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WO2018095392A1 - 有机混合物、组合物以及有机电子器件 - Google Patents

有机混合物、组合物以及有机电子器件 Download PDF

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Publication number
WO2018095392A1
WO2018095392A1 PCT/CN2017/112713 CN2017112713W WO2018095392A1 WO 2018095392 A1 WO2018095392 A1 WO 2018095392A1 CN 2017112713 W CN2017112713 W CN 2017112713W WO 2018095392 A1 WO2018095392 A1 WO 2018095392A1
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organic
group
organic compound
compound
aromatic
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French (fr)
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潘君友
何锐锋
谭甲辉
黄宏
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Guangzhou Chinaray Optoelectronic Materials Ltd
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Guangzhou Chinaray Optoelectronic Materials Ltd
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Application filed by Guangzhou Chinaray Optoelectronic Materials Ltd filed Critical Guangzhou Chinaray Optoelectronic Materials Ltd
Priority to US16/463,339 priority Critical patent/US20190378991A1/en
Priority to EP17874611.1A priority patent/EP3547385B1/en
Priority to CN201780059600.7A priority patent/CN109791993B/zh
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    • H—ELECTRICITY
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    • H10K85/60—Organic compounds having low molecular weight
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    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
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    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
    • C07D239/72—Quinazolines; Hydrogenated quinazolines
    • C07D239/74—Quinazolines; Hydrogenated quinazolines with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to ring carbon atoms of the hetero ring
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
    • C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
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    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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    • 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
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/30—Highest occupied molecular orbital [HOMO], lowest unoccupied molecular orbital [LUMO] or Fermi energy values
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    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present application relates to electronic devices, and in particular to an organic mixture, composition, and organic electronic device.
  • OLEDs Organic light-emitting diodes
  • An organic mixture comprising an organic compound H1 and an organic compound H2, 1) min ((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1)) ⁇ min(E T (H1), E T (H2)) + 0.1 eV, wherein LUMO (H1), HOMO (H1), and E T (H1) are the lowest unoccupied orbital, highest occupied orbital, and triplet energy levels of the organic compound H1, respectively, LUMO ( H2), HOMO(H2) and E T (H2) are the lowest unoccupied orbital, highest occupied orbital and triplet energy levels of the organic compound H2, respectively; 2) (LUMO+1)(H1)-LUMO(H1) ⁇ 0.1 eV, wherein (LUMO+1) (H1) is the second lowest unoccupied orbital level of the organic compound H1.
  • the organic compound H1 is a compound represented by the formula (1):
  • Ar 1 represents an H atom, an aromatic group having 5 to 90 ring atoms or an aromatic heterocyclic group having 5 to 90 ring atoms;
  • A is an electron-deficient group; and
  • n is an integer of 1 to 6; When n is greater than 1, a plurality of the electron-deficient groups are the same or different.
  • the electron deficient group is F or a cyano group, in which case Ar 1 is not a H atom; or the electron deficient group comprises a group formed by one or more of the following structures:
  • m is 1, 2 or 3;
  • X 1 -X 8 is selected from CR or N, and at least one is N;
  • R 1 , R 2 , R 3 and R 3 each independently represent an alkyl group, an alkoxy group, an amino group, an alkene group, an alkyne group, an aralkyl group, a heteroalkyl group, an aryl group or a heteroaryl group.
  • the organic compound H2 is a compound represented by the general formula (2):
  • Ar 2 represents an H atom, ring atoms having 5 to 90 aromatic ring atoms or a group having 5 to 90 aromatic group; D is an electron rich group; O is an integer of 1-6; when When o is greater than 1, a plurality of the electron-rich groups are the same or different.
  • the electron-rich group comprises a group formed by one or more of the following structures:
  • Y represents an aromatic group having 5 to 40 carbon atoms or an aromatic hetero group having 5 to 40 carbon atoms
  • R 3 , R 4 and R 5 each independently represent an alkyl group, Alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl or heteroaryl.
  • Ar 1 or Ar 2 comprises a group formed by one or more of the following structures:
  • n 1, 2 or 3.
  • the organic compound H1 is selected from one or more of the compounds represented by the following structural formula:
  • the organic compound H1 is selected from one or more of the following compounds:
  • the organic compound H2 is one or more of the compounds represented by the following general formulae (7) to (10):
  • L 1 each independently represents an aromatic group having 5 to 60 ring atoms or an aromatic hetero group having 5 to 60 ring atoms;
  • L 2 represents a single bond, an aromatic group having 5 to 30 ring atoms or an aromatic hetero group having 5 to 30 ring atoms;
  • Ar 5 to Ar 10 each independently represent an aromatic group having 5 to 20 ring atoms or an aromatic hetero group having 5 to 20 ring atoms;
  • o is an integer of 1-6.
  • the organic compound H2 is one or more of the following compounds:
  • the molar ratio of the organic compound H1 to the organic compound H2 is from 2:8 to 8:2.
  • the difference in molecular weight between the organic compound H1 and the organic compound H2 does not exceed 100 Dalton.
  • the difference in sublimation temperature between the organic compound H1 and the organic compound H2 does not exceed 30K.
  • the organic mixture further comprises a luminescent material selected from at least one of a fluorescent illuminant, a phosphorescent illuminant, and a TADF material.
  • a luminescent material selected from at least one of a fluorescent illuminant, a phosphorescent illuminant, and a TADF material.
  • a composition comprising the organic mixture and an organic solvent.
  • An organic electronic device comprising a functional layer comprising the organic mixture.
  • the organic electronic device is 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, an organic sensor or an organic plasma.
  • OLED organic light emitting diode
  • OLED organic photovoltaic cell
  • OEEC organic light emitting cell
  • OFET organic field effect transistor
  • OLED organic light emitting field effect transistor
  • the functional layer is a light-emitting layer.
  • the method for preparing the functional layer comprises:
  • the organic compound H1 and the organic compound H2 are uniformly mixed and deposited as a source; or
  • the organic compound H1 and the organic compound H2 are vapor-deposited as separate sources.
  • An organic mixture composed of an electron type compound and a hole type compound according to the present application as a host material, which is applied to an organic light emitting diode, can provide high luminous efficiency and device lifetime.
  • the possible reasons are as follows, but are not limited thereto.
  • the bipolar mixture has suitable HOMO and LUMO energy levels, which is beneficial to reduce the barrier of electron and hole injection, and easy to achieve balance of carrier transport, thereby reducing The illuminating voltage and roll-off effect of the OLED device; at the same time, the compound having electron transporting property in the mixture has a large (LUMO+1)-LUMO, so that the device is stable at work; and a singlet state is formed between the two host materials.
  • the energy transfer intermediate state of the exciplex with a small difference in triplet energy level can more fully utilize the energy of the exciton, thereby effectively improving the efficiency and lifetime of the device.
  • composition and the printing ink, or the ink have the same meaning, and they are interchangeable;
  • the host material, the matrix material, the Host or the Matrix material have the same meaning, and they are interchangeable;
  • the metal organic network Compounds, metal organic complexes, organometallic complexes have the same meaning and are interchangeable;
  • electron-rich groups have the same meaning as electron-donating groups, and electron-deficient groups have the same meaning as electron-withdrawing groups.
  • the application provides an organic mixture comprising an organic compound H1 and an organic compound H2, wherein 1) min((LUMO(H1)-HOMO(H2), LUMO(H2)-HOMO(H1)) ⁇ min(E T ( H1), E T (H2) ) + 0.1eV, wherein, LUMO (H1), HOMO ( H1) and E T (H1) are the lowest unoccupied molecular orbital of the organic compound H1, and the highest occupied molecular orbital energy level of the triplet , LUMO (H2), HOMO (H2) and E T (H2) are the lowest unoccupied orbital, highest occupied orbital and triplet energy levels of organic compound H2, respectively; 2) (LUMO+1)-LUMO of organic compound H1 ⁇ 0.1eV.
  • the organic compound H1 and the organic compound H2 may form a type II heterojunction structure.
  • the organic compound H1 comprises an electron deficient group.
  • min ((LUMO (H1) -HOMO (H2), LUMO (H2) -HOMO (H1)) ⁇ min (E T (H1), E T (H2));
  • the energy level structure of the organic material the triplet energy levels E T , HOMO, and LUMO play a key role.
  • the following is an introduction to the determination of these energy levels.
  • the HOMO and LUMO levels can be measured by photoelectric effect, such as XPS (X-ray photoelectron spectroscopy) and UPS (UV photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV).
  • photoelectric effect such as XPS (X-ray photoelectron spectroscopy) and UPS (UV photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV).
  • quantum chemical methods such as density functional theory (hereinafter referred to as DFT) have also become effective methods for calculating molecular orbital energy levels.
  • the triplet energy level E T of organic materials can be measured by low temperature time-resolved luminescence spectroscopy, or by quantum simulation calculations (eg by Time-dependent DFT), as by commercial software Gaussian 03W (Gaussian Inc.), specific simulation methods. See WO2011141110 or as described below in the examples.
  • the absolute values of HOMO, LUMO, E T depend on the measurement method or calculation method used. Even for the same method, different evaluation methods, such as starting point and peak point on the CV curve, can give different HOMO/ LUMO value. Therefore, reasonable and meaningful comparisons should be made using the same measurement method and the same evaluation method.
  • the values of HOMO, LUMO, and E T are simulations based on Time-dependent DFT, but do not affect the application of other measurement or calculation methods.
  • the organic compound H1 and the organic compound H2 are capable of forming an exciplex, wherein one possible benefit is that the excited state of the system will preferentially occupy the lowest excited composite excited state or facilitate the organic compound H1 or the organic compound H2.
  • the energy of the triplet excited state is transferred to the composite excited state, thereby increasing the concentration of the composite excited state in the OLED organic light-emitting layer.
  • the organic mixture can serve as a phosphorescent host material.
  • (HOMO-1) is defined as the second highest occupied orbital level
  • (HOMO-2) is the third highest occupied orbital level
  • (LUMO+1) is defined as the second lowest unoccupied orbital level
  • (LUMO+2) is the third lowest occupied orbital level, and so on.
  • min((LUMO H1 -HOMO H2 ), (LUMO H2 -HOMO H1 )) is less than or equal to the triplet excited state level of the organic compound H1 and the triplet excited state level of the organic compound H2.
  • the energy of the organic compound H1 to form a complex excited state with the organic compound H2 depends on min ((LUMO H1 - HOMO H2 ), (LUMO H2 - HOMO H1 )).
  • ⁇ ((LUMO+1)-LUMO) of the organic compound H1 is ⁇ 0.15 eV; in a more preferred embodiment, ⁇ ((LUMO+1)-LUMO) of the organic compound H1 ⁇ 0.2 eV; in a highly preferred embodiment, ⁇ ((LUMO+1)-LUMO) of the organic compound H1 ⁇ 0.3 eV; in a most preferred embodiment, ⁇ ((LUMO+1) of the organic compound H1 )-LUMO) ⁇ 0.4 eV.
  • At least one of the organic compound H1 and the organic compound H2 has ⁇ ((HOMO-(HOMO-1)) ⁇ 0.2 eV, preferably ⁇ 0.25 eV, more preferably ⁇ 0.3 eV, More preferably, it is ⁇ 0.35 eV, very preferably ⁇ 0.4 eV, preferably ⁇ 0.45 eV, wherein the compound ⁇ ((HOMO-(HOMO-1))) is large, which is favorable for the stability of hole transport.
  • the ⁇ of the organic compound H2 ((HOMO-(HOMO-1)) ⁇ 0.2 eV, preferably ⁇ 0.25 eV, more preferably ⁇ 0.3 eV, more preferably ⁇ 0.35 eV, Very good is ⁇ 0.4 eV, preferably ⁇ 0.45 eV.
  • the organic compound H2 is mainly in hole transport, and its hole transport stability is more important.
  • the organic compound H1 is at least one of the compounds represented by the general formula (1):
  • Ar 1 represents an H atom, an aromatic group having 5 to 90 ring atoms or an aromatic heterocyclic group having 5 to 90 ring atoms; and A is an electron deficient group;
  • n is an integer of 1-6; when n is greater than 1, the n electron-deficient groups A may be the same or different.
  • the electron-deficient group A described above may be selected from the group consisting of F and a cyano group, in which case, Ar 1 is not a hydrogen atom; or the electron-deficient group A may comprise a structure having the following groups:
  • m is 1, 2 or 3;
  • X 1 -X 8 is selected from CR or N, and at least one is N;
  • R 1 , R 2 , R 3 and R 3 each independently represent an alkyl group, an alkoxy group, an amino group, an alkene group, an alkyne group, an aralkyl group, a heteroalkyl group, an aryl group or a heteroaryl group.
