ink are important parameters when used in the printing process. Suitable surface tension parameters for the ink are suitable for the particular substrate and the particular printing method.
  • the ink according to the present invention has a surface tension of from 19 dyne/cm to 50 dyne/cm at 25 ° C to 300 ° C. Further, the ink according to the present invention has a surface tension in the range of 22 dyne/cm to 35 dyne/cm at 25 ° C to 300 ° C. Further, the ink according to the present invention has a surface tension in the range of 25 dyne/cm to 33 dyne/cm at 25 ° C to 300 ° C.
  • the ink according to the present invention has a viscosity of from 1 cps to 100 cps at a temperature of from 25 ° C to 300 ° C. Further, the ink according to the present invention has a viscosity of from 1 cps to 50 cps at 25 ° C to 300 ° C. Further, the viscosity of the ink according to the present invention at from 25 ° C to 300 ° C is from 1.5 cps to 20 cps. Further, the viscosity of the ink according to the present invention at from 25 ° C to 300 ° C is from 4.0 cps to 20 cps.
  • the composition so formulated will be suitable for ink jet printing.
  • the viscosity can be adjusted by different methods, such as by selection of a suitable solvent and concentration of the functional material in the ink.
  • the ink containing the compound or polymer according to the present invention facilitates the adjustment of the printing ink to an appropriate range in accordance with the printing method used.
  • the composition according to the invention comprises a weight ratio of organic functional material of from 0.3% by weight to 30% by weight.
  • the composition according to the present invention comprises the organic functional material in a weight ratio of from 0.5% by weight to 20% by weight.
  • the composition according to the present invention comprises the organic functional material in a weight ratio of from 0.5% by weight to 15% by weight.
  • the composition according to the invention comprises a weight ratio of organic functional material of from 0.5% by weight to 10% by weight.
  • the composition according to the invention comprises a weight ratio of organic functional material of from 1% by weight to 5% by weight.
  • the at least one organic solvent is selected from the group consisting of aromatic or heteroaromatic based solvents, particularly aromatic solvents substituted by aliphatic chains, substituted by aromatic rings. a family solvent, an aromatic ketone solvent or an aromatic ether solvent.
  • organic solvents suitable for the present invention are, but are not limited to, aromatic or heteroaromatic based solvents: p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-di Methylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, methylene Ethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, Di
  • the at least one organic solvent may be selected from the group consisting of: an aliphatic ketone, for example, 2-nonanone, 3-fluorenone, 5-nonanone, 2-nonanone, 2, 5 -hexanedione, 2,6,8-trimethyl-4-indolone, phorone, di-n-pentyl ketone, etc.; or an aliphatic ether, for example, pentyl ether, hexyl ether, dioctyl ether, ethylene Dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether , tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and the like.
  • an aliphatic ketone for example, 2-non
  • the printing ink further comprises another organic solvent.
  • another organic solvent include, but are not limited to, methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine , toluene, o-xylene, m-xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1, 1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydrogen Naphthalene, decalin, hydrazine and/or mixtures thereof.
  • the composition according to the invention is a solution.
  • composition according to the invention is a suspension.
  • the solution or suspension may additionally contain one or more components such as surface active compounds, lubricants, wetting agents, dispersing agents, hydrophobic agents, binders and the like for adjusting viscosity, film forming properties, adhesion, and the like.
  • surface active compounds such as surface active compounds, lubricants, wetting agents, dispersing agents, hydrophobic agents, binders and the like for adjusting viscosity, film forming properties, adhesion, and the like.
  • the invention further relates to the use of the composition as an ink in the preparation of an organic electronic device, particularly preferably by a printing or coating process.
  • suitable printing or coating techniques include, but are not limited to, inkjet printing, inkjet printing (Nozzle Printing), letterpress Printing, screen printing, dip coating, spin coating, knife coating, roller printing, torsion roll printing, lithography, flexographic printing, rotary printing, spray coating, brushing or pad printing, Nozzle printing, Slit type extrusion coating, etc.
  • suitable printing or coating techniques are ink jet printing, slit type extrusion coating, jet printing or gravure printing.
  • the present invention also provides the use of a compound or polymer as described above in an organic electronic device.
  • the organic electronic device may be selected from, but not limited to, an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, and an organic Lasers, organic spintronic devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diode), especially OLEDs.
  • the organic compound is used in an electron transport layer or a light-emitting layer of an OLED device.
  • the present invention relates to an organic electronic device comprising at least one compound or polymer as described above.
  • an organic electronic device comprises at least one cathode, an anode and a functional layer between the cathode and the anode, wherein the functional layer comprises at least one compound or polymer as described above.
  • the organic electronic device may be selected from, but not limited to, an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, and an organic Laser, organic spintronics, organic sensor or organic plasmon emitting diode (Organic Plasmon Emitting Diode).
  • the organic electronic device is an electroluminescent device, such as an OLED, comprising a substrate, an anode, a cathode, and a luminescent layer at least between the anode and the cathode. It should be noted that the organic electronic device may further include a hole transport layer or an electron transport layer. In one embodiment, the organic electronic device comprises an electron transport layer or an electron injection layer, the electron transport layer or the electron injection layer comprising a compound or polymer according to the invention. In one embodiment, the organic electronic device comprises a light-emitting layer comprising a compound or polymer according to the invention. Further, the luminescent layer comprises a compound or polymer according to the invention and at least one luminescent material, the luminescent material being a fluorescent illuminant or a TADF material.
  • the device structure of the electroluminescent device will be described below, but is not limited thereto.
  • the substrate can be opaque or transparent.
  • a transparent substrate can be used to make a transparent light-emitting component. See, for example, Bulovic et al. Nature 1996, 380, p29, and Gu et al, Appl. Phys. Lett. 1996, 68, p2606.
  • the substrate can be rigid or elastic.
  • the substrate can be plastic, metal, semiconductor wafer or glass. Further, the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice.
  • the substrate is flexible and can be selected from polymeric films or plastics.
  • the glass transition temperature Tg of the substrate is greater than or equal to 150 °C.
  • the glass transition temperature of the substrate is greater than or equal to 200 °C.
  • the glass transition temperature of the substrate is greater than or equal to 250 °C.
  • the glass transition temperature of the substrate is greater than or equal to 300 °C.
  • suitable materials for the flexible substrate are poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).
  • the anode can comprise a conductive metal or metal oxide, or a conductive polymer.
  • the anode can easily inject holes into a hole injection layer (HIL) or a hole transport layer (HTL) or a light-emitting layer.
  • HIL hole injection layer
  • HTL hole transport layer
  • the absolute value of the difference between the work function of the anode and the HOMO level or the valence band level of the illuminant in the luminescent layer or the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) is less than 0.5eV.
  • the absolute value of the difference between the work function of the anode and the HOMO level or the valence band level of the illuminant in the luminescent layer or the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) is less than 0.3eV. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or the valence band level of the illuminant in the luminescent layer or the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) is less than 0.2eV.
  • Example of anode material Including but not limited to: Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like.
  • suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art.
  • the anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
  • the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices in accordance with the present invention.
  • the cathode can comprise a conductive metal or metal oxide.
  • the cathode can easily inject electrons into the EIL, ETL or luminescent layer.
  • the work function of the cathode and the LUMO level of the illuminant or the n-type semiconductor material as an electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer (HBL) in the luminescent layer or
  • the absolute value of the difference in the conduction band energy level is less than 0.5 eV.
  • the work function of the cathode and the LUMO level of the illuminant or the n-type semiconductor material as an electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer (HBL) in the luminescent layer or
  • the absolute value of the difference in conduction band energy levels is less than 0.3 eV.
  • the absolute value of the difference in conduction band energy levels is less than 0.2 eV.
  • cathode materials for the devices of the invention.
  • the cathode material include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, and the like.
  • the cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.
  • the OLED may further include other functional layers such as a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer. (HBL).
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • the electron transport layer or the electron injecting layer contains the compound or polymer of the present invention.
  • the light-emitting device according to the invention has an emission wavelength between 300 nm and 1000 nm.
  • the light-emitting device according to the invention has an emission wavelength between 350 nm and 900 nm.
  • the light-emitting device according to the present invention has an emission wavelength of between 400 nm and 800 nm.
  • the invention further relates to the use of an organic electronic device according to the invention in various electronic devices, including, but not limited to, display devices, illumination devices, light sources, sensors and the like.
  • N-(3-fluoranthene)-3,6-dibromo-oxazole (10 g, 19.04 mmol) and 4-(3-pyridyl)benzeneboronic acid (9.47 g, 47.6 mmol) were placed in a 500 mL double-mouth round bottom.
  • reaction solution was transferred to a rotary steaming flask, and most of the solvent was evaporated to dryness, extracted with dichloromethane, washed with water three times, dried over anhydrous magnesium sulfate, filtered and dried and purified to give N-(3-fluoranthene)-3. , 6-bis(4-(3-pyridyl)phenyl)carbazole, and the yield was 78%.
  • N-(3-fluoranthene)-3-bromocarbazole (10 g, 22.40 mmol) and 4-(3-pyridyl)benzeneboronic acid (5.35 g, 26.88 mmol) were placed in a 500 mL double-necked round bottom flask. 250 mL of toluene (ie solvent) was added, then potassium carbonate (7.42 g, 53.76 mmol) was completely dissolved with 30 mL of water, and the above-mentioned round bottom flask was added, followed by Pd(PPh3)4 (0.78 g, 0.67 mmol).
  • N-(1-indole)-3,6-dibromocarbazole (10 g, 19.95 mmol) and 4-(3-pyridyl)benzeneboronic acid (9.93 g, 49.88 mmol) were placed in a 500 mL double-necked round bottom flask. 250 mL of toluene (ie solvent) was added, then potassium carbonate (11.01 g, 79.80 mmol) was completely dissolved in 30 mL of water, added to the round bottom flask, and then Pd(PPh3)4 (1.38 g, 1.19 mmol) was added.
  • N-(2-fluoranthene)-3,6-dibromocarbazole (10 g, 19.95 mmol) and 4-(3-pyridyl)benzeneboronic acid (9.93 g, 49.88 mmol) in a 500 mL double-necked round bottom flask
  • Toluene ie solvent
  • potassium carbonate 11.01g, 79.80mmol
  • Pd(PPh3)4 (1.38g, 1.19mmol
  • reaction liquid was transferred to a rotary steaming flask, and most of the solvent was evaporated to dryness, extracted with dichloromethane, washed three times with water, dried over anhydrous magnesium sulfate, filtered and dried and purified to give N-(2- ⁇ )-3,6 Bis(4-(3-pyridyl)phenyl)carbazole with a yield of 80%.
  • N-(1- ⁇ )-3,6-dibromocarbazole (10 g, 19.04 mmol), 4-(3-pyridine)benzeneboronic acid (9.47 g, 47.6 mmol) was placed in a 500 mL double-necked round bottom flask.
  • the oil in the bottle was removed by an oil pump, nitrogen gas was introduced, and the mixture was heated under reflux for 12 hours and cooled.
