CN108137558B

CN108137558B - Carbazole derivatives, high polymers, mixtures, compositions, organic electronic devices and uses thereof

Info

Publication number: CN108137558B
Application number: CN201680059919.5A
Authority: CN
Inventors: 黄宏; 潘君友
Original assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Current assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Priority date: 2016-01-07
Filing date: 2016-10-13
Publication date: 2021-04-16
Anticipated expiration: 2036-10-13
Also published as: WO2017118137A1; CN108137558A

Abstract

A carbazole derivative having a general formula represented by any one of general formulae (1) to (8) and use thereof. Wherein the general formula (1) is shown below:

wherein Ar is₁、Ar₂、Ar₃Independently of one another, unsubstituted or substituted by one or more radicals R¹A substituted aromatic group having 6 to 20 carbon atoms, a heteroaromatic or non-aromatic ring system having 2 to 20 carbon atoms. Ar (Ar)₄Is unsubstituted or substituted by one or more radicals R¹A substituted aromatic, heteroaromatic or nonaromatic ring system having 6 to 40 carbon atoms and 2 to 40 carbon atoms.

Description

Carbazole derivatives, high polymers, mixtures, compositions, organic electronic devices and uses thereof

The technical field is as follows:

the invention relates to the field of organic electroluminescent materials, in particular to a carbazole derivative, a high polymer, a mixture, a composition, an organic electronic device and application thereof.

Background art:

the diversity and synthesizability of the organic electroluminescent materials lay a solid foundation for realizing a large-area novel display device. In order to improve the light emitting efficiency of the organic light emitting diode, a light emitting material system based on fluorescence and phosphorescence has been developed so far, and the organic light emitting diode using a fluorescent material has a high reliability, but its internal electroluminescence quantum efficiency under electrical excitation is limited to 25% because the branching ratio of the singlet excited state and the triplet excited state of excitons is 1: 3. In contrast, the organic light emitting diode using the phosphorescent material has achieved almost 100% internal electroluminescence quantum efficiency. However, the stability of phosphorescent OLEDs is still to be improved. The stability of OLEDs, in addition to the emitter itself, is critical for the host material.

Carbazole derivatives have the advantages of high carrier transport capability, photoelectric response property, thermal stability and the like, so that the carbazole derivatives become the focus of attention in academia and industry, and are widely applied to organic light emitting diodes. Because carbazole 3, 6-site has certain activity, most carbazole derivatives developed at present still have the defect of poor chemical/environmental stability, mainly because lone-pair electrons of nitrogen atoms in the structure of the material are conjugated to benzene rings to form C-H bonds with high electron cloud density and high reaction activity, so that the compound has poor chemical/environmental stability and short device life.

In order to improve the stability and device lifetime of carbazole derivatives, methods for reducing the reactivity of the C-H bond at the 3, 6-position have been sought. One scheme is to introduce an electron-deficient unit on a 9-bit N atom, so that an electron cloud is transferred to the direction of the electron-deficient unit, and the electron cloud density and the reactivity of C-H are reduced. However, the introduction of electron deficiency may cause problems such as the change of electrochemical energy level (adv. funct. mater., 2014, 24, 3551-3561).

The ever-increasing demands on the stability of materials and device lifetime have forced the search for more stable materials with optoelectronic properties.

The invention content is as follows:

based on the above, there is a need for carbazole derivatives with good stability, polymers, mixtures, compositions, organic electronic devices containing the carbazole derivatives and applications of the carbazole derivatives and the organic electronic devices.

A carbazole derivative having a general formula represented by any one of the following general formulae (1) to (8):

and

wherein Ar is₁Is unsubstituted or substituted by one or more radicals R¹A substituted aromatic group having 6 to 20 carbon atoms, a heteroaromatic or non-aromatic ring system having 2 to 20 carbon atoms;

Ar₂is unsubstituted or substituted by one or more radicals R¹A substituted aromatic group having 6 to 20 carbon atoms, a heteroaromatic or non-aromatic ring system having 2 to 20 carbon atoms;

Ar₃is unsubstituted or substituted by one or more radicals R¹A substituted aromatic group having 6 to 20 carbon atoms, a heteroaromatic or non-aromatic ring system having 2 to 20 carbon atoms;

Ar₄is not takenOr by one or more radicals R¹A substituted aromatic group having 6 to 40 carbon atoms, a heteroaromatic or non-aromatic ring system having 2 to 40 carbon atoms;

Ar₁、Ar₂and Ar₃Identical or different, radicals R₁May be the same or different in multiple occurrences;

r is hydrogen, or R is unsubstituted or substituted by one or more radicals R₀A substituted aromatic group having 6 to 20 carbon atoms, a heteroaromatic or nonaromatic ring system having 2 to 20 carbon atoms, or R is a linear alkane having 1 to 20 carbon atoms, an alkane ether, an alkane aromatic ring system, an alkane heteroaromatic or an alkane nonaromatic ring system, the group R being₀May be the same or different in multiple occurrences;

n is 0, 1, 2, 3 or 4;

R₀and R₁In each occurrence, the same or different, is selected from the group consisting of-H, -F, -Cl, -Br, -I, -D, -CN, -NO₂，-CF₃，-B(OR₂)₂，-Si(R₂)₃Straight-chain alkane, alkane ether, alkane thioether containing 1-10 carbon atoms, branched alkane, cycloalkane or alkane ether group containing 3-10 carbon atoms;

R₀and R₁In which one or more non-adjacent methylene groups are unsubstituted or substituted by R₂C＝CR₂，C＝C，Si(R₂)₂，Ge(R₂)₂，Sn(R₂)₂，C＝O，C＝S，C＝Se，C＝NR₂O, -COO-or CONR₂-replacing; or, R₀And R₁Wherein one or more non-adjacent methylene groups are unsubstituted or substituted by one or more active R groups₂Or an aromatic group and a heteroaromatic ring substituted aromatic amine, or substituted or unsubstituted carbazole;

R₂in each occurrence, the same or different is selected from H, D, aliphatic alkanes containing 1-10 carbon atoms, aromatic hydrocarbons, substituted or unsubstituted aromatic rings or heteroaromatic groups containing 5-10 ring atoms.

A polymer, wherein a compound corresponding to a repeating unit of the polymer contains the carbazole derivative.

A mixture comprising the carbazole derivative and an organic functional material, or the high polymer and the organic functional material;

the organic functional material is at least one selected from a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitting body, a main body material and an organic dye.

A composition comprising the carbazole derivative and at least one organic solvent;

alternatively, the composition comprises the above-mentioned high polymer and at least one organic solvent;

alternatively, the composition comprises the above mixture and at least one organic solvent.

