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WO2017118137A1 - 咔唑衍生物、高聚物、混合物、组合物、有机电子器件及其应用 - Google Patents

咔唑衍生物、高聚物、混合物、组合物、有机电子器件及其应用 Download PDF

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WO2017118137A1
WO2017118137A1 PCT/CN2016/101998 CN2016101998W WO2017118137A1 WO 2017118137 A1 WO2017118137 A1 WO 2017118137A1 CN 2016101998 W CN2016101998 W CN 2016101998W WO 2017118137 A1 WO2017118137 A1 WO 2017118137A1
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carbazole derivative
organic
aromatic
high polymer
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French (fr)
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黄宏
潘君友
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Guangzhou Chinaray Optoelectronic Materials Ltd
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Guangzhou Chinaray Optoelectronic Materials Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/10—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • 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

Definitions

  • the present invention relates to the field of organic electroluminescent materials, and more particularly to a carbazole derivative, a polymer, a mixture, a composition, an organic electronic device, and applications thereof.
  • organic electroluminescent materials have laid a solid foundation for the realization of large-area new display devices.
  • luminescent material systems based on fluorescence and phosphorescence have been developed so far, and organic light-emitting diodes using fluorescent materials have high reliability, but their internal electroluminescence under electrical excitation
  • the quantum efficiency is limited to 25% because the branch ratio of the singlet excited state and the triplet excited state of the exciton is 1:3.
  • organic light-emitting diodes using phosphorescent materials have achieved nearly 100% internal electroluminescence quantum efficiency.
  • the stability of phosphorescent OLEDs needs to be improved.
  • the stability of the OLED, in addition to the illuminant itself, the main material is the key.
  • carbazole derivatives Due to its high carrier transport capacity, photoelectric response properties and thermal stability, carbazole derivatives have become the focus of academic and industrial circles and are widely used in organic light-emitting diodes. Due to the certain activity of the 3,6-position of carbazole, most of the carbazole derivatives currently developed still have insufficient chemical/environmental stability, mainly due to the lone pair of nitrogen atoms in the structure of such materials. Conjugated to the benzene ring to form a CH bond with a high electron cloud density and high reactivity, resulting in poor chemical/environmental stability and short device life of this type of compound.
  • Ar 1 is an aromatic or 6 to 20 carbon atom heteroaromatic or non-aromatic ring system which is unsubstituted or substituted by one or more groups R 1 ;
  • Ar 2 is a heteroaromatic or non-aromatic ring system having 6 to 20 carbon atoms and 6 to 20 carbon atoms which are unsubstituted or substituted by one or more groups R 1 ;
  • Ar 3 is a heteroaromatic or non-aromatic ring system having 6 to 20 carbon atoms and 6 to 20 carbon atoms which are unsubstituted or substituted by one or more groups R 1 ;
  • Ar 4 is an aromatic or non-aromatic ring system having 6 to 40 carbon atoms or 6 to 40 carbon atoms which is unsubstituted or substituted by one or more groups R 1 ;
  • Ar 1 , Ar 2 and Ar 3 are the same or different, and the group R 1 may be the same or different when it occurs multiple times;
  • R is hydrogen, or R is an aromatic of 6 to 20 carbon atoms or a heteroaromatic or non-aromatic ring system of 2 to 20 carbon atoms which is unsubstituted or substituted by one or more groups R 0 , Or R is a linear alkane, an alkane ether, an alkane aromatic ring system, an alkane heteroaromatic or an alkane non-aromatic ring system of 1 to 20 carbon atoms, and the group R 0 may be the same or different when it occurs multiple times;
  • n 0, 1, 2, 3 or 4;
  • R 0 and R 1 in each occurrence the same or different selected from -H, -F, -Cl, -Br, -I, -D, -CN, -NO 2 , -CF 3 , -B (OR 2 ) 2 ,-Si(R 2 ) 3 , a linear alkane, an alkane ether, an alkane sulfide having 1 to 10 carbon atoms, a branched alkane, a cycloalkane or an alkane ether group having 3 to 10 carbon atoms;
  • the methylene group is an aromatic amine which is not replaced or substituted by one or more active R 2 or an aromatic group and a heteroaromatic ring, or a substituted or unsubstituted carbazole;
  • R 2 in each occurrence, the same or different selected from H, D, an aliphatic alkane having 1 to 10 carbon atoms, an aromatic hydrocarbon containing 5 to 10 ring atoms substituted or unsubstituted aromatic ring or aromatic Group.
  • a high polymer the compound corresponding to the repeating unit of the high polymer comprising the above carbazole derivative.
  • the organic functional material is selected from at least one of a hole injecting material, a hole transporting material, an electron transporting material, an electron injecting material, an electron blocking material, a hole blocking material, an illuminant, a host material, and an organic dye.
  • composition comprising the above carbazole derivative and at least one organic solvent
  • the composition includes the above high polymer and at least one organic solvent;
  • the composition comprises the above mixture and at least one organic solvent.
  • An organic electronic device comprising the above carbazole derivative, the above high polymer or a mixture thereof.
  • the above carbazole derivative comprises at least three aromatic ring or heteroaromatic ring conjugated units, which has good stability and can be used as an electrophosphorescent light-emitting host material.
  • the carbazole derivative can improve the luminous efficiency and lifetime of the electroluminescent device by blending with a suitable guest material; the carbazole derivative can also be used as a fluorescent host material or a luminescent material through a suitable fluorescent host material. Or the guest material is matched to facilitate the improvement of the efficiency and the lifetime of the electroluminescent device, and provides a solution for the light-emitting device with low manufacturing cost, high efficiency and long life.
  • the present invention provides a carbazole derivative, a high polymer, a mixture, a composition, an organic electronic device, and an application thereof, and the present invention will be further described in detail below in order to clarify and clarify the object, the technical solution and the effect of the present invention. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
  • composition and the printing ink, or ink have the same meaning and are interchangeable.
  • the subject material, the matrix material, the Host or the Matrix material have the same meaning, and they are interchangeable.
  • metal organic complexes, metal organic complexes, and organometallic complexes have the same meaning and are interchangeable.
  • Ar 1 is an aromatic or 6 to 20 carbon atom heteroaromatic or non-aromatic ring system which is unsubstituted or substituted by one or more groups R 1 ;
  • Ar 2 is an aromatic or 6 to 20 carbon atom heteroaromatic or non-aromatic ring system which is unsubstituted or substituted by one or more groups R 1 and has 6 to 20 carbon atoms.
  • Ar 3 is an aromatic or 6 to 20 carbon atom heteroaromatic or non-aromatic ring system which is unsubstituted or substituted by one or more groups R 1 and has 6 to 20 carbon atoms.
  • Ar 4 is an aromatic or non-aromatic ring system having 6 to 40 carbon atoms and 2 to 40 carbon atoms which are unsubstituted or substituted by one or more groups R 1 .
  • Ar 1 , Ar 2 and Ar 3 are the same or different, and the groups R 1 may be the same or different when they occur multiple times.
  • R may be the same or different when it occurs multiple times.
  • R is hydrogen, or R is an aromatic of 6 to 20 carbon atoms or a heteroaromatic or non-aromatic ring system of 2 to 20 carbon atoms which is unsubstituted or substituted by one or more groups R 0 ,
  • R is a linear alkane, an alkane ether, an alkane aromatic ring system, an alkane heteroaromatic or an alkane non-aromatic ring system of 1 to 20 carbon atoms, and the group R 0 may be the same or different when it occurs multiple times.
  • n 0, 1, 2, 3 or 4.
  • R 0 and R 1 in each occurrence the same or different selected from -H, -F, -Cl, -Br, -I, -D, -CN, -NO 2 , -CF 3 , -B (OR 2 ) 2 ,-Si(R 2 ) 3 , a linear alkane, an alkane ether, an alkane sulfide having 1 to 10 carbon atoms, a branched alkane, a cycloalkane or an alkane ether group having 3 to 10 carbon atoms.
  • the methylene group is an aromatic amine which is not replaced or substituted by one or more active R 2 or an aromatic group and a heteroaromatic ring, or a substituted or unsubstituted carbazole.
  • R 2 in each occurrence, the same or different selected from H, D, an aliphatic alkane having 1 to 10 carbon atoms, an aromatic hydrocarbon containing 5 to 10 ring atoms substituted or unsubstituted aromatic ring or aromatic Group.
  • Ar 1 -Ar 4 , and at least one R may have the same or different ones selected from unsubstituted or substituted by R 1 in each occurrence.
  • the aromatic ring system contains 5 to 18 carbon atoms in the ring system.
  • the heteroaromatic ring system contains 2 to 18 carbon atoms and at least one hetero atom in the ring system. Further, the total number of carbon atoms and hetero atoms in the heteroaromatic ring is at least 4.
  • the aromatic ring system contains from 5 to 16 carbon atoms in the ring system
  • the heteroaromatic ring system contains from 2 to 16 carbon atoms and at least one hetero atom in the ring system.
  • the aromatic ring system contains 5 to 13 carbon atoms in the ring system
  • the heteroaromatic ring system contains 2 to 13 carbon atoms and at least one hetero atom in the ring system.
  • the hetero atom is selected from the group consisting of Si, N, P, O, S, and/or Ge. Further, the hetero atom is selected from the group consisting of Si, N, P, O, and/or S.
  • An aromatic ring system or aromatic group refers to a hydrocarbon group containing at least one aromatic ring, including a monocyclic group and a polycyclic ring system.
  • a heteroaromatic or heteroaromatic group refers to a hydrocarbyl group (containing heteroatoms) comprising at least one heteroaromatic ring, including monocyclic groups and polycyclic ring systems. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, a fused ring. At least one of these rings of the polycyclic ring is aromatic or heteroaromatic.
  • aromatic or heteroaromatic ring systems include not only aromatic or heteroaromatic systems, but also multiple aryl or heteroaryl 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, benzofluorene, triphenylene, anthracene, anthracene, and derivatives thereof.
  • heteroaromatic groups 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.
  • At least one of Ar 1 -Ar 4 comprises a non-aromatic ring system having from 2 to 20 carbon atoms which is unsubstituted or substituted with R 1 .