  • reaction liquid was transferred to a rotary steaming flask, and most of the solvent was evaporated to dryness, extracted with dichloromethane, washed with water three times, dried over anhydrous magnesium sulfate, filtered and dried and purified to give N-(1-indole)-3. 6-bis(4-(3-pyridyl)phenyl)carbazole with a yield of 82%.
  • the energy level of the compound is determined by TD-DFT (time-dependent density functional theory) by Gaussian 09W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110. Specifically, the density function method "Ground State/DFT/Default Spin/B3LYP" and the base group "6-31G(d)” (Charge 0/Spin Singlet) are used to optimize the geometry of the compound.
  • the energy structure of the compound is determined by TD- The DFT (Time-Dependent Density Functional Theory) method calculates "TD-SCF/DFT/Default Spin/B3PW91" and the base group "6-31G(d)” (Charge 0/Spin Singlet).
  • the HOMO and LUMO levels are calculated according to the following calibration formulas (1) and (2), and S 1 and T 1 are used directly.
  • HOMO(eV) [(HOMO(G) ⁇ 27.212)-0.9899]/1.1206 calibration formula (1)
  • HOMO(G) is directly calculated by Gaussian 03W, and the unit is Hartree;
  • LUMO(G) is directly calculated by Gaussian 03W, and the unit is Hartree.
  • Table 1 shows the HOMO level, LUMO level, T 1 level and S 1 level of the compounds of Examples 1 to 6.
  • Example 1 -5.73 -3.03 2.19 2.75
  • Example 2 -5.75 -2.99 2.19 2.80
  • Example 3 -5.69 -2.94 1.72 2.86
  • Example 4 -5.63 -2.92 1.74 2.89
  • Example 5 -5.68 -2.83 2.03 3.04
  • Example 6 -5.56 -2.83 1.66 2.83
  • the compounds of Examples 1 to 5 have a small difference in energy level between HOMO and LUMO, indicating that the stability of the compounds of Examples 1 to 5 is good, and at the same time, the ⁇ E ST of the compounds of Examples 1 to 5 [i.e., ⁇ (S 1 -T 1 ), the energy level difference between the singlet energy level and the triplet energy level] is small, indicating that the materials including the compounds of Examples 1 to 5 have high luminous efficiency.
  • the luminous efficiency was measured by the XX method.
  • the luminescent color was measured by the XX method.
  • the current-voltage (JV) characteristics of the OLED device are characterized by a characterization device while recording the lifetime value of the OLED device, and the lifetime is represented by T 95 , 1000 nits, and the lifetimes of Examples 1-5 are relative to the lifetime of Example 6. relative value.
  • the results are shown in Table 2.
  • the specific process is as follows:
  • the structure of the OLED is:
  • ITO/HIL 50 nm
  • HTL 35 nm
  • luminescent layer (20 nm) / ETL (28 nm) / LiQ (1 nm) / Al (150 nm) / cathode, ("/" in the above structure represents lamination).
  • HIL 4,4',4"-tris[2-naphthylphenylamino]triphenylamine (2-TNATA);
  • the material of the HTL is N,N'-bis(1-naphthyl)-N,N'-diphenyl-4,4'-diamine (NPD);
  • the luminescent layer is made of a mixture of the host material and the auxiliary material at a mass ratio of 95:5.
  • the main material is
  • the material of the ETL is selected from the compounds of Example 1.
  • HIL HTL
  • luminescent layer ETL
  • cathode LiQ and Al
  • LiQ LiQ and Al
  • the structure of the OLED is: OLED/HIL (50 nm) / HTL (35 nm) / luminescent layer (20 nm) / ETL (28 nm) / LiQ (1 nm) / Al (150 nm) / cathode OLED, (" /" in the above structure represents Cascade).
  • the compound of Example 2 was used as a material of ETL. The rest is the same as Test Example 1.
  • the structure of the OLED is: OLED of TO/HIL (50 nm) / HTL (35 nm) / luminescent layer (20 nm) / ETL (28 nm) / LiQ (1 nm) / Al (150 nm) / cathode, ("/" represents the above structure Cascade).
  • the compound of Example 3 was used as a material of ETL. The rest is the same as Test Example 1.
  • the structure of the OLED is: OLED of TO/HIL (50 nm) / HTL (35 nm) / luminescent layer (20 nm) / ETL (28 nm) / LiQ (1 nm) / Al (150 nm) / cathode, ("/" represents the above structure Cascade).
  • the compound of Example 4 was used as a material of ETL. The rest is the same as Test Example 1.
  • the structure of the OLED is: OLED of TO/HIL (50 nm) / HTL (35 nm) / luminescent layer (20 nm) / ETL (28 nm) / LiQ (1 nm) / Al (150 nm) / cathode, ("/" represents the above structure Cascade).
  • the compound of Example 5 was used as a material of ETL. The rest is the same as Test Example 1.
  • the structure of the OLED is: OLED of TO/HIL (50 nm) / HTL (35 nm) / luminescent layer (20 nm) / ETL (28 nm) / LiQ (1 nm) / Al (150 nm) / cathode, ("/" represents the above structure Cascade).
  • the compound of Example 6 is a material of ETL material. The rest is the same as Test Example 1.
  • Luminous efficiency (cd/A) Life (T 95 , 1000 nits) Luminous color Test example 1 6.2 4.00 blue Test example 2 6.5 3.75 blue Test Example 3 6.0 3.45 blue Test Example 4 5.7 3.125 blue Test Example 5 5.3 2.75 blue Test Example 6 3.6 1 blue