The carbazole derivative or the high polymer is applied to an organic electronic device.

An organic electronic device comprising the carbazole derivative, the high polymer, or the mixture.

The carbazole derivative contains at least three aromatic ring or heteroaromatic ring conjugated units, has good stability, and can be used as an electrophosphorescent luminescent main body material. The carbazole derivative can be matched with a proper guest material, so that the luminous efficiency and the service life of the carbazole derivative as an electroluminescent device can be improved; the carbazole derivative can also be used as a fluorescent host material or a luminescent material, and is matched with a proper fluorescent host material or a proper guest material, so that the efficiency and the service life of the carbazole derivative serving as an electroluminescent device are improved, and a solution is provided for the luminescent device with low manufacturing cost, high efficiency and long service life.

Detailed Description

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 described in further detail below in order to make the objects, technical solutions and effects of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

In the present invention, the composition and the printing ink, or ink, have the same meaning and are interchangeable. In the present invention, the subject material, Matrix material, Host or Matrix material have the same meaning and are interchangeable. In the present invention, the metal-organic complex, and the organometallic complex have the same meanings and may be interchanged.

and

Ar₂is unsubstituted or substituted by one or more radicals R¹A substituted aromatic group having 6 to 20 carbon atoms, a heteroaromatic or non-aromatic ring system having 2 to 20 carbon atoms.

Ar₃Is unsubstituted or substituted by one or more radicals R¹A substituted aromatic group having 6 to 20 carbon atoms, a heteroaromatic or non-aromatic ring system having 2 to 20 carbon atoms.

Ar₄Is unsubstituted or substituted by one or more radicals R¹A substituted aromatic group having 6 to 40 carbon atoms, a heteroaromatic or non-aromatic ring system having 2 to 40 carbon atoms.

Ar₁、Ar₂And Ar₃Identical or different, radicals R₁And may be the same or different in multiple occurrences.

R, when present in multiple instances, may be the same or different. R is hydrogen, or R is unsubstituted or substituted by one or more radicals R₀A substituted aromatic group having 6 to 20 carbon atoms, a heteroaromatic or nonaromatic ring system having 2 to 20 carbon atoms, or R is a linear alkane having 1 to 20 carbon atoms, an alkane ether, an alkane aromatic ring system, an alkane heteroaromatic or an alkane nonaromatic ring system, the group R being₀And may be the same or different in multiple occurrences.

n is 0, 1, 2, 3 or 4.

R₀And R₁In each occurrence, the same or different, is selected from the group consisting of-H, -F, -Cl, -Br, -I, -D, -CN, -NO₂，-CF₃，-B(OR₂)₂，-Si(R₂)₃Straight-chain alkane, alkane ether, alkane thioether containing 1-10 carbon atoms, branched alkane, cycloalkane or alkane ether group containing 3-10 carbon atoms.

R₀And R₁In which one or more non-adjacent methylene groups are unsubstituted or substituted by R₂C＝CR₂，C＝C，Si(R₂)₂，Ge(R₂)₂，Sn(R₂)₂，C＝O，C＝S，C＝Se，C＝NR₂O, -COO-or CONR₂-replacing; or, R₀And R₁Wherein one or more non-adjacent methylene groups are unsubstituted or substituted by one or more active R groups₂Or an aromatic group and a heteroaromatic ring substituted aromatic amine, or substituted or unsubstituted carbazole.

Specifically, in the general formulae (1) to (8), Ar¹-Ar⁴And at least one R in each occurrence, which may be the same or different, is selected from unsubstituted or substituted by R₁Substituted C6-C20An aromatic ring or a heteroaromatic ring having 2 to 20 carbon atoms.

Specifically, the aromatic ring system contains 5 to 18 carbon atoms in the ring system. The heteroaromatic ring system contains 2-18 carbon atoms and at least one heteroatom in the ring system, and further the total number of carbon atoms and heteroatoms in the heteroaromatic ring is at least 4. In one embodiment, the aromatic ring system contains 5 to 16 carbon atoms and the heteroaromatic ring system contains 2 to 16 carbon atoms and at least one heteroatom. Further, the aromatic ring system contains 5 to 13 carbon atoms, and the heteroaromatic ring system contains 2 to 13 carbon atoms and at least one heteroatom. The heteroatom is selected from Si, N, P, O, S and/or Ge, and further, the heteroatom is selected from 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 monocyclic groups and polycyclic ring systems. Heteroaromatic ring systems or heteroaromatic groups refer to hydrocarbon groups (containing heteroatoms) that contain 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, i.e., fused rings. At least one of these ring species of the polycyclic ring is aromatic or heteroaromatic. For the purposes of the present invention, aromatic or heteroaromatic ring systems include not only aromatic or heteroaromatic systems, but also systems in which a plurality of aryl or heteroaryl groups may also be interrupted by short nonaromatic units (< 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9, 9' -spirobifluorene, 9, 9-diarylfluorene, triarylamines, diaryl ethers, etc., are likewise considered aromatic ring systems for the purposes of the present invention.

Specifically, examples of aromatic groups are: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, pyrene, benzopyrene, triphenylene, acenaphthene, fluorene, and derivatives thereof.

Specifically, examples of heteroaromatic groups are: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, phthalazine, quinoxaline, phenanthridine, primadine, quinazoline, quinazolinone, and derivatives thereof.

In certain embodiments, Ar¹-Ar⁴At least one of which contains an unsubstituted or substituted radical R₁A substituted nonaromatic ring system having 2 to 20 carbon atoms.

For the purposes of the present invention, 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 ring systems which may be unsubstituted or substituted by a single or multiple radicals R₁And (4) substitution. Radical R₁May be the same or different in each occurrence and may also contain one or more heteroatoms, specifically, R₁Is Si, N, P, O, S and/or Ge, further, R₁Is Si, N, P, O and/or S. Examples of these are cyclohexyl-like or piperidine-like systems, but also cyclooctadiene-like cyclic systems. The term also applies to fused non-aromatic ring systems.