  • R, R 1 and R 2 each independently represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aromatic group having 6 to 40 carbon atoms. a hydrocarbon group or an aromatic heterocyclic group having 3 to 40 carbon atoms; and in a more preferred embodiment, R, R 1 and R 2 each independently represent an alkyl group having 1 to 15 carbon atoms and 3 to 3 carbon atoms. a cycloalkyl group of 15 having 6 to 30 aromatic hydrocarbon groups or an aromatic heterocyclic group having 3 to 30 carbon atoms; and in a most preferred embodiment, R, R 1 and R 2 are each independently represented. An alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms or an aromatic heterocyclic group having 3 to 20 carbon atoms.
  • R, R 1 , and R 2 are each independently selected from the group consisting of methyl, isopropyl, t-butyl, isobutyl, hexyl, octyl, 2-ethylhexyl, benzene, and hydrazine.
  • the organic compound H1 according to the formula (1) of the present application is one or more of the following structural formulas:
  • the organic compound H2 is a compound of the formula (2):
  • Ar 2 represents an H atom, an aromatic group having a ring number of 5 to 90 or an aromatic group having 5 to 90 ring atoms; D is an electron-rich group; and o is an integer of 1 to 6. When o is greater than 1, the o electron-rich groups D may be the same or different.
  • the electron-rich group D described above may preferably be derived from a structure comprising any of the following groups:
  • Y represents an aromatic group having 5 to 40 carbon atoms or an aromatic hetero group having 5 to 40 carbon atoms
  • R 3 , R 4 and R 5 each independently represent an alkyl group, Alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl or heteroaryl.
  • the electron-rich group D is selected as one of the following formulas:
  • the electron-rich group D is selected as one of the following formulas:
  • R 3 and R 4 are as described above.
  • the organic compound H2 according to the formula (2) of the present application is one of the following structural formulas:
  • Ar 2 , Z 2 , Z 3 , Y have the meanings as described above or as follows.
  • Ar 1 represented by the formula (1) and Ar 2 represented by the formula (2) are an aromatic group having 6 to 70 ring atoms or 6 ring atoms.
  • An aromatic ring system or an aromatic group refers to a hydrocarbon group containing at least one aromatic ring, including a monocyclic group and a polycyclic ring system.
  • the aromatic heterocyclic or aromatic hetero group refers to a hydrocarbon group (containing a hetero atom) containing at least one aromatic heterocyclic ring, and includes a monocyclic group and a polycyclic ring system.
  • the heteroatoms are preferably selected from the group consisting of Si, N, P, O, S and/or Ge, particularly preferably selected from the group consisting of Si, N, P, O and/or S.
  • These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, a fused ring.
  • an aromatic or aromatic heterocyclic ring system includes not only a system of an aryl or a aryl group, but also a plurality of aryl or aryl groups may also be interrupted by short non-aromatic units ( ⁇ 10%).
  • Non-H atoms preferably less than 5% of non-H atoms, such as C, N or O atoms).
  • systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, etc., are also considered to be aromatic ring systems for the purposes of the present invention.
  • examples of the aromatic group are: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzopyrene, triphenylene, anthracene, anthracene, and derivatives thereof.
  • examples of the aromatic hetero group are: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, anthracene, anthracene Oxazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrol, furanfuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, Pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-diazine, quinoxaline, phenanthridine, carbaidine, quinazoline, quinazolinone, and derivatives thereof.
  • Ar 1 and Ar 2 are each independently: benzene, biphenyl, naphthalene, anthracene, phenanthrene, triphenylene, anthracene, pyridine, pyrimidine, triazine, anthracene, sulfonium, silicon germanium, a group such as carbazole, thiophene, furan, thiazole, triphenylamine, triphenylphosphine oxide, tetraphenyl silicon, snail, or samarium; more preferably benzene, biphenyl, naphthalene, anthracene, phenanthrene, benzo A group such as phenanthrenequinone or snail.
  • Ar 2 may comprise the following structural groups of one or more of a combination of:
  • X 1 -X 8 respectively represent CR 3 or N;
  • R 3 , R 4 , and R 5 are a hydrogen atom, a halogen atom, or a linear alkyl group, an alkoxy group or a thioalkoxy group having 1 to 20 C atoms, or have 3 to 20 C atoms.
  • a branched or cyclic alkyl, alkoxy or thioalkoxy group is either a silyl group, or a substituted keto group having from 1 to 20 C atoms, or from 2 to 20
  • Ar 1 or Ar 2 may be selected from structures comprising groups having the following groups:
  • n 1, 2 or 3.
  • the organic compound H1 is selected from at least one of the compounds represented by the general formulae (3) to (6):
  • Ar 3 and Ar 4 are each independently represented as an aromatic group or an aromatic heterocyclic group having 5 to 60 ring atoms; q is an integer of 1 to 6; and X 1 and X in the general formulae (3) to (6) 2 , X 3 , M 1 , M 2 , and M 3 have the same meanings as X 1 , X 2 , X 3 , M 1 , M 2 , and M 3 in the formula (1), and are not described herein again.
  • the organic compound H2 may be selected from at least one of the compounds represented by the following formula:
  • Each of Ar 5 to Ar 11 may be independently selected from the group consisting of a cyclic aromatic hydrocarbon compound such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalrene, phenanthrene, anthracene, anthracene, fluorene, anthracene, anthracene; Heterocyclic compounds such as dibenzothiophene, dibenzofuran, furan, thiophene, benzofuran, benzothiophene, oxazole, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, evil Triazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, acesulfazine, oxadiazine, hydrazine
  • the organic compound H2 may be selected from at least one of the compounds represented by the following general formulae (7) to (10):
  • L 1 independently represents an aromatic group having 5 to 60 ring atoms or an aromatic hetero group having 5 to 60 ring atoms;
  • L 2 represents a single bond, an aromatic group having 5 to 30 ring atoms or an aromatic heterocyclic group having 5 to 30 ring atoms, and the linking position of L 2 may be any carbon atom on the ring;
  • Ar 5 to Ar 10 each independently represent an aromatic group having 5 to 20 ring atoms or an aromatic hetero group having 5 to 20 ring atoms;
  • Z 1 , Z 2 , Z 3 are as defined above;
  • Z 4 to Z 9 are defined as Z 2 , but Z 4 and Z 5 are not a single bond at the same time, and Z 6 and Z 7 are not a single bond at the same time, Z 8 When it is different from Z 9 , it is a single bond;
  • o is an integer from 1 to 6; when o is greater than 1, the o electron-rich groups may be the same or different.
  • organic mixture according to the invention wherein H2 is selected from one of the following structural formulae:
  • organic mixture according to the invention wherein the organic compound H2 is selected from one of the following structural formulae:
  • organic mixture according to the invention wherein the organic compound H2 is selected from one of the following structural formulae:
  • organic mixture according to the invention wherein the organic compound H2 is selected from one of the following structural formulae:
  • Ar 6 , Ar 7 , Ar 8 , Ar 9 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 , Z 7 , Z 8 , Z 9 , R 6 and R 7 have the same meanings as described above.
  • organic compound H1 represented by the general formula (1) and the general formulae (3) to (6) of the present application are exemplified below, but are not limited to:
  • organic compound H2 represented by the general formula (2) and the general formulae (7) to (10) are exemplified below, but are not limited to:
  • the molar ratio of the organic compound H1 to the organic compound H2 is from 2:8 to 8:2; the preferred molar ratio is from 3:7 to 7:3; a more preferred molar ratio is 4:6. To 6:4.
  • the difference in molecular weight between the organic compound H1 and the organic compound H2 does not exceed 100 Dalton; the difference in preferred molecular weight does not exceed 60 Dalton; the more preferred molecular weight does not differ by more than 30 Dalton.
  • the difference in molecular weight between the organic compound H1 and the organic compound H2 is small, which is advantageous for the proportional stability of the two materials when they are prepared into an electronic device.
  • the difference in sublimation temperatures of the organic compound H1 and the organic compound H2 does not exceed 30 K; the difference in preferred sublimation temperatures does not exceed 20 K; more preferably, the difference in sublimation temperature does not exceed 10K.
  • the difference in sublimation temperature between the organic compound H1 and the organic compound H2 is small, which is advantageous for the proportional stability of the two materials in the preparation of the vapor-deposited electronic device.
  • the organic compound H1 and the organic compound H2 are a small molecule material.
  • the organic mixture according to the present application is used in an evaporative OLED device.
  • the molecular weight of the organic compound H1 and the organic compound H2 is ⁇ 1000 mol/kg, preferably ⁇ 900 mol/kg, very preferably ⁇ 850 mol/kg, more preferably ⁇ 800 mol/kg, most preferably ⁇ 700 mol/kg.
  • small molecule refers to a molecule that is not a polymer, oligomer, dendrimer, or blend. In particular, there are no repeating structures in small molecules.
  • the molecular weight of the small molecule is ⁇ 3000 g/mol, preferably ⁇ 2000 g/mol, preferably ⁇ 1500 g/mol.
  • the polymer that is, the polymer, includes a homopolymer, a copolymer, and a block copolymer. Also in the present application, the high polymer also includes a dendrimer.
  • a dendrimer For the synthesis and application of the tree, see [Dendrimers and Dendrons, Wiley-VCH Verlag GmbH & Co. KGaA, 2002, Ed. George R. Newkome, Charles N. Moorefield, Fritz Vogtle.].
  • the conjugated polymer is a high polymer, and its backbone backbone is mainly composed of sp2 hybrid orbitals of C atoms.
  • Famous examples are: polyacetylene polyacetylene and poly(phenylene vinylene), the main chain thereof.
  • the C atom on it can also be replaced by other non-C atoms, and when the sp2 hybrid on the main chain is interrupted by some natural defects, it is still considered to be a conjugated polymer.
  • the conjugated high polymer also includes an aryl amine, an aryl phosphine and other heteroarmotics, and an organometallic complexes in the main chain. )Wait.
  • the application also relates to a mixture comprising the organic mixture, and at least one other organic functional material.
  • the organic functional materials include holes (also called holes) injection or transport materials (HIM/HTM), hole blocking materials (HBM), electron injecting or transporting materials (EIM/ETM), electron blocking materials (EBM), At least one of an organic host material (Host), a singlet illuminant (fluorescent illuminant), a heavy illuminator (phosphorescent illuminant), and an organic thermal excitation delayed fluorescent material (TADF material), particularly a luminescent organic metal complexkind.
  • holes also called holes injection or transport materials
  • HBM hole blocking materials
  • EIM/ETM electron injecting or transporting materials
  • EBM electron blocking materials
  • At least one of an organic host material (Host) a singlet illuminant (fluorescent illuminant), a heavy illuminator (phosphorescent illuminant), and an organic thermal excitation delayed fluorescent material (TADF material), particularly
  • organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1, and WO 2011110277A1, the entire contents of which are hereby incorporated by reference.
  • the organic functional material may be a small molecule and a high polymer material.
  • the organic functional material is a luminescent material selected from a fluorescent illuminant, a phosphorescent illuminant, or a TADF material.
  • the mixture comprises the organic mixture and a phosphorescent emitter.
  • the organic The mixture may be used as a host, wherein the phosphorescent emitter is ⁇ 30% by weight, preferably ⁇ 25% by weight, more preferably ⁇ 20% by weight.
  • the mixture comprises the organic mixture and a fluorescent illuminant.
  • the organic mixture may be used as a fluorescent host material, wherein the fluorescent illuminant is ⁇ 15% by weight, preferably ⁇ 10% by weight, more preferably ⁇ 8% by weight.
  • the mixture comprises the organic mixture and a fluorescent host material.
  • the organic mixture may be used as a fluorescent luminescent material in a weight percentage of ⁇ 15% by weight, preferably ⁇ 10% by weight, more preferably ⁇ 8% by weight.
  • the mixture comprises the organic mixture, a phosphorescent emitter, and a host material.
  • the organic mixture may act as an auxiliary luminescent material having a weight ratio to the phosphorescent emitter of from 1:2 to 2:1.
  • the excimer complex of the organic mixture has an energy level higher than that of the phosphorescent emitter.
  • the mixture comprises the organic mixture and a TADF material.
  • the organic mixture may be used as the TADF host material, wherein the weight percent of the TADF material is ⁇ 15 wt%, preferably ⁇ 10 wt%, more preferably ⁇ 8 wt%.