  • the color coordinates (X ⁇ 0.15, Y ⁇ 0.10) of the OLEDs obtained by using the compounds of Examples 1 to 5 as the material of the ETL are superior to those of the compound of Example 6 as the material of the ETL.
  • the luminescence efficiency of the OLED obtained by using the compounds of Examples 1 to 5 as the material of the ETL was 5.3 cd/A to 6.2 cd/A, and the luminescence efficiency of the OLED obtained by using the compound of Example 6 as the material of the ETL was improved by 47.2.
  • the compounds of Examples 1 to 5 are more advantageous for the preparation of an electronic device having higher luminous efficiency.
  • the T 95 of the OLED obtained by using the compounds of Examples 1 to 5 as the material of the ETL was twice or more than that of the Example 6 at 1000 nits, indicating that the compounds of Examples 1 to 5 are more advantageous for the preparation of a longer life. Electronic device.
  • the structure of the above carbazole compound makes the compound have better carrier transport, photoelectric response and energy level matching, and the photoelectric properties and stability of the compound are better, and finally the compound containing the compound is finally obtained.
  • Electronic devices have higher luminous efficiency, longer life and better blue coordinates.

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Abstract

本发明涉及一种咔唑类化合物及其应用。该化合物具有如下结构式：上述咔唑类化合物能够用于制备具有较高稳定性、较高发光效率及较长寿命的电子器件。

Description

咔唑类化合物及其应用 技术领域
本发明涉及电子领域，特别是涉及一种咔唑类化合物及其应用。
背景技术
有机半导体材料由于其分子结构设计的多样性、制造成本相对较低、光电性能优越等特性，在许多光电装置上巨大的应用潜力，如有机发光二极管(OLED)、有机光伏电池(OPV)、有机场效应管(OFET)等。尤其从1987年邓青云等(C.W.Tang and S.A.Van Slyke,Appl.Phys.Lett.,1987,51,913)报道了双层OLED结构以来，有机半导体材料在平板显示和照明领域得到了飞速的发展。
有机薄膜发光元件必须满足发光效率的提升、驱动电压的降低、耐久性的提升等。但是，目前仍有许多技术性课题，其中，元件的高效率与长寿命并存是许多难题之一。
为了加速推动OLED大范围产业化的进程，提高其光电性能，各种新型有机光电材料体系被广泛地设计开发生产。其中，咔唑类有机半导体材料由于其优越的光电性能、氧化还原性能、稳定性等，使其在光电器件中有着广泛的应用。此外，稠环结构的芳香基团或芳杂基团，如荧蒽、蒽、芘、菲、二氮菲、苯并荧蒽等，由于其分子的平面结构，一般具有好的载流子传输性能和光电响应。然而目前报道的咔唑类或者具有稠环结构的有机半导体材料在光电器件中载流子传输能力、稳定性、寿命等还存在一定的局限性。
CN 104350627 A公开了苯环上被氮原子取代的咔唑基团与含有苯并荧蒽的稠环基团相连的化合物。这类化合物被用作蓝光OLED器件的电子传输层，使器件的电压得到了降低，寿命也有所提高。然而，稠环咔唑这个体系的电子传输材料还没有得到进一步深入的研究。
CN 104768926 A公开了三苯胺与稠环基团相连的化合物。这类化合物被用作蓝光OLED器件的电子传输层，使器件的电压得到了降低，寿命也有所提高。然而，常与三苯胺类比，咔唑作为一类有着更大共轭的传输材料单元，其与稠环结构的设计结合对器件性能和寿命的影响，还没有得到进一步的比较和研究。
为了进一步发掘这类材料的光电性能，新型结构的咔唑稠环相结合的材料仍待设计开发。咔唑与稠环新型的设计结合方式赋予了此类结构优越的光电性能。
发明内容
基于此，有必要提供一种能够制作具有较高稳定性、较高发光效率及较长寿命的电子器件的咔唑类化合物及其应用。
一种咔唑类化合物，具有如下结构式：
Figure PCTCN2017115309-appb-000001
其中，Ar1为环原子数为13～60的稠芳基或环原子数为13～60的稠杂芳基；
Ar2、Ar3为分别独立的选自碳原子数为6～60的芳基、碳原子数为3～60的杂芳基、碳原子数为7～60的稠芳基、碳原子数为4～60的稠杂芳基或上述基团中至少两个相互连接形成的组合基团中的一种，且所述Ar2、所述Ar3中至少一个包含具有N原子的杂芳基；
R1选自H、D、F、CN、NO2、CF3、烯基、炔基、胺基、酰基、酰胺基、氰基、异氰基、烷氧基、羟基、羰基、砜基、碳原子数为1～60的烷基、碳原子数为3～60的环烷基、碳原子数为6～60的芳基、碳原子数为3～60的杂芳基、碳原子数为7～60的稠芳基、碳原子数为4～60的稠杂芳基及上述基团中至少两个相互连接形成的组合基团中的一种，且所述L2及L3中至少一个包含具有N原子的杂芳基；
n为0～20的整数；
p及q分别独立选自0～4的整数中的一个，且p和q不同时为0。
上述咔唑类化合物通过将咔唑的氮原子与平面结构的稠芳基或稠杂芳基直接相连，有利于实现更好的载流子传输、光电响应及能级匹配，提高了该化合物的光电性能及稳定性，进而使得包括该化合物的光电器件具有较高稳定性、较高发光效率及较长寿命的器件。经试验验证，包括上述咔唑类化合物的材料的HOMO与LUMO的能级差较小，说明上述咔唑类化合物的稳定性较好，上述咔唑类化合物的ΔEST均较小，说明包括上述咔唑类化合物的材料的器件寿命较长，包括上述咔唑类化合物的有机发光二极管的器件寿命是未包括上述咔唑类化合物的有机发光二极管的器件寿命的2倍以上，同时，包括上述咔唑类化合物的有机发光二极管的发光效率比未包括上述咔唑类化合物的有机发光二极管的发光效率至少提高了47.2％。上述咔唑类化合物能够用于制备具有较高稳定性、较高发光效率及较长寿命的电子器件。
具体实施方式
为了便于理解本发明，下面对本发明进行更全面的描述。但是，本发明可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本发明的公开内容的理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。
以下实施方式中，如未特别说明，芳基指至少包含一个芳环的烃基。杂芳基指包含至少一个杂原子的芳香烃基。其中，杂原子例如可以为O、N或S。当然，需要说明的是，芳基或杂芳基不仅包括具有芳环或杂芳环的基团，而且包含具有非芳环的基团，例如吡啶基、噻吩基、吡咯基、吡唑基、三唑基、咪唑基、噁唑基、噁二唑基、噻唑基、四唑基、吡嗪基、哒嗪基、嘧啶基、三嗪基或卡宾基等基团也认为是芳基或杂芳基。需要说明的是，芳基或杂芳基还可以包括至少两个芳环或杂芳环被非芳环基连接而构成的基团，其中，非芳环基中的非H原子的数量小于10％。在其中一个实施方式中，非芳环基中的非H原子的数量小于5％。在其中一个实施方式中，非芳环基为C原子、N原子或O原子。
具体地，芳基为苯基、二联苯基、三联苯基、甲苯基、氯苯基或上述基团的衍生物。杂芳基为吡啶基、噻吩基、吡咯基、吡唑基、三唑基、咪唑基、噁唑基、噁二唑基、噻唑基、 四唑基、吡嗪基、哒嗪基、嘧啶基、三嗪基、卡宾基或上述基团的衍生物。
稠芳基指具有两个或多个环的芳基，且其中相邻两个环共用两个碳原子(即稠环)。稠杂芳基指包含至少一个杂原子的稠芳基。其中，杂原子例如可以为N、O或S。当然，需要说明的是，稠芳基或稠杂芳基不仅包括具有芳香环或杂芳环的基团，还可以包括至少两个芳环或杂芳环被非芳环基连接而构成的基团，其中，非芳环基中的非H原子的数量小于10％。在其中一个实施方式中，非芳环基中的非H原子的数量小于5％。在其中一个实施方式中，非芳环基为C原子、N原子或O原子。在其中一个实施方式中，9,9'-螺二芴基、9,9-二芳基芴基、三芳胺基及二芳基醚基也认为是稠芳基或稠杂芳基。
具体地，稠芳基为萘基、蒽基、荧蒽基、菲基、苯并菲基、二萘嵌苯基、并四苯基、芘基、苯并芘基、苊基、芴基或上述基团的衍生物。稠杂芳基为苯并呋喃基、苯并噻吩基、吲哚基、咔唑基、吡咯并咪唑基、吡咯并吡咯基、噻吩并吡咯基、噻吩并噻吩基、呋喃并吡咯基、呋喃并呋喃基、噻吩并呋喃基、苯并异噁唑基、苯并异噻唑基、苯并咪唑基、喹啉基、异喹啉基、邻二氮萘基、喹喔啉基、菲啶基、伯啶基、喹唑啉基、喹唑啉酮基及上述基团的衍生物。
一实施方式的咔唑类化合物，具有如下结构式：
Figure PCTCN2017115309-appb-000002
其中，Ar1为环原子数为13～60的稠芳基或环原子数为13～60的稠杂芳基；
Ar2、Ar3为分别独立的选自碳原子数为6～60的芳基、碳原子数为3～60的杂芳基、碳原子数为7～60的稠芳基、碳原子数为4～60的稠杂芳基或上述基团中至少两个相互连接形成的组合基团中的一种，且Ar2、Ar3中至少一个包含具有N原子的杂芳基；
R1选自H、D、F、CN、NO2、CF3、烯基、炔基、胺基、酰基、酰胺基、氰基、异氰基、烷氧基、羟基、羰基、砜基、碳原子数为1～60的烷基、碳原子数为3～60的环烷基、碳原子数为6～60的芳基、碳原子数为3～60的杂芳基、碳原子数为7～60的稠芳基、碳原子数为4～60的稠杂芳基及上述基团中至少两个相互连接形成的组合基团中的一种；
n为0～20的整数；
p及q分别独立选自0～4的整数中的一个，且p和q不同时为0。
在其中一个实施方式中，Ar1为环原子数为13～50的稠芳基或环原子数为13～50的稠杂芳基。
在其中一个实施方式中，Ar1为环原子数为13～40的稠芳基或环原子数为13～40的稠杂芳基。
在其中一个实施方式中，Ar1为环原子数为13～30的稠芳基或环原子数为13～30的稠杂芳基。
在其中一个实施方式中，Ar1为环原子数为13～20的稠芳基或环原子数为13～20的稠杂芳基。
在其中一个实施方式中，Ar1为稠杂芳基，Ar1的杂原子为Si、N、P、O、S或Ge。
在其中一个实施方式中，Ar1为稠杂芳基，Ar1的杂原子为Si、N、P、O或S。
在其中一个实施方式中，Ar1为稠杂芳基，Ar1的杂原子为N、O或S。
在其中一个实施方式中，Ar1为环原子数为3～20的稠环基。Ar1为三元环基、四元环基、五元环基或六元环基。