For the purposes of the present invention, where the H atom on NH or the bridging group CH₂The group can be represented by R¹Radical substitution, R¹Alternatively, (1) the C1-C10 alkyl group may be, for example, the following group: 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, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, and octynyl; (2) C1-C10 alkoxy, which may be, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy or 2-methylbutoxy; (3) c2 to C10 aryl or heteroarylAryl, which may be monovalent or divalent depending on the use, may in each case also be represented by the radicals R mentioned above¹Substituted and may be attached to the aromatic or heteroaromatic ring via any desired position, for example the following groups: benzene, naphthalene, anthracene, pyrene, chrysene, perylene, fluoranthene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzofluorene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5, 6-quinoline, benzo-6, 7-quinoline, benzo-7, 8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalimidazole, oxazole, benzoxazole, naphthoxazole, anthraoxazole, phenanthroizole, isoxazole, 1, 2-thiazole, 1, 3-thiazole, benzothiazole, pyridazine, benzopyrazine, pyrimidine, benzopyrimidine, quinoxaline, Pyrazine, diazaanthracene, 1, 5-naphthyridine, azocarbazole, benzocarbazine, phenanthroline, 1, 2, 3-triazole, 1, 2, 4-triazole, benzotriazole, 1, 2, 3-oxadiazole, 1, 2, 4-oxadiazole, 1, 2, 5-oxadiazole, 1, 3, 4-oxadiazole, 1, 2, 3-thiadiazole, 1, 2, 4-thiadiazole, 1, 2, 5-thiadiazole, 1, 3, 4-thiadiazole, 1, 3, 5-triazine, 1, 2, 4-triazine, 1, 2, 3-triazine, tetrazole. 1, 2, 4, 5-tetrazine, 1, 2, 3, 4-tetrazine, 1, 2, 3, 5-tetrazine, purine, pteridine, indolizine and benzothiadiazole. For the purposes of the present invention, aromatic and heteroaromatic ring systems are to be understood as meaning, in particular, biphenylene, terphenylene, fluorene, spirobifluorene, dihydrophenanthrene, tetrahydropyrene and cis-or trans-indenofluorene, in addition to the abovementioned aryl and heteroaryl groups.

In particular, compounds according to the general formulae (1) to (8), wherein Ar¹，Ar²，Ar³Which may be identical or different on each occurrence, are selected from aromatic, heteroaromatic or nonaromatic ring systems having from 2 to 10 carbon atoms which may be unsubstituted or substituted by one or more R₁And (4) substituting the group. Specific aromatic or heteroaromatic groups may be benzene, naphthalene, anthracene, phenanthrene, pyridine,A pyrene or thiophene.

Further, compounds according to the general formulae (1) to (8), Ar₁、Ar₂And Ar₃The same or different is selected from one of the following structural groups:

wherein, X₁Is CR³Or N; y is₁Selected from the group consisting of CR⁴R⁵，SiR⁶R⁷，NR⁸Or, C (═ O), S, or O;

R₃，R₄，R₅，R₆，R₇，R₈is H, or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20C atoms or a silyl group, or a substituted keto group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group (-CN), a carbamoyl group (-C (═ O) NH₂) A haloformyl group (-C (═ O) -X wherein X represents a halogen atom), a formyl group (-C (═ O) -H), an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, CF₃A group, Cl, Br, F, a crosslinkable group or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms.

Further, R₃，R₄，R₅，R₆，R₇，R₈And may also be selected from combinations of the corresponding groups mentioned above, where one or more radicals R₃，R₄，R₅，R₆，R₇，R₈The rings which may be bonded to each other and/or to the radicals form mono-or polycyclic aliphatic or aromatic rings.

Specifically, Ar in the general formulae (1) to (8)₁、Ar₂And Ar₃The same or different is selected from one of the following structural groups:

or Ar₁、Ar₂And Ar₃The structural groups, which may be identical or different, are selected from the above groups by one or more radicals R₁A substituted structural group.

Specifically, R or Ar₄In multiple occurrences, the same or different is selected from one of the following structural groups:

wherein m is 0, 1, 2, 3 or 4.

More specifically, the carbazole derivative according to the invention is selected from one of the following structural formulae:

wherein Ar is₄R, etc. have the meanings given above.

In another embodiment, the carbazole derivative may be a structural group obtained by further substituting the above general structural formula.

Specifically, the carbazole derivative according to the present invention can be used as a host material of a light emitting layer in an electroluminescent device. The carbazole derivative has high triplet energy level (T)₁) Generally, T can be reached₁Not less than 2.10eV, and further reaching T₁Not less than 2.40eV, and further reaching T₁Not less than 2.60eV, and further reaching T₁Not less than 2.70eV, and further reaching T₁≥2.80eV。

In another embodiment, the carbazole derivative according to the invention has its triplet energy level T₁Not less than 2.2 eV. In this case, the organic compound can be preferably used as a phosphorescent host material.

In another embodiment, the compounds according to the present invention may be applied to a fluorescent host material or a light emitting material of a light emitting layer in an electroluminescent device. The carbazole derivative has high singlet state energy level (S)₁) And a lower triplet energy level (T)₁) General formula S₁≥2.80eV，T₁Less than or equal to 2.10eV, and further, S₁≥2.90eV，T₁Less than or equal to 2.00eV, and further S₁≥2.90eV，T₁Less than or equal to 1.90eV, and further S₁≥2.90eV，T₁≤1.8eV。

In certain embodiments, the singlet energy level (S) of the carbazole derivative₁) And triplet energy level (T)₁) Difference Δ E (S) of₁-T₁) The size of the fluorescent material is relatively large, and the compound can be used as a fluorescent host material of a light-emitting layer. General Δ E (S)₁-T₁) Not less than 0.60eV, and further Δ E (S)₁-T₁) Not less than 0.80eV, and further Δ E (S)₁-T₁) Not less than 1.0eV, and further Δ E (S)₁-T₁)≥1.1eV。

In other embodiments, the carbazole derivative according to the present invention has a smaller Δ E (S)₁-T₁) General Δ E (S)₁-T₁) 0.30eV or less, and further Delta E (S)₁-T₁) 0.25eV or less, and further Delta E (S)₁-T₁) 0.20eV or less, still further,. DELTA.E (S)₁-T₁) 0.15eV or less, and further,. DELTA.F (S)₁-T₁)≤0.10eV。

Specifically, compounds according to the general formulae (1) to (38) wherein R or Ar₄At multiple occurrences, at least one R or Ar₄Comprising an electron-donating group, and/or at least one R or Ar₄Comprises an electron-withdrawing group.

Specifically, the electron-donating group is selected from one of the following groups D1-D10:

specifically, the electron-withdrawing group is selected from F, cyano, or the electron-withdrawing group is selected from one of the following structural groups:

and

wherein, a is 1, 2, 3 or 4;

X²～X⁹selected from CR or N, and at least one is N;

Z₁、Z₂、Z₃each independently represents N (R), C (R)₂、Si(R)₂、O、C＝N(R)、C＝C(R)₂、P(R)、P(＝O)R、S、S＝O、SO₂Or none, but at least one is not; wherein R may be selected from one of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl, and heteroaryl.