  • non-aromatic ring systems contain from 1 to 10, preferably from 1 to 6 carbon atoms in the ring system, and include not only saturated but also partially unsaturated cyclic systems which may be unsubstituted or grouped. Single or multiple R 1 substitutions.
  • the groups R 1 may be the same or different in each occurrence, and may also contain one or more heteroatoms, specifically, R 1 is Si, N, P, O, S and/or Ge, further, R 1 It is Si, N, P, O and/or S.
  • These examples may be cyclohexyl- or piperidine-like systems or ring-like octadiene ring systems.
  • the term also applies to fused non-aromatic ring systems.
  • the H atom or the bridging group CH 2 group on NH may be substituted by an R 1 group, and R 1 may be selected from (1) a C1 to C10 alkyl group, for example, may be a group as follows : methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, N-hexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoromethyl, 2,2,2-trifluoroethyl, ethylene Base, propenyl, butenyl, pentenyl, cyclopentenyl, ethylene Base, propenyl
  • aromatic and heteroaromatic ring systems are considered to be especially in addition to the above-mentioned aryl and heteroaryl groups, but also to biphenylene, benzene terphenyl, anthracene, spirobifluorene, dihydrogen. Phenanthrene, tetrahydroanthracene and cis or trans fluorene.
  • Ar 1 , Ar 2 and Ar 3 may be the same or different, each is selected from the group consisting of aromatic and heteroaromatic groups having 2 to 10 carbon atoms. Or non-aromatic ring systems which may be unsubstituted or substituted by one or more R 1 groups.
  • the specific aromatic or heteroaryl group may be benzene, naphthalene, anthracene, phenanthrene, pyridine, perylene or thiophene.
  • Ar 1 , Ar 2 and Ar 3 are the same or differently selected from one of the following structural groups:
  • X 1 is CR 3 or N;
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 may also be selected from a combination of the above corresponding groups, wherein one or more of the groups R 3 , R 4 , R 5 , R 6 , R 7 , R 8 may form a monocyclic or polycyclic aliphatic or aromatic ring to each other and/or to the ring to which the group is bonded.
  • Ar 1 , Ar 2 and Ar 3 are the same or different ones selected from the group consisting of the following structural groups:
  • Ar 1 , Ar 2 and Ar 3 are identical or differently selected from the structural groups in which the above-mentioned structural group is substituted by one or more groups R 1 .
  • n 0, 1, 2, 3 or 4.
  • carbazole derivative according to the present invention is selected from one of the following structural formulae:
  • the carbazole derivative may also be a structural group obtained by further substituting the above structural formula.
  • the carbazole derivative according to the present invention can be used as a light-emitting layer host material in an electroluminescent device.
  • the carbazole derivative has a higher triplet energy level (T 1 ), generally reaching T 1 ⁇ 2.10 eV, further reaching T 1 ⁇ 2.40 eV, and further reaching T 1 ⁇ 2.60 eV, and further reaching T 1 ⁇ 2.70 eV, and further up to T 1 ⁇ 2.80 eV.
  • the carbazole derivative according to the invention has a triplet energy level T 1 ⁇ 2.2 eV. At this time, this organic compound can be preferentially used as a phosphorescent host material.
  • the compound according to the invention may be applied to a luminescent layer fluorescent host material or luminescent material in an electroluminescent device.
  • the carbazole derivative has a higher singlet energy level (S 1 ) and a lower triplet energy level (T 1 ), generally S 1 ⁇ 2.80 eV, T 1 ⁇ 2.10 eV, further, S 1 ⁇ 2.90 eV, T 1 ⁇ 2.00 eV, further S 1 ⁇ 2.90 eV, T 1 ⁇ 1.90 eV, and further S 1 ⁇ 2.90 eV, T 1 ⁇ 1.8 eV.
  • the difference ⁇ E(S 1 -T 1 ) between the singlet energy level (S 1 ) and the triplet energy level (T 1 ) of the carbazole derivative is relatively large, and such a compound can be used as a luminescence.
  • the fluorescent host material of the layer The general ⁇ E(S 1 -T 1 ) ⁇ 0.60eV, further ⁇ E(S 1 -T 1 ) ⁇ 0.80eV, further ⁇ E(S 1 -T 1 ) ⁇ 1.0eV, further ⁇ E(S 1 -T 1 ) ⁇ 1.1eV.
  • the carbazole derivative according to the invention has a smaller ⁇ E(S 1 -T 1 ), a general ⁇ E(S 1 -T 1 ) ⁇ 0.30 eV, and further ⁇ E (S 1 -T 1 ) ⁇ 0.25eV, further ⁇ E(S 1 -T 1 ) ⁇ 0.20eV, further ⁇ E(S 1 -T 1 ) ⁇ 0.15eV, further ⁇ E(S 1 -T 1 ) ⁇ 0.10eV.
  • An electron donating group is included, and/or at least one R or Ar 4 contains an electron withdrawing group.
  • the electron donating group is selected from one of the following groups D1 to D10:
  • the electron withdrawing group is selected from the group consisting of F, a cyano group, or an electron withdrawing group selected from the group consisting of:
  • a is 1, 2, 3 or 4;
  • X 2 to X 9 are selected from CR or N, and at least one is N;
  • the carbazole derivative according to the invention is a small molecule material.
  • 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 ⁇ 4000 g/mol, further the molecular weight is ⁇ 3000 g/mol, further the molecular weight is ⁇ 2000 g/mol, and further the molecular weight is ⁇ 1500 g/mol.
  • the polymer that is, the polymer, includes a homopolymer, a copolymer, and a block copolymer. Further in the present invention, 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 sp 2 hybrid orbitals of C atoms. Famous examples are: polyacetylene polyacetylene and poly(phenylene vinylene).
  • the C atom on the chain can also be substituted by other non-C atoms, and is still considered a conjugated polymer when the sp 2 hybrid on the backbone is interrupted by some natural defects.
  • 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 solubility of the organic small molecule compound is ensured by the substituent R on the units of the formulae (1) to (38) and optionally on the unit additionally present, and by adjusting the position of the bond between the core structure and the substituent. .
  • substituents can also promote solubility if other substituents are present.
  • the structural units of the general formulae (1) to (38) are suitable for various functions in organic small molecule compounds depending on the substitution pattern. Therefore, they are preferably used as the main skeleton of the small molecule compound or as an illuminant.
  • examples of the units of the general formulae (1) to (38) may be the following structures. Further these structures can be substituted at all possible points of substitution.
  • the above carbazole derivative comprises at least three aromatic ring or heteroaromatic ring conjugated units, which has good stability and can be used as an electrophosphorescent light-emitting host material.
  • the carbazole derivative can improve the luminous efficiency and lifetime of the electroluminescent device by blending with a suitable guest material; the carbazole derivative can also be used as a fluorescent host material or a luminescent material through a suitable fluorescent host material. Or the guest material is matched to facilitate the improvement of the efficiency and the lifetime of the electroluminescent device, and provides a solution for the light-emitting device with low manufacturing cost, high efficiency and long life.
  • the present invention also relates to a high polymer in which at least one compound corresponding to the repeating unit contains any of the structures represented by the general formulae (1) to (8).
  • the high polymer in certain embodiments is a non-conjugated high polymer in which the structural unit represented by the general formulae (1) to (8) is located on the side chain of the high polymer. In another embodiment, the high polymer is a conjugated high polymer.
  • the invention relates to a mixture comprising the above-mentioned carbazole derivative and an organic functional material.
  • the mixture includes the above high polymer and an organic functional material.
  • Organic functional materials are selected from the group consisting of holes (also known as holes) injection or transport materials (HIM/HTM), hole blocking materials (HBM), electron injecting or transporting materials (EIM/ETM), electron blocking materials (EBM), organic At least one of a host material, a singlet illuminant (fluorescent illuminant), a heavy illuminator (phosphorescent illuminant), an organic thermal excitation delayed fluorescent material (TADF material), particularly a luminescent organic metal complex .
  • Various organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1, and WO2011110277A1, the entire disclosure of which is hereby incorporated by reference.
  • the organic functional material may be a small molecule and a high polymer material.
  • the mixture comprises a carbazole derivative or polymer according to the invention, and a phosphorescent emitter.
  • the carbazole derivative or polymer according to the present invention may be used as a host, wherein the phosphorescent emitter accounts for ⁇ 30% by weight, further ⁇ 25% by weight, and further ⁇ 20% by weight in the mixture.
  • the mixture comprises a carbazole derivative or polymer according to the invention, and a fluorescent illuminant.
  • the carbazole derivative or polymer according to the present invention can be used as a fluorescent host material, wherein the fluorescent illuminant accounts for ⁇ 15% by weight, further ⁇ 10% by weight, and further ⁇ 8% by weight in the mixture.
  • the mixture comprises a carbazole derivative or polymer according to the invention, and a fluorescent host material.
  • the carbazole derivative or polymer according to the invention may be used as a fluorescent luminescent material, the carbazole derivative or polymer in the mixture by weight percentage ⁇ 15% by weight, further ⁇ 10% by weight, further ⁇ 8% by weight .
  • the mixture comprises a carbazole derivative or polymer according to the invention, a phosphorescent emitter and a host material.
  • the carbazole derivative or polymer according to the present invention may be used as an auxiliary luminescent material, and the weight ratio of the carbazole derivative or polymer to the phosphorescent emitter may be from 1:2 to 2:1.
  • the carbazole derivative according to the present invention, the polymer or a T 1 higher than the phosphorescent emitter may be used as auxiliary luminescent material, and the weight ratio of the carbazole derivative or polymer to the phosphorescent emitter may be from 1:2 to 2:1.
  • the carbazole derivative according to the present invention, the polymer or a T 1 higher than the phosphorescent emitter may be used as auxiliary luminescent material, and the weight ratio of the carbazole derivative or polymer to the phosphorescent emitter may be from 1:2 to 2:1.
  • the carbazole derivative according to the present invention, the polymer or a T 1 higher than the phosphorescent emitter
  • the mixture comprises a carbazole derivative or polymer according to the invention, and a TADF material.
  • the carbazole derivative or polymer according to the present invention may be used as the TADF host material, wherein the TADF material accounts for ⁇ 15% by weight, further ⁇ 10% by weight, and further ⁇ 8% by weight in the mixture.