  • the fluorescent luminescent material or singlet illuminant, phosphorescent or triplet illuminant 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.
  • 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 in a fused ring system, and preferably has at least 14 aromatic ring atoms.
  • Preferred examples thereof are aromatic decylamine, aromatic quinone diamine, aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine.
  • aromatic amide refers to a compound in which a diaryl arylamine group is attached directly to the oxime, preferably at the position of 9.
  • 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.
  • Aromatic guanamine, aromatic guanidine diamine, The definitions of aromatic arylamine and aromatic quinone diamine are similar, wherein the diaryl arylamine group is preferably bonded to the 1 or 1,6 position of hydrazine.
  • 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, spirobifluorene, aryl hydrazine (such as US20060222886), arylene vinyl (such as US5121029, US5130603), cyclopentane Alkene such as tetraphenylcyclopentadiene, rub
  • 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 ( ⁇ E st ), and triplet excitons can be converted into singlet exciton luminescence by inter-system 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%.
  • the TADF material needs to have a small singlet-triplet energy level difference, typically ⁇ E st ⁇ 0.3eV, preferably ⁇ E st ⁇ 0.2eV, more preferably ⁇ E st ⁇ 0.1eV, and most preferably ⁇ E st ⁇ 0.05eV.
  • TADF has better fluorescence quantum efficiency.
  • TADF luminescent 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:
  • Triplet emitters are also known as phosphorescent emitters.
  • the triplet emitter is a metal complex of the formula M(L) n , wherein M is a metal atom, and each occurrence of L may be the same or different and is an organic ligand. It is bonded to the metal atom M by one or more positional bonding or coordination, and n is an integer greater than 1, preferably 1, 2, 3, 4, 5 or 6.
  • these metal complexes are coupled to a polymer by one or more positions, preferably by an organic ligand.
  • the metal atom M is selected from a transition metal element or a lanthanide or a lanthanide element, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu or Ag, particularly preferably Os, Ir, Ru, Rh, Re, Pd or Pt.
  • the triplet emitter comprises a chelating ligand, ie a ligand, coordinated to the metal by at least two bonding sites, it is particularly preferred to consider that the triplet emitter comprises two or three identical or different pairs Tooth or multidentate ligand. Chelating ligands are beneficial for increasing the stability of metal complexes.
  • Examples of the organic ligand may be selected from a phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2(2-thienyl)pyridine derivative, a 2(1-naphthyl)pyridine derivative, or a 2 benzene.
  • a quinolinol derivative All of these organic ligands may be substituted, for example by fluorine or trifluoromethyl.
  • the ancillary ligand may preferably be derived from acetone acetate or picric acid.
  • the metal complex that can be used as the triplet emitter has the following form:
  • M 1 is a metal selected from transition metal elements or lanthanides or actinides
  • Ar 1 may be the same or different at each occurrence, and is a cyclic group containing at least one donor atom, that is, an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which a cyclic group is coordinated to a metal.
  • Ar 2 may be the same or different each time it appears, is a cyclic group containing at least one C atom through which a cyclic group is attached to the metal; Ar 1 and Ar 2 are bonded by a covalent bond Together, each may carry one or more substituent groups which may also be joined together by a substituent group; each occurrence of L may be the same or different and is an ancillary ligand, preferably a bidentate chelate ligand Preferred is a monoanionic bidentate chelate ligand; b is 1, 2 or 3, preferably 2 or 3, particularly preferably 3; a is 0, 1, or 2, preferably 0 or 1, Particularly preferably 0;
  • triplet emitters Some examples of suitable triplet emitters are listed in the table below:
  • Another object of the present application is to provide a material solution for printing OLEDs.
  • At least one of the organic compound H1 and the organic compound H2 has a molecular weight of ⁇ 700 mol/kg, preferably ⁇ 900 mol/kg, very preferably ⁇ 900 mol/kg, more preferably ⁇ 1000 mol/kg, most preferably ⁇ 1100 mol/kg.
  • the solubility of the organic mixture in toluene is > 10 mg/ml, preferably > 15 mg/ml, and most preferably > 20 mg/ml at 25 °C.
  • the application still further relates to a composition or ink comprising an organic mixture as described above and at least one organic solvent.
  • 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 application has a surface tension at an operating temperature or at 25 ° C in the range of from about 19 dyne/cm to 50 dyne/cm; more preferably in the range of from 22 dyne/cm to 35 dyne/cm; It is in the range of 25dyne/cm to 33dyne/cm.
  • the viscosity of the ink according to the present application at an operating temperature or 25 ° C is in the range of about 1 cps to 100 cps; preferably in the range of 1 cps to 50 cps; more preferably in the range of 1.5 cps to 20 cps; Good is in the range of 4.0cps to 20cps.
  • the composition so formulated will facilitate 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 metal organic complex or polymer according to the present application can facilitate the adjustment of the printing ink in an appropriate range according to the printing method used.
  • the composition according to the present application comprises a functional material in a weight ratio ranging from 0.3% to 30% by weight, preferably from 0.5% to 20% by weight, more preferably from 0.5% to 15% by weight, even more preferably. It is in the range of 0.5% to 10% by weight, preferably in the range of 1% to 5% by weight.
  • the at least one organic solvent is selected from aromatic or heteroaromatic based solvents, particularly aliphatic chain/ring substituted aromatic solvents, or aromatic ketones. Solvent, or aromatic ether solvent.
  • organic solvents suitable for the present application 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-fluorenone, 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, tetrahydronaphthalene , decalin, hydrazine and/or mixtures thereof.
  • the composition according to the present application is a solution.
  • composition according to the present application is a suspension.
  • composition in the examples of the present application may comprise from 0.01 to 20% by weight of the organic mixture according to the present application, preferably from 0.1 to 15% by weight, more preferably from 0.2 to 10% by weight, most preferably from 0.25 to 5% by weight.
  • Organic mixture preferably from 0.01 to 20% by weight of the organic mixture according to the present application, preferably from 0.1 to 15% by weight, more preferably from 0.2 to 10% by weight, most preferably from 0.25 to 5% by weight.
  • the present application also relates to the use of the composition as a coating or printing 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, Nozzle Printing, typography, screen printing, dip coating, spin coating, blade coating, roller printing, torsion rolls. Printing, lithography, flexographic printing, rotary printing, spraying, brushing or pad printing, slit-type extrusion coating, etc. Preferred are gravure, inkjet and inkjet printing.
  • the solution or suspension may additionally comprise 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.
  • the present application also provides an application of the organic mixture as described above, that is, the organic mixture is applied to an organic electronic device, which may be selected from, but not limited to, an organic light emitting diode (OLED). ), organic photovoltaic cells (OPV), organic light-emitting cells (OLEEC), organic field effect transistors (OFETs), organic light-emitting field effect transistors, organic lasers, organic spintronic devices, organic sensors and organic plasmon emitting diodes ( Organic Plasmon Emitting Diode), etc., especially OLED.
  • OLED organic light emitting diode
  • OLED organic photovoltaic cells
  • OLED organic light-emitting cells
  • OFETs organic field effect transistors
  • organic light-emitting field effect transistors organic lasers
  • organic spintronic devices organic spintronic devices
  • organic sensors and organic plasmon emitting diodes Organic Plasmon Emitting Diode
  • the application further relates to an organic electronic device comprising at least one organic mixture as described above.
  • the 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 organic mixture 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 Lasers, organic spintronic devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diode), etc., particularly preferred are organic electroluminescent devices such as OLED, OLEEC, organic light-emitting field effect transistors.
  • the organic electroluminescent device has an emissive layer comprising one of said organic mixtures, or comprises one of said organic mixture and a phosphorescent emitter, or comprises a The organic mixture and a host material, or comprise one of the organic mixtures, a phosphorescent emitter and a host material.
  • a substrate an anode, at least one light-emitting layer, and a cathode are included.
  • 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.
  • the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice.
  • the substrate is flexible, optionally in the form of a polymer film or plastic, having a glass transition temperature Tg of 150 ° C or higher, preferably more than 200 ° C, more preferably more than 250 ° C, preferably More than 300 ° C. Examples of suitable flexible substrates are poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).
  • PET poly(ethylene terephthalate)
  • PEN polyethylene glycol (2,6-na
  • 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 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV.
  • anode material examples include, but are 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 application.
  • the cathode can include a conductive metal or metal oxide.
  • the cathode can easily inject electrons into the EIL or ETL or directly into the 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
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • the absolute value of the difference in conduction band energy levels is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV.
  • all materials which can be used as cathodes for OLEDs are possible as cathode materials for the devices of the present application.
  • cathode material examples include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF 2 /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.
  • 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 light-emitting layer thereof contains the mixture according to the present application.
  • the luminescent layer can be prepared preferentially by a method comprising the following two steps:
  • a mixture containing H1 and H2 is deposited as a source. This can be prepared by printing using the composition according to the present application, or by vacuum evaporation of the mixture as a source.
  • H1 and H2 are deposited as separate sources.
  • the light-emitting device has an emission wavelength of between 300 and 1000 nm, preferably between 350 and 900 nm, more preferably between 400 and 800 nm.
  • the present application also relates to the use of electroluminescent devices according to the present application in various electronic devices, including, but not limited to, display devices, illumination devices, light sources, sensors, and the like.
  • Comparative Example Ref-4 For the synthesis of Comparative Example Ref-4, please refer to prior art patent WO 2015041428.
  • the energy level of the organic material can be obtained by quantum calculation, for example, by TD-DFT (time-dependent density functional theory) by Gaussian 03W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110.
  • TD-DFT time-dependent density functional theory
  • Gaussian 03W Gaussian Inc.
  • the specific simulation method can be found in WO2011141110.
  • the semi-empirical method “Ground State/Semi-empirical/Default Spin/AM1" (Charge 0/Spin Singlet) is used to optimize the molecular geometry, and then the energy structure of the organic molecule is determined by TD-DFT (time-dependent density functional theory) method.
  • 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 formula, and S1 and T1 are used directly.
  • HOMO(eV) ((HOMO(G) ⁇ 27.212)-0.9899)/1.1206
  • HOMO(G) and LUMO(G) are direct calculation results of Gaussian 03W, and the unit is Hartree.
  • the results are shown in Table 1:
  • HATCN, SFNFB, Ir(p-ppy) 3 , NaTzF 2 , Liq are all commercially available, such as Jilin Elound (Jilin OLED Material Tech Co., Ltd, www.jl-oled.com), or The synthesis methods are all known in the prior art. For details, refer to the references in the prior art, and details are not described herein again.
  • the preparation process using the above OLED device will be described in detail below by way of specific embodiments.
  • the structure of the OLED device (such as Table 2) is: ITO/HATCN/SFNFB/host material: Ir(p-ppy) 3 (10%)/NaTzF 2 : Liq/Liq/Al, the preparation steps are as follows:
  • ITO indium tin oxide
  • a conductive glass substrate cleaning using a variety of solvents (such as one or several of chloroform, acetone or isopropanol) cleaning, and then UV ozone treatment;
  • HATCN (30nm), SNFFB (50nm), host material: 10% Ir(p-ppy) 3 (40nm), NaTzF 2 : Liq (30nm), Liq (1nm), Al (100nm) in high vacuum (1 ⁇ 10 -6 mbar) formed by thermal evaporation;
  • the device is encapsulated in a nitrogen glove box with an ultraviolet curable resin.
  • the main material can be produced in three forms:
  • J-V current-voltage
  • the lifetimes of the OLED 11 and the OLED 12 are significantly lower than those of the OLED 7 and the OLED 8, and it can be seen that an OLED device prepared by simultaneously satisfying the organic mixture of the conditions 1) and 2), Its life expectancy has been greatly improved.
  • the organic compound H1 and the organic compound H2 of the present application facilitate formation of an exciplex and have balanced charge transport properties, and the organic compound H1 has high stability to electron transport, thereby effectively improving correlation
  • the efficiency and longevity of electronic devices provide an effective solution for improving the overall performance of electronic devices.