In one embodiment, the carbazole derivative according to the present invention is a small molecule material.

The term "small molecule" as defined herein refers to a molecule that is not a polymer, oligomer, dendrimer, or blend. In particular, there is no repeat structure in small molecules. Generally, the small molecules have a molecular weight of 4000 g/mol or less, more preferably 3000 g/mol or less, still more preferably 2000 g/mol or less, and still more preferably 1500 g/mol or less.

Polymers, i.e., polymers, include homopolymers (homo polymers), copolymers (copolymers), and block copolymers. In addition, the term "polymer" as used herein also includes Dendrimers (dendromers), and reference is made to the synthesis and use of Dendrimers, Wiley-VCH Verlag GmbH & Co.KGaA, 2002, Ed.George R.Newkome, Charles N.Moorefield, Fritz Vogtle.

Conjugated polymer is a polymer whose main chain backbone is mainly sp of C atoms²Hybrid track formation, notable examples are: polyacetylene and poly (phenylene vinylene), wherein the C atom of the main chain can be substituted by other non-C atoms, and when sp is present on the main chain²Hybridization is interrupted by some natural defect and is still considered a conjugated polymer. In the present invention, the conjugated polymer may include arylamines (aryl amines), aryl phosphines (aryl phosphines) and other heterocyclic aromatic hydrocarbons (heterocyclic aromatics), organic metal complexes (organometallic complexes) in the main chain.

In particular, the solubility of the small organic molecule compounds is ensured by the substituents R on the units of the formulae (1) to (38) and optionally on the units additionally present, and by the adjustment of the position of the bond between the core structure and the substituents. If other substituents are present, these substituents may also promote solubility.

Depending on the substitution pattern, the structural units of the formulae (1) to (38) are suitable for a wide variety of functions in small organic molecule compounds. Therefore, they are preferably usable as main frameworks for small molecule compounds or as luminophores.

Specifically, examples of the units of the general formulae (1) to (38) may have the following structures. Further these structures may be substituted at all possible points of substitution.

And

The invention also relates to a high polymer, wherein the compound corresponding to at least one repeating unit comprises any structure shown in general formulas (1) to (8). In some embodiments, the polymer is a non-conjugated polymer, wherein the structural units represented by the general formulae (1) to (8) are located in the side chains of the polymer. In another embodiment, the polymer is a conjugated polymer.

In addition, the invention also relates to a mixture which comprises the carbazole derivative and an organic functional material. Or a mixture comprising the above-mentioned high polymer and an organic functional material.

The organic functional material is selected from at least one of hole (also called hole) injection or transport materials (HIM/HTM), Hole Blocking Materials (HBM), electron injection or transport materials (EIM/ETM), Electron Blocking Materials (EBM), organic Host materials (Host), singlet state light emitters (fluorescent light emitters), heavy state light emitters (phosphorescent light emitters), organic thermal excitation delay fluorescent materials (TADF materials) and especially light-emitting organic metal complexes. Various organic functional materials are described in detail, for example, in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of this 3 patent document being hereby incorporated by reference. The organic functional material can be small molecule and high polymer material.

In one embodiment, the mixture comprises a carbazole derivative or polymer according to the invention and a phosphorescent emitter. The carbazole derivatives or polymers according to the invention can be used as hosts, in which the phosphorescent emitters are present in the mixture in a proportion by weight of 30% or less, in particular 25% or less, and in particular 20% or less.

In another embodiment, the mixture comprises a carbazole derivative or polymer according to the invention and a fluorescent emitter. The carbazole derivatives or polymers according to the invention can be used as fluorescent host materials, wherein the fluorescent emitters are present in the mixture in a proportion of 15 wt.% or less, in particular 10 wt.% or less, and in particular 8 wt.% or less.

In another embodiment, the mixture comprises a carbazole derivative or polymer according to the invention and a fluorescent host material. The carbazole derivative or high polymer according to the invention can be used as a fluorescent light-emitting material, and the carbazole derivative or high polymer accounts for less than or equal to 15 wt%, further less than or equal to 10 wt% and even further less than or equal to 8 wt% in the mixture.

In one embodiment, the mixture comprises a carbazole derivative or polymer according to the invention, a phosphorescent emitter and a host material. In one embodiment, the carbazole derivative or high polymer according to the invention may serve as an auxiliary light-emitting material, and the weight ratio of the carbazole derivative or high polymer to the phosphorescent emitter may be from 1: 2 to 2: 1. In another preferred embodiment, T of the carbazole derivative or the high polymer according to the invention₁Higher than the phosphorescent emitter.

In another preferred embodiment, the mixture comprises a carbazole derivative or polymer according to the invention, and a TADF material. The carbazole derivative or the high polymer according to the present invention can be used as a TADF host material, wherein the TADF host material is present in an amount of 15 wt% or less, further 10 wt% or less, and further 8 wt% or less, based on the weight of the mixture.

Host materials, phosphorescent and fluorescent host materials, fluorescent light emitting materials and TADF materials are described in some more detail below (but not limited thereto).

1. Host material (tripletlost):

examples of the triplet host material are not particularly limited, and any metal complex or organic compound may be used as the host as long as the triplet energy thereof is higher than that of a light emitter, particularly a triplet light emitter or a phosphorescent light emitter. Examples of metal complexes that can be used as triplet hosts (Host) include, but are not limited to, the following general structures:

m is a metal; (Y)³-Y⁴) Is a bidentate ligand, Y³And Y⁴Independently selected from C, N, O, P, and S; l is an ancillary ligand; m is an integer having a value from 1 to the maximum coordination number of the metal; m + n is the maximum coordination number of the metal.

In one embodiment, the metal complexes useful as triplet hosts are of the form:

(O-N) is a bidentate ligand in which the metal is coordinated to both the O and N atoms.

In one embodiment, M may be selected from Ir and Pt.

Examples of the organic compound which can be a triplet host are selected from compounds containing a cyclic aromatic hydrocarbon group such as benzene, biphenyl, triphenyl, benzo, fluorene; compounds containing aromatic heterocyclic groups, such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridine indole, pyrrole bipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indolizine, indole, benzimidazole, indazole, oxazole, dibenzooxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, phthalazine, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranpyridine, furopyridine, benzothiophenpyridine, thiophenopyridine, benzoselenophenepyridine, and selenophenebenzobipyridine; groups having 2 to 10 ring structures, which may be the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups, are bonded to each other directly or through at least one group selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an alicyclic group. Wherein each Ar may be further substituted, and the substituents may be selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl, and heteroaryl.