  • the subject material, the phosphorescent material and the fluorescent host material, the fluorescent material and the TADF material are described in some detail below (but are not limited thereto).
  • the example of the triplet host material is not particularly limited, and any metal complex or organic compound may be used as the host as long as its triplet energy is higher than that of the illuminant, particularly the triplet illuminant or the phosphorescent illuminant.
  • metal complexes that can be used as the triplet host include, but are not limited to, the following general structure:
  • M is a metal
  • (Y 3 -Y 4 ) is a bidentate ligand, Y 3 and Y 4 are independently selected from C, N, O, P, and S
  • L is an ancillary ligand
  • m is an integer , the value from 1 to the maximum coordination number of this metal
  • m + n is the maximum coordination number of this metal.
  • the metal complex that can be used as the triplet host has the following form:
  • (O-N) is a two-tooth ligand in which the metal is coordinated to the O and N atoms.
  • M can be selected from Ir and Pt.
  • Examples of the organic compound which can be used as the host of the triplet state are selected from compounds containing a cyclic aromatic hydrocarbon group such as benzene, biphenyl, triphenyl, benzo, anthracene; compounds containing an aromatic heterocyclic group such as dibenzothiophene, Dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, carbazole, pyridinium, pyrrole dipyridine, pyrazole, imidazole, three Azole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, thiazide, dioxazin, hydrazine Anthracen
  • the triplet host material can be selected from compounds comprising at least one of the following groups:
  • R 1 to R 7 may be independently selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl, when they are aromatic Or a heteroaryl group, which has the same meaning as Ar 1 and Ar 2 described above; n is an integer from 0 to 20; X 1 -X 8 is selected from CH or N; and X 9 is selected from CR 1 R 2 or NR. 1 .
  • 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. Alternatively, 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, especially preferred 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, with particular preference being given to the triplet emitter comprising 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 selected from the group consisting of acetone acetate or picric acid.
  • the metal complex that can be used as the triplet emitter has the following form:
  • M 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; m is 1, 2 or 3, preferably 2 or 3, particularly preferably 3; n is 0, 1, or 2, preferably 0 or 1, Particularly preferred is 0.
  • 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 preferred 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, and it is particularly preferred 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 selected from the group consisting of acetone acetate or picric acid.
  • the metal complex that can be used as the triplet emitter has the following form:
  • M is a metal selected from transition metal elements or lanthanides or actinides
  • Ar1 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.
  • Ar2 may be the same or different at each occurrence, and is a cyclic group containing at least one C atom through which a cyclic group is bonded to a metal; Ar1 and Ar2 are linked by a covalent bond, respectively Carrying one or more substituent groups, which may also be linked 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, preferably a monoanionic bidentate chelate ligand; m is 1, 2 or 3, preferably 2 or 3, particularly preferably 3; n 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:
  • the example of the singlet host material is not particularly limited, and any organic compound may be used as the host as long as its singlet energy is higher than that of the illuminant, particularly the singlet illuminant or the luminescent illuminant.
  • Examples of the organic compound used as the singlet host material may be selected from the group consisting of a cyclic aromatic compound such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, anthracene, phenanthrene, anthracene, anthracene, fluorene, fluorene, fluorene, An aromatic heterocyclic compound such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, oxazole, carbazole, pyridine Anthraquinone, pyrrole dipyridine, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, triazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrim
  • the singlet host material can be selected from compounds comprising at least one of the following groups:
  • R1 may be independently selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl;
  • Ar1 is aryl or hetero An aryl group having the same meaning as Ar1 defined in the above HTM;
  • n is an integer from 0 to 20;
  • X1 to X8 are selected from CH or N; and
  • X9 and X10 are selected from CR1R2 or NR1.
  • 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 aromatic amine.
  • 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.
  • Preferred examples thereof are aromatic decylamine, aromatic quinone diamine, aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine.
  • 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, two of which The diarylamine groups are attached directly to the oxime, preferably at the 9,10 position.
  • the definitions of aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine are similar, wherein the diaryl aryl 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: WO2006/000388, WO2006/058737, WO2006/000389, WO2007/065549, WO2007/115610, US 7250532 B2, DE 102005058557 A1, CN 1583691 A, JP 08053397 A, US Pat. No. 6,251,531 B1, US 2006/210830 A, EP 1 957 606 A1 and US 2008/0113101 A1, the entire contents of each of which is hereby incorporated by reference.
  • Further preferred singlet emitters are selected from the group consisting of an indeno-amine and an indeno-diamine, as disclosed in WO2006/122630, benzoindolo-amine and benzoindeno-diamine, Dibenzoindolo-amine and dibenzoindenoindole-diamine as disclosed in WO 2008/006449, 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
  • 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%.
  • the material structure is controllable, the property is stable, the price is cheap, no precious metal is needed, and the application prospect in the OLED field is broad.
  • the TADF material needs to have a small singlet-triplet energy level difference, preferably ⁇ Est ⁇ 0.3 eV, and secondly ⁇ Est ⁇ 0.2 eV, preferably ⁇ Est ⁇ 0.1 eV.
  • the TADF material has a relatively small ⁇ Est, and in another preferred embodiment, the TADF has a 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:
  • Another object of the invention is to provide a material solution for printing OLEDs.
  • the carbazole derivative according to the invention has a molecular weight of ⁇ 700 g/mol, a further molecular weight ⁇ 900 g/mol, a further molecular weight ⁇ 900 g/mol, and further a molecular weight ⁇ 1000 g/mol. Further molecular weight ⁇ 1100g / mol.
  • the carbazole derivative according to the invention has a solubility in toluene of > 10 mg/ml at 25 ° C, a further solubility of ⁇ 15 mg/ml, and further a solubility of ⁇ 20 mg/ml.
  • the invention still further relates to a composition or ink comprising a carbazole derivative as described above and at least one organic solvent.
  • the composition is a high polymer as described above and at least one organic solvent.
  • the composition comprises the above mixture 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 invention 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. Further, the surface tension is in the range of 22 dyne/cm to 35 dyne/cm. Further, the surface tension is in the range of 25 dyne/cm to 33 dyne/cm.
  • the ink according to the present invention has a viscosity at an operating temperature or 25 ° C ranging from about 1 cps to 100 cps. Further, the viscosity is in the range of 1 cps to 50 cps. Further, the viscosity is in the range of 1.5 cps to 20 cps. Further, the viscosity is in the range of 4.0 cps to 20 cps.
  • 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 invention can facilitate 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 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. In the range of 0.5% to 10% by weight, The most preferred range is from 1% to 5% by weight.
  • the at least one organic solvent is selected from the group consisting of aromatic or heteroaromatic based solvents, particularly aliphatic chain/ring substituted aromatic solvents, or aromatic ketones, in accordance with the inks of the present invention.
  • Solvent, or aromatic ether solvent is selected from the group consisting of aromatic or heteroaromatic based solvents, particularly aliphatic chain/ring substituted aromatic solvents, or aromatic ketones, in accordance with the inks of the present invention.
  • Solvent, or aromatic ether solvent is selected from the group consisting of aromatic or heteroaromatic based solvents, particularly aliphatic chain/ring substituted aromatic solvents, or aromatic ketones, in accordance with the inks of the present invention.
  • Solvent, or aromatic ether solvent is selected from the group consisting of aromatic or heteroaromatic based solvents, particularly aliphatic chain/ring substituted aromatic solvents, or aromatic ketones, in accordance with the inks of the present invention.
  • Solvent, or aromatic ether solvent is selected from the
  • 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-dimethyl Naphthalene, 3-isopropylbiphenyl, p-methyl cumene, dipentylbenzene, triphenylbenzene, pentyltoluene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethyl Benzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, two Hexylbenzene, di
  • the at least one 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-nonan
  • 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 invention is a solution.
  • composition according to the invention is a suspension.
  • composition in the examples of the present invention may comprise from 0.010% by weight to 20% by weight of the carbazole derivative according to the invention or a mixture thereof, further from 0.1 to 15% by weight, further further from 0.2 to 10% by weight, further It is 0.25 to 5 wt% of an organic compound or a mixture thereof.
  • the invention relates to the use of the composition as a coating or printing ink in the preparation of an organic electronic device, particular preference being given to a preparation process by printing or coating.
  • 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 invention also provides an application of the carbazole derivative as described above, that is, the carbazole derivative is applied to an organic electronic device, and the organic electronic device can be selected from, but not limited to, organic light emission.
  • Diodes OLEDs
  • OLEDs Organic Photovoltaic Cells
  • OLEDs Organic Light Emitting Cells
  • OFETs Organic Field Effect Transistors
  • Organic Light Emitting Fields Organic Lasers, Organic Spintronics, Organic Sensors and Organic Plasmons Organic Plasmon Emitting Diode, etc., especially OLED.
  • the organic compound is preferably used in a light-emitting layer of an OLED device.
  • the invention further relates to an organic electronic device comprising at least one carbazole derivative, polymer or mixture 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 contains at least one organic 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 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 electroluminescent device has a light-emitting layer comprising at least one of the carbazole derivatives or at least one of the high polymers.
  • the luminescent layer of the electroluminescent device comprises one of said carbazole derivatives and a phosphorescent illuminant, a fluorescent illuminant or a host material.
  • the luminescent layer luminescent layer of the electroluminescent device comprises one of said high polymer and a host material and a phosphorescent illuminant, a fluorescent illuminant or a host material.
  • the light-emitting layer of the electroluminescent device comprises one of the above-mentioned carbazole derivatives, a phosphorescent emitter and a host material.
  • the luminescent layer of the electroluminescent device comprises a high polymer, a phosphorescent illuminant and a host Body 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 invention.
  • 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 invention.
  • 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 is prepared by the composition according to the invention.
  • a light-emitting device has an emission wavelength of between 300 and 1000 nm, preferably between 350 and 900 nm. More preferably, it is between 400 and 800 nm.
  • the invention further relates to the use of oxazole derivatives according to the invention in various electronic devices, including, but not limited to, display devices, illumination devices, light sources, sensors and the like.
  • the invention further relates to an electronic device comprising an organic electronic device according to the invention, including, but not limited to, a display device, a lighting device, a light source, a sensor and the like.