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Abstract

本申请公开一种有机混合物，包括有机化合物H1和有机化合物H2，其中所述有机化合物H1具有电子传输性能，所述有机化合物H1的Δ((LUMO+1)-LUMO)≥0.1eV，且min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(ET(H1),ET(H2))。所述有机化合物H1和所述有机化合物H2便于形成激基复合物，且具有平衡的电荷传输性质，所述有机化合物H1具有较高的对电子传输的稳定性，因而可有效提高相关电子器件的效率和寿命，为提高电子器件的整体性能提供一种行之有效的方案。

Description

有机混合物、组合物以及有机电子器件
相关申请
本申请要求2016年11月23日申请的，申请号为201611046904.3，名称为“一种有机混合物及其在有机电子器件中的应用”的中国专利申请的优先权，在此将其全文引入作为参考。
技术领域
本申请涉及电子器件，具体涉及一种有机混合物、组合物以及有机电子器件。
背景技术
有机发光二极管(OLED)具有质轻、主动发光、视角广、对比度高、发光效率高、能耗低、易制备柔性和大尺寸面板等，被业界视为最有希望的下一代的显示技术。
为了推进有机发光二极管大范围产业化进程，进一步提高有机发光二极管的发光性能和寿命是目前的急需解决的关键问题，高性能的有机光电材料体系仍需进一步的开发。
要获得高效长寿命的发光二极管，主体材料是关键。使用磷光材料的有机发光二极管可以取得几乎100％的内部电致发光量子效率,因此成为目前业界的主流材料体系,特别是红绿光。但磷光OLED,由于器件中电荷不平衡等原因,存在一显著的问题，就是Roll-off效应(滚降效应)，即发光效率随电流或电压的增加而迅速降低，这对高亮度的应用尤为不利。为了解决这个问题，Kim等(参见Kim等Adv.Func.Mater.2013 DOI:10.1002/adfm.201300547,及Kim等Adv.Func.Mater.2013，DOI:10.1002/adfm.201300187)通过利用能形成复合受激态(exciplex)的共主体(Co-host)，另加一金属配合物作为磷光发光体，实现了低Roll-off、很高效率的OLEDs。
但这类含有共主体的OLED器件的寿命尚需大幅提高。人们到目前为止还不清楚如何去设计，搭配两个不同的主体，以实现高性能的OLED。
发明内容
鉴于上述现有技术的不足，本申请的目的在于提供一种有机混合物，为共主体的OLED器件的材料提供有效的技术选项，并指明一种共主体的设计方法。
本发明的技术方案如下：
一种有机混合物，包括有机化合物H1和有机化合物H2，1)min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(ET(H1),ET(H2))+0.1eV，其中，LUMO(H1)、HOMO(H1)及ET(H1)分别是所述有机化合物H1的最低未占有轨道、最高占有轨道及三线态的能级，LUMO(H2)、HOMO(H2)及ET(H2)分别是所述有机化合物H2的最低未占有轨道、最高占有轨道及三线态的能 级；2)(LUMO+1)(H1)-LUMO(H1)≥0.1eV，其中，(LUMO+1)(H1)是所述有机化合物H1的第二低的未占有轨道的能级。
优选地，(LUMO+1)(H1)-LUMO(H1)≥0.15eV。
优选地，所述有机化合物H1为如通式(1)所示的化合物：
Figure PCTCN2017112713-appb-000001
其中，Ar1表示为H原子、环原子数为5～90的芳香基团或环原子数为5～90的芳杂基团；A为缺电子基团；n为一个1-6的整数；当n大于1时，多个所述缺电子基团相同或不同。
优选地，所述缺电子基团为F或氰基，此时Ar1不为H原子；或所述缺电子基团包含有如下一种或多种结构形成的基团：
Figure PCTCN2017112713-appb-000002
其中，m为1、2或3；X1-X8选于CR或N，并且至少有一个是N；M1、M2、M3分别独立表示N(R)、C(R)2、Si(R)2、O、C＝N(R)、C＝C(R)2、P(R)、P(＝O)R、S、S＝O、SO2或无；其中R1、R2、R3、R3分别独立表示烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基或杂芳基。
优选地，所述有机化合物H2为如通式(2)所示的化合物：
Figure PCTCN2017112713-appb-000003
其中，Ar2表示为H原子、环原子数为5～90的芳香基团或环原子数为5～90的芳香基团；D为富电子基团；o为一个1-6的整数；当o大于1时，多个所述富电子基团相同或不相同。
优选地，所述富电子基团包含有如下一种或多种结构形成的基团：
Figure PCTCN2017112713-appb-000004
其中，Y表示碳原子数为5～40的芳香基团或碳原子数为5～40的芳杂基团；Z1、Z2、Z3分 别独立地表示单键、N(R)、C(R)2、Si(R)2、O、S、C＝N(R)、C＝C(R)2或P(R)；R3、R4、R5分别独立地表示烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基或杂芳基。
优选地，Ar1或Ar2包含有如下一种或多种结构形成的基团：
Figure PCTCN2017112713-appb-000005
其中，m为1、2或3。
优选地，所述有机化合物H1选自如下结构式所代表的化合物中的一种或多种：
Figure PCTCN2017112713-appb-000006
其中，Ar3和Ar4分别独立地为环原子数为5～60的芳香基团或环原子数为5～60的芳杂基团；q为一个1-6的整数；X1、X2、X3分别独立地为CR或N，并且至少有一个是N；M1、M2、M3分别独立表示N(R)、C(R)2、Si(R)2、O、C＝N(R)、C＝C(R)2、P(R)、P(＝O)R、S、S＝O、SO2或无；其中R表示烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基或杂芳基。
优选地，所述有机化合物H1选自下列化合物中的一种或多种：
Figure PCTCN2017112713-appb-000007
优选地，所述有机化合物H2为如下通式(7)～(10)所表示的化合物中的一种或多种：
Figure PCTCN2017112713-appb-000008
Figure PCTCN2017112713-appb-000009
其中，L1分别独立地表示环原子为5～60的芳香基团或环原子为5～60的芳杂基团；
L2表示单键、环原子数为5～30的芳香基团或环原子数为5～30的芳杂基团；
Ar5～Ar10分别独立地表示环原子数为5～20的芳香基团或环原子数为5～20的芳杂基团；
Z1～Z9分别独立表示CH2、N(R)、C(R)2、Si(R)2、O、S、C＝N(R)、C＝C(R)2或P(R)，且Z4和Z5不同时为单键，Z6和Z7不同时为单键，Z8和Z9不同时为单键；
o为一个1-6的整数。
优选地，所述有机化合物H2为下列化合中的一种或多种：
Figure PCTCN2017112713-appb-000010
优选地，所述有机化合物H1和所述有机化合物H2的摩尔比为从2：8到8：2。
优选地，所述有机化合物H1和所述有机化合物H2的分子量的差不超过100Dalton。
优选地，所述有机化合物H1和所述有机化合物H2的升华温度的差不超过30K。
优选地，所述有机混合物进一步包含发光材料，所述发光材料选于荧光发光体、磷光发光体和TADF材料中的至少一种。
一种组合物，包括所述有机混合物以及有机溶剂。
一种有机电子器件，包括功能层，所述功能层包括所述有机混合物。
优选地，所述有机电子器件为有机发光二极管(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、有机传感器或有机等离激元发射二极管(Organic Plasmon Emitting Diode)。
优选地，所述功能层为发光层。
优选地，所述功能层的制备方法包括：
所述有机化合物H1和所述有机化合物H2混合均匀后作为一个源进行沉积；或者
所述有机化合物H1和所述有机化合物H2作为单独的两个源进行蒸镀。
有益效果：按照本申请的由电子型化合物和空穴型化合物组成的有机混合物作为主体材料，应用到有机发光二极管中，能提供较高的发光效率和器件寿命。其可能的原因如下，但不限于此，该类双极性混合物有比较合适的HOMO和LUMO能级，有利于降低电子和空穴注入的势垒，易于实现载流子传输的平衡，从而降低OLED器件的启亮电压和滚降效应；同时混合物中具有电子传输特性的化合物具有较大的(LUMO+1)-LUMO，使器件在工作是比较稳定；且两种主体材料之间形成单线态和三线态能级差较小的激基复合物能量传输中间态，能更充分地利用激子的能量，从而有效提高器件的效率和寿命。
具体实施方式
为使本申请的目的、技术方案和优点更加清楚，下面将结合附图对本申请实施方式作进一步地详细描述。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
在本申请中，组合物和印刷油墨，或油墨具有相同的含义，它们之间可以互换；主体材料，基质材料，Host或Matrix材料具有相同的含义，它们之间可以互换；金属有机络合物，金属有机配合物，有机金属配合物具有相同的含义，可以互换；富电子基团与供电子基团具有相同的含义，缺电子基团与吸电子基团具有相同的含义。
本申请提供一种有机混合物，包括有机化合物H1和有机化合物H2，其中，1)min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(ET(H1),ET(H2))+0.1eV，其中，LUMO(H1)、HOMO(H1)及ET(H1)分别是有机化合物H1的最低未占有轨道、最高占有轨道及三线态的能级，LUMO(H2)、HOMO(H2)及ET(H2)分别是有机化合物H2的最低未占有轨道、最高占有轨道及三线态的能级；2)有机化合物H1的(LUMO+1)-LUMO≥0.1eV。
在某些优先的实施方案中，有机化合物H1和有机化合物H2可以形成II型异质结结构。
在某些较为优先的实施方案中，有机化合物H1包含有缺电子基团。
在一个优先的实施例中，min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(ET(H1),ET(H2))；
在一个较为优先的实施例中，min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(ET(H1),ET(H2))-0.05eV；
在一个更为优先的实施例中，min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(ET(H1),ET(H2))-0.1eV；
在一个非常优先的实施例中，min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(ET(H1),ET(H2))-0.15eV；
在一个最为优先的实施例中，min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(ET(H1),ET(H2))-0.2eV；
在本申请中，有机材料的能级结构三线态能级ET、HOMO、LUMO起着关键的作用。以下对这些能级的确定做一介绍。
HOMO和LUMO能级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)或通过循环伏安法(以下简称CV)。最近，量子化学方法，例如密度泛函理论(以下简称DFT)，也成为行之有效的计算分子轨道能级的方法。
有机材料的三线态能级ET可通过低温时间分辨发光光谱来测量，或通过量子模拟计算(如通过Time-dependent DFT)得到，如通过商业软件Gaussian 03W(Gaussian Inc.)，具体的模拟方法可参见WO2011141110或如下在实施例中所述。
应该注意，HOMO、LUMO、ET的绝对值取决于所用的测量方法或计算方法，甚至对于相同的方法，不同评价的方法，例如在CV曲线上起始点和峰点可给出不同的HOMO/LUMO值。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。本申请实施例的描述中，HOMO、LUMO、ET的值是基于Time-dependent DFT的模拟，但不影响其他测量或计算方法的应用。
在本申请中，有机化合物H1和有机化合物H2能够形成激基复合物，其中，一个可能的好处是系统的激发态将优先占据能量最低的复合受激态或便于有机化合物H1或有机化合物H2上的三重激发态的能量向复合受激态转移，从而提高OLED有机发光层中复合受激态的浓度。
在一个优选的实施例中，所述有机混合物可作为磷光主体材料。
在本申请中，(HOMO-1)定义为第二高的占有轨道能级，(HOMO-2)为第三高的占有轨道能级，以此类推。(LUMO+1)定义为第二低的未占有轨道能级，(LUMO+2)为第三低的占有轨道能级，以此类推。
在本申请中，min((LUMOH1-HOMOH2)，(LUMOH2-HOMOH1))小于或等于有机化合物H1的三重激发态能级及有机化合物H2的三重激发态能级。有机化合物H1与有机化合物H2形成复合受激态的能量取决于min((LUMOH1-HOMOH2)，(LUMOH2-HOMOH1))。
在另一些优选的实施方案中，有机化合物H1的Δ((LUMO+1)-LUMO)≥0.15eV；在一个更加优选的实施方案中，有机化合物H1的Δ((LUMO+1)-LUMO)≥0.2eV；在一个非常优选的实施方案中，有机化合物H1的Δ((LUMO+1)-LUMO)≥0.3eV；在一个最优选的实施方案中，有机化合物H1的Δ((LUMO+1)-LUMO)≥0.4eV。