In one embodiment, the triplet host material may be selected from compounds comprising at least one of the following groups:

R¹～R⁷can be selected independently of one another from the following groups: hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl, when they are aryl or heteroaryl, with Ar as described above¹And Ar²The meanings are the same; n is an integer from 0 to 20; x¹-X⁸Selected from CH or N; x⁹Is selected from CR¹R²Or NR¹。

Examples of suitable triplet host materials are listed in the following table:

and

2. phosphorescent light-emitting material

Phosphorescent light emitting materials are also known as triplet emitters. In a preferred embodiment, the triplet emitter is a metal complex of the general formula M (L) n, where M is a metal atom, L, which may be the same or different at each occurrence, is an organic ligand which is bonded or coordinately bound to the metal atom M via one or more positions, and n is an integer greater than 1, preferably 1, 2, 3, 4, 5 or 6. Optionally, the metal complexes are coupled to a polymer through one or more sites, preferably through organic ligands.

In a preferred embodiment, the metal atom M is chosen from transition metals or lanthanides or actinides, 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.

Preferably, the triplet emitter comprises a chelating ligand, i.e. a ligand, which coordinates to the metal via at least two binding sites, particularly preferably the triplet emitter comprises two or three identical or different bidentate or polydentate ligands. Chelating ligands are advantageous for increasing the stability of the metal complex.

Examples of organic ligands may be selected from phenylpyridine derivatives, 7, 8-benzoquinoline derivatives, 2 (2-thienyl) pyridine derivatives, 2 (1-naphthyl) pyridine derivatives, or 2-phenylquinoline derivatives. All of these organic ligands may be substituted, for example, with fluorine-containing or trifluoromethyl groups. The ancillary ligand may preferably be selected from acetone acetate or picric acid.

In one embodiment, the metal complexes useful as triplet emitters are of the form:

wherein M is a metal selected from the group consisting of transition metals or lanthanides or actinides;

Ar¹each occurrence of which may be the same or different, is a cyclic group containing at least one donor atom, i.e., an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which the cyclic group is coordinately bound to the metal; ar (Ar)²Each occurrence, which may be the same or different, is a cyclic group containing at least one C atom through which the cyclic group is attached to the metal; ar (Ar)¹And Ar²Linked together by a covalent bond, which may each carry one or more substituent groups, which may in turn be linked together by substituent groups; l, which may be the same or different at each occurrence, is an ancillary ligand, preferably a bidentate chelating ligand, most preferably a monoanionic bidentate chelating 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 are also known as phosphorescent emitters. In one embodiment, the triplet emitter is a metal complex having the general formula M (L) n, wherein M is a metal atom, L, which may be the same or different at each occurrence, is an organic ligand which is bonded or coordinately linked to the metal atom M through one or more positions, and n is an integer greater than 1, preferably 1, 2, 3, 4, 5 or 6. Optionally, the metal complexes are coupled to a polymer through one or more sites, preferably through organic ligands.

In one embodiment, the metal atom M is chosen from transition metals or lanthanides or actinides, 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.

In particular, the triplet emitters comprise chelate ligands, i.e. ligands which coordinate to the metal via at least two binding sites, particular preference being given to triplet emitters comprising two or three identical or different bidentate or polydentate ligands. Chelating ligands are advantageous for increasing the stability of the metal complex.

ar1, which may be the same or different at each occurrence, is a cyclic group containing at least one donor atom, i.e., an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which the cyclic group is coordinately bound to the metal; ar2, which may be the same or different at each occurrence, is a cyclic group containing at least one C atom through which the cyclic group is attached to the metal; ar1 and Ar2 are linked together by a covalent bond, may each carry one or more substituent groups, which may in turn be linked together by a substituent group; l, which may be the same or different at each occurrence, is an ancillary ligand, preferably a bidentate chelating ligand, most preferably a monoanionic bidentate chelating 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;

examples of the extreme use of some triplet emitter materials can be found in the following patent documents and literature: WO 200070655, WO 200141512, WO 200202714, WO 200215645, EP 1191613, EP 1191612, EP 1191614, WO 1191614, WO 1191614, US 1191614, WO 1191614, WO 1191614, WO 1191614, WO 1191614, WO 1191614, WO 1191614, WO 1191614, WO 1191614, US 1191614, US 1191614A 1191614, US 1191614A 1191614, Baldo, Thompson et al Nature 403, (2000), 750 zones 753, US 1191614A 1191614, US 1191614A 1191614, Adachi et al. appl. Phys. Lett.78 (1622) 1624, J. Kido et al. Phys. Lett.65(1994), 2124, Kido et al. chem. Lett.657, 1990, US 1191614A 1191614, Johnson et al 1191614, WO 993, WO 1772, US 1191614, US 1191614, US 1191614A 1191614, US 1191614A 1191614, US 1191614A 1191614, US 1191614, US 1191614, US 1191614A 1191614, US 1191614A 1191614, US 3672,72,72,72,72,72,72,72,72,72,72,3672,72,72,72,72, WO 3672,3672,72,72,3672,72,72,72,72,72,72,72,72,72, WO 2011157339A1, CN 102282150A, WO 2009118087A 1. The entire contents of the above listed patent documents and literature are hereby incorporated by reference.

Some examples of suitable triplet emitters are listed in the following table:

3. singlet Host material (Singlet Host):

examples of the singlet host material are not particularly limited, and any organic compound may be used as the host as long as the singlet energy thereof is higher than that of the light emitter, particularly, the singlet light emitter or the fluorescent light emitter.

Examples of the organic compound used as the singlet host material may be selected from the group consisting of cyclic aromatic hydrocarbon-containing compounds such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; aromatic heterocyclic compounds, such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridine indole, pyrrole bipyridine, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, oxatriazole, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuran pyridine, furan bipyridine, benzothiophene pyridine, thiophene bipyridine, benzoselenophene pyridine, and selenophene bipyridine; groups having 2 to 10 ring structures, which may be the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups, are bonded to each other directly or through at least one group selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an alicyclic group.

In one embodiment, the singlet host material may be selected from compounds comprising at least one of the following groups:

wherein R1 can be selected independently of each other from the following groups: hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl, and heteroaryl; ar1 is aryl or heteroaryl, and is as defined for Ar1 above in the HTM; n is an integer from 0 to 20; X1-X8 are selected from CH or N; x9 and X10 are selected from CR1R2 or NR 1.

Some examples of anthracene-based singlet host materials are listed in the following table:

4. fluorescent luminous body (Singlet Emitter)

Singlet emitters tend to have longer conjugated pi-electron systems. To date, there have been many examples such as styrylamine and its derivatives disclosed in JP2913116B and WO2001021729a1, and indenofluorene and its derivatives disclosed in WO2008/006449 and WO 2007/140847.