  • the synthesis procedure was similar to that of Example 1. Into a 250 ml three-necked flask was added 3.19 g, 10 mmol of phenanthroline and oxazole, 4.3 g, and 11 mmol of 2-(3-bromophenyl)-4,6-diphenyl-1,3. , 5-triazine, 6.9 g, 50 mmol potassium carbonate, 0.26 g, 1 mmol 18-crown-6, 3.0 g, 15 mmol copper iodide and 150 ml o-dichlorobenzene, reacted in a N 2 atmosphere at 160 ° C, TLC tracking The progress of the reaction, until the reaction is over, is lowered to room temperature.
  • the energy level of the organic compound material can be obtained by quantum calculation, for example, by TD-DFT (time-dependent density functional theory) through Gaussian 09W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110.
  • TD-DFT time-dependent density functional theory
  • 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 S 1 , T 1 and the resonance factor f(S 1 ) are used directly.
  • HOMO(eV) ((HOMO(G) ⁇ 27.212)-0.9899)/1.1206
  • HOMO (G) and LUMO (G) are direct calculation results of Gaussian 09W, the unit is Hartree.
  • the calculation results of the materials prepared in Examples 1 to 6 are shown in Table 1:
  • the materials (1) and materials (2) can be applied to the green phosphorescent host material, and the materials (3) to (6) can be used for the blue fluorescent host material or the luminescent material to satisfy various conditions of the luminescent layer material.
  • the host material of the currently used carbazole material architecture is labeled with Ref 1 :
  • ITO/HATCN (10 nm) / NPB (35 nm) / TCTA (5 nm) / (1) ⁇ (2): 5% Ir (ppy) 3 / B3PYMPM (40 nm) / LiF (1 nm) / Al (150 nm), OLED
  • the preparation steps of the device are as follows:
  • a, cleaning of the conductive glass substrate when used for the first time, can be washed with a variety of solvents, such as chloroform, ketone, isopropyl alcohol, and then UV ozone plasma treatment;
  • cathode LiF / Al (1nm / 150nm) in a high vacuum (1 ⁇ 10 -6 mbar) in the thermal evaporation;
  • the device is encapsulated in a nitrogen glove box with an ultraviolet curable resin.
  • the current-voltage (J-V) characteristics of each OLED device are characterized by characterization equipment while recording important parameters such as efficiency, lifetime and external quantum efficiency.
  • the luminous efficiency and lifetime of OLED1 are more than three times that of OLED Ref1 (corresponding material (Ref1)), and the luminous efficiency of OLED2 (corresponding material (2)) is four times that of OLED Ref1.
  • the life is 5 More than double, especially the maximum external quantum efficiency of OLED 2 is over 19%. It can be seen that the OLED device prepared by using the organic mixture of the invention has greatly improved luminous efficiency and lifetime, and the external quantum efficiency is also significantly improved.

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Abstract

一种咔唑衍生物及其应用，该咔唑衍生物具有通式(1)～(8)任一个所示的通式。其中通式(1)如下所示：其中，Ar1、Ar2、Ar3相互独立的为未被取代或是被一个或多个基团R1取代的具有6～20个碳原子的芳香族、2～20个碳原子的杂芳香族或者非芳香族环系。Ar4为未被取代或是被一个或多个基团R1取代的具有6～40个碳原子的芳香族、2～40个碳原子杂芳香族或者非芳香族环系。

Description

咔唑衍生物、高聚物、混合物、组合物、有机电子器件及其应用 技术领域：
本发明涉及有机电致发光材料领域，尤其涉及一种咔唑衍生物、高聚物、混合物、组合物、有机电子器件及其应用。
背景技术：
有机电致发光材料的多样性以及可合成性，为实现大面积新型显示器件奠定了坚实的基础。为了提高有机发光二极管的发光效率，目前为止，基于荧光和磷光的发光材料体系已被开发出来，使用荧光材料的有机发光二极管具有可靠性高的特点，但其在电气激发下其内部电致发光量子效率被限制为25％，这是因为激子的单重激发态和三重激发态的分支比为1:3。与此相反，使用磷光材料的有机发光二极管已经取得了几乎100％的内部电致发光量子效率。然而，磷光OLED的稳定性还需提高。而OLED的稳定性，除了发光体本身，主体材料是关键。
咔唑类衍生物由于具有较高的载流子传输能力、光电响应性质和热稳定性等优点，成为学术界和产业界关注的焦点，并广泛应用于有机发光二极管中。由于咔唑3,6-位具有一定的活性，目前开发的大部分咔唑类衍生物仍然存在着化学/环境稳定性较差的不足，主要是因为这类材料结构中氮原子的孤对电子，共轭到苯环中，形成电子云密度较大、反应活性较高的C-H键，致使这类型化合物的化学/环境稳定性较差、器件寿命较短。
为了提高咔唑类衍生物的稳定性及器件寿命，人们寻求降低3,6-位C-H键的反应活性的方法。一种方案是9-位N原子上引入缺电子单元，使得电子云向缺电子单元的方向转移，降低C-H的电子云密度及反应活性。但缺电子的引入同时可能会带来电化学能级的变化等问题(Adv.Funct.Mater.,2014,24,3551-3561)。
对材料的稳定性和器件寿命不断提高的需求，迫使人们寻求更稳定的光电性能材料。
发明内容：
基于此，有必要提供一种稳定性能好的咔唑衍生物，包含其的高聚物、混合物、组合物、有机电子器件及其应用。
一种咔唑衍生物，具有如下通式(1)～(8)中任何一个所示的通式：
Figure PCTCN2016101998-appb-000001
其中，Ar1为未被取代或是被一个或多个基团R1取代的具有6～20个碳原子的芳香族、2～20个碳原子的杂芳香族或者非芳香族环系；
Ar2为未被取代或是被一个或多个基团R1取代的具有6～20个碳原子的芳香族、2～20个碳原子的杂芳香族或者非芳香族环系；
Ar3为未被取代或是被一个或多个基团R1取代的具有6～20个碳原子的芳香族、2～20个碳原子的杂芳香族或者非芳香族环系；
Ar4为未被取代或是被一个或多个基团R1取代的具有6～40个碳原子的芳香族、2～40个碳原子的杂芳香族或者非芳香族环系；
Ar1、Ar2及Ar3相同或不同，基团R1在多次出现时可以是相同或不同；
R为氢，或者R为未被取代或是被一个或多个基团R0取代的6～20个碳原子的芳香族、2～20个碳原子的杂芳香族或者非芳香族环系，或者R为1～20个碳原子的直链烷烃、烷烃醚、烷烃芳香环系、烷烃杂芳香族或者烷烃非芳香族环系，基团R0在多次出现时可以是相同或不同；
n为0、1、2、3或4；
R0和R1在每一次出现中，相同或不同的选自-H,-F,-Cl,-Br,-I,-D,-CN,-NO2,-CF3,-B(OR2)2,-Si(R2)3，直链烷烃，烷烃醚，含1～10个碳原子烷烃硫醚，支链烷烃，环烷烃或者含有3～10个碳原子的烷烃醚基团；
R0和R1中一个或多个非相邻的亚甲基为未被替换或是被R2C＝CR2，C＝C，Si(R2)2，Ge(R2)2，Sn(R2)2，C＝O，C＝S，C＝Se，C＝NR2，O，-COO-或CONR2-替换；或者，R0和R1中一个或多个非相邻的亚甲基为未被替换或是被一个或多个活性R2或者一个芳香基团以及杂芳香环取代的芳香胺，或者被取代或未被取代的咔唑替换；
R2在每一次出现中，相同或不同的选自H，D，含1～10个碳原子脂肪族烷烃，芳香碳氢化合物，含5～10个环原子取代或未取代芳香环或芳杂基团。
一种高聚物，所述高聚物的重复单元对应的化合物包含了上述咔唑衍生物。
一种混合物，所述混合物包括上述咔唑衍生物以及有机功能材料，或者，所述混合物上述高聚物以及有机功能材料；
所述的有机功能材料选自空穴注入材料，空穴传输材料，电子传输材料，电子注入材料，电子阻挡材料，空穴阻挡材料，发光体，主体材料和有机染料中的至少一种。
一种组合物，所述组合物上述咔唑衍生物以及至少一种有机溶剂；
或者，所述组合物包括上述高聚物以及至少一种有机溶剂；
或者，所述组合物包括上述混合物以及至少一种有机溶剂。
上述咔唑衍生物或者上述高聚物在有机电子器件中的应用。
一种有机电子器件，包括上述咔唑衍生物、上述高聚物或上述混合物。
上述咔唑衍生物包含有至少三个芳香环或杂芳香环共轭单元，具有较好的稳定性，可作为电致磷光发光主体材料。该咔唑衍生物可通过与合适的客体材料配合，能提高其作为电致发光器件的发光效率及寿命；该咔唑衍生物也可作为荧光主体材料或发光材料，通过与合适的荧光主体材料或者客体材料配合，便于提高其作为电致发光器件的效率与寿命，为制造成本低、效率高、寿命长的发光器件提供了一种解决方案。