在其中一个实施方式中，Ar1为环原子数为3～10的稠环基。
在其中一个实施方式中，Ar1为环原子数为3～5的稠环基。
在其中一个实施方式中，Ar1的结构式选自如下结构式中的一种：
Figure PCTCN2017115309-appb-000003
其中，X1为C-R2或N；
Y1选自C-R3-R4、Si-R5-R6、N-R7、C(＝O)、S(＝O)2、O及S中的一种；
-R2、-R3、-R4、-R5、-R6及-R7分别独立选自单键、-H、-D、-F、-CN、-NO2、-CF3、烯基、炔基、胺基、酰基、酰胺基、氰基、异氰基、烷氧基、羟基、羰基、砜基、碳原子数为1～60的烷基、碳原子数为3～60的环烷基、碳原子数为6～60的芳基、碳原子数为3～60的杂芳基、碳原子数为7～60的稠芳基、碳原子数为4～60的稠杂芳基及上述基团中至少两个相互连接形成的组合基团中的一种。
在其中一个实施方式中，Y1选自C-R3-R4及O中的一种。
在其中一个实施方式中，-R2、-R3、-R4、-R5、-R6及-R7分别独立选自取代的碳原子数为 1～60的烷基、取代的碳原子数为3～60的环烷基、取代的碳原子数为6～60的芳基、取代的碳原子数为3～60的杂芳基、取代的碳原子数为7～60的稠芳基及取代的碳原子数为4～60的稠杂芳基中的一种。
在其中一个实施方式中，-R2、-R3、-R4、-R5、-R6及-R7分别独立选自单键、-H、-D、-F、-CN、-NO2、-CF3、烯基、炔基、胺基、酰基、酰胺基、氰基、异氰基、烷氧基、羟基、羰基、砜基、碳原子数为1～30的烷基、碳原子数为3～30的环烷基、碳原子数为6～30的芳基、碳原子数为3～30的杂芳基、碳原子数为7～30的稠芳基、碳原子数为4～30的稠杂芳基及上述基团中至少两个相互连接形成的组合基团中的一种。
在其中一个实施方式中，-R2、-R3、-R4、-R5、-R6及-R7分别独立选自取代的碳原子数为1～30的烷基、取代的碳原子数为3～30的环烷基、取代的碳原子数为6～30的芳基、取代的碳原子数为3～30的杂芳基、取代的碳原子数为7～30的稠芳基及取代的碳原子数为4～30的稠杂芳基中的至少一种。
在其中一个实施方式中，-R2、-R3、-R4、-R5、-R6及-R7均能够自身形成单环脂族环基、多环脂族环基、单环的芳基或多环的芳基。
在其中一个实施方式中，-R2能够与-R3、-R4、-R5、-R6或-R7形成单环脂族环基、多环脂族环基、单环的芳基或多环的芳基。
在其中一个实施方式中，-R7能够与-R2、-R3、-R4、-R5或-R6形成单环脂族环基、多环脂族环基、单环的芳基或多环的芳基。
在其中一个实施方式中，-R3和-R4之间能够相互形成单环脂族环基、多环脂族环基、单环的芳基或多环的芳基。
在其中一个实施方式中，-R5和-R6之间能够相互形成单环脂族环基、多环脂族环基、单环的芳基或多环的芳基。
在其中一个实施方式中，Ar1选自蒽基、荧蒽基、菲基、苯并菲基、二萘嵌苯基、并四苯基、芘基、苯并芘基、苊基、芴基、咔唑基、二苯并呋喃基及二苯并噻吩基中的一种。
在其中一个实施方式中，Ar1的结构式选自如下结构式中的一种：
Figure PCTCN2017115309-appb-000004
在其中一个实施方式中，具有N原子的杂芳基的结构式选自如下结构式中的一种：
Figure PCTCN2017115309-appb-000005
其中，X2为C-R8或N，且具有N原子的杂芳基的结构式中至少有一个X2为N；
Y2选自C-R9-R10、Si-R11-R12、N-R13、C(＝O)、S(＝O)2、O及S中的一种；
-R8、-R9、-R10、-R11、-R12及-R13分别独立选自单键、-H、-D、-F、-CN、-NO2、-CF3、烯基、炔基、胺基、酰基、酰胺基、氰基、异氰基、烷氧基、羟基、羰基、砜基、碳原子数为1～60的烷基、碳原子数为3～60的环烷基、碳原子数为6～60芳基、碳原子数为3～60杂芳基、碳原子数为7～60的稠芳基、碳原子数为4～60的稠杂芳基及上述基团中至少两个相互连接形成的组合基团中的一种。
在其中一个实施方式中，-R8、-R9、-R10、-R11、-R12及-R13分别独立选自分别独立选自取代的碳原子数为1～60的烷基、取代的碳原子数为3～60的环烷基、取代的碳原子数为6～60的芳基、取代的碳原子数为3～60的杂芳基、取代的碳原子数为7～60的稠芳基及取代的碳原子数为4～60的稠杂芳基中的一种。
在其中一个实施方式中，-R8、-R9、-R10、-R11、-R12及-R13分别独立选自单键、-H、-D、-F、-CN、-NO2、-CF3、烯基、炔基、胺基、酰基、酰胺基、氰基、异氰基、烷氧基、羟基、羰基、砜基、碳原子数为1～30的烷基、碳原子数为3～30的环烷基、碳原子数为6～30芳基、碳原子数为3～30杂芳基、碳原子数为7～30的稠芳基、碳原子数为4～30的稠杂芳基及上述基团中至少两个相互连接形成的组合基团中的一种。
在其中一个实施方式中，-R8、-R9、-R10、-R11、-R12及-R13分别独立选自分别独立选自取代的碳原子数为1～30的烷基、取代的碳原子数为3～30的环烷基、取代的碳原子数为6～30的芳基、取代的碳原子数为3～30的杂芳基、取代的碳原子数为7～30的稠芳基及取代的碳原子数为4～30的稠杂芳基中的一种。
在其中一个实施方式中，-R8、-R9、-R10、-R11、-R12及-R13均能够自身形成单环脂族环基、多环脂族环基、单环的芳基或多环的芳基。
在其中一个实施方式中，-R8能够与-R9、-R10、-R11、-R12或-R13形成单环脂族环基、多环脂族环基、单环的芳基或多环的芳基。
在其中一个实施方式中，-R13能够与-R8、-R9、-R10、-R11或-R12形成单环脂族环基、多环脂族环基、单环的芳基或多环的芳基。
在其中一个实施方式中，-R9和-R10之间能够相互形成单环脂族环基、多环脂族环基、单 环的芳基或多环的芳基。
在其中一个实施方式中，-R11和-R12之间能够相互形成单环脂族环基、多环脂族环基、单环的芳基或多环的芳基。
在其中一个实施方式中，具有N原子的杂芳基的结构式选自如下结构式中的一种：
Figure PCTCN2017115309-appb-000006
在其中一个实施方式中，Ar2及Ar3分别独立包括如下结构式或如下结构式中至少两个相互之间形成的组合基团中的一种：
Figure PCTCN2017115309-appb-000007
其中，n1为1～4的整数。
在其中一个实施方式中，L2和L3中至少一个为具有至少一个N原子的杂芳基。
在其中一个实施方式中，n为0～20的整数。
在其中一个实施方式中，n为0～10的整数。
在其中一个实施方式中，n为0～5的整数。
在其中一个实施方式中，n为0～3的整数。
在其中一个实施方式中，p及q分别独立选自0～4的整数中的一个，且p和q不同时为 0。
在其中一个实施方式中，p及q分别独立选自0～3的整数中的一个，且p和q不同时为0。
在其中一个实施方式中，p及q分别独立选自0～2的整数中的一个，且p和q不同时为0。
在其中一个实施方式中，p及q分别独立选自0～1的整数中的一个，且p和q不同时为0。
在其中一个实施方式中，咔唑类化合物的电子迁移率为大于或等于10-5cm2·V-1·S-1。上述咔唑类化合物具有较高的电子迁移率，使得通过相同电流时，功耗越小，电流承载能力越大。
在其中一个实施方式中，咔唑类化合物的电子迁移率为大于或等于10-4cm2·V-1·S-1。
在其中一个实施方式中，咔唑类化合物的电子迁移率为大于或等于10-3cm2·V-1·S-1。
在其中一个实施方式中，咔唑类化合物的玻璃化转变温度大于或等于100℃。较高的玻璃化转变温度，使得该咔唑类化合物的稳定性较好，具有较好的使用性能，有利于该咔唑类化合物的广泛应用。
在其中一个实施方式中，咔唑类化合物的玻璃化转变温度大于或等于110℃。
在其中一个实施方式中，咔唑类化合物的玻璃化转变温度大于或等于120℃。
在其中一个实施方式中，咔唑类化合物的玻璃化转变温度大于或等于140℃。
在其中一个实施方式中，咔唑类化合物的最低未占有轨道能级(LUMO)小于或等于-2.7eV。
在其中一个实施方式中，咔唑类化合物的LUMO小于或等于-2.8eV。
在其中一个实施方式中，咔唑类化合物的LUMO小于或等于-2.9eV。
在其中一个实施方式中，咔唑类化合物的LUMO小于或等于-3.0eV。
在其中一个实施方式中，咔唑类化合物的最高被占有轨道能级(HOMO)小于或等于-5.6eV。在其中一个实施方式中，咔唑类化合物的HOMO小于或等于-5.65eV。
在其中一个实施方式中，咔唑类化合物的HOMO小于或等于-5.7eV。
在其中一个实施方式中，咔唑类化合物的三线态能级(T1)大于或等于1.7eV。
在其中一个实施方式中，咔唑类化合物的T1大于或等于1.9eV。
在其中一个实施方式中，咔唑类化合物的T1大于或等于2.15eV。
在其中一个实施方式中，咔唑类化合物的T1大于或等于2.4eV。
在其中一个实施方式中，最低未占有轨道能级及最高被占有轨道能级均可以通过光电效应进行测量，例如XPS(X射线光电子光谱法)和UPS(紫外光电子能谱)，也均可以通过CV(循环伏安法)进行测定，还均可以通过量子化学方法进行测定，例如DFT(密度泛函理论)。
在其中一个实施方式中，三线态能级T1可通过低温时间分辨发光光谱来测量，也可以通过量子模拟计算得到，例如通过Time-dependent DFT模拟计算或通过商业软件Gaussian 03W(Gaussian Inc.)模拟计算。其中，具体的模拟模拟方法可参见WO2011141110。
当然，需要说明的是，HOMO、LUMO及T1的绝对值取决于所用的测量方法、计算方法或评 价方法。因此，合理有意义的比较应该用相同的测量方法和相同的评价方法进行。不同方法确定的能级值应进行相互标定。在本实施方式中，HOMO、LUMO及T1的值是基于Time-dependent DFT的模拟，但不影响其他测量方法或计算方法的应用。
在其中一个实施方式中，咔唑类化合物能够作为电子传输材料(ETM)，电子注入材料(EIM)，空穴阻挡材料(HBM)，主体材料(Host)应用于应用于电子器件。
在其中一个实施方式中，咔唑类化合物中H有10％～40％被氘取代。
在其中一个实施方式中，咔唑类化合物中10％的H被氘取代。
在其中一个实施方式中，咔唑类化合物中20％的H被氘取代。
在其中一个实施方式中，咔唑类化合物中30％的H被氘取代。
在其中一个实施方式中，咔唑类化合物中40％的H被氘取代。
在其中一个实施方式中，咔唑类化合物为小分子化合物，即不是聚合物、低聚物、树枝状聚合物或共聚物的分子。
在其中一个实施方式中，咔唑类化合物的摩尔质量为700克/摩尔～3000克/摩尔。
在其中一个实施方式中，咔唑类化合物的摩尔质量小于或等于3000克/摩尔。
在其中一个实施方式中，咔唑类化合物的摩尔质量小于或等于2000克/摩尔。
在其中一个实施方式中，咔唑类化合物的摩尔质量小于或等于1500克/摩尔。
在其中一个实施方式中，咔唑类化合物的摩尔质量小于或等于1000克/摩尔。咔唑类化合物的摩尔质量小于或等1000克/摩尔，使得该咔唑类化合物能够作为蒸镀型OLED的原材料。
在其中一个实施方式中，咔唑类化合物的摩尔质量小于或等于900克/摩尔。
在其中一个实施方式中，咔唑类化合物的摩尔质量小于或等于850克/摩尔。
在其中一个实施方式中，咔唑类化合物的摩尔质量小于或等于800克/摩尔。
在其中一个实施方式中，咔唑类化合物的摩尔质量小于或等于700克/摩尔。
在其中一个实施方式中，咔唑类化合物的摩尔质量大于或等于700克/摩尔。咔唑类化合物的摩尔质量大于或等700克/摩尔，使得该咔唑类化合物能够作为印刷型OLED的原材料。