在某些优先的实施例中，有机化合物H1和有机化合物H2中至少有一个其Δ((HOMO-(HOMO-1))≥0.2eV，较好是≥0.25eV，更好是≥0.3eV，更更好是≥0.35eV，非常好是≥0.4eV，最好是≥0.45eV。其中，化合物的Δ((HOMO-(HOMO-1))较大，有利于空穴传输的稳定性。
在一个较为优先的实施例中，有机化合物H2的Δ((HOMO-(HOMO-1))≥0.2eV，较好是≥0.25eV，更好是≥0.3eV，更更好是≥0.35eV，非常好是≥0.4eV，最好是≥0.45eV。其中，在混合物中，有机化合物H2在空穴传输方面为主，其空穴传输稳定性更为重要。
在某些优选的实施方案中，有机化合物H1为如通式(1)所示的化合物中的至少一种：
Figure PCTCN2017112713-appb-000011
其中，Ar1表示为H原子、环原子数为5～90的芳香基团或环原子数为5～90的芳杂基团；A为缺电子基团；
n为一个1-6的整数；当n大于1时，n个缺电子基团A可以相同，也可以不相同。
在某些优选的实施方案中，上述的缺电子基团A可选自F和氰基，此时，Ar1不是氢原子；或所述缺电子基团A可包含有如下基团的结构：
Figure PCTCN2017112713-appb-000012
其中，m为1、2或3；X1-X8选于CR或N，并且至少有一个是N；M1、M2、M3分别独立表示N(R)、C(R)2、Si(R)2、O、C＝N(R)、C＝C(R)2、P(R)、P(＝O)R、S、S＝O、SO2或无；其中R1、 R2、R3、R3分别独立表示烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基或杂芳基。
在某些优选的实施例中，R、R1、R2分别独立地表示碳原子数1～20的烷基、碳原子数3～20的环烷基、碳原子数为6～40芳香族烃基或碳原子数为3～40的芳香族杂环基；在更加优选的实施例中，R、R1、R2分别独立地表示碳原子数1～15的烷基、碳原子数3～15的环烷基、碳原子数为6～30芳香族烃基或碳原子数为3～30的芳香族杂环基；在最为优选的实施例中，R、R1、R2分别独立地表示碳原子数1～10的烷基、碳原子数3～10的环烷基、碳原子数为6～20芳香族烃基或碳原子数为3～20的芳香族杂环基。
在一个优选的实施方案中，R、R1、R2分别独立地选自：甲基、异丙基、叔丁基、异丁基、己基、辛基、2-乙基己基、苯、联苯、萘、蒽、菲、苯并菲、芘、吡啶、嘧啶、三嗪、芴、硫芴、硅芴、咔唑、噻吩、呋喃、噻唑、三苯胺、三苯基氧磷，四苯基硅、螺芴、螺硅芴等基团；更加优选的为甲基、异丙基、叔丁基、异丁基、苯、联苯、萘、蒽、菲、苯并菲芴、螺芴等基团。
在一些较为优选的实施例中，按照本申请通式(1)所示的有机化合物H1是如下结构式中的一个或多个：
Figure PCTCN2017112713-appb-000013
在某些优先的实施例中，有机化合物H2为如通式(2)所示的化合物：
Figure PCTCN2017112713-appb-000014
其中，Ar2表示为H原子、环原子数为5～90的芳香基团或环原子数为5～90的芳杂基团；D为一富电子基团；o为一个1-6的整数；当o大于1时，o个富电子基团D可以相同，也可以不相同。
在某些优选的实施方案中，上述的富电子基团D可以优选自包含有如下任一基团的结构：
Figure PCTCN2017112713-appb-000015
其中，Y表示碳原子数为5～40的芳香基团或碳原子数为5～40的芳杂基团；Z1、Z2、Z3分别独立地表示单键、N(R)、C(R)2、Si(R)2、O、S、C＝N(R)、C＝C(R)2或P(R)；R3、R4、R5分别独立地表示烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基或杂芳基。
在一个优选的实施方案中，富电子基团D选为下式中的一种：
Figure PCTCN2017112713-appb-000016
其中，Y、Z2、Z3、R的含义如上说述。
在一个更加优选的实施方案中，富电子基团D选为下式中的一种：
Figure PCTCN2017112713-appb-000017
其中，R3、R4的含义如上说述。
在一些较为优选的实施例中，按照本申请通式(2)所示的有机化合物H2是如下结构式中的一个：
Figure PCTCN2017112713-appb-000018
Figure PCTCN2017112713-appb-000019
其中Ar2、Z2、Z3、Y的含义如上或如下所述。
在某些优选的实施例中，通式(1)中所示的Ar1和通式(2)中所示的Ar2为环原子数为6～70的芳香基团或环原子数为6～70的芳杂基团；在更加优选的实施例中，Ar1、Ar2为环原子数为6～60的芳香基团或环原子数为6～60的芳杂基团；在非常优选的实施例中，Ar1、Ar2为环原子数为6～50的芳香基团或环原子数为6～50的芳杂基团；在最为优选的实施例中，Ar1、Ar2为环原子数为6～40的芳香基团或环原子数为6～40的芳杂基团。
芳香环系或芳香基团指至少包含一个芳环的烃基，包括单环基团和多环的环系统。芳杂环系或芳杂基团指包含至少一个芳杂环的烃基(含有杂原子)，包括单环基团和多环的环系统。杂原子优选选自Si、N、P、O、S和/或Ge，特别优选选自Si、N、P、O和/或S。这些多环的环可以具有两个或多个环，其中两个碳原子被两个相邻的环共用，即稠环。多环的这些环种，至少一个是芳族的或杂芳族的。对于本申请的目的，芳香族或芳杂族环系不仅包括芳香基或芳杂基的体系，而且，其中多个芳基或芳杂基也可以被短的非芳族单元间断(<10％的非H原子，优选小于5％的非H原子,比如C、N或O原子)。因此，比如9,9'-螺二芴，9,9-二芳基芴，三芳胺，二芳基醚等体系，对于该发明目的同样认为是芳香族环系。
具体地，芳香基团的例子有：苯、萘、蒽、菲、二萘嵌苯、并四苯、芘、苯并芘、三亚苯、苊、芴、及其衍生物。
具体地，芳杂族基团的例子有：呋喃、苯并呋喃、噻吩、苯并噻吩、吡咯、吡唑、三唑、咪唑、噁唑、噁二唑、噻唑、四唑、吲哚、咔唑、吡咯并咪唑、吡咯并吡咯、噻吩并吡咯、噻吩并噻吩、呋喃并吡咯、呋喃并呋喃、噻吩并呋喃、苯并异噁唑、苯并异噻唑、苯并咪唑、吡啶、吡嗪、哒嗪、嘧啶、三嗪、喹啉、异喹啉、邻二氮萘、喹喔啉、菲啶、伯啶、喹唑啉、喹唑啉酮、及其衍生物。
在一个优选的实施方案中，Ar1、Ar2分别独立地为：苯、联苯、萘、蒽、菲、苯并菲、芘、吡啶、嘧啶、三嗪、芴、硫芴、硅芴、咔唑、噻吩、呋喃、噻唑、三苯胺、三苯基氧磷，四 苯基硅、螺芴、螺硅芴等基团；更加优选的为苯、联苯、萘、蒽、菲、苯并菲芴、螺芴等基团。
在一个优选的实施例中，化学式(1)中的Ar1化学式(2)中的Ar2可包含如下结构基团中的一种或多种组合：
Figure PCTCN2017112713-appb-000020
其中，
X1-X8分别独立表示CR3或N；
Y1、Y2分别独立表示CR4R5、SiR4R5、NR3、C(＝O)、S或O；
R3、R4、R5是氢原子、氘原子、或具有1至20个C原子的直链烷基、烷氧基或硫代烷氧基基团，或者具有3至20个C原子的支链或环状的烷基、烷氧基或硫代烷氧基基团或者是甲硅烷基基团，或具有1至20个C原子的取代的酮基基团，或具有2至20个C原子的烷氧基羰基基团，或具有7至20个C原子的芳氧基羰基基团，氰基基团(-CN)，氨基甲酰基基团(-C(＝O)NH2)，卤甲酰基基团(-C(＝O)-X其中X代表卤素原子),甲酰基基团(-C(＝O)-H)，异氰基基团，异氰酸酯基团，硫氰酸酯基团或异硫氰酸酯基团，羟基基团，硝基基团，CF3基团，Cl，Br，F，可交联的基团或者具有5至40个环原子的取代或未取代的芳族或杂芳族环系，或具有5至40个环原子的芳氧基或杂芳氧基基团，或这些体系的组合，其中一个或多个基团R3，R4，R5可以彼此和/或与所述基团键合的环形成单环或多环的脂族或芳族环。
在一个特别优选的实施例中,Ar1或Ar2可选自包含有如下基团的结构：
Figure PCTCN2017112713-appb-000021
Figure PCTCN2017112713-appb-000022
其中，m为1、2或3。
在一个特别优选的实施例中，所述有机化合物H1选自通式(3)～通式(6)所代表的化合物中的至少一种:
Figure PCTCN2017112713-appb-000023
其中，Ar3、Ar4分别独立表示为环原子数为5～60的芳香基团或芳杂基团；q为1-6的整数；通式(3)～(6)中X1、X2、X3、M1、M2、M3的含义与通式(1)中X1、X2、X3、M1、M2、M3的含义相同，在此不再赘述。
在某些实施例中，有机化合物H2可选自如下的通式所代表的化合物中的至少一种：
Figure PCTCN2017112713-appb-000024
每个Ar5～Ar11可独立选自环芳香烃化合物，如苯、联苯、三苯基、苯并、萘、蒽、非那烯、菲、芴、芘、屈、苝、薁；芳香杂环化合物，如二苯并噻吩、二苯并呋喃、呋喃、噻吩、苯并呋喃、苯并噻吩、咔唑、吡唑、咪唑、三氮唑、异恶唑、噻唑、恶二唑、恶三唑、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪、恶嗪、恶噻嗪、恶二嗪、吲哚、苯并咪唑、吲唑、吲哚嗪、苯并恶唑、苯异恶唑、苯并噻唑、喹啉、异喹啉、邻二氮(杂)萘、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、吩恶嗪、二苯并硒吩、苯并硒吩、苯并呋喃吡啶、吲哚咔唑、吡啶吲哚、吡咯二吡啶、呋喃二吡啶、苯并噻吩吡啶、噻吩吡啶、苯并硒吩吡啶和硒吩二吡啶；包含有2至10环结构的基团，它们可以是相同或不同类型的环芳香烃基团或芳香杂环基团，并彼此直接或通过至少一个以下的基团连结在一起,如氧原子、氮原子、硫原子、硅原子、磷原子、硼原子、链结构单元和脂肪环基团。其中，每个Ar可以进一步被取代，取代基可选为氢、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基和杂芳基。
在某些优先的实施例中，有机化合物H2可选自如下通式(7)～(10)代表的化合物中的至少一种：
Figure PCTCN2017112713-appb-000025
其中，
L1分别独立表示环原子为5～60的芳香基团或环原子为5～60的芳杂基团；
L2表示单键、环原子数为5～30的芳香基团或环原子为5～30的芳杂基团，L2的连接位置可以是环上任意一碳原子上；
Ar5～Ar10分别独立地表示环原子数为5～20的芳香基团或环原子数为5～20的芳杂基团；
Z1、Z2、Z3的定义如上所述；Z4～Z9的定义如Z2，但Z4和Z5不同时为单键，Z6和Z7不同时为单键，Z8和Z9不同时为单键；
o为一个1-6的整数；当o大于1时，o个富电子基团可以相同，也可以不相同。
在一些较为优先的实施例中，按照本发明的有机混合物，其中H2选自如下结构式中的一个：
Figure PCTCN2017112713-appb-000026
其中、Ar5、Ar6、R6、R7、L1、o的含义如上所述。
在另一些较为优先的实施例中，按照本发明的有机混合物，其中有机化合物H2选自如下结构式中的一个：
Figure PCTCN2017112713-appb-000027
其中、Ar5、Ar8、Z2、Z3、Z4、Z5、R6、R7的含义如上所述。
在另一些较为优先的实施例中，按照本发明的有机混合物，其中有机化合物H2选自如下结构式中的一个：
Figure PCTCN2017112713-appb-000028
其中Ar5、Ar7、Z1、Z2、Z3、R6、R7、L1、o的含义如上所述。
在另一些较为优先的实施例中，按照本发明的有机混合物，其中有机化合物H2选自如下结构式中的一个：
Figure PCTCN2017112713-appb-000029
其中Ar6、Ar7、Ar8、Ar9、Z2、Z3、Z4、Z5、Z6、Z7、Z8、Z9、R6、R7的含义如上所述。
下面举例按照本申请的通式(1)和通式(3)～(6)所示的有机化合物H1的具体例子，但并不限定于:
Figure PCTCN2017112713-appb-000030
Figure PCTCN2017112713-appb-000031
Figure PCTCN2017112713-appb-000032
Figure PCTCN2017112713-appb-000033
Figure PCTCN2017112713-appb-000034
下面举例按照通式(2)和通式(7)～(10)所示的有机化合物H2的具体例子，但并不限定于:
Figure PCTCN2017112713-appb-000035
Figure PCTCN2017112713-appb-000036
Figure PCTCN2017112713-appb-000037
Figure PCTCN2017112713-appb-000038
Figure PCTCN2017112713-appb-000039
Figure PCTCN2017112713-appb-000040
Figure PCTCN2017112713-appb-000041
Figure PCTCN2017112713-appb-000042
Figure PCTCN2017112713-appb-000043
Figure PCTCN2017112713-appb-000044
在一个优选的实施例中，有机化合物H1和有机化合物H2的摩尔比为从2：8到8：2；优选的摩尔比为3:7到7:3；更加优选的摩尔比为4:6到6:4。
在一个优选的实施例中，有机化合物H1和有机化合物H2的分子量的差不超过100Dalton；优选的分子量的差不超过60Dalton；更加优选的分子量的差不超过30Dalton。其中，有机化合物H1和有机化合物H2的分子量的差小，有利于这两种材料在制备成电子器件时的比例稳定性。
在另一个优选的实施例中，有机化合物H1和有机化合物H2的升华温度的差不超过30K；优选的升华温度的差不超过20K；更加优选的升华温度的差不超过10K。其中，有机化合物H1和有机化合物H2的升华温度的差小，有利于这两种材料在制备成蒸镀型的电子器件时的比例稳定性。