具体实施方式
本发明提供一种咔唑衍生物、高聚物、混合物、组合物、有机电子器件及其应用，为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。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。
在本发明中，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。在本发明中，主题材料，基质材料，Host或Matrix材料具有相同的含义，它们之间可以互换。在本发明中，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。
一种咔唑衍生物，具有如下通式(1)～(8)中任何一个所示的通式：
Figure PCTCN2016101998-appb-000002
其中，Ar1为未被取代或是被一个或多个基团R1取代的具有6～20个碳原子的芳香族、2～20个碳原子的杂芳香族或者非芳香族环系；
Ar2为未被取代或是被一个或多个基团R1取代的具有6～20个碳原子的芳香族、2～20个碳原子的杂芳香族或者非芳香族环系。
Ar3为未被取代或是被一个或多个基团R1取代的具有6～20个碳原子的芳香族、2～20个碳原子的杂芳香族或者非芳香族环系。
Ar4为未被取代或是被一个或多个基团R1取代的具有6～40个碳原子的芳香族、2～40个碳原子的杂芳香族或者非芳香族环系。
Ar1、Ar2及Ar3相同或不同，基团R1在多次出现时可以是相同或不同。
R在多次出现时，可相同或不同。R为氢，或者R为未被取代或是被一个或多个基团R0取代的6～20个碳原子的芳香族、2～20个碳原子的杂芳香族或者非芳香族环系，或者R为1～20个碳原子的直链烷烃、烷烃醚、烷烃芳香环系、烷烃杂芳香族或者烷烃非芳香族环系，基团 R0在多次出现时可以是相同或不同。
n为0、1、2、3或4。
R0和R1在每一次出现中，相同或不同的选自-H,-F,-Cl,-Br,-I,-D,-CN,-NO2,-CF3,-B(OR2)2,-Si(R2)3，直链烷烃，烷烃醚，含1～10个碳原子烷烃硫醚，支链烷烃，环烷烃或者含有3～10个碳原子的烷烃醚基团。
R0和R1中一个或多个非相邻的亚甲基为未被替换或是被R2C＝CR2，C＝C，Si(R2)2，Ge(R2)2，Sn(R2)2，C＝O，C＝S，C＝Se，C＝NR2，O，-COO-或CONR2-替换；或者，R0和R1中一个或多个非相邻的亚甲基为未被替换或是被一个或多个活性R2或者一个芳香基团以及杂芳香环取代的芳香胺，或者被取代或未被取代的咔唑替换。
R2在每一次出现中，相同或不同的选自H，D，含1～10个碳原子脂肪族烷烃，芳香碳氢化合物，含5～10个环原子取代或未取代芳香环或芳杂基团。
具体的，在通式(1)～(8)中，Ar1-Ar4，及至少一个的R在每一次出现中，可以相同或不同的选自未被取代或是被R1取代的具有6～20个碳原子的芳香族环或2～20个碳原子杂芳香族环。
具体的，芳香环系在环系中包含5～18个碳原子。杂芳香环系在环系中包含2～18个碳原子和至少一个杂原子，进一步的，杂芳香环中碳原子和杂原子的总数至少为4。在一个实施例中，芳香环系在环系中包含5～16个碳原子，杂芳香环系在环系中包含2～16个碳原子和至少一个杂原子。进一步的，芳香环系在环系中包含5～13个碳原子，杂芳香环系在环系中包含2～13个碳原子和至少一个杂原子。杂原子选自Si、N、P、O、S和/或Ge，进一步的，杂原子选自Si、N、P、O和/或S。
芳香环系或芳族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。杂芳香环系或杂芳族基团指包含至少一个杂芳环的烃基(含有杂原子)，包括单环基团和多环的环系统。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。对于本发明的目的，芳香族或杂芳香族环系不仅包括芳香基或杂芳香基的体系，而且，其中多个芳基或杂芳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，芳族基团的例子有：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，杂芳族基团的例子有：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。
在某些实施例中，Ar1-Ar4至少有一个包含一个未被取代或是被R1取代的具有2～20个碳 原子的非芳香族环系。
对于本发明的目的，非芳香族环系在环系中包含1～10优选1-6个碳原子，且不仅包括饱和而且包括部分不饱和的环状体系，它们可以未被取代或被基团单个或多个R1取代。基团R1在每一次出现中可以相同或者不同，并且还可以包含一个或多个杂原子，具体的，R1为Si、N、P、O、S和/或Ge，进一步的，R1为Si、N、P、O和/或S。这些例子可以是类环己基或类哌啶体系，也可以是类环辛二烯环状体系。该术语同样适用于稠合的非芳香环系。
对于本发明的目的，其中NH上的H原子或桥联基CH2基团可以被R1基团取代，R1可选于，(1)C1～C10烷基，例如可以为如下的基团：甲基、乙基、正丙基、异丙基、环丙基、正丁基、异丁基、仲丁基、叔丁基、环丁基、2-甲基丁基、正戊基、正己基、环己基、正庚基、环庚基、正辛基、环辛基、2-乙基己基、三氟甲基、五氟甲基、2,2,2-三氟乙基、乙烯基、丙烯基、丁烯基、戊烯基、环戊烯基、己烯基、环己烯基、庚烯基、环庚烯基、辛烯基、环辛烯基、乙炔基、丙炔基、丁炔基、戊炔基、己炔基和辛炔基；(2)C1～C10烷氧基，例如可以为甲氧基，乙氧基，正丙氧基，异丙氧基，正丁氧基，异丁氧基，仲丁氧基，叔丁氧基或者2-甲基丁氧基；(3)C2到C10芳基或杂芳基，取决于用途其可以是一价或二价的，在每一情况下也可以被上述提及的基团R1取代并可以通过任何希望的位置与芳香族或杂芳香环连接，例如可以为以下的基团：苯、萘、蒽、嵌二萘、二氢芘、屈、茈、萤蒽、丁省、戊省、苯并芘、呋喃、苯并呋喃、异苯并呋喃、二苯并呋喃、噻吩、苯并噻吩、异苯并噻吩、硫芴、吡咯、吲哚、异吲哚、咔唑、吡啶、喹啉、异喹啉、吖啶、菲啶、苯并-5,6-喹啉、苯并-6,7-喹啉、苯并-7,8-喹啉、吩噻嗪、吩恶嗪、吡唑、吲唑、咪唑、苯并咪唑、萘并咪唑、菲并咪唑、吡啶并咪唑、吡嗪并咪唑、喹喔啉并咪唑、恶唑、苯并恶唑、萘并恶唑、蒽并恶唑、菲并恶唑、异恶唑、1,2-噻唑、1,3-噻唑、苯并噻唑、哒嗪、苯并哒嗪、嘧啶、苯并嘧啶、喹喔啉、吡嗪、二氮蒽、1,5-二氮杂萘、氮咔唑、苯并咔啉、菲咯啉、1,2,3-三唑、1,2,4-三唑、苯并三唑、1,2,3-恶二唑、1,2,4-恶二唑、1,2,5-恶二唑、1,3,4-恶二唑、1,2,3-噻二唑、1,2,4-噻二唑、1,2,5-噻二唑、1,3,4-噻二唑、1,3,5-三嗪、1,2,4-三嗪、1,2,3-三嗪、四唑。1,2,4,5-四嗪、1,2,3,4-四嗪、1,2,3,5-四嗪、嘌呤、蝶啶、中氮茚和苯并噻二唑。用于本发明的目的，芳香和杂芳族环系认为特别是除上述提及的芳基和杂芳基之外，还指亚联苯基、亚三联苯、芴、螺二芴、二氢菲、四氢芘和顺式或者反式茚并芴。
具体的，按照通式(1)～(8)的化合物，其中Ar1,Ar2,Ar3可相同或不同的在每一次出现中选自具有2到10个碳原子的芳香、杂芳族或者非芳香族环系，它们可以未被取代或者被一个或多个R1基团取代。具体的芳族基或者杂芳基可以为苯、萘、蒽、菲、吡啶、嵌二萘或噻吩。
进一步的，按照通式(1)～(8)的化合物，Ar1、Ar2及Ar3相同或不同地选自如下结构基团中的一种：
Figure PCTCN2016101998-appb-000003
其中，X1是CR3或N；Y1选自CR4R5，SiR6R7，NR8或，C(＝O)，S，或O；
R3，R4，R5，R6，R7，R8是H，或D，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5～40个环原子的芳氧基或杂芳氧基基团。
进一步的，R3，R4，R5，R6，R7，R8还可以选自上述对应基团的组合，其中一个或多个基团R3，R4，R5，R6，R7，R8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。
具体的，通式(1)～(8)其中的Ar1、Ar2及Ar3相同或不同地选自如下结构基团中的一种：
Figure PCTCN2016101998-appb-000004
或者Ar1、Ar2及Ar3相同或不同地选自如上结构基团被一个或多个基团R1取代的结构基团。
具体的，R或Ar4在多次出现时，相同或不同地选自如下结构基团中的一种:
Figure PCTCN2016101998-appb-000005
Figure PCTCN2016101998-appb-000006
其中，m为0、1、2、3或4。
更具体的，按照本发明的咔唑衍生物选自如下结构式中的一个：
Figure PCTCN2016101998-appb-000007
Figure PCTCN2016101998-appb-000008
Figure PCTCN2016101998-appb-000009
其中，Ar4、R等的含义如上所述。
在另一个实施方式中，咔唑衍生物还可以为上述结构通式被进一步取代得到的结构基团。
具体的，按照本发明的咔唑衍生物可以作为电致发光器件中的发光层主体材料。该咔唑衍生物具有较高的三重态能级(T1)，一般可达到T1≥2.10eV，进一步可达到T1≥2.40eV，再进一步可达到T1≥2.60eV，再进一步可达到T1≥2.70eV，再进一步可达到T1≥2.80eV。
在另一个实施例中，按照本发明的咔唑衍生物，其三重态能级T1≥2.2eV。此时，此有机化合物可优先作为磷光主体材料。
在另一个实施例中，按照本发明的化合物可以应用于电致发光器件中的发光层荧光主体材料或发光材料。该咔唑衍生物具有较高的单重态能级(S1)以及较低的三重态能级(T1)，一般的S1≥2.80eV，T1≤2.10eV，进一步的，S1≥2.90eV，T1≤2.00eV，再进一步的S1≥2.90eV，T1≤1.90eV，再进一步的S1≥2.90eV，T1≤1.8eV。
在某些实施例中，该咔唑衍生物的单重态能级(S1)和三重态能级(T1)的差ΔE(S1-T1)比较大，这类化合物可作为发光层的荧光主体材料。一般的ΔE(S1-T1)≥0.60eV，再进一步的ΔE(S1-T1)≥0.80eV，再进一步的ΔE(S1-T1)≥1.0eV，再进一步的ΔE(S1-T1)≥1.1eV。
在另一些实施例中，按照本发明的咔唑衍生物，具有较小的ΔE(S1-T1)，一般的ΔE(S1-T1)≤0.30eV，再进一步的ΔE(S1-T1)≤0.25eV，再进一步的ΔE(S1-T1)≤0.20eV，更再进一步的ΔE(S1-T1)≤0.15eV，再进一步的ΔE(S1-T1)≤0.10eV。
具体的，按照通式(1)～(38)的化合物其中R或Ar4在多次出现时，至少有一个R或Ar4包
括一供电子基，和/或至少有一个R或Ar4包含一吸电子基。
具体的，供电子基选自如下基团D1～D10中的一个：
Figure PCTCN2016101998-appb-000010
具体的，吸电子基选自F，氰基，或吸电子基选自如下结构基团中的一个：
Figure PCTCN2016101998-appb-000011
其中，其中，a为1、2、3或4；
X2～X9选于CR或N，并且至少有一个是N；
Z1、Z2、Z3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，但至少有一个不是无；其中R可选自氢、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基和杂芳基中的一个。