在其中一个实施方式中，咔唑类化合物的摩尔质量大于或等于800克/摩尔。
在其中一个实施方式中，咔唑类化合物的摩尔质量大于或等于900克/摩尔。
在其中一个实施方式中，咔唑类化合物的摩尔质量大于或等于1000克/摩尔。
在其中一个实施方式中，咔唑类化合物的摩尔质量大于或等于1100克/摩尔。
在其中一个实施方式中，咔唑类化合物能够在甲苯、氯苯或二甲苯中溶解。
在其中一个实施方式中，咔唑类化合物于25℃下在甲苯中的溶解度大于或等于10mg/mL。咔唑类化合物在甲苯中的高溶解度，使得该化合物能够更好的被广泛应用。
在其中一个实施方式中，咔唑类化合物于25℃下在甲苯中的溶解度大于或等于15mg/mL。
在其中一个实施方式中，咔唑类化合物于25℃下在甲苯中的溶解度大于或等于20mg/mL。
在其中一个实施方式中，咔唑类化合物的结构式选自如下结构式中的一种：
Figure PCTCN2017115309-appb-000008
Figure PCTCN2017115309-appb-000009
Figure PCTCN2017115309-appb-000010
Figure PCTCN2017115309-appb-000011
Figure PCTCN2017115309-appb-000012
Figure PCTCN2017115309-appb-000013
Figure PCTCN2017115309-appb-000014
Figure PCTCN2017115309-appb-000015
Figure PCTCN2017115309-appb-000016
Figure PCTCN2017115309-appb-000017
Figure PCTCN2017115309-appb-000018
Figure PCTCN2017115309-appb-000019
Figure PCTCN2017115309-appb-000020
Figure PCTCN2017115309-appb-000021
Figure PCTCN2017115309-appb-000022
Figure PCTCN2017115309-appb-000023
Figure PCTCN2017115309-appb-000024
Figure PCTCN2017115309-appb-000025
Figure PCTCN2017115309-appb-000026
Figure PCTCN2017115309-appb-000027
Figure PCTCN2017115309-appb-000028
Figure PCTCN2017115309-appb-000029
Figure PCTCN2017115309-appb-000030
Figure PCTCN2017115309-appb-000031
Figure PCTCN2017115309-appb-000032
Figure PCTCN2017115309-appb-000033
Figure PCTCN2017115309-appb-000035
Figure PCTCN2017115309-appb-000036
上述结构式中，一个结构式代表一种咔唑类化合物，相邻结构式之间的交错仅是文档排版问题，不具有其他意义。
一实施方式的咔唑类化合物至少具有以下优点：
(1)上述咔唑类化合物通过将咔唑的氮原子与平面结构的稠芳基或稠杂芳基直接相连，有利于实现更好的载流子传输、光电响应及能级匹配，提高了该化合物的光电性能及稳定性，进而使得包括该化合物的光电器件具有较高稳定性、较高发光效率及较长寿命的器件。经试验验证，包括上述咔唑类化合物的材料的HOMO与LUMO的能级差较小，说明上述咔唑类化合物的稳定性较好，上述咔唑类化合物的ΔEST均较小，说明包括上述咔唑类化合物的材料的器件寿命较长，包括上述咔唑类化合物的有机发光二极管的器件寿命是未包括上述咔唑类化合物的有机发光二极管的器件寿命的2倍以上，同时，包括上述咔唑类化合物的有机发光二极管的发光效率比未包括上述咔唑类化合物的有机发光二极管的发光效率至少提高了47.2％。上述咔唑类化合物能够用于制备具有较高稳定性、较高发光效率及较长寿命的电子器件。
(2)上述咔唑类化合物的Tg(玻璃化转变温度)大于或等于100℃，使得该咔唑类化合物的稳定性较好，具有较好的使用性能，有利于该咔唑类化合物的广泛应用。
(3)上述咔唑类化合物能够作为电子传输材料(ETM)，电子注入材料(EIM)，空穴阻挡材料(HBM)，主体材料(Host)应用于电子器件中。
(4)上述咔唑类化合物在甲苯中的高溶解度，使得该化合物能够更好的被广泛应用。
一实施方式的咔唑类聚合物包括上述咔唑类化合物形成的重复单元。
在其中一个实施方式中，咔唑类聚合物为均聚物(homopolymer)，即该聚合物仅由一种 重复单元聚合而成；即咔唑类聚合物仅包括上述咔唑类化合物形成的重复单元。
在其中一个实施方式中，咔唑类聚合物为共聚物(copolymer)，即该聚合物由两种或两种以上的重复单元聚合而成。
在其中一个实施方式中，咔唑类聚合物为由两种单体聚合而成的共聚物，两种单体中的一种为上述咔唑类化合物或其衍生基团。优选地，两种单体中的另一种为芳胺类化合物。
在其中一个实施方式中，咔唑类聚合物为嵌段共聚物(block copolymer)，即该聚合物由两种或两种以上性质不同的聚合物链段连接而成。其中一个中聚合物链段为上述咔唑类化合物形成的聚合物链段，另一种聚合物链段为芳胺类结构。
在其中一个实施方式中，咔唑类聚合物为树枝状聚合物(dendrimer)。有关树状聚合物的结构及应用请参见[Dendrimers and Dendrons,Wiley-VCH Verlag GmbH&Co.KGaA,2002,Ed.George R.Newkome,Charles N.Moorefield,Fritz Vogtle.]，此处不再赘述。
在其中一个实施方式中，咔唑类聚合物的重复单元的数量10～1000。当然，需要说明的是，重复单元的数量可以根据需要进行设置。
在其中一个实施方式中，咔唑类聚合物为共轭聚合物，即聚合物的主链主要是由C原子的sp2杂化轨道构成。当然，需要说明的是，当聚合物的主链上的C原子被其他非C原子取代或者主链上的sp2杂化被一些自然的缺陷打断时，该聚合物仍然被认为是共轭聚合物。同时，当聚合物的主链上包含有芳香胺(aryl amine)、芳基磷化氢(aryl phosphine)、其他杂环芳烃(heteroarmotics)及有机金属络合物(organometallic complexes)等基团时，该聚合物仍然被认为是共轭聚合物。
在其中一个实施方式中，咔唑类聚合物为非共轭聚合物，且上述咔唑类化合物位于该聚合物的侧链上。
一实施方式的咔唑类聚合物至少具有如下优点：
上述咔唑类聚合物包括上述咔唑类化合物，使得该聚合物具有良好的溶解性、稳定性及光电性能，能够作为空穴注入材料(HIM)、空穴传输材料(HTM)、电子传输材料(ETM)、电子注入材料(EIM)、电子阻挡材料(EBM)，空穴阻挡材料(HBM)、发光体(Emitter)及主体材料(Host)应用于电子器件中，应用范围广，且包括咔唑类聚合物的材料及器件的稳定性好、发光效率高且寿命长。
第一实施方式的有机电致发光材料包括上述咔唑类化合物及上述咔唑类聚合物中的至少一种及有机功能材料。
在其中一个实施方式中，有机功能材料选自空穴注入材料(HIM)、空穴传输材料(HTM)、电子注入材料(EIM)、电子传输材料(ETM)、空穴阻挡材料(HBM)、电子阻挡材料(EBM)、主体材料(Host)、单重态发光体、热激活延迟荧光发光材料(TADF)、三重态发光体、主体材料及有机染料中的至少一种。其中，WO 2010135519A1、US 20090134784A1及WO 2011110277A1中对各种有机功能材料均进行了有详细的描述，这三篇专利中的有机功能材料均能够作为本实施方式中的有机电致发光材料中的有机功能材料，此处不再赘述。
本发明进一步涉及一种混合物，包含至少一种按照本发明的咔唑类化合物或聚合物，及至少一种的有机功能材料。
这里所述一种的有机功能材料为空穴(也称电洞)注入或传输材料(HIM/HTM)、空穴阻挡材料(HBM)、电子注入或传输材料(EIM/ETM)、电子阻挡材料(EBM)、有机基质材料(Host)、单重态发光体(荧光发光体)、热激活延迟荧光发光材料(TADF)、三重态发光体(磷光发光体)或有机染料。进一步地，三重态发光体为发光金属有机配合物。例如在WO2010135519A1,US20090134784A1和WO 2011110277A1中对各种有机功能材料有详细的描述，特此将此3专利文件中的全部内容并入本文作为参考。
有机功能材料可以是小分子材料或聚合物材料。
在某些实施例中，按照本发明的混合物中，所述的咔唑类化合物的含量为50wt％～99wt％。按照本发明的混合物中，所述的咔唑类化合物的含量为60wt％～97wt％。按照本发明的混合物中，所述的咔唑类化合物的含量为60wt％～95wt％。。按照本发明的混合物中，所述的咔唑类化合物的含量为70wt％～90wt％。
在一个实施方案中，按照本发明的混合物包含一种按照本发明的化合物或聚合物和一种荧光发光材料(单重态发光体)。
在另一个实施方案中，按照本发明的混合物包含一种按照本发明的化合物或聚合物和一种热激活延迟荧光发光材料(TADF)。
在另一个实施方案中，按照本发明的混合物包含一种按照本发明的化合物或聚合物，一种荧光发光材料和一种TADF材料。
下面对荧光发光材料或单重态发光体(荧光发光材料)和TADF材料作一些较详细的描述(但不限于此)。
1.单重态发光体(Singlet Emitter)
单重态发光体往往有较长的共轭π电子系统。迄今，已有许多例子，例如在JP2913116B和WO2001021729A1中公开的苯乙烯胺及其衍生物，和在WO2008/006449和WO2007/140847中公开的茚并芴及其衍生物。
在一个优先的实施方案中，单重态发光体可选自一元苯乙烯胺、二元苯乙烯胺、三元苯乙烯胺、四元苯乙烯胺、苯乙烯膦、苯乙烯醚和芳胺中的至少一种。
一个一元苯乙烯胺是指一化合物，它包含一个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个二元苯乙烯胺是指一化合物，它包含二个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个三元苯乙烯胺是指一化合物，它包含三个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个四元苯乙烯胺是指一化合物，它包含四个无取代或取代的苯乙烯基组和至少一个胺，最好是芳香胺。一个优选的苯乙烯是二苯乙烯，其可能会进一步被取代。相应的膦类和醚类的定义与胺类相似。芳基胺或芳香胺是指一种化合物，包含三个直接联接氮的无取代或取代的芳香环或杂环系统。这些芳香族或杂环的环系统中至少有一个优先选于稠环系统，并最好有至少14个芳香环原子。在其中一个实施方式中，芳香胺Wie芳香蒽胺，芳香蒽二胺，芳香芘胺，芳香芘二胺，芳香屈胺或芳香屈二胺。一个芳香蒽胺是指一化合物，其中一个二元芳基胺基团直接联到蒽上，最好是在9的位置上。一个芳香蒽二胺是指一化合物，其中二个二元芳基胺基团直接联到蒽上，最好是在9,10的位置上。芳香芘胺、芳香芘二胺、芳香屈胺和芳香屈二胺的定义类似，其中二元芳基胺基团最好 联到芘的1或1,6位置上.