在一个优选的实施例中，有机化合物H1和有机化合物H2是一种小分子材料。
在一个优选的实施方案中，按照本申请的有机混合物用于蒸镀性OLED器件。用于这个目的，有机化合物H1和有机化合物H2的分子量≤1000mol/kg，优选≤900mol/kg，很优选≤850mol/kg，更优选≤800mol/kg，最优选≤700mol/kg。
在一个优选的实施例中，有机化合物H1和有机化合物H2的玻璃化温度Tg≥100℃，在一个优选的实施例中，Tg≥120℃，在一个较为优选的实施例中，Tg≥140℃，在一个更为优选的实施例中，Tg≥160℃，在一个最为优选的实施例中，Tg≥180℃。
本文中所定义的术语“小分子”是指不是聚合物，低聚物，树枝状聚合物，或共混物的分子。特别是，小分子中没有重复结构。小分子的分子量≤3000克/摩尔，较好是≤2000克/摩尔，最好是≤1500克/摩尔。
高聚物，即Polymer，包括均聚物(homopolymer)，共聚物(copolymer)，镶嵌共聚物(block copolymer)。另外在本申请中，高聚物也包括树状物(dendrimer)，有关树状物的合成及应用请参见[Dendrimers and Dendrons,Wiley-VCH Verlag GmbH&Co.KGaA,2002,Ed.George R.Newkome,Charles N.Moorefield,Fritz Vogtle.]。
共轭高聚物(conjugated polymer)是一高聚物，它的主链backbone主要是由C原子的sp2杂化轨道构成，著名的例子有：聚乙炔polyacetylene和poly(phenylene vinylene)，其主链上的C原子的也可以被其他非C原子取代，而且当主链上的sp2杂化被一些自然的缺陷打断时，仍然被认为是共轭高聚物。另外在本申请中共轭高聚物也包括主链上包含有芳基胺(aryl amine)、芳基磷化氢(aryl phosphine)及其他杂环芳烃(heteroarmotics)、有机金属络合物(organometallic complexes)等。
本申请还涉及一种混合物，包括所述有机混合物，以及至少还包括另一种有机功能材料。所述有机功能材料包括空穴(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)、有机主体材料(Host)、单重态发光体(荧光发光体)、重态发光体(磷光发光体)和有机热激发延迟荧光材料(TADF材料)特别是发光有机金属络合物中的至少一种。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。所述有机功能材料可以是小分子和高聚物材料。某些优先的实施方案中，所述有机功能材料是发光材料，所述发光材料选于荧光发光体、磷光发光体或TADF材料。
在一个优先的实施例中，所述混合物包括所述有机混合物和一种磷光发光体。所述有机 混合物可以作为主体，其中所述磷光发光体重量百分比≤30wt％，较好是≤25wt％,更好是≤20wt％。
在另一个优先的实施例中，所述混合物包括所述有机混合物和一种荧光发光体。所述有机混合物可以作为荧光主体材料，其中所述荧光发光体重量百分比≤15wt％,较好是≤10wt％,更好是≤8wt％。
在另一个优先的实施例中，所述混合物包括所述有机混合物和一种荧光主体材料。所述有机混合物可以作为荧光发光材料，其重量百分比≤15wt％,较好是≤10wt％,更好是≤8wt％。
在一个较为优先的实施例中，混合物包括所述有机混合物、一种磷光发光体和一种主体材料。在这种实施例中，所述有机混合物可以作为辅助发光材料，其与磷光发光体的重量比为从1:2到2:1。在另一种优选的实施例中，所述有机混合物的激基络合物的能级高于所述的磷光发光体。
在另一个优先的实施例中，所述混合物包括所述有机混合物和一种TADF材料。所述有机混合物可以作为TADF主体材料，其中所述TADF材料的重量百分比≤15wt％,较好是≤10wt％,更好是≤8wt％。
下面对荧光发光材料或单重态发光体，磷光发光材料或三重态发光体和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。
在一个优选的实施方案中,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。
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选于稠环系统，并最好有至少14个芳香环原子。其中优选的例子有芳香蒽胺，芳香蒽二胺，芳香芘胺，芳香芘二胺，芳香屈胺和芳香屈二胺。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 5121029。
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US5121029，US5130603),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 4769292,US 6020078,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 PCTCN2017112713-appb-000045
Figure PCTCN2017112713-appb-000046
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ΔEst<0.3eV，较好是ΔEst<0.2eV，更好是ΔEst<0.1eV，最好是ΔEst<0.05eV。在一个优选的实施方案中，TADF有较好的荧光量子效率。一些TADF发光的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 PCTCN2017112713-appb-000047
Figure PCTCN2017112713-appb-000048
3.三重态发光体(Triplet Emitter)
三重态发光体也称磷光发光体。在一个优选的实施方案中，三重态发光体是有通式M(L)n的金属络合物,其中M是一金属原子，L每次出现时可以是相同或不同，是一有机配体，它通过一个或多个位置键接或配位连接到金属原子M上,n是一个大于1的整数，较好选是1，2，3，4，5或6。可选地，这些金属络合物通过一个或多个位置联接到一个聚合物上，最好是通过有机配体。
在一个优选的实施方案中,金属原子M选于过渡金属元素或镧系元素或锕系元素,优选Ir,Pt,Pd,Au,Rh,Ru,Os,Sm,Eu,Gd,Tb,Dy,Re,Cu或Ag，特别优选Os,Ir,Ru,Rh,Re,Pd或Pt。
优选地,三重态发光体包含有螯合配体，即配体，通过至少两个结合点与金属配位，特别优选考虑的是三重态发光体包含有两个或三个相同或不同的双齿或多齿配体。螯合配体有利于提高金属络合物的稳定性。
有机配体的例子可选自苯基吡啶衍生物，7,8-苯并喹啉衍生物，2(2-噻吩基)吡啶衍生物，2(1-萘基)吡啶衍生物，或2苯基喹啉衍生物。所有这些有机配体都可能被取代，例如被含氟或三氟甲基取代。辅助配体可优选自乙酸丙酮或苦味酸。
在一个优选的实施方案中，可用作三重态发光体的金属络合物有如下形式：
Figure PCTCN2017112713-appb-000049
其中M1是一金属,选于过渡金属元素或镧系元素或锕系元素；
Ar1每次出现时可以是相同或不同,是一个环状基团,其中至少包含有一个施主原子，即有一孤对电子的原子，如氮或磷，通过它环状基团与金属配位连接；Ar2每次出现时可以是相同或不同,是一个环状基团,其中至少包含有一个C原子,通过它环状基团与金属连接；Ar1 和Ar2由共价键联接在一起,可各自携带一个或多个取代基团，它们也可再通过取代基团联接在一起；L每次出现时可以是相同或不同,是一个辅助配体,优选于双齿螯合配体，最好是单阴离子双齿螯合配体；b是1,2或3,优选地是2或3,特别优选地是3；a是0,1,或2,优选地是0或1,特别优选地是0；
一些三重态发光体的材料极其应用的例子可在下述专利文件和文献中找到:WO 200070655,WO 200141512,WO 200202714,WO 200215645,EP 1191613,EP 1191612,EP 1191614,WO 2005033244,WO 2005019373,US 2005/0258742,WO 2009146770,WO 2010015307,WO 2010031485,WO 2010054731,WO 2010054728,WO 2010086089,WO 2010099852,WO 2010102709,US 20070087219 A1,US 20090061681 A1,US 20010053462 A1,Baldo,Thompson et al.Nature 403,(2000),750-753,US 20090061681 A1,US 20090061681 A1,Adachi et al.Appl.Phys.Lett.78(2001),1622-1624,J.Kido et al.Appl.Phys.Lett.65(1994),2124,Kido et al.Chem.Lett.657,1990,US 2007/0252517 A1,Johnson et al.,JACS 105,1983,1795,Wrighton,JACS 96,1974,998,Ma et al.,Synth.Metals 94,1998,245,US 6824895,US 7029766,US 6835469,US 6830828,US 20010053462 A1,WO 2007095118 A1,US 2012004407A1,WO 2012007088A1,WO2012007087A1,WO 2012007086A1,US 2008027220A1,WO 2011157339A1,CN 102282150A,WO 2009118087A1。特此将上述列出的专利文件和文献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三重态发光体的例子:
Figure PCTCN2017112713-appb-000050
Figure PCTCN2017112713-appb-000051
Figure PCTCN2017112713-appb-000052
本申请的另一个目的是为印刷OLED提供材料解决方案。
用于这个目的，有机化合物H1和有机化合物H2中至少有一个分子量≥700mol/kg，优选≥900mol/kg，很优选≥900mol/kg，更优选≥1000mol/kg，最优选≥1100mol/kg。
在某些实施例中，在25℃时，所述有机混合物在甲苯中的溶解度≥10mg/ml，优选≥15mg/ml，最优选≥20mg/ml。
本申请还进一步涉及一种组合物或油墨，包含有一种如上所述的有机混合物及至少一种有机溶剂。
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。
在一个优选的实施例中，按照本申请的油墨在工作温度或在25℃下的表面张力约在19dyne/cm到50dyne/cm范围；更好是在22dyne/cm到35dyne/cm范围；最好是在25dyne/cm到33dyne/cm范围。
在另一个优选的实施例中，按照本申请的油墨在工作温度或25℃下的粘度约在1cps到100cps范围；较好是在1cps到50cps范围；更好是在1.5cps到20cps范围；最好是在4.0cps到20cps范围。如此配制的组合物将便于喷墨印刷。
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。按照本申请的包含有所述地金属有机配合物或高聚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，按照本申请的组合物包含的功能材料的重量比为0.3％～30wt％范围，较好的为0.5％～20wt％范围，更好的为0.5％～15wt％范围，更更好的为0.5％～10wt％范围，最好的为1％～5wt％范围。
在一些实施例中，按照本申请的油墨，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，特别是脂肪族链/环取代的芳族溶剂、或芳族酮溶剂，或芳族醚溶剂。
适合本申请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、-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，按照本申请的油墨，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括(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。
在一个优选的实施方案中，按照本申请的组合物是一溶液。
在另一个优选的实施方案中，按照本申请的组合物是一悬浮液。
本申请实施例中的组合物中可以包括0.01至20wt％的按照本申请的有机混合物，较好的是0.1至15wt％，更好的是0.2至10wt％，最好的是0.25至5wt％的有机混合物。
本申请还涉及所述组合物作为涂料或印刷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括(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，狭缝型挤压式涂布等。首选的是凹版印刷，喷印及喷墨印刷。溶液或悬浮液可以另外包括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，如溶剂及浓度，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。
基于上述有机混合物，本申请还提供一种如上所述的有机混合物的应用，即将所述有机混合物应用于有机电子器件，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。本申请实施例中，优选将所述有机化合物用于OLED器件的发光层。