In a preferred embodiment, the singlet emitters may be selected from the group consisting of monostyrenes, distyrenes, tristyrenes, tetrastyrenes, styrylphosphines, styryl ethers, and arylamines.

A monostyrene amine is a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine. A distyrene amine refers to a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A tristyrenylamine refers to a compound comprising three unsubstituted or substituted styrene groups and at least one amine, preferably an aromatic amine. A tetrastyrene amine refers to a compound comprising four unsubstituted or substituted styrene groups and at least one amine, preferably an aromatic amine. One preferred styrene is stilbene, which may be further substituted. The corresponding phosphines and ethers are defined analogously to the amines. Arylamine or aromatic amine refers to a compound comprising three unsubstituted or substituted aromatic rings or heterocyclic systems directly linked to nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably a fused ring system and preferably has at least 14 aromatic ring atoms. Among them, preferred examples are aromatic anthracenamines, aromatic anthracenediamines, aromatic pyrenediamines, aromatic chrysenamines and aromatic chrysenediamines. An aromatic anthracylamine refers to a compound in which a diarylamine group is attached directly to the anthracene, preferably at the 9 position. An aromatic anthracenediamine refers to a compound in which two diarylamine groups are attached directly to the anthracene, preferably at the 9, 10 positions. Aromatic pyrene amines, aromatic pyrene diamines, aromatic chrysene amines and aromatic chrysene diamines are similarly defined, wherein the diarylamine groups are preferably attached to the 1 or 1, 6 position of pyrene.

Examples, which are also preferred, of singlet emitters based on vinylamines and arylamines can be found in the following patent documents: WO2006/000388, WO2006/058737, WO2006/000389, WO 2007/065549, WO2007/115610, US 7250532B 2, DE 102005058557A 1, CN 1583691A, JP 08053397A, US 6251531B 1, US 2006/210830A, EP 1957606A 1 and US 2008/0113101A 1 the entire contents of the patent documents listed above are hereby incorporated by reference.

An example of singlet emitters based on stilbene and its derivatives is US 5121029.

Further preferred singlet emitters may be selected from indenofluorene-amines and indenofluorene-diamines, as disclosed in WO2006/122630, benzindenofluorene-amines and benzindenofluorene-diamines, as disclosed in WO2008/006449, dibenzoindenofluorene-amines and dibenzoindenofluorene-diamines, as disclosed in WO 2007/140847.

Other materials which can be used as singlet emitters are polycyclic aromatic compounds, in particular derivatives of the following compounds: anthracenes such as 9, 10-bis (2-naphthoanthracene), naphthalene, tetraphenes, xanthenes, phenanthrenes, pyrenes (e.g. 2, 5, 8, 11-tetra-t-butylperylene), indenopyrenes, phenylenes such as (4, 4 '-bis (9-ethyl-3-carbazolylethenyl) -1, 1' -biphenyl), diindenopyrenes, decacycloalkenes, coronenes, fluorenes, spirobifluorenes, arylpyrenes (e.g. US20060222886), aryleneethylenes (e.g. US5121029, US5130603), cyclopentadienes such as tetraphenylcyclopentadiene, rubrene, coumarin, rhodamine, quinacridones, pyrans such as 4 (dicyanomethylene) -6- (4-p-dimethylaminostyryl-2-methyl) -4H-pyran (DCM), thiopyran, bis (azinyl) imine boron compounds (US 2007/0092753A1), bis (azinyl) methylene compounds, carbostyryl compounds, oxazinones, benzoxazoles, benzothiazoles, benzimidazoles and pyrrolopyrrolediones. Some singlet emitter materials can be found in the following patent documents: US 20070252517 a1, US 4769292, US 6020078, US 2007/0252517 a1, US 2007/0252517 a 1. The entire contents of the above listed patent documents are hereby incorporated by reference.

Some examples of suitable singlet emitters are listed in the following table:

5. TADF material

The traditional organic fluorescent material can only emit light by utilizing 25% singlet excitons formed by electric excitation, and the internal quantum efficiency of the device is low (up to 25%). Although the phosphorescence material enhances the intersystem crossing due to the strong spin-orbit coupling of the heavy atom center, the singlet excitons and the triplet excitons formed by the electric excitation can be effectively used for emitting light, so that the internal quantum efficiency of the device reaches 100 percent. However, the application of the phosphorescent material in the OLED is limited by the problems of high price, poor material stability, serious efficiency roll-off of the device and the like. The thermally activated delayed fluorescence emitting material is a third generation organic emitting material developed after organic fluorescent materials and organic phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (Δ Est), and triplet excitons may be converted to singlet excitons for emission by intersystem crossing. This can make full use of singlet excitons and triplet excitons formed upon electrical excitation. The quantum efficiency in the device can reach 100%. Meanwhile, the material has controllable structure, stable property, low price and no need of noble metal, and has wide application prospect in the field of OLED.

TADF materials are required to have a small singlet-triplet level difference, preferably Δ Est < 0.3eV, less preferably Δ Est < 0.2eV, and most preferably Δ Est < 0.1 eV. In one embodiment, the TADF material has a relatively small Δ Est, and in another preferred embodiment, the TADF has a relatively good fluorescence quantum efficiency. Some 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.leman, 98, 2011, 083302, Adachi, et.al.phys.lett.101, 2012, 093306, Adachi, nat.chem.comm.no., 48, 2012, 11392, Adachi, et.natu.otoconi, 6, 2012, 253, Adachi, natu.560234, 234, adhi.11392, Adachi, 2012.c. 2012, 7, adhi.t.7, addi.7, addi.t.7, addi.7.t.7, addi.7, addi.7.t.7, addi.t.7, addi.7, addi.7.7, addi.t.7, addi.7, addi.c. 7, addi.7, addi.t. et 3, addi.7, add.

Some examples of suitable TADF phosphors are listed in the following table:

it is another object of the present invention to provide a material solution for printing OLEDs.

In certain embodiments, the carbazole derivative according to the invention has a molecular weight of 700g/mol or more, a further molecular weight of 900g/mol or more, a further molecular weight of 1000g/mol or more, and a further molecular weight of 1100g/mol or more.

In other embodiments, the carbazole derivative according to the invention has a solubility in toluene of 10mg/ml or more, further of 15mg/ml or more, and further of 20mg/ml or more at 25 ℃.

The present invention still further relates to a composition or ink comprising the carbazole derivative described above and at least one organic solvent. Or the composition comprises the high polymer and at least one organic solvent. Still alternatively, the composition comprises the above mixture and at least one organic solvent.