基于乙烯胺及芳胺的单重态发光体的例子，也是优选的例子，可在下述专利文件中找到:WO 2006/000388,WO 2006/058737,WO 2006/000389,WO 2007/065549,WO 2007/115610,US 7250532 B2,DE 102005058557 A1,CN 1583691 A,JP 08053397 A,US 6251531 B1,US 2006/210830 A,EP 1957606 A1和US 2008/0113101 A1特此上述列出的专利文件中的全部内容并入本文作为参考。
基于均二苯乙烯极其衍生物的单重态发光体的例子有US 5121029A。
进一步的优选的单重态发光体可选于茚并芴-胺和茚并芴-二胺，如WO 2006/122630所公开的，苯并茚并芴-胺和苯并茚并芴-二胺，如WO 2008/006449所公开的，二苯并茚并芴-胺和二苯并茚并芴-二胺，如WO2007/140847所公开的。
其他可用作单重态发光体的材料有多环芳烃化合物，特别是如下化合物的衍生物:蒽如9,10-二(2-萘并蒽)，萘,四苯，氧杂蒽，菲,芘(如2,5,8,11-四-t-丁基苝)，茚并芘，苯撑如(4,4’-双(9-乙基-3-咔唑乙烯基)-1,1’-联苯)，二茚并芘,十环烯,六苯并苯,芴，螺二芴,芳基芘(如US20060222886)，亚芳香基乙烯(如US5121029A，US5130603A),环戊二烯如四苯基环戊二烯,红荧烯，香豆素，若丹明，喹吖啶酮，吡喃如4(二氰基亚甲基)-6-(4-对二甲氨基苯乙烯基-2-甲基)-4H-吡喃(DCM),噻喃,双(吖嗪基)亚胺硼化合物(US 2007/0092753 A1),双(吖嗪基)亚甲基化合物,carbostyryl化合物,噁嗪酮,苯并恶唑,苯并噻唑,苯并咪唑及吡咯并吡咯二酮。一些单重态发光体的材料可在下述专利文件中找到:US 20070252517 A1,US 4769292A,US 6020078A,US 2007/0252517 A1,US 2007/0252517 A1。特此将上述列出的专利文件中的全部内容并入本文作为参考。
在下面的表中列出一些合适的单重态发光体的例子:
Figure PCTCN2017115309-appb-000037
Figure PCTCN2017115309-appb-000038
2.热激活延迟荧光发光材料(TADF)：
传统有机荧光材料只能利用电激发形成的25％单线态激子发光，器件的内量子效率较低(最高为25％)。尽管磷光材料由于重原子中心强的自旋-轨道耦合增强了系间穿越，可以有效利用电激发形成的单线态激子和三线态激子发光，使器件的内量子效率达到100％。但磷光材料昂贵，材料稳定性差，器件效率滚降严重等问题限制了其在OLED中的应用。热激活延迟荧光发光材料是继有机荧光材料和有机磷光材料之后发展的第三代有机发光材料。该类材料一般具有小的单线态-三线态能级差(ΔEst)，三线态激子可以通过反系间穿越转变成单线态激子发光。这可以充分利用电激发下形成的单线态激子和三线态激子。器件内量子效率可达到100％。
TADF材料需要具有较小的单线态-三线态能级差，一般是TADF材料的ΔEst<0.3eV。进一步地，TADF材料的ΔEst<0.2eV。进一步地，TADF材料的ΔEst<0.1eV。进一步地，TADF材料的ΔEst<0.05eV。在一个实施方案中，TADF材料有较好的荧光量子效率。一些TADF材料可在下述专利文件中找到:CN103483332(A)，TW201309696(A)，TW201309778(A)，TW201343874(A)，TW201350558(A)，US20120217869(A1)，WO2013133359(A1)，WO2013154064(A1)，Adachi,et.al.Adv.Mater.,21,2009,4802，Adachi,et.al.Appl.Phys.Lett.,98,2011,083302，Adachi,et.al.Appl.Phys.Lett.,101,2012,093306，Adachi,et.al.Chem.Commun.,48,2012,11392，Adachi,et.al.Nature Photonics,6,2012,253，Adachi,et.al.Nature,492,2012,234，Adachi,et.al.J.Am.Chem.Soc,134,2012,14706，Adachi,et.al.Angew.Chem.Int.Ed,51,2012,11311，Adachi,et.al.Chem.Commun.,48,2012,9580，Adachi,et.al.Chem.Commun.,48,2013,10385，Adachi,et.al.Adv.Mater.,25,2013,3319，Adachi,et.al.Adv.Mater.,25,2013,3707，Adachi,et.al.Chem.Mater.,25,2013,3038，Adachi,et.al.Chem.Mater.,25,2013,3766，Adachi,et.al.J.Mater.Chem.C.,1,2013,4599，Adachi,et.al.J.Phys.Chem.A.,117,2013,5607，特此将上述列出的专利或文章文件中的全部内容并入本文作为参考。
在下面的表中列出一些合适的TADF发光材料的例子:
Figure PCTCN2017115309-appb-000039
Figure PCTCN2017115309-appb-000040
Figure PCTCN2017115309-appb-000041
以上出现的有机功能材料出版物为公开的目的以参考方式并入本申请。
本发明涉及一种组合物或油墨包含一种按照本发明的化合物或聚合物或混合物，以及至少一种有机溶剂。需要说明的是，本实施方式中的组合物和油墨的含义相同。进一步地，本发明提供一种从溶液中制备包含有按照本发明的化合物或聚合物的薄膜。
用于印刷工艺时，油墨的粘度、表面张力是重要的参数。合适的油墨的表面张力参数适合于特定的基板和特定的印刷方法。
在其中一个实施例中，按照本发明的油墨在25℃～300℃下的表面张力为19dyne/cm～50 dyne/cm。进一步地，按照本发明的油墨在25℃～300℃下的表面张力为22dyne/cm～35 dyne/cm范围。进一步地，按照本发明的油墨在25℃～300℃下的表面张力为25dyne/cm～33 dyne/cm范围。
在其中一个实施例中，按照本发明的油墨在25℃～300℃的粘度为1cps～100cps。进一步地，按照本发明的油墨在25℃～300℃的粘度为1cps～50cps。进一步地，按照本发明的油墨在25℃～300℃的粘度为1.5cps～20cps。进一步地，按照本发明的油墨在25℃～300℃的粘度为4.0cps～20cps。如此配制的组合物将适合于喷墨印刷。
粘度可以通过不同的方法调节，如通过合适的溶剂选取和油墨中功能材料的浓度。按照本发明的包含有所述地化合物或聚合物的油墨可方便人们将印刷油墨按照所用的印刷方法在适当的范围调节。一般地，按照本发明的组合物包含的有机功能材料的重量比为0.3wt％～30wt％。按照本发明的组合物包含的有机功能材料的重量比为0.5wt％～20wt％按照本发明的组合物包含的有机功能材料的重量比为0.5wt％～15wt％。按照本发明的组合物包含的有机功能材料的重量比为0.5wt％～10wt％。按照本发明的组合物包含的有机功能材料的重量比为1wt％～5wt％。
在一些实施例中，按照本发明的油墨，所述的至少一种的有机溶剂选自基于芳族或杂芳族的溶剂，特别是被脂肪族链取代的芳族溶剂、脂肪环取代的芳族溶剂、芳族酮溶剂或芳族醚溶剂。
适合本发明的有机溶剂的例子有，但不限于：基于芳族或杂芳族的溶剂:对二异丙基苯、戊苯、四氢萘、环己基苯、氯萘、1,4-二甲基萘、3-异丙基联苯、对甲基异丙苯、二戊苯、三戊苯、戊基甲苯、邻二甲苯、间二甲苯、对二甲苯、邻二乙苯、间二乙苯、对二乙苯、1,2,3,4-四甲苯、1,2,3,5-四甲苯、1,2,4,5-四甲苯、丁苯、十二烷基苯、二己基苯、二丁基苯、对二异丙基苯、1-甲氧基萘、环己基苯、二甲基萘、3-异丙基联苯、对甲基异丙苯、1-甲基萘、 1,2,4-三氯苯、1,3-二丙氧基苯、4,4-二氟二苯甲烷、1,2-二甲氧基-4-(1-丙烯基)苯、二苯甲烷、2-苯基吡啶、3-苯基吡啶、N-甲基二苯胺、4-异丙基联苯、α,α-二氯二苯甲烷、4-(3-苯基丙基)吡啶、苯甲酸苄酯、1,1-双(3,4-二甲基苯基)乙烷、2-异丙基萘、二苄醚等；基于酮的溶剂:1-四氢萘酮，2-四氢萘酮，2-(苯基环氧)四氢萘酮，6-(甲氧基)四氢萘酮，苯乙酮、苯丙酮、二苯甲酮、及它们的衍生物，如4-甲基苯乙酮、3-甲基苯乙酮、2-甲基苯乙酮、4-甲基苯丙酮、3-甲基苯丙酮、2-甲基苯丙酮，异佛尔酮、2,6,8-三甲基-4-壬酮、葑酮、2-壬酮、3-壬酮、5-壬酮、2-癸酮、2,5-己二酮、佛尔酮、二正戊基酮；芳族醚溶剂：3-苯氧基甲苯、丁氧基苯、苄基丁基苯、对茴香醛二甲基乙缩醛、四氢-2-苯氧基-2H-吡喃、1,2-二甲氧基-4-(1-丙烯基)苯、1,4-苯并二噁烷、1,3-二丙基苯、2,5-二甲氧基甲苯、4-乙基本乙醚、1,2,4-三甲氧基苯、4-(1-丙烯基)-1,2-二甲氧基苯、1,3-二甲氧基苯、缩水甘油基苯基醚、二苄基醚、4-叔丁基茴香醚、反式-对丙烯基茴香醚、1,2-二甲氧基苯、1-甲氧基萘、二苯醚、2-苯氧基甲醚、2-苯氧基四氢呋喃、乙基-2-萘基醚、戊醚c己醚、二辛醚、乙二醇二丁醚、二乙二醇二乙醚、二乙二醇丁基甲醚、二乙二醇二丁醚、三乙二醇二甲醚、三乙二醇乙基甲醚、三乙二醇丁基甲醚、三丙二醇二甲醚、四乙二醇二甲醚；酯类溶剂：辛酸烷酯、癸二酸烷酯、硬脂酸烷酯、苯甲酸烷酯、苯乙酸烷酯、肉桂酸烷酯、草酸烷酯、马来酸烷酯、烷内酯、油酸烷酯等。
进一步，按照本发明的油墨，所述的至少一种的有机溶剂可选自：脂肪族酮，例如，2-壬酮、3-壬酮、5-壬酮、2-癸酮、2,5-己二酮、2,6,8-三甲基-4-壬酮、佛尔酮、二正戊基酮等；或脂肪族醚，例如，戊醚、己醚、二辛醚、乙二醇二丁醚、二乙二醇二乙醚、二乙二醇丁基甲醚、二乙二醇二丁醚、三乙二醇二甲醚、三乙二醇乙基甲醚、三乙二醇丁基甲醚、三丙二醇二甲醚、四乙二醇二甲醚等。
在另一些实施例中，所述的印刷油墨进一步包含有另一种有机溶剂。另一种有机溶剂的例子，包含(但不限于)：甲醇、乙醇、2-甲氧基乙醇、二氯甲烷、三氯甲烷、氯苯、邻二氯苯、四氢呋喃、苯甲醚、吗啉、甲苯、邻二甲苯、间二甲苯、对二甲苯、1,4二氧杂环己烷、丙酮、甲基乙基酮、1,2二氯乙烷、3-苯氧基甲苯、1,1,1-三氯乙烷、1,1,2,2-四氯乙烷、醋酸乙酯、醋酸丁酯、二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、四氢萘、萘烷、茚和/或它们的混合物。
在一个实施方案中，按照本发明的组合物为溶液。
在一个实施方案中，按照本发明的组合物为悬浮液。
溶液或悬浮液可以另外包含一个或多个组份例如表面活性化合物，润滑剂，润湿剂，分散剂，疏水剂，粘接剂等，用于调节粘度，成膜性能，提高附着性等。有关打印技术及其对有关溶液的相关要求，如溶剂、浓度及粘度等，的详细信息请参见Helmut Kipphan主编的《印刷媒体手册:技术和生产方法》(Handbook of Print Media:Technologies and Production Methods),ISBN 3-540-67326-1。
本发明还涉及所述组合物作为油墨在制备有机电子器件时的用途，特别优选的是通过打印或涂布的制备方法。
其中，适合的打印或涂布技术包含(但不限于)喷墨打印、喷印(Nozzle Printing)、活版 印刷、丝网印刷、浸涂、旋转涂布、刮刀涂布、辊筒印花、扭转辊印刷、平版印刷、柔版印刷、轮转印刷、喷涂、刷涂或移印、喷印刷(Nozzle printing)、狭缝型挤压式涂布等。进一步地，适合的打印或涂布技术为喷墨印刷、狭缝型挤压式涂布、喷印刷或凹版印刷。