本申请进一步涉及一种有机电子器件，至少包含一种如上所述的有机混合物。一般地， 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有机混合物。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，有机传感器及有机等离激元发射二极管(Organic Plasmon Emitting Diode)等，特别优选的是有机电致发光器件，如OLED，OLEEC，有机发光场效应管。
在某些特别优先的实施例中，所述有机电致发光器件，其发光层包含一种所述的有机混合物，或包含一种所述的有机混合物和一种磷光发光体，或包含一种所述的有机混合物和一种主体材料，或包含一种所述的有机混合物、一种磷光发光体和一种主体材料。
在以上所述的发光器件，特别是OLED中，包括一基片，一阳极，至少一发光层，一阴极。
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。最好是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。在一个优选的实施例中，基片是柔性的，可选于聚合物薄膜或塑料，其玻璃化温度Tg为150℃以上，较好是超过200℃，更好是超过250℃，最好是超过300℃。合适的柔性基板的例子有聚(对苯二甲酸乙二醇酯)(PET)和聚乙二醇(2,6-萘)(PEN)。
阳极可包括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，较好是小于0.3eV，最好是小于0.2eV。阳极材料的例子包括但不限于：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，包括射频磁控溅射，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申请的器件。
阴极可包括一导电金属或金属氧化物。阴极可以容易地注入电子到EIL或ETL或直接到发光层中。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，较好是小于0.3eV，最好是小于0.2eV。原则上，所有可用作OLED的阴极的材料都可能作为本申请器件的阴极材料。阴极材料的例子包括但不限于：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，包括射频磁控溅射，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在上面及在WO2010135519A1、US20090134784A1和WO2011110277A1中有详细的描述，特此将此3篇专利文件中的全部内容并入本文作为参考。
在一个优选的实施例中，按照本申请的发光器件中，其发光层包含有按照本申请的混合物。所述的发光层可优先地通过包含以下两种步骤的方法制备而成：
(1)包含有H1和H2的混合物是作为一个源沉积而成的。这可利用按照本申请的组合物通过打印的方法制备而成，或混合物作为一个源真空蒸镀而成。
(2)H1和H2是作为单独的两个源蒸镀而成的。
按照本申请的发光器件，其发光波长在300到1000nm之间，较好的是在350到900nm之间，更好的是在400到800nm之间。
本申请还涉及按照本申请的电致发光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，传感器等等。
下面将结合优选实施例对本申请进行了说明，但本申请并不局限于下述实施例，应当理解，所附权利要求概括了本申请的范围在本申请构思的引导下本领域的技术人员应意识到，对本申请的各实施例所进行的一定的改变，都将被本申请的权利要求书的精神和范围所覆盖。
具体实施例
1.按照本申请的化合物的合成方法举例，但本申请并不局限于下述实施例。
(1)化合物(1-36)的合成：
Figure PCTCN2017112713-appb-000053
Figure PCTCN2017112713-appb-000054
氮气环境下，将(31.6g,80mmol)的化合物1-36-1和200mL无水四氢呋喃加入到500mL的三口瓶中，降温到-78℃，缓慢滴加85mmol正丁基锂，反应2小时，一次性注入 90mmol异丙醇频哪醇硼酸酯，让反应自然升到室温，继续反应12小时，加入纯净水淬灭反应，旋走大部分溶剂后，用二氯甲烷萃取并水洗3遍，收集有机相，旋干后重结晶，产率90％。
Figure PCTCN2017112713-appb-000055
氮气环境下，将(26.5g,60mmol)的化合物1-36-2和(13.6g,60mmol)的化合物1-36-3，(3.45g,3mmol)四(三苯基磷)钯，(2.6g,8mmol)四丁基溴化铵，(3.2g,80mmol)氢氧化钠，(20mL)水和(150mL)甲苯加入250mL的三口瓶中，加热80℃搅拌反应12小时，结束反应，将反应液旋转蒸发掉大部分溶剂，用二氯甲烷溶解水洗3遍，收集有机液拌硅胶过柱进行纯化，产率70％。
Figure PCTCN2017112713-appb-000056
氮气环境下，将(10.1g,20mmol)的化合物1-36-4和(4g,20mmol)的化合物1-36-5，(1.15g,1mmol)四(三苯基磷)钯，(1.3g,4mmol)四丁基溴化铵，(1.6g,40mmol)氢氧化钠，(10mL)水和(60mL)甲苯加入150mL的三口瓶中，加热80℃搅拌反应12小时，结束反应，将反应液旋转蒸发掉大部分溶剂，用二氯甲烷溶解水洗3遍，收集有机液拌硅胶过柱进行纯化，产率80％。
(2)化合物(1-37)的合成：
Figure PCTCN2017112713-appb-000057
Figure PCTCN2017112713-appb-000058
氮气环境下，将(10.1g,20mmol)的化合物1-36-4和(5.6g,20mmol)的化合物1-37-1，(1.15g,1mmol)四(三苯基磷)钯，(1.3g,4mmol)四丁基溴化铵，(1.6g,40mmol)氢氧化钠，(10mL)水和(60mL)甲苯加入150mL的三口瓶中，加热80℃搅拌反应12小时，结束反应，将反应液旋转蒸发掉大部分溶剂，用二氯甲烷溶解水洗3遍，收集有机液拌硅胶过柱进行纯化，产率80％。
(3)化合物(1-44)的合成：
Figure PCTCN2017112713-appb-000059
Figure PCTCN2017112713-appb-000060
氮气环境下，将(8g,40mmol)的化合物1-44-1和(11.2g,40mmol)的化合物1-37-1，(2.3g,2mmol)四(三苯基磷)钯，(2.6g,8mmol)四丁基溴化铵，(3.2g,80mmol)氢氧化钠，(20mL)水和(120mL)甲苯加入250mL的三口瓶中，加热80℃搅拌反应12小时，结束反应，将反应液旋转蒸发掉大部分溶剂，用二氯甲烷溶解水洗3遍，收集有机液拌硅胶过柱进行纯化，产率80％。
Figure PCTCN2017112713-appb-000061
氮气环境下，将(8.8g,20mmol)的化合物1-36-2和(6.3g,20mmol)的化合物1-44-2，(1.15g,1mmol)四(三苯基磷)钯，(1.3g,4mmol)四丁基溴化铵，(1.6g,40mmol)氢氧化钠，(10mL)水和(60mL)甲苯加入150mL的三口瓶中，加热110℃搅拌反应12小时，结束反应，将反应液旋转蒸发掉大部分溶剂，用二氯甲烷溶解水洗3遍，收集有机液拌硅胶过柱进行纯化，产率75％。
(4)对比实施例Ref-1：
Figure PCTCN2017112713-appb-000062
Figure PCTCN2017112713-appb-000063
氮气环境下，将(9.1g,50mmol)的化合物Ref-1-1，(23.2g,100mmol)的化合物Ref-1-2，(2.6g,2.5mmol)四(三苯基膦)钯，(32.6g,100mmol)碳酸铯，(100mL)水和(200mL)1，4-二氧六环加入到500mL的两口瓶中，加热回流搅拌反应12小时，结束反应。分掉水层后，抽滤，滤渣重结晶，产率70％。
(5)化合物(2-46)的合成：
Figure PCTCN2017112713-appb-000064
Figure PCTCN2017112713-appb-000065
氮气环境下，将(16.7g,100mmol)的化合物2-46-1，(24.5g,105mmol)的化合物2-46-2，(0.65g,10mmol)铜粉，(13.8g,100mmol)碳酸钾和(2.65g,5mmol)18-冠醚-6和(200mL)邻二氯苯加入到500mL的两口瓶中，加热150℃搅拌反应24个小时， 结束反应，将反应液减压蒸馏掉大部分溶剂，用二氯甲烷溶解水洗3遍，收集有机液拌硅胶过柱进行纯化，产率80％。
Figure PCTCN2017112713-appb-000066
将(19.1g,60mmol)的化合物2-46-3和100mL N,N-二甲基甲酰胺加入250mL单口瓶中，冰浴下滴加60mmol NBS的N,N-二甲基甲酰胺溶液，避光搅拌反应12小时，结束反应，将反应液倒入到500mL水中，抽滤，滤渣重结晶，产率90％。
Figure PCTCN2017112713-appb-000067
氮气环境下，将(15.9g,40mmol)的化合物2-46-4和300mL无水四氢呋喃加入到500mL的三口瓶中，降温到-78℃，缓慢滴加50mmol正丁基锂，反应2小时，一次性注入55mmol异丙醇频哪醇硼酸酯，让反应自然升到室温，继续反应12小时，加入纯净水淬灭反应，旋走大部分溶剂后，用二氯甲烷萃取并水洗3遍，收集有机相，旋干后重结晶，产率80％。
Figure PCTCN2017112713-appb-000068
氮气环境下，将(16.7g,100mmol)的化合物2-46-1，(24.5g,105mmol)的化合物2-46-5，(0.65g,10mmol)铜粉，(13.8g,100mmol)碳酸钾和(2.65g,5mmol)18-冠醚-6和(200mL)邻二氯苯加入到500mL的两口瓶中，加热150℃搅拌反应24个小时，结束反应，将反应液减压蒸馏掉大部分溶剂，用二氯甲烷溶解水洗3遍，收集有机液拌硅胶过柱进行纯化，产率75％。
Figure PCTCN2017112713-appb-000069
Figure PCTCN2017112713-appb-000070
将(19.1g,60mmol)的化合物2-46-6和100mL N,N-二甲基甲酰胺加入250mL单口瓶中，冰浴下滴加60mmol NBS的N,N-二甲基甲酰胺溶液，避光搅拌反应12小时，结束反应，将反应液倒入到500mL水中，抽滤，滤渣重结晶，产率88％。
Figure PCTCN2017112713-appb-000071
氮气环境下，将(4.45g,20mmol)的化合物2-46-5和(3.98g,20mmol)的化合物2-46-7，(1.15g,1mmol)四(三苯基磷)钯，(2.6g,8mmol)四丁基溴化铵，(3.2g,80mmol)氢氧化钠，(10mL)水和(100mL)甲苯加入250mL的三口瓶中，加热80℃搅拌反应12小时，结束反应，将反应液旋转蒸发掉大部分溶剂，用二氯甲烷溶解水洗3遍，收集有机液拌硅胶过柱进行纯化，产率80％。
(6)化合物(2-49)的合成：
Figure PCTCN2017112713-appb-000072
Figure PCTCN2017112713-appb-000073
Figure PCTCN2017112713-appb-000074
氮气环境下，将(10g,60mmol)的化合物2-49-1，(18.4g,60mmol)的化合物3-49-2，(0.39g,6mmol)铜粉，(8.28g,60mmol)碳酸钾和(2.65g,5mmol)18-冠醚-6和(150mL)邻二氯苯加入到300mL的两口瓶中，加热150℃搅拌反应24个小时，结束反应，将反应液减压蒸馏掉大部分溶剂，用二氯甲烷溶解水洗3遍，收集有机液拌硅胶过柱进行纯化，产率85％。
(7)化合物(2-92)的合成：
Figure PCTCN2017112713-appb-000075
Figure PCTCN2017112713-appb-000076
氮气环境下，将(31.5g,80mmol)的化合物2-46-7和300mL无水四氢呋喃加入到500mL的三口瓶中，降温到-78℃，缓慢滴加85mmol正丁基锂，反应2小时，一次性注入90mmol异丙醇频哪醇硼酸酯，让反应自然升到室温，继续反应12小时，加入纯净水淬灭反应，旋走大部分溶剂后，用二氯甲烷萃取并水洗3遍，收集有机相，旋干后重结晶，产率90％。
Figure PCTCN2017112713-appb-000077
Figure PCTCN2017112713-appb-000078
氮气环境下，将(26.7g,60mmol)的化合物2-92-1和(12.1g,60mmol)的化合物2-92-2，(3.45g,3mmol)四(三苯基磷)钯，(7.8g,24mmol)四丁基溴化铵，(4.8g,120mmol)氢氧化钠，(15mL)水和(120mL)甲苯加入250mL的三口瓶中，加热80℃搅拌反应12小时，结束反应，将反应液旋转蒸发掉大部分溶剂，用二氯甲烷溶解水洗3遍，收集有机液拌硅胶过柱进行纯化，产率80％。
Figure PCTCN2017112713-appb-000079
氮气环境下，将(13.2g,30mmol)的化合物9-1-11和(10g,60mmol)的三乙基磷加入150mL两口瓶中，加热190℃搅拌反应12小时，结束反应，将反应液减压蒸馏掉大部分溶剂，用二氯甲烷溶解水洗3遍，收集有机液拌硅胶过柱进行纯化，产率85％。
Figure PCTCN2017112713-appb-000080