在一个实施例中，按照本发明的咔唑衍生物是一种小分子材料。
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。一般的，小分子的分子量≤4000克/摩尔，进一步的是分子量≤3000克/摩尔，再进一步的是分子量≤2000克/摩尔，更进一步的是分子量≤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)。另外在本发明中，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。另外在本发明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。
特别是通过在通式(1)～(38)单元上和任选在另外存在的单元上的取代基R，以及调整核心结构与取代基之间的连接位置，保证了有机小分子化合物的溶解度。如果存在其他的取代基，这些取代基也可以促进溶解度。
取决于取代型式，通式(1)～(38)的结构单元适合于有机小分子化合物中的各种各样的功能。因此，它们优选可用作小分子化合物的主要骨架或者作为发光体。
具体的，通式(1)～(38)单元的例子可以是以下的结构。进一步的这些结构可以在所有的可能取代的点上被取代。
Figure PCTCN2016101998-appb-000012
Figure PCTCN2016101998-appb-000013
Figure PCTCN2016101998-appb-000014
Figure PCTCN2016101998-appb-000015
Figure PCTCN2016101998-appb-000016
Figure PCTCN2016101998-appb-000017
Figure PCTCN2016101998-appb-000018
Figure PCTCN2016101998-appb-000019
Figure PCTCN2016101998-appb-000020
Figure PCTCN2016101998-appb-000021
上述咔唑衍生物包含有至少三个芳香环或杂芳香环共轭单元，具有较好的稳定性，可作为电致磷光发光主体材料。该咔唑衍生物可通过与合适的客体材料配合，能提高其作为电致发光器件的发光效率及寿命；该咔唑衍生物也可作为荧光主体材料或发光材料，通过与合适的荧光主体材料或者客体材料配合，便于提高其作为电致发光器件的效率与寿命，为制造成本低、效率高、寿命长的发光器件提供了一种解决方案。
本发明还涉及一种高聚物，其中至少有一个重复单元对应的化合物包含有如通式(1)～(8)所示的任一结构。在某些实施例中的高聚物是非共轭高聚物，其中如通式(1)～(8)所示的结构单元位于高聚物的侧链上。在另一个实施例中，高聚物是共轭高聚物。
此外，本发明还涉及一种混合物，混合物包括上述咔唑衍生物以及有机功能材料。或混合物包括上述高聚物以及一种有机功能材料。
有机功能材料选自空穴(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)，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WO2011110277A1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和高聚物材料。
在一个实施例中，所述的混合物包含一种按照本发明的咔唑衍生物或高聚物，和一种磷光发光体。这里按照本发明的咔唑衍生物或高聚物可以作为主体，其中磷光发光体在混合物中占的重量百分比≤30wt％，进一步的≤25wt％,再进一步的≤20wt％。
在另一个实施例中，所述的混合物包含一种按照本发明的咔唑衍生物或高聚物，和一种荧光发光体。这里按照本发明的咔唑衍生物或高聚物可以作为荧光主体材料，其中荧光发光体在混合物中占的重量百分比≤15wt％,进一步的≤10wt％，再进一步的≤8wt％。
在另一个实施例中，所述的混合物包含一种按照本发明的咔唑衍生物或高聚物，和一种荧光主体材料。这里按照本发明的咔唑衍生物或高聚物可以作为荧光发光材料，咔唑衍生物或高聚物在混合物中占的重量百分比≤15wt％,进一步的≤10wt％，再进一步的≤8wt％。
在一个实施例中，所述的混合物包含一种按照本发明的咔唑衍生物或高聚物，一种磷光发光体和一种主体材料。在一种实施例中，按照本发明的咔唑衍生物或高聚物可以作为辅助发光材料，咔唑衍生物或高聚物与磷光发光体的重量比可以从1:2到2:1。在另一种优选的实施例中，按照本发明的咔唑衍生物或高聚物的T1高于所述的磷光发光体。
在另一个优先的实施例中，所述的混合物包含一种按照本发明的咔唑衍生物或高聚物，和一种TADF材料。这里按照本发明的咔唑衍生物或高聚物可以作为TADF主体材料，其中所述的TADF材料在混合物中占的的重量百分比≤15wt％,进一步的≤10wt％,再进一步的≤8wt％。
下面对主体材料，磷光发光材料及荧光主体材料、荧光发光材料及TADF材料作一些较详细的描述(但不限于此)。
1、主体材料(TripletHost):
三重态主体材料的例子并不受特别的限制，任何金属络合物或有机化合物都可能被用作为主体,只要其三重态能量比发光体,特别是三重态发光体或磷光发光体更高。可用作三重态主体(Host)的金属络合物的例子包括(但不限于)如下的一般结构:
Figure PCTCN2016101998-appb-000022
M是一金属；(Y3-Y4)是一两齿配体,Y3和Y4独立地选自C,N,O,P,和S；L是一个辅助配体；m是一整数，其值从1到此金属的最大配位数；m+n是此金属的最大配位数。
在一个实施方案中，可用作三重态主体的金属络合物有如下形式：
Figure PCTCN2016101998-appb-000023
(O-N)是一两齿配体,其中金属与O和N原子配位。
在某一个实施方案中,M可选于Ir和Pt。
可作为三重态主体的有机化合物的例子选自包含有环芳香烃基的化合物，例如苯、联苯、三苯基、苯并、芴；包含有芳香杂环基的化合物，如二苯并噻吩、二苯并呋喃、二苯并硒吩、呋喃、噻吩、苯并呋喃、苯并噻吩、苯并硒吩、咔唑、吲哚咔唑、吡啶吲哚、吡咯二吡啶、吡唑、咪唑、三唑类、恶唑、噻唑、恶二唑、恶三唑、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪类、恶嗪、恶噻嗪、恶二嗪、吲哚、苯并咪唑、吲唑、恶唑、二苯并恶唑、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、苯并呋喃吡啶、呋喃并吡啶、苯并噻吩吡啶、噻吩吡啶、苯并硒吩吡啶和硒吩苯并二吡啶；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。
在一个实施方案中,三重态主体材料可选于包含至少一个以下基团的化合物:
Figure PCTCN2016101998-appb-000024
Figure PCTCN2016101998-appb-000025
R1～R7可相互独立地选于如下的基团:氢，烷基，烷氧基，氨基，烯，炔，芳烷基，杂烷基，芳基和杂芳基，当它们是芳基或杂芳基时，它们与上述的Ar1和Ar2意义相同；n是一个从0到20的整数；X1-X8选于CH或N；X9选于CR1R2或NR1。
在下面的表中列出合适的三重态主体材料的例子:
Figure PCTCN2016101998-appb-000026
2、磷光发光材料
磷光发光材料也称三重态发光体。在一个优先的实施方案中，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。
在一个优先的实施方案中,金属原子M选于过渡金属元素或镧系元素或锕系元素,优先选择Ir,Pt,Pd,Au,Rh,Ru,Os,Sm,Eu,Gd,Tb,Dy,Re,Cu或Ag，特别优先选择Os,Ir,Ru,Rh,Re, Pd或Pt。
优先地,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，特别优先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。辅助配体可优先选自乙酸丙酮或苦味酸。
在一个实施方案中，可用作三重态发光体的金属络合物有如下形式：
Figure PCTCN2016101998-appb-000027
其中M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；m是1,2或3,优先地是2或3,特别优先地是3；n是0,1,或2,优先地是0或1,特别优先地是0。
三重态发光体也称磷光发光体。在一个实施方案中，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，优先选择Ir,Pt,Pd,Au,Rh,Ru,Os,Sm,Eu,Gd,Tb,Dy,Re,Cu或Ag，特别优先选择Os,Ir,Ru,Rh,Re,Pd或Pt。
具体的，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，特别优先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。辅助配体可优先选自乙酸丙酮或苦味酸。
在一个实施方案中，可用作三重态发光体的金属络合物有如下形式：
Figure PCTCN2016101998-appb-000028
其中M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；m是1,2或3,优先地是2或3,特别优先地是3；n是0,1,或2,优先地是0或1,特别优先地是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 PCTCN2016101998-appb-000029
Figure PCTCN2016101998-appb-000030
Figure PCTCN2016101998-appb-000031
Figure PCTCN2016101998-appb-000032
Figure PCTCN2016101998-appb-000033
Figure PCTCN2016101998-appb-000034
Figure PCTCN2016101998-appb-000035
Figure PCTCN2016101998-appb-000036
3.单重态主体材料(Singlet Host)：
单重态主体材料的例子并不受特别的限制，任何有机化合物都可能被用作为主体,只要其单重态能量比发光体,特别是单重态发光体或荧光发光体更高。
作为单重态主体材料使用的有机化合物的例子可选自含有环芳香烃化合物，如苯、联苯、三苯基、苯并、萘、蒽、萉、菲、芴、芘、屈、苝、薁；芳香杂环化合物，如二苯并噻吩、二苯并呋喃、二苯并硒吩、呋喃、噻吩、苯并呋喃、苯并噻吩、苯并硒吩、咔唑、吲哚咔唑、吡啶吲哚、吡咯二吡啶、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、噌啉、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、吩恶嗪、苯并呋喃吡啶、呋喃二吡啶、苯并噻吩吡啶、噻吩二吡啶、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。
在一个实施方案中，单重态主体材料可选于包含至少一个以下基团的化合物：
Figure PCTCN2016101998-appb-000037
其中，R1可相互独立地选于如下的基团：氢、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基和杂芳基；Ar1是芳基或杂芳基，它与上述的HTM中定义的Ar1意义相同；n是一个从0到20的整数；X1～X8选于CH或N；X9和X10选于CR1R2或NR1。
在下面的表中列出一些蒽基单重态主体材料的例子：