基于上述化合物，本发明还提供一种如上所述的化合物或聚合物在有机电子器件的应用。所述的有机电子器件可选于，但不限于，有机发光二极管(OLED)，有机光伏电池(OPV)，有机发光电池(OLEEC)，有机场效应管(OFET)，有机发光场效应管，有机激光器，有机自旋电子器件，有机传感器及有机等离激元发射二极管(Organic Plasmon Emitting Diode)等，特别是OLED。本发明实施例中，将所述有机化合物用于OLED器件的电子传输层或发光层中。
进一步地，本发明涉及一种有机电子器件，该有机电子器件至少包含一种如上所述的化合物或聚合物。一般的，此种有机电子器件至少包含一个阴极、一个阳极及位于阴极和阳极之间的一个功能层，其中，所述的功能层中至少包含一种如上所述的化合物或聚合物。所述的有机电子器件可选于，但不限于，有机发光二极管(OLED)，有机光伏电池(OPV)，有机发光电池(OLEEC)，有机场效应管(OFET)，有机发光场效应管，有机激光器，有机自旋电子器件，有机传感器或有机等离激元发射二极管(Organic Plasmon Emitting Diode)。
在一个实施例中，所述的有机电子器件是电致发光器件，例如为OLED，其中包含基片、阳极、阴极和至少位于阳极和阴极之间的发光层。需要说明的是，有机电子器件还可以包含空穴传输层或电子传输层。在一个实施例中，所述的有机电子器件包含电子传输层或电子注入层，电子传输层或电子注入层中包含一按照本发明的化合物或聚合物。在一个实施方案中，所述的有机电子器件包含一发光层，发光层包含一按照本发明的化合物或聚合物。进一步地所述的发光层中包含一按照本发明的化合物或聚合物及至少一种发光材料，发光材料为荧光发光体或TADF材料。
下面对电致发光器件的器件结构做一描述，但不限于。
基片可以是不透明或透明。一个透明的基板可以用来制造一个透明的发光元器件。例如可参见，Bulovic等Nature 1996,380,p29，和Gu等，Appl.Phys.Lett.1996,68,p2606。基片可以是刚性的或弹性的。基片可以是塑料、金属、半导体晶片或玻璃。进一步地，基片有一个平滑的表面。无表面缺陷的基板是特别理想的选择。在一个实施例中，基片是柔性的，可选于聚合物薄膜或塑料。基片的玻璃化转化温度Tg大于或等于150℃。基片的玻璃化转化温度大于或等于200℃。基片的玻璃化转化温度大于或等于250℃。基片的玻璃化转化温度大于或等于300℃。合适作为柔性基板的材料的例子有聚(对苯二甲酸乙二醇酯)(PET)和聚乙二醇(2,6-萘)(PEN)。
阳极可包含一导电金属或金属氧化物，或导电聚合物。阳极可以容易地注入空穴到空穴注入层(HIL)或空穴传输层(HTL)或发光层中。在一个的实施例中，阳极的功函数和发光层中的发光体或作为HIL或HTL或电子阻挡层(EBL)的p型半导体材料的HOMO能级或价带能级的差的绝对值小于0.5eV。在一个的实施例中，阳极的功函数和发光层中的发光体或作为HIL或HTL或电子阻挡层(EBL)的p型半导体材料的HOMO能级或价带能级的差的绝对值小于0.3eV。在一个的实施例中，阳极的功函数和发光层中的发光体或作为HIL或HTL或电子阻挡层(EBL)的p型半导体材料的HOMO能级或价带能级的差的绝对值小于0.2eV。阳极材料的例子 包含但不限于：Al、Cu、Au、Ag、Mg、Fe、Co、Ni、Mn、Pd、Pt、ITO、铝掺杂氧化锌(AZO)等。其他合适的阳极材料是已知的，本领域普通技术人员可容易地选择使用。阳极材料可以使用任何合适的技术沉积，如一合适的物理气相沉积法，包含射频磁控溅射，真空热蒸发，电子束(e-beam)等。在某些实施例中，阳极是图案结构化的。图案化的ITO导电基板可在市场上买到，并且可以用来制备根据本发明的器件。
阴极可包含一导电金属或金属氧化物。阴极可以容易地注入电子到EIL、ETL或发光层中。在一个的实施例中，阴极的功函数和发光层中发光体或作为电子注入层(EIL)或电子传输层(ETL)或空穴阻挡层(HBL)的n型半导体材料的LUMO能级或导带能级的差的绝对值小于0.5eV。在一个的实施例中，阴极的功函数和发光层中发光体或作为电子注入层(EIL)或电子传输层(ETL)或空穴阻挡层(HBL)的n型半导体材料的LUMO能级或导带能级的差的绝对值小于0.3eV。在一个的实施例中，阴极的功函数和发光层中发光体或作为电子注入层(EIL)或电子传输层(ETL)或空穴阻挡层(HBL)的n型半导体材料的LUMO能级或导带能级的差的绝对值小于0.2eV。原则上，所有可用作OLED的阴极的材料都可能作为本发明器件的阴极材料。阴极材料的例子包含但不限于：Al、Au、Ag、Ca、Ba、Mg、LiF/Al、MgAg合金、BaF2/Al、Cu、Fe、Co、Ni、Mn、Pd、Pt、ITO等。阴极材料可以使用任何合适的技术沉积，如一合适的物理气相沉积法，包含射频磁控溅射，真空热蒸发，电子束(e-beam)等。
OLED还可以包含其他功能层，如空穴注入层(HIL)、空穴传输层(HTL)、电子阻挡层(EBL)、电子注入层(EIL)、电子传输层(ETL)、空穴阻挡层(HBL)。适合用于这些功能层中的材料为本领域的业者所熟知，并容易在文献中找到。
在一个优选的实施例中，按照本发明的发光器件中，电子传输层或电子注入层包含本发明的化合物或聚合物。
按照本发明的发光器件的发光波长在300nm到1000nm之间。按照本发明的发光器件的发光波长在350nm到900nm之间。按照本发明的发光器件的发光波长在400nm到800nm之间。
本发明还涉及按照本发明的有机电子器件在各种电子设备中的应用，包含，但不限于，显示设备，照明设备，光源，传感器等。
以下为具体实施例部分。
实施例1
本实施例的咔唑类化合物N-(3-荧蒽)-3,6-二(4-(3-吡啶)苯基)咔唑的合成过程如下：
Figure PCTCN2017115309-appb-000042
取N-(3-荧蒽)-3,6-二溴-咔唑(10g，19.04mmol)及4-(3-吡啶)苯硼酸(9.47g，47.6mmol)置于500mL的双口圆底烧瓶中，加入250mL的甲苯(即溶剂)，然后取碳酸钾(10.51g， 76.16mmol)用30mL水使其完全溶解，加入上述圆底烧瓶中，再加入Pd(PPh3)4(1.32g，1.14mmol)，用油泵抽去瓶中空气，通入氮气，恒温加热回流反应12小时，冷却。将反应液转移到旋蒸瓶中，旋转蒸发干大部分溶剂，用二氯甲烷萃取、水洗三次，无水硫酸镁干燥，过滤旋干，纯化，得到的N-(3-荧蒽)-3,6-二(4-(3-吡啶)苯基)咔唑，且产率为78％。
实施例2
本实施例的咔唑类化合物N-(3-荧蒽)-3-(4-(3-吡啶)苯基)咔唑的合成过程如下：
Figure PCTCN2017115309-appb-000043
取N-(3-荧蒽)-3-溴咔唑(10g，22.40mmol)及4-(3-吡啶)苯硼酸(5.35g，26.88mmol)，置于500mL的双口圆底烧瓶中，加入250mL的甲苯(即溶剂)，然后取碳酸钾(7.42g,53.76mmol)用30mL的水使其完全溶解，加入上述圆底烧瓶，再加入Pd(PPh3)4(0.78g,0.67mmol)，用油泵抽去瓶中空气，通入氮气，恒温加热回流12小时，冷却。将反应液转移到旋蒸瓶中，旋转蒸发干大部分溶剂，用二氯甲烷萃取、水洗三次，无水硫酸镁干燥，过滤旋干，纯化，得到N-(3-荧蒽)-3-(4-(3-吡啶)苯基)咔唑，且产率为80％。
实施例3
本实施例的咔唑类化合物N-(1-蒽)-3,6-二(4-(3-吡啶)苯基)咔唑的合成过程如下：
取N-(1-蒽)-3,6-二溴咔唑(10g，19.95mmol)及4-(3-吡啶)苯硼酸(9.93g，49.88mmol)置于500mL的双口圆底烧瓶中，加入250mL的甲苯(即溶剂)，然后取碳酸钾(11.01g，79.80mmol)用30mL的水使其完全溶解，加入上述圆底烧瓶，再加入Pd(PPh3)4(1.38g，1.19mmol)，用油泵抽去瓶中空气，通入氮气，恒温加热回流12小时，冷却。将反应液转移到旋蒸瓶中，旋转蒸发干大部分溶剂，用二氯甲烷萃取、水洗三次，无水硫酸镁干燥，过滤旋干，纯化，得到Xg的N-(1-蒽)-3,6-二(4-(3-吡啶)苯基)咔唑，且产率为83％。
实施例4
本实施例的咔唑类化合物N-(2-蒽)-3,6-二(4-(3-吡啶)苯基)咔唑的合成过程如下：
Figure PCTCN2017115309-appb-000045
取N-(2-荧蒽)-3,6-二溴咔唑(10g，19.95mmol)及4-(3-吡啶)苯硼酸(9.93g，49.88mmol)，于500mL的双口圆底烧瓶中，加入250mL的甲苯(即溶剂)，然后取碳酸钾(11.01g，79.80mmol)用30mL水使其完全溶解，加入上述圆底烧瓶，再加入Pd(PPh3)4(1.38g，1.19mmol)，用油泵抽去瓶中空气，通入氮气，恒温加热回流12小时，冷却。将反应液转移到旋蒸瓶中，旋转蒸发干大部分溶剂，用二氯甲烷萃取、水洗三次，无水硫酸镁干燥，过滤旋干，纯化，得到N-(2-蒽)-3,6-二(4-(3-吡啶)苯基)咔唑，且产率为80％。
实施例5
本实施例的咔唑类化合物N-(1-芘)-3,6-二(4-(3-吡啶)苯基)咔唑的合成过程如下：
Figure PCTCN2017115309-appb-000046
取N-(1-芘)-3,6-二溴咔唑(10g，19.04mmol)、4-(3-吡啶)苯硼酸(9.47g，47.6mmol)置于500mL的双口圆底烧瓶中，加入250mL的甲苯(即溶剂)，然后取碳酸钾(10.51g，76.16mmol)用30mL的水使其完全溶解，加入上述圆底烧瓶，再加入Pd(PPh3)4(1.32g,1.14mmol)，用油泵抽去瓶中空气，通入氮气，恒温加热回流12小时，冷却。将反应液转移到旋蒸瓶中，旋转蒸发干大部分溶剂，用二氯甲烷萃取、水洗三次，无水硫酸镁干燥，过滤旋干，纯化，得到的N-(1-芘)-3,6-二(4-(3-吡啶)苯基)咔唑，且产率为82％。
实施例6
本实施例的咔唑类化合物2-(4-(9,10-二(2-萘)蒽-2-)苯基)-1-苯基-1-H-苯并咪唑的合成过程如下：
Figure PCTCN2017115309-appb-000047
取9,10-二(2-萘)蒽-2-硼酸(47.4g，0.1mol)及2-(4-溴苯)-1-苯基-1-H-苯并咪唑 (34.9g，0.1mol)，置于1L的双口圆底烧瓶中，加入500mL的甲苯(即溶剂)，然后取碳酸钾(20.7g,0.15mol)用100mL的水使其完全溶解，加入上述圆底烧瓶，再加入Pd(PPh3)4(3.4g,0.003mol)，用油泵抽去瓶中空气，通入氮气，恒温加热回流12小时，冷却。将反应液转移到旋蒸瓶中，旋转蒸发干大部分溶剂，用二氯甲烷萃取、水洗三次，无水硫酸镁干燥，过滤旋干，纯化，得到2-(4-(9,10-二(2-萘)蒽-2-)苯基)-1-苯基-1-H-苯并咪唑，且产率为74％。
检测：
1、对实施例1～6的化合物的能量结构进行测定
化合物的能级利用TD-DFT(含时密度泛函理论)通过Gaussian09W(Gaussian Inc.)，具体的模拟方法可参见WO2011141110。具体地，用密度函数方法“Ground State/DFT/Default Spin/B3LYP”与基组“6-31G(d)”(Charge 0/Spin Singlet)来优化化合物的几何结构，化合物的能量结构由TD-DFT(含时密度泛函理论)方法算得“TD-SCF/DFT/Default Spin/B3PW91”与基组“6-31G(d)”(Charge 0/Spin Singlet)。HOMO和LUMO能级按照下面的校准公式(1)和(2)计算，S1和T1直接使用。