For the printing process, the viscosity of the ink, surface tension, is an important parameter. Suitable inks have surface tension parameters suitable for a particular substrate and a particular printing process.

In one embodiment, the surface tension of an ink according to the present invention at operating temperature or at 25 ℃ is in the range of about 19dyne/cm to about 50 dyne/cm. Further, the surface tension is in the range of 22dyne/cm to 35 dyne/cm. Further, the surface tension is in the range of 25dyne/cm to 33 dyne/cm.

In another embodiment, the viscosity of the ink according to the invention is in the range of about 1cps to about 100cps at the operating temperature or 25 ℃. Further, the viscosity is in the range of 1cps to 50 cps. Further, the viscosity is in the range of 1.5cps to 20 cps. Further, the viscosity is in the range of 4.0cps to 20 cps. The composition so formulated will facilitate ink jet printing.

The viscosity can be adjusted by different methods, such as by appropriate solvent selection and concentration of the functional material in the ink. The inks according to the invention comprising the organometallic complexes or polymers described facilitate the adjustment of the printing inks to the appropriate range according to the printing process used. Generally, the composition according to the present invention comprises the functional material in a weight ratio ranging from 0.3% to 30% by weight, preferably ranging from 0.5% to 20% by weight, more preferably ranging from 0.5% to 15% by weight, still more preferably ranging from 0.5% to 10% by weight, and most preferably ranging from 1% to 5% by weight.

In some embodiments, the ink according to the invention, the at least one organic solvent is chosen from aromatic or heteroaromatic-based solvents, in particular aliphatic chain/ring-substituted aromatic solvents, or aromatic ketone solvents, or aromatic ether solvents.

Examples of solvents suitable for the present invention are, but not limited to: aromatic or heteroaromatic-based solvents: p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1, 2, 3, 4-tetramethylbenzene, 1, 2, 3, 5-tetramethylbenzene, 1, 2, 4, 5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1, 2, 4-trichlorobenzene, 1, 3-dipropoxybenzene, 4-difluorodiphenylmethane, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 2-dimethoxy-4-benzen, Diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenylmethane, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 1-bis (3, 4-dimethylphenyl) ethane, 2-isopropylnaphthalene, dibenzyl ether, and the like; ketone-based solvent: 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, isophorone, 2, 6, 8-trimethyl-4-nonanone, fenchytone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2, 5-hexanedione, phorone, di-n-amyl ketone; aromatic ether solvent: 3-phenoxytoluene, butoxybenzene, benzylbutylbenzene, p-anisaldehyde dimethylacetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxane, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylbenylether, 1, 2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidylphenyl ether, dibenzyl ether, 4-t-butylanisole, trans-p-propenylanisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, and the like, Ethyl-2-naphthyl ether, amyl ether c-hexyl ether, dioctyl ether, ethylene glycol 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; ester solvent: alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like.

Further, according to the ink of the present invention, the at least one organic solvent may be selected from: aliphatic ketones such as 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2, 5-hexanedione, 2, 6, 8-trimethyl-4-nonanone, phorone, di-n-amyl ketone and the like; or aliphatic ethers such as amyl ether, hexyl ether, dioctyl ether, ethylene glycol 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.

In other embodiments, the printing ink further comprises another organic solvent. Examples of another organic solvent include (but are not limited to): methanol, ethanol, 2-methoxyethanol, methylene chloride, 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, indene, and/or mixtures thereof.

In one embodiment, the composition according to the invention is a solution.

In another embodiment, the composition according to the invention is a suspension.

The composition in the embodiment of the present invention may include 0.010 wt% to 20 wt% of the carbazole derivative or the mixture thereof according to the present invention, further 0.1 to 15 wt%, further 0.2 to 10 wt%, further 0.25 to 5 wt% of the organic compound or the mixture thereof.

The invention further relates to the use of said compositions as coatings or printing inks for producing organic electronic components, particularly preferably by printing or coating.

Suitable Printing or coating techniques include, but are not limited to, ink jet Printing, letterpress, screen Printing, dip coating, spin coating, doctor blade coating, roll Printing, twist roll Printing, lithographic Printing, flexographic Printing, rotary Printing, spray coating, brush or pad Printing, slot die coating, and the like. Gravure printing, jet printing and ink jet printing are preferred. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, and the like, for adjusting viscosity, film forming properties, enhancing adhesion, and the like. For details on printing techniques and their requirements relating to the solutions, such as solvents and concentrations, viscosities, etc., see the printed media handbook, edited by Helmut Kipphan: techniques and Production Methods (Handbook of Print Media: Technologies and Production Methods), ISBN3-540 and 67326-1.

Based on the above Organic compounds, the present invention also provides an application of the carbazole derivative as described above, i.e., the carbazole derivative is applied to an Organic electronic device, which can 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 (efet), an Organic laser, an Organic spintronic device, an Organic sensor, and an Organic Plasmon Emitting Diode (Organic Plasmon Emitting Diode), etc., especially an OLED. In the embodiment of the present invention, the organic compound is preferably used for 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. Generally, such an organic electronic device comprises at least a cathode, an anode and a functional layer disposed between the cathode and the anode, wherein the functional layer comprises at least one organic compound or polymer as described above. The Organic electronic device can be selected from, but not limited to, Organic Light Emitting Diodes (OLEDs), Organic photovoltaic cells (OPVs), Organic light Emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), Organic light Emitting field effect transistors (fets), Organic lasers, Organic spintronic devices, Organic sensors, Organic Plasmon Emitting diodes (Organic Plasmon Emitting diodes), and the like, and particularly preferred are Organic electroluminescent devices such as OLEDs, OLEECs, Organic light Emitting field effect transistors.

In certain particular embodiments, the light-emitting layer of said electroluminescent device comprises at least one said carbazole derivative or at least one said high polymer. In certain embodiments, the light-emitting layer of an electroluminescent device comprises one of the carbazole derivatives and one of a phosphorescent emitter, a fluorescent emitter, or a host material. In some embodiments, the light-emitting layer of the electroluminescent device comprises a polymer as described and a host material and a phosphorescent emitter, a fluorescent emitter or a host material. Further, the light-emitting layer of the electroluminescent device comprises one of the carbazole derivatives, a phosphorescent emitter and a host material. The light-emitting layer of the electroluminescent device comprises the high polymer, a phosphorescent emitter and a host material.

In the above-mentioned light emitting device, especially an OLED, it comprises a substrate, an anode, at least one light emitting layer, and a cathode.