氮气环境下，将(8.16g,20mmol)的化合物2-49-4，(4.66g,60mmol)的化合物3-46-2，(0.26g,4mmol)铜粉，(5.5g,40mmol)碳酸钾和(2.12g,4mmol)18-冠醚-6和(100mL)邻二氯苯加入到250mL的两口瓶中，加热150℃搅拌反应24个小时，结束反应，将反应液减压蒸馏掉大部分溶剂，用二氯甲烷溶解水洗3遍，收集有机液拌硅胶过柱进行纯化，产率85％。
(8)对比实施例Ref-2：
Figure PCTCN2017112713-appb-000081
Figure PCTCN2017112713-appb-000082
氮气环境下，将(16.8g,50mmol)的化合物Ref-2-1，(20.7g,100mmol)的化合物Ref-2-2，(2.3g,2.5mmol)pd2(dba)3，(1g,5mmol)三叔丁基磷，(9.6g,100mmol)叔丁醇钠和(150mL)甲苯加入到250mL的两口瓶中，加热回流搅拌反应12小时，结束反应。将反应液减压蒸馏掉大部分溶剂，用二氯甲烷溶解水洗3遍，收集有机液拌硅胶过柱进行纯化，产率70％。
(9)对比实施例Ref-3：
Figure PCTCN2017112713-appb-000083
购于长春奥来德。
(10)对比实施例Ref-4：
Figure PCTCN2017112713-appb-000084
对比实施例Ref-4的合成请参考现有技术专利WO 2015041428。
2.有机化合物的能量结构
有机材料的能级可通过量子计算得到，比如利用TD-DFT(含时密度泛函理论)通过Gaussian03W(Gaussian Inc.)，具体的模拟方法可参见WO2011141110。首先用半经验方法“Ground State/Semi-empirical/Default Spin/AM1”(Charge 0/Spin Singlet)来优化分子几何结构，然后有机分子的能量结构由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计算，S1和T1直接使用。
HOMO(eV)＝((HOMO(G)×27.212)-0.9899)/1.1206
LUMO(eV)＝((LUMO(G)×27.212)-2.0041)/1.385
其中HOMO(G)和LUMO(G)是Gaussian 03W的直接计算结果，单位为Hartree。结果如表一所示：
表一
Figure PCTCN2017112713-appb-000085
3.OLED器件的制备及表征
在本实施例中，分别用化合物(1-36):(2-46)＝1:1、(1-36):(2-49)＝1:1、(1-37):(2-46)＝1:1、(1-37):(2-49)＝1:1和(Ref-1):(Ref-2)＝1:1(质量比)作为主体材料，如下图的Ir(p-ppy)3作为发光材料，HATCN作为空穴注入材料，SFNFB作为空穴传输材料，NaTzF2作为电子传输材料，Liq作为电子注入材料，构造成器件结构为ITO/HATCN/SFNFB/主体材料:Ir(p-ppy)3(10％)/NaTzF2:Liq/Liq/Al的电致发光器件。
Figure PCTCN2017112713-appb-000086
上述材料HATCN、SFNFB、Ir(p-ppy)3、NaTzF2、Liq均是可商业购得，如吉林奥莱德(Jilin OLED Material Tech Co.,Ltd，www.jl-oled.com)，或其合成方法均为现有技术，详见现有技术中的参考文献，在此不再赘述。
下面通过具体实施例来详细说明采用上述的OLED器件的制备过程，OLED器件(如表2)的结构为：ITO/HATCN/SFNFB/主体材料:Ir(p-ppy)3(10％)/NaTzF2:Liq/Liq/Al，制备步骤如下：
a、ITO(铟锡氧化物)导电玻璃基片的清洗：使用各种溶剂(例如氯仿、丙酮或异丙醇中的一种或几种)清洗，然后进行紫外臭氧处理；
b、HATCN(30nm),SFNFB(50nm),主体材料:10％Ir(p-ppy)3(40nm)，NaTzF2:Liq(30nm)，Liq(1nm)，Al(100nm)在高真空(1×10-6毫巴)中热蒸镀而成；
c、封装:器件在氮气手套箱中用紫外线硬化树脂封装。
其中，主体材料的制作方法可通过一下三种形式：
(1)简单共混，将两种主体材料称好一定的配比后，掺杂在一起，在室温下进行研磨，所得的混合物放在一个有机源中进行蒸镀。
(2)有机合金，将两种主体材料称好一定的配比后，掺杂在一起，在真空度低于10-3torr下，加热搅拌直至混合物熔融，降温后，将混合物进行研磨，所得的混合物放在一个有机源中进行蒸镀。
表2
OLED器件 主体材料 T90@1000nits
OLED1 (1-36):(2-46)＝1:1简单共混 3.2
OLED2 (1-36):(2-46)＝1:1有机合金 4.7
OLED3 (1-36):(2-49)＝1:1简单共混 2.5
OLED4 (1-36):(2-49)＝1:1有机合金 3.8
OLED5 (1-37):(2-46)＝1:1简单共混 4.8
OLED6 (1-37):(2-46)＝1:1有机合金 6.5
OLED7 (1-37):(2-49)＝1:1简单共混 3.6
OLED8 (1-37):(2-49)＝1:1有机合金 5.2
OLED9 (Ref-1):(Ref-2)＝1:1简单共混 1
OLED10 (Ref-1):(Ref-2)＝1:1有机合金 1.2
OLED11 (Ref-3):(Ref-4)＝1:1简单共混 1.4
OLED12 (Ref-3):(Ref-4)＝1:1简单共混 1.6
各OLED器件的电流电压(J-V)特性通过表征设备来表征，同时记录重要的参数如效率，寿命(如表2)及外部量子效率。表2中，所有寿命都是相对OLED9的相对值。可见，基于有机合金的器件OLED2、OLED4、OLED6、OLED8和OLED10的发光寿命在同类型器件中是相对较高的，其中，基于OLED6的器件寿命比RefOELD的6.5倍。且在条件1)相同且条件2)不符合的情况下，OLED11和OLED12的寿命显著低于OLED7和OLED8的寿命，可见，采用同时满足条件1)和条件2)的有机混合物制备的OLED器件，其寿命得到大大提高。
本申请的所述有机化合物H1和所述有机化合物H2便于形成激基复合物，且具有平衡的电荷传输性质，所述有机化合物H1具有较高的对电子传输的稳定性，因而可有效提高相关电子器件的效率和寿命，为提高电子器件的整体性能提供一种行之有效的方案。
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本申请的保护范围之中。

Claims (20)

  1. 一种有机混合物，包括有机化合物H1和有机化合物H2，其特征在于，
    1)min((LUMO(H1)-HOMO(H2),LUMO(H2)-HOMO(H1))≤min(ET(H1),ET(H2))+0.1eV，其中，LUMO(H1)、HOMO(H1)及ET(H1)分别是所述有机化合物H1的最低未占有轨道、最高占有轨道及三线态的能级，LUMO(H2)、HOMO(H2)及ET(H2)分别是所述有机化合物H2的最低未占有轨道、最高占有轨道及三线态的能级；
    2)(LUMO+1)(H1)-LUMO(H1)≥0.1eV，其中，(LUMO+1)(H1)是所述有机化合物H1的第二低的未占有轨道能级。
  2. 根据权利要求1所述的有机混合物，其特征在于，(LUMO+1)(H1)-LUMO(H1)≥0.15eV。
  3. 根据权利要求1-2中任一项所述的有机混合物，其特征在于，所述有机化合物H1为如通式(1)所示的化合物：
    Figure PCTCN2017112713-appb-100001
    其中，Ar1表示为H原子、环原子数为5～90的芳香基团或环原子数为5～90的芳杂基团；A为缺电子基团；n为一个1-6的整数；当n大于1时，多个所述缺电子基团相同或不同。
  4. 根据权利要求3所述的有机混合物，其特征在于，所述缺电子基团为F或氰基，此时Ar1不为H原子；或所述缺电子基团包含有如下一种或多种结构形成的基团：
    Figure PCTCN2017112713-appb-100002
    其中，m为1、2或3；X1-X8选于CR或N，并且至少有一个是N；M1、M2、M3分别独立表示N(R)、C(R)2、Si(R)2、O、C＝N(R)、C＝C(R)2、P(R)、P(＝O)R、S、S＝O、SO2或无；其中R1、R2、R3、R3分别独立表示烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基或杂芳基。
  5. 根据权利要求1-4中任一项所述的有机混合物，其特征在于，所述有机化合物H2为如通式(2)所示的化合物：
    Figure PCTCN2017112713-appb-100003
    其中，Ar2表示为H原子、环原子数为5～90的芳香基团或环原子数为5～90的芳香基团； D为富电子基团；o为一个1-6的整数；当o大于1时，多个所述富电子基团相同或不相同。
  6. 根据权利要求5所述的有机混合物，其特征在于，所述富电子基团包含有如下一种或多种结构形成的基团：
    Figure PCTCN2017112713-appb-100004
    其中，Y表示碳原子数为5～40的芳香基团或碳原子数为5～40的芳杂基团；Z1、Z2、Z3分别独立地表示单键、N(R)、C(R)2、Si(R)2、O、S、C＝N(R)、C＝C(R)2或P(R)；R3、R4、R5分别独立地表示烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基或杂芳基。
  7. 根据权利要求3-6中任一项所述的有机混合物，其特征在于，Ar1或Ar2包含有如下一种或多种结构形成的基团：
    Figure PCTCN2017112713-appb-100005
    Figure PCTCN2017112713-appb-100006
    其中，m为1、2或3。
  8. 根据权利要求2-7中任一项所述的有机混合物，其特征在于，所述有机化合物H1选自如下通式(3)～(6)所代表的化合物中的一种或多种：
    Figure PCTCN2017112713-appb-100007
    其中，Ar3和Ar4分别独立地为环原子数为5～60的芳香基团或环原子数为5～60的芳杂基团；q为一个1-6的整数；X1、X2、X3分别独立地为CR或N，并且至少有一个是N；M1、M2、M3分别独立表示N(R)、C(R)2、Si(R)2、O、C＝N(R)、C＝C(R)2、P(R)、P(＝O)R、S、S＝O、SO2或无；其中R表示烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基或杂芳基。
  9. 根据权利要求2-8中任一项所述的有机混合物，其特征在于，所述有机化合物H1选自下列化合物中的一种或多种：
    Figure PCTCN2017112713-appb-100008
    Figure PCTCN2017112713-appb-100009
  10. 根据权利要求2～9所述的有机混合物，其特征在于，所述有机化合物H2为如下通式(7)～(10)所表示的化合物中的一种或多种：
    Figure PCTCN2017112713-appb-100010
    其中，L1分别独立地表示环原子为5～60的芳香基团或环原子为5～60的芳杂基团；
    L2表示单键、环原子数为5～30的芳香基团或环原子数为5～30的芳杂基团；
    Ar5～Ar10分别独立地表示环原子数为5～20的芳香基团或环原子数为5～20的芳杂基团；
    Z1～Z9分别独立表示CH2、N(R)、C(R)2、Si(R)2、O、S、C＝N(R)、C＝C(R)2或P(R)，且Z4和Z5不同时为单键，Z6和Z7不同时为单键，Z8和Z9不同时为单键；
    o为一个1-6的整数。
  11. 根据权利要求2-10任一项所述的有机混合物，其特征在于，所述有机化合物H2为下列化合中的一种或多种：
    Figure PCTCN2017112713-appb-100011
    Figure PCTCN2017112713-appb-100012
  12. 根据权利要求1至11任一项所述的有机混合物，其特征在于，所述有机化合物H1和所述有机化合物H2的摩尔比为从2：8到8：2。
  13. 根据权利要求1至12任一项所述的有机混合物，其特征在于，所述有机化合物H1和所述有机化合物H2的分子量的差不超过100Dalton。
  14. 根据权利要求1至13任一项所述的有机混合物，其特征在于，所述有机化合物H1和所述有机化合物H2的升华温度的差不超过30K。
  15. 根据权利要求1至14任一项所述的有机混合物，其特征在于，进一步包含发光材料，所述发光材料选于荧光发光体、磷光发光体和TADF材料中的至少一种。
  16. 一种组合物，包括根据权利要求1至15任一项所述的有机混合物以及有机溶剂。
  17. 一种有机电子器件，其特征在于，包括功能层，所述功能层包括根据权利要求1～15任一项所述的有机混合物。
  18. 根据权利要求17所述的有机电子器件，其特征在于，所述有机电子器件为有机发光二极管(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、有机传感器或有机等离激元发射二极管(Organic Plasmon Emitting Diode)。
  19. 根据权利要求17或18所述的有机电子器件，其特征在于，所述功能层为发光层。
  20. 根据权利要求17-19中任一项所述的有机电子器件，其特征在于，所述功能层的制备方法包括：
    所述有机化合物H1和所述有机化合物H2混合均匀后作为一个源进行沉积；或者
    所述有机化合物H1和所述有机化合物H2作为单独的两个源进行蒸镀。
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