HOMO(eV)＝[(HOMO(G)×27.212)-0.9899]/1.1206校准公式(1)，
其中，HOMO(G)通过Gaussian 03W的直接计算结果，单位为Hartree；
LUMO(eV)＝((LUMO(G)×27.212)-2.0041)/1.385校准公式(2)，
其中，LUMO(G)通过Gaussian 03W的直接计算结果，单位为Hartree。
表1表示的是实施例1～6的化合物的HOMO能级、LUMO能级、T1能级及S1能级。
表1
  HOMO[eV] LUMO[eV] T1[eV] S1[eV]
实施例1 -5.73 -3.03 2.19 2.75
实施例2 -5.75 -2.99 2.19 2.80
实施例3 -5.69 -2.94 1.72 2.86
实施例4 -5.63 -2.92 1.74 2.89
实施例5 -5.68 -2.83 2.03 3.04
实施例6 -5.56 -2.83 1.66 2.83
由表1可以看出，实施例1～5的化合物的HOMO与LUMO的能级差较小，说明实施例1～5的化合物的稳定性较好，同时，实施例1～5的化合物的ΔEST[即Δ(S1-T1)，单线态能级与三线态能级之间的能级差]均较小，说明包括实施例1～5的化合物的材料的发光效率较高。
2、测定实施例1～6的化合物分别作为有机电致发光器件(OLED)的ETL的材料时，该OLED的发光效率、寿命及发光颜色。其中，通过XX方法测定发光效率。通过XX方法测定发光颜色。OLED器件的电流电压(J-V)特性通过表征设备来表征，同时记录该OLED器件寿命的数值，且寿命由T95，1000nits表示，且实施例1～5的寿命为相对于实施例6的寿命的相对值。结果详见表2。具体过程如下：
测试例1
OLED的结构为：
ITO/HIL(50nm)/HTL(35nm)/发光层(20nm)/ETL(28nm)/LiQ(1nm)/Al(150nm)/阴极，(上述结构中“/”代表层叠)。
其中，
HIL的材料为4,4',4”-三[2-萘基苯基氨基]三苯基胺(2-TNATA)；
HTL的材料为N,N’-双(1-萘基)-N,N’-二苯基-4,4’-二胺(NPD)；
发光层由主体材料与辅助材料以质量比为95：5混合制成，
主体材料为
Figure PCTCN2017115309-appb-000048
辅助材料为
Figure PCTCN2017115309-appb-000049
ETL的材料选自实施例1化合物。
上述OLED的制备过程具体如下：
(1)导电玻璃基片的清洗:首次使用时，可用多种溶剂进行清洗，例如氯仿、酮、异丙醇进行清洗，然后进行紫外臭氧等离子处理；
(2)通过热蒸镀的方式于1×10-6毫巴下在导电玻璃基板上依次形成HIL、HTL、发光层、ETL、阴极、LiQ及Al，并在氮气手套箱中用紫外线硬化树脂封装，得到OLED。
测试例2
OLED的结构为：ITO/HIL(50nm)/HTL(35nm)/发光层(20nm)/ETL(28nm)/LiQ(1nm)/Al(150nm)/阴极的OLED，(上述结构中“/”代表层叠)。其中，用实施例2化合物为ETL的材料。其余与测试例1相同。
测试例3
OLED的结构为：TO/HIL(50nm)/HTL(35nm)/发光层(20nm)/ETL(28nm)/LiQ(1nm)/Al(150nm)/阴极的OLED，(上述结构中“/”代表层叠)。其中，用实施例3化合物为ETL的材料。其余与测试例1相同。
测试例4
OLED的结构为：TO/HIL(50nm)/HTL(35nm)/发光层(20nm)/ETL(28nm)/LiQ(1nm)/Al(150nm)/阴极的OLED，(上述结构中“/”代表层叠)。其中，用实施例4化合物为ETL的材料。其余与测试例1相同。
测试例5
OLED的结构为：TO/HIL(50nm)/HTL(35nm)/发光层(20nm)/ETL(28nm)/LiQ(1nm)/Al(150nm)/阴极的OLED，(上述结构中“/”代表层叠)。其中，用实施例5化合物为ETL的材料。其余与测试例1相同。
测试例6
OLED的结构为：TO/HIL(50nm)/HTL(35nm)/发光层(20nm)/ETL(28nm)/LiQ(1nm)/Al(150nm)/阴极的OLED，(上述结构中“/”代表层叠)。其中，用实施例6化合物为ETL的材 料。其余与测试例1相同。
表2
  发光效率(cd/A) 寿命(T95,1000nits) 发光颜色
测试例1 6.2 4.00 蓝色
测试例2 6.5 3.75 蓝色
测试例3 6.0 3.45 蓝色
测试例4 5.7 3.125 蓝色
测试例5 5.3 2.75 蓝色
测试例6 3.6 1 蓝色
由表2可以看出，采用实施例1～5的化合物作为ETL的材料得到的OLED的色坐标(X<0.15，Y<0.10)均优于实施例6的化合物作为ETL的材料得到的OLED的色坐标。采用实施例1～5的化合物作为ETL的材料得到的OLED的发光效率均处于5.3cd/A～6.2cd/A，至少比实施例6的化合物作为ETL的材料得到的OLED的发光效率提高了47.2％，明显优于实施例6的化合物作为ETL的材料得到的OLED的发光效率，说明实施例1～5的化合物更有利于制备具有较高发光效率的电子器件。同时，采用实施例1～5的化合物作为ETL的材料得到的OLED在1000nits下的T95均为实施例6的2倍以上，说明实施例1～5的化合物更有利于制备具有较长寿命的电子器件。
综上所述，上述咔唑类化合物的结构使得该化合物具有较好的载流子传输、光电响应及能级匹配，进而该化合物的光电性能及稳定性均较好，最终使含有该化合物的电子器件具有更高的发光效率、更长的寿命以及更好的蓝色坐标。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (12)

  1. 一种咔唑类化合物，其特征在于，具有如下结构式：
    Figure PCTCN2017115309-appb-100001
    其中，Ar1为环原子数为13～60的稠芳基或环原子数为13～60的稠杂芳基；
    Ar2、Ar3为分别独立的选自碳原子数为6～60的芳基、碳原子数为3～60的杂芳基、碳原子数为7～60的稠芳基、碳原子数为4～60的稠杂芳基或上述基团中至少两个相互连接形成的组合基团中的一种，且所述Ar2、所述Ar3中至少一个包含具有N原子的杂芳基；
    R1独立选自H、D、F、CN、NO2、CF3、烯基、炔基、胺基、酰基、酰胺基、氰基、异氰基、烷氧基、羟基、羰基、砜基、碳原子数为1～60的烷基、碳原子数为3～60的环烷基、碳原子数为6～60的芳基、碳原子数为3～60的杂芳基、碳原子数为7～60的稠芳基、碳原子数为4～60的稠杂芳基及上述基团中至少两个相互连接形成的组合基团中的一种；
    n为0～20的整数；
    p及q分别独立选自0～4的整数中的一个，且p和q不同时为0。
  2. 根据权利要求1所述的咔唑类化合物，其特征在于，所述Ar1选自如下结构式中的一种：
    Figure PCTCN2017115309-appb-100002
    其中，X1为C-R2或N；
    Y1选自C-R3-R4、Si-R5-R6、N-R7、C(＝O)、S(＝O)2、O及S中的一种；
    所述-R2、所述-R3、所述-R4、所述-R5、所述-R6及所述-R7分别独立选自单键、H、D、F、CN、NO2、CF3、烯基、炔基、胺基、酰基、酰胺基、氰基、异氰基、烷氧基、羟基、羰基、砜基、碳原子数为1～60的烷基、碳原子数为3～60的环烷基、碳原子数为6～60的芳基、碳原子数为3～60的杂芳基、碳原子数为7～60的稠芳基、碳原子数为4～60的稠杂芳基及上述基团中至少两个相互连接形成的组合基团中的一种。
  3. 根据权利要求1～2任一项所述的咔唑类化合物，其特征在于，所述Ar1选自如下结构式中的一种：
    Figure PCTCN2017115309-appb-100003
  4. 根据权利要求1～3任一项所述的咔唑类化合物，其特征在于，所述具有N原子的杂芳基的结构式选自如下结构式中的一种：
    Figure PCTCN2017115309-appb-100004
    其中，X2为C-R8或N，
    Y2选自C-R9-R10、Si-R11-R12、N-R13、C(＝O)、S(＝O)2、O及S中的一种；
    所述-R8、所述-R9、所述-R10、所述-R11、所述-R12及所述-R13分别独立选自单键、H、D、F、CN、NO2、CF3、烯基、炔基、胺基、酰基、酰胺基、氰基、异氰基、烷氧基、羟基、羰基、砜基、碳原子数为1～60的烷基、碳原子数为3～60的环烷基、碳原子数为6～60的芳基、碳原子数为3～60的杂芳基、碳原子数为7～60的稠芳基、碳原子数为4～60的稠杂芳基及上述基团中至少两个相互连接形成的组合基团中的一种；
    所述具有N原子的杂芳基的结构式中至少有一个X2为N。
  5. 根据权利要求1～4任一项所述的咔唑类化合物，其特征在于，所述具有N原子的杂芳基的结构式选自如下结构式中的一种：
    Figure PCTCN2017115309-appb-100005
  6. 根据权利要求1所述的咔唑类化合物，其特征在于，所述咔唑类化合物的电子迁移率大于或等于10-5cm2·V-1·S-1；及/或，
    所述咔唑类化合物的玻璃化转变温度大于或等于100℃；及/或，
    所述咔唑类化合物的最低未占有轨道的能级小于或等于-2.7eV；及/或，
    所述咔唑类化合物的最高被占有轨道的能级小于或等于-5.6eV；及/或，
    所述咔唑类化合物的三线态能级大于或等于1.7eV；及/或，
    所述咔唑类化合物的摩尔质量小于或等于3000克/摩尔。
  7. 一种咔唑类聚合物，其特征在于，包括权利要求1～6任一项所述的咔唑类化合物形成的重复单元。
  8. 一种混合物，其特征在于，包含权利要求1～6任一项所述的咔唑类化合物或权利要求7所述的咔唑类聚合物及至少另外一种有机功能材料，所述有机功能材料选自空穴注入材料、空穴传输材料、电子注入材料、电子传输材料、空穴阻挡材料、电子阻挡材料、发光材料、有机基质材料或有机染料，其中，所述有机功能材料与权利要求1～6任一项所述的咔唑类化合物或权利要求7所述的咔唑类聚合物的质量比为0.01：99.9～50：50。
  9. 一种组合物，其特征在于，包含权利要求1～6任一项所述的咔唑类化合物、权利要求7所述的咔唑类聚合物及权利要求8所述的混合物中至少一种、有机溶剂，其中，所述有机溶剂与权利要求1～6任一项所述的咔唑类化合物、权利要求7所述的聚合物、权利要求8所述的混合物中的至少一种的质量比为70：30～99.7：0.3，所述有机溶剂选自芳香族溶剂、芳杂族溶剂、酯类溶剂、酮类溶剂及醚类溶剂中的至少一种。
  10. 一种电子器件，其特征在于，所述的电子器件包含功能层，所述功能层包括权利要求1～6任一项所述的咔唑类化合物、权利要求7所述的聚合物及权利要求8所述的混合物中的至少一种。
  11. 根据权利要求10所述的电子器件，其特征在于，所述电子器件为有机电致发光器件、有机光伏电池、有机发光电池、有机场效应管、有机发光场效应管，有机激光器、有机自旋电子器件、有机传感器或有机等离激元发射二极管。
  12. 根据权利要求10所述的电子器件，其特征在于，所述功能层为电子注入层、电子传输层或发光层。
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