Figure PCTCN2016101998-appb-000038
4.荧光发光体(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。
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。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:WO2006/000388,WO2006/058737,WO2006/000389,WO 2007/065549,WO2007/115610,US 7250532 B2,DE102005058557 A1,CN 1583691 A,JP 08053397 A,US6251531 B1,US 2006/210830 A,EP1957606 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US5121029。
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WO2006/122630所公开的，苯并茚并芴-胺和苯并茚并芴-二胺，如WO2008/006449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 PCTCN2016101998-appb-000039
Figure PCTCN2016101998-appb-000040
5、TADF材料
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％。同时材料结构可控，性质稳定，价格便宜无需要贵金属，在OLED领域的应用前景广阔。
TADF材料需要具有较小的单线态-三线态能级差，较好是ΔEst<0.3eV，次好是ΔEst<0.2eV，最好是ΔEst<0.1eV。在一个实施方案中，TADF材料有比较小的ΔEst，在另一个优先的实施方案中,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 PCTCN2016101998-appb-000041
Figure PCTCN2016101998-appb-000042
Figure PCTCN2016101998-appb-000043
Figure PCTCN2016101998-appb-000044
本发明的另一个目的是为印刷OLED提供材料解决方案。
在某些实施例中，按照本发明的咔唑衍生物，其分子量≥700g/mol，进一步的分子量≥900g/mol，更进一步的其分子量≥900g/mol，更进一步的其分子量≥1000g/mol，再进一步的其分子量≥1100g/mol。
在另一些实施例中，按照本发明的咔唑衍生物，在25℃时，在甲苯中的溶解度≥10mg/ml，进一步的其溶解度≥15mg/ml，更进一步的其溶解度≥20mg/ml。
本发明还进一步涉及一种组合物或油墨，组合物包括上述咔唑衍生物以及至少一种有机溶剂。或者，该组合物上述高聚物以及至少一种有机溶剂。再或者，组合物包括上述混合物以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。
在一个实施例中，按照本发明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。进一步的，表面张力是在22dyne/cm到35dyne/cm范围。进一步的，表面张力在25dyne/cm到33dyne/cm范围。
在另一个实施例中，按照本发明的油墨在工作温度或25℃下的粘度约在1cps到100cps范围。进一步的，粘度是在1cps到50cps范围。进一步的，粘度是在1.5cps到20cps范围。进一步的，粘度是在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。按照本发明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，按照本发明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。
适合本发明的溶剂的例子有，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。
在一个实施方案中，按照本发明的组合物是一溶液。
在另一个实施方案中，按照本发明的组合物是一悬浮液。
本发明实施例中的组合物中可以包括0.010wt％～20wt％的按照本发明的咔唑衍生物或其混合物，再进一步的是0.1至15wt％，再进一步的是0.2至10wt％，更进一步的是0.25至5wt％的有机化合物或其混合物。
此外，本发明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。
基于上述有机化合物，本发明还提供一种如上所述咔唑衍生物的应用，即将所述咔唑衍生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。本发明实施例中，优选将所述有机化合物用于OLED器件的发光层。
本发明进一步涉及一种有机电子器件，至少包含一种如上所述的咔唑衍生物、高聚物或混合物。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，其中的功能层中至少包含一种如上所述的有机化合物或高聚物。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。
在某些特别的实施例中，所述的电致发光器件，其发光层包含至少一种所述的咔唑衍生物或至少一种所述的高聚物。在某些实施例中，电致发光器件的发光层包含一种所述的咔唑衍生物以及一种磷光发光体、一种荧光发光体或一种主体材料。在某些实施例中，电致发光器件的发光层发光层包含一种所述的高聚物和一种主体材料以及一种磷光发光体、一种荧光发光体或一种主体材料。进一步的，电致发光器件的发光层包含一种所述的咔唑衍生物，一种磷光发光体和一种主体材料。电致发光器件的发光层包含一种所述的高聚物，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发明的器件。
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发明器件的阴极材料。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，按照本发明的有机发光器件中，其发光层是通过按照本发明的组合物制备而成。
按照本发明的发光器件，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。
本发明还涉及按照本发明的咔唑衍生物在各种电子设备中的应用，包括，但不限于，显示设备，照明设备，光源，传感器等等。
本发明还涉及包含有按照本发明的有机电子器件的电子设备，包括，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发明进行了说明，但本发明并不局限于下述实施例，应当理解，所附权利要求概括了本发明的范围在本发明构思的引导下本领域的技术人员应意识到，对本发明的各实施例所进行的一定的改变，都将被本发明的权利要求书的精神和范围所覆盖。
具体实施例
实施例1
15-(3-(4,6-二苯基-1,3,5-三嗪-2-yl)苯基)-15H-菲并[9,10-a]咔唑的制备，其结构式如下(1)所示：
Figure PCTCN2016101998-appb-000045
250ml的三口烧瓶中加入3.18g，10mmol15H-菲并[9,10-a]咔唑、4.3g，11mmol 2-(3-溴苯基)-4,6-二苯基-1,3,5-三嗪、6.9g，50mmol碳酸钾，0.26g，1mmol18-冠醚-6，3.0g，15mmol碘化亚铜和150ml邻二氯苯，在N2气氛中，160℃反应，TLC跟踪反应进程，待反应结束，降至室温。把反应液倒入水中，洗涤除去K2CO3，然后抽滤，得到固体产品，用二氯甲烷洗涤。用二氯甲烷/乙醇重结晶，得产品固体粉末15-(3-(4,6-二苯基-1,3,5-三嗪-2-yl)苯基)-15H-菲并[9,10-a]咔唑5.2g。MS(ASAP)＝624.7。
实施例2
12-(4,6-二苯基-1,3,5-三嗪-2-yl)-15-苯基-15H-菲并[9,10-a]咔唑的制备，其结构式如下(2)所示：
Figure PCTCN2016101998-appb-000046
250ml的三口烧瓶中加入4.11g，10mmol(15-苯基-15H-菲并[9,10-a]咔唑-12-yl)硼酸、3.0g，11mmol2-氯-4,6-二苯基-1,3,5-三嗪、6.9g，50mmol碳酸钾，0.58g，0.5mmolPd(PPh3)4，100ml甲苯，25ml水以及25ml乙醇，在N2气氛中，110℃反应，TLC跟踪反应进程，待反应结束，降至室温。把反应液倒入水中，洗涤除去K2CO3，然后抽滤，得到固体产品，用二氯甲烷洗涤。粗品用二氯甲烷、乙醇重结晶，得产品12-(4,6-二苯基-1,3,5-三嗪-2-yl)-15-苯基-15H-菲并[9,10-a]咔唑5.5g，MS(ASAP)＝624.4。
实施例3
11-(3-(4,6-二苯基-1,3,5-三嗪-2-yl)苯基)-11H-菲并[1,9-ab]咔唑的制备，其结构式如下(3)所示：
Figure PCTCN2016101998-appb-000047
合成步骤与实施例1相似，250ml的三口烧瓶中加入3.18g，10mmol芘并咔唑，4.3g，11mmol 2-(3-溴苯基)-4,6-二苯基-1,3,5-三嗪、6.9g，50mmol碳酸钾，0.26g，1mmol18-冠醚-6，3.0g，15mmol碘化亚铜和150ml邻二氯苯，在N2气氛中，160℃反应，TLC跟踪反应进程，待反应结束，降至室温。把反应液倒入水中，洗涤除去K2CO3，然后抽滤，得到固体产品，用二氯甲烷洗涤。用甲苯/石油醚混合溶剂重结晶，得产品白色固体粉末11-(3-(4,6-二苯基-1,3,5-三嗪-2-yl)苯基)-11H-菲并[1,9-ab]咔唑5.0g。MS(ASAP)＝598.4。
实施例4
8-(4,6-二苯基-1,3,5-三嗪-2-yl)-11-苯基-11H-菲并[1,9-ab]咔唑的制备，其结构式如下(4)所示：
Figure PCTCN2016101998-appb-000048
合成步骤与实施例2似，250ml的三口烧瓶中加入4.11g，10mmol(11-苯基-11H-菲并[1,9-ab]咔唑-8-yl)硼酸、3.0g，11mmol2-氯-4,6-二苯基-1,3,5-三嗪、6.9g，50mmol碳酸钾，0.58g，0.5mmolPd(PPh3)4，100ml甲苯，25ml水以及25ml乙醇，在N2气氛中，110℃反应，TLC跟踪反应进程，待反应结束，降至室温。把反应液倒入水中，洗涤除去K2CO3，然后抽滤，得到固 体产品，用二氯甲烷洗涤。用二氧六烷重结晶，得产品固体粉末8-(4,6-二苯基-1,3,5-三嗪-2-yl)-11-苯基-11H-菲并[1,9-ab]咔唑4.0g。MS(ASAP)＝598.2。
实施例5
10-(4,6-二苯基-1,3,5-三嗪-2-yl)-7-苯基-7H-菲并[1,9-bc]咔唑的制备，其结构式如下(5)所示：
Figure PCTCN2016101998-appb-000049
合成步骤与实施例2似，250ml的三口烧瓶中加入4.11g，10mmol(7-苯基-7H-菲罗并[1,9-bc]咔唑-10-yl)硼酸、3.0g，11mmol2-氯-4,6-二苯基-1,3,5-三嗪、6.9g，50mmol碳酸钾，0.58g，0.5mmolPd(PPh3)4，100ml甲苯，25ml水以及25ml乙醇，在N2气氛中，110℃反应，TLC跟踪反应进程，待反应结束，降至室温。把反应液倒入水中，洗涤除去K2CO3，然后抽滤，得到固体产品，用二氯甲烷洗涤。用二氧六烷、乙醇重结晶，得产品固体粉末10-(4,6-二苯基-1,3,5-三嗪-2-yl)-7-苯基-7H-菲并[1,9-bc]咔唑4.8g。MS(ASAP)＝598.2。
实施例6
14-(3-(4,6-二苯基-1,3,5-三嗪-2-yl)苯基)-3b,14-二氢吡嗪[2',3':5,6]菲并[1,8-ab]咔唑的制备，其结构式如下(6)所示：
Figure PCTCN2016101998-appb-000050
合成步骤与实施例1相似，250ml的三口烧瓶中加入3.19g，10mmol氮杂菲并咔唑，4.3g，11mmol 2-(3-溴苯基)-4,6-二苯基-1,3,5-三嗪、6.9g，50mmol碳酸钾，0.26g，1mmol18-冠醚-6，3.0g，15mmol碘化亚铜和150ml邻二氯苯，在N2气氛中，160℃反应，TLC跟踪反应进程，待反应结束，降至室温。把反应液倒入水中，洗涤除去K2CO3，然后抽滤，得到固体产品，用二氯甲烷洗涤。用甲苯/石油醚混合溶剂重结晶，得产品白色固体粉末14-(3-(4,6-二苯基-1,3,5-三嗪-2-yl)苯基)-3b,14-二氢吡嗪[2',3':5,6]菲并[1,8-ab]咔唑4.5g。MS(ASAP)＝613.3。
有机化合物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Gaussian09W(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，T1和谐振因子f(S1)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 09W的直接计算结果，单位为Hartree。实施例1～6制备得到的材料的计算结果如表1所示：
表1
材料 HOMO[eV] LUMO[eV] T1[eV] S1[eV]
(1) -5.82 -2.79 2.59 3.17
(2) -5.89 -2.71 2.58 3.24
(3) -5.38 -2.90 2.03 2.61
(4) -5.49 -2.71 2.02 3.06
(5) -5.58 -2.75 1.97 3.09
(6) -5.52 2.78 2.01 3.06
其中，材料(1)与材料(2)可应用于绿光磷光主体材料，材料(3)～(6)可用于蓝光荧光主体材料或发光材料，满足发光层材料的各项条件。
与上述磷光主体材料进行比较的是目前常用的咔唑类材料体系结构的主体材料以Ref 1标记：
Figure PCTCN2016101998-appb-000051
OLED器件的制备：
具有ITO/HATCN(10nm)/NPB(35nm)/TCTA(5nm)/(1)～(2)：5％Ir(ppy)3/B3PYMPM(40nm)/LiF(1nm)/Al(150nm)，OLED器件的制备步骤如下:
a、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；
b、HTL(35nm)，EML(15nm)，ETL(65nm)：在高真空(1×10-6毫巴，mbar)中热蒸镀而成；
c、阴极:LiF/Al(1nm/150nm)在高真空(1×10-6毫巴)中热蒸镀而成；
d、封装:器件在氮气手套箱中用紫外线硬化树脂封装。
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，寿命及外部量子效率。经检测，OLED1(对应材料(1))的发光效率和寿命都是OLED Ref1(对应材料(Ref1))的3倍以上，OLED2(对应材料(2))的发光效率是OLED Ref1的4倍，而寿命是5 倍以上，特别是OLED2的最大外部量子效率达到19％以上。可见，采用本发明的有机混合物制备的OLED器件，其发光效率和寿命均得到大大提高，且外部量子效率也得到明显提高。
应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。

Claims (20)

  1. 一种咔唑衍生物，其特征在于，具有如下通式(1)～(8)中任何一个所示的通式：
    Figure PCTCN2016101998-appb-100001
    其中，Ar1为未被取代或是被一个或多个基团R1取代的具有6～20个碳原子的芳香族、2～20个碳原子的杂芳香族或者非芳香族环系；
    Ar2为未被取代或是被一个或多个基团R1取代的具有6～20个碳原子的芳香族、2～20个碳原子的杂芳香族或者非芳香族环系；
    Ar3为未被取代或是被一个或多个基团R1取代的具有6～20个碳原子的芳香族、2～20个碳原子的杂芳香族或者非芳香族环系；
    Ar4为未被取代或是被一个或多个基团R1取代的具有6～40个碳原子的芳香族、2～40个碳原子的杂芳香族或者非芳香族环系；
    Ar1、Ar2及Ar3相同或不同，基团R1在多次出现时可以是相同或不同；
    R为氢，或者R为未被取代或是被一个或多个基团R0取代的6～20个碳原子的芳香族、2～20 个碳原子的杂芳香族或者非芳香族环系，或者R为1～20个碳原子的直链烷烃、烷烃醚、烷烃芳香环系、烷烃杂芳香族或者烷烃非芳香族环系，基团R0在多次出现时可以是相同或不同；
    n为0、1、2、3或4；
    R0和R1在每一次出现中，相同或不同的选自-H,-F,-Cl,-Br,-I,-D,-CN,-NO2,-CF3,-B(OR2)2,-Si(R2)3，直链烷烃，烷烃醚，含1～10个碳原子烷烃硫醚，支链烷烃，环烷烃或者含有3～10个碳原子的烷烃醚基团；
    R0和R1中一个或多个非相邻的亚甲基为未被替换或是被R2C＝CR2，C＝C，Si(R2)2，Ge(R2)2，Sn(R2)2，C＝O，C＝S，C＝Se，C＝NR2，O，-COO-或CONR2-替换；或者，R0和R1中一个或多个非相邻的亚甲基为未被替换或是被一个或多个活性R2或者一个芳香基团以及杂芳香环取代的芳香胺，或者被取代或未被取代的咔唑替换；
    R2在每一次出现中，相同或不同的选自H，D，含1～10个碳原子脂肪族烷烃，芳香碳氢化合物，含5～10个环原子取代或未取代芳香环或芳杂基团。
  2. 根据权利要求1所述的咔唑衍生物，其特征在于，Ar1、Ar2及Ar3相同或不同地选自如下结构基团中的一种：
    Figure PCTCN2016101998-appb-100002
    其中，
    X1是CR3或N；
    Y1选自CR4R5，SiR6R7，NR8或，C(＝O)，S，或O；
    R3，R4，R5，R6，R7，R8是H，或D，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，氨基甲酰基基团，卤甲酰基基团，甲酰基基团，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5～40个环原子的芳氧基或杂芳氧基基团。
  3. 根据权利要求1所述的咔唑衍生物，其特征在于，其中通式(1)～(8)中的Ar1、Ar2及Ar3相同或不同地选自如下结构基团中的一种:
    Figure PCTCN2016101998-appb-100003
  4. 根据权利要求1所述的咔唑衍生物，其特征在于，R或Ar4在多次出现时，相同或不同地选自如下结构基团中的一种:
    Figure PCTCN2016101998-appb-100004
    Figure PCTCN2016101998-appb-100005
    其中，m为0、1、2、3或4。
  5. 根据权利要求1所述的咔唑衍生物，其特征在于，所述咔唑衍生物选自咔唑衍生物如下结构式(9)～(38)中的一个：
    Figure PCTCN2016101998-appb-100006
    Figure PCTCN2016101998-appb-100007
    Figure PCTCN2016101998-appb-100008
  6. 根据权利要求1～5中任一项所述的咔唑衍生物，其特征在于，所述咔唑衍生物的三线态能级T1≥2.2eV。
  7. 根据权利要求1～5中任一项所述的咔唑衍生物，其特征在于，所述咔唑衍生物的单重态能级S1≥2.80eV，且所述咔唑衍生物的三线态能级T1≤2.1eV。
  8. 根据权利要求1～5中任一项所述的咔唑衍生物，其特征在于，其中R和Ar4在多次出现时，至少有一个R或Ar4包含一供电子基，和/或至少有一个R或Ar4包含一吸电子基。
  9. 根据权利要求8所述的咔唑衍生物，其特征在于，所述的供电子基选自如下基团D1～D10中的一个：
    Figure PCTCN2016101998-appb-100009
  10. 根据权利要求8所述的咔唑衍生物，其特征在于，所述吸电子基选自F，氰基，或所述吸电子基选自如下结构基团中的一个：
    Figure PCTCN2016101998-appb-100010
    其中，a为1、2、3或4；
    X2～X9选于CR或N，并且至少有一个是N；
    Z1、Z2、Z3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，但至少有一个不是无；其中R可选自氢、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基和杂芳基中的一个。
  11. 一种高聚物，其特征在于，所述高聚物的重复单元对应的化合物包含了如权利要求1～10中任一项所述的咔唑衍生物。
  12. 根据权利要求11所述的高聚物，其特征在于，所述高聚物为非共轭高聚物，如权利要求1～10中任一项所述的咔唑衍生物位于所述高聚物的侧链上。
  13. 根据权利要求11所述的高聚物，其特征在于，所述高聚物为共轭高聚物。
  14. 一种混合物，其特征在于，所述混合物包括如权利要求1～10中任一项所述的咔唑衍生物以及有机功能材料，或者，所述混合物包括如权利要求11～13中任一项所述的高聚物以及有机功能材料；
    所述的有机功能材料选自空穴注入材料，空穴传输材料，电子传输材料，电子注入材料，电子阻挡材料，空穴阻挡材料，发光体，主体材料和有机染料中的至少一种。
  15. 一种组合物，其特征在于，所述组合物包括如权利要求1～10中任一项所述的咔唑衍生物以及至少一种有机溶剂；
    或者，所述组合物包括如权利要求11～13中任一项所述的高聚物以及至少一种有机溶剂；
    或者，所述组合物包括如权利要求14所述的混合物以及至少一种有机溶剂。
  16. 一种如权利要求1～10中任一项所述咔唑衍生物或者如权利要求11～13中任一项所述的高聚物在有机电子器件中的应用。
  17. 一种有机电子器件，其特征在于，包括如权利要求1～10中任一项所述的咔唑衍生物、如权利要求11～13中任一项所述的高聚物或如权利要求14所述的混合物。
  18. 根据权利要求17所述的有机电子器件，其特征在于，所述有机电子器件选自有机发光二极管、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、有机传感器及有机等离激元发射二极中的至少一种。
  19. 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电致发光器件，所述电致发光器件的发光层包括至少一种如权利要求1～10中任一项所述的咔唑衍生物；
    或者，所述的发光层包括至少一种如权利要求11～13中任一项所述的高聚物。
  20. 根据权利要求19所述的有机电子器件，其特征在于，所述电致发光器件的发光层包括至少一种如权利要求1～10中任一项所述的咔唑衍生物以及一种磷光发光体、一种荧光发光体或一种主体材料；
    或者，所述的发光层包括至少一种如权利要求11～13中任一项所述的高聚物以及一种磷光发光体、一种荧光发光体或一种主体材料。
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