The substrate may be opaque or transparent. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, Bulovic et al Nature 1996, 380, p29, and Gu et al appl. Phys. Lett.1996, 68, p 2606. The substrate may be rigid or flexible. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. A substrate free of surface defects is a particularly desirable choice. In a preferred embodiment, the substrate is flexible, and may be selected from polymeric films or plastics having a glass transition temperature Tg of 150 deg.C or greater, preferably greater than 200 deg.C, more preferably greater than 250 deg.C, and most preferably greater than 300 deg.C. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).

The anode may 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 an emission layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or the p-type semiconductor material acting as a HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. Examples of anode materials 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. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is pattern structured. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.

The cathode may comprise a conductive metal or metal oxide. Yin (kidney)It is very easy to inject electrons into the EIL or ETL or directly into the light emitting layer. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the emitter in the light-emitting layer or of the n-type semiconductor material as Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes in OLEDs are possible as cathode materials for the device according to the invention. Examples of cathode materials include, but are not limited to: al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF₂Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

The OLED may also comprise further 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), a Hole Blocking Layer (HBL). Suitable materials for use in these functional layers are described in detail above and in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of these 3 patent documents being hereby incorporated by reference.

In a preferred embodiment, in the organic light-emitting device according to the invention, the light-emitting layer is prepared from the composition according to the invention.

The light-emitting device according to the present invention emits light at a wavelength of 300 to 1000nm, preferably 350 to 900nm, more preferably 400 to 800 nm.

The present invention also relates to the use of the carbazole derivatives according to the present invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, and the like.

The invention also relates to electronic devices including, but not limited to, display devices, lighting devices, light sources, sensors, etc., comprising the organic electronic device according to the invention.

The present invention will be described in connection with preferred embodiments, but the present invention is not limited to the following embodiments, and it should be understood that the appended claims outline the scope of the present invention and those skilled in the art, guided by the inventive concept, will appreciate that certain changes may be made to the embodiments of the invention, which are intended to be covered by the spirit and scope of the appended claims.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

Example 1

Preparation of 15- (3- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) -15H-phenanthro [9, 10-a ] carbazole, the structural formula of which is shown in the following (1):

a250 ml three-necked flask was charged with 3.18g, 10mmol of 15H-phenanthro [9, 10-a ]]Carbazole, 4.3g, 11mmol of 2- (3-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine, 6.9g, 50mmol of potassium carbonate, 0.26g, 1mmol of 18-crown-6, 3.0g, 15mmol of cuprous iodide and 150ml of o-dichlorobenzene in N₂Reacting at 160 ℃ in the atmosphere, tracking the reaction process by TLC, and cooling to room temperature after the reaction is finished. Pouring the reaction solution into water, washing to remove K₂CO₃Then, the solid product was obtained by suction filtration, and washed with dichloromethane. Recrystallizing with dichloromethane/ethanol to obtain solid powder 15- (3- (4, 6-diphenyl-1, 3, 5-triazine-2-yl) phenyl) -15H-phenanthro [9, 10-a ] of product]5.2g of carbazole. Ms (asap) ═ 624.7.

Example 2

Preparation of 12- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -15-phenyl-15H-phenanthro [9, 10-a ] carbazole, the structural formula of which is shown in the following (2):

a250 ml three-necked flask was charged with 4.11g, 10mmol of (15-phenyl-15H-phenanthro [9, 10-a ]]Carbazole-12-yl) boronic acid, 3.0g, 11mmol of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine, 6.9g, 50mmol of potassium carbonate, 0.58g, 0.5mmol of Pd (PPh)₃)₄100ml of toluene, 25ml of water and 25ml of ethanol in N₂Reacting at 110 ℃ in the atmosphere, tracking the reaction process by TLC, and cooling to room temperature after the reaction is finished. Pouring the reaction solution into water, washing to remove K₂CO₃Then, the solid product was obtained by suction filtration, and washed with dichloromethane. Recrystallizing the crude product with dichloromethane and ethanol to obtain the product 12- (4, 6-diphenyl-1, 3, 5-triazine-2-yl) -15-phenyl-15H-phenanthro [9, 10-a ]]Carbazole 5.5g, ms (asap) ═ 624.4.

Example 3

Preparation of 11- (3- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) -11H-phenanthro [1, 9-ab ] carbazole, the structural formula of which is shown in the following (3):

synthesis procedure analogously to example 1, 3.18g, 10mmol of pyrenecarbazole, 4.3g, 11mmol of 2- (3-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine, 6.9g, 50mmol of potassium carbonate, 0.26g, 1mmol of 18-crown-ether-6, 3.0g, 15mmol of cuprous iodide and 150ml of o-dichlorobenzene were placed in a 250ml three-necked flask₂Reacting at 160 ℃ in the atmosphere, tracking the reaction process by TLC, and cooling to room temperature after the reaction is finished. Pouring the reaction solution into water, washing to remove K₂CO₃Then, the solid product was obtained by suction filtration, and washed with dichloromethane. Recrystallizing with toluene/petroleum ether mixed solvent to obtain white solid powder 11- (3- (4, 6-diphenyl-1, 3, 5-triazine-2-yl) phenyl) -11H-phenanthro [1, 9-ab ] of product]5.0g of carbazole. Ms (asap) ═ 598.4.

Example 4

Preparation of 8- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -11-phenyl-11H-phenanthro [1, 9-ab ] carbazole, the structural formula of which is shown in the following (4):

synthesis procedure similar to example 2, in a 250ml three-necked flask, 4.11g, 10mmol of (11-phenyl-11H-phenanthro [1, 9-ab)]Carbazole-8-yl) boronAcid, 3.0g, 11mmol 2-chloro-4, 6-diphenyl-1, 3, 5-triazine, 6.9g, 50mmol potassium carbonate, 0.58g, 0.5mmol Pd (PPh)₃)₄100ml of toluene, 25ml of water and 25ml of ethanol in N₂Reacting at 110 ℃ in the atmosphere, tracking the reaction process by TLC, and cooling to room temperature after the reaction is finished. Pouring the reaction solution into water, washing to remove K₂CO₃Then, the solid product was obtained by suction filtration, and washed with dichloromethane. Recrystallizing with dioxane to obtain solid powder 8- (4, 6-diphenyl-1, 3, 5-triazine-2-yl) -11-phenyl-11H-phenanthro [1, 9-ab ]]4.0g of carbazole. Ms (asap) ═ 598.2.

Example 5

Preparation of 10- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) -7-phenyl-7H-phenanthro [1, 9-bc ] carbazole, whose structural formula is shown in the following (5):

synthesis procedure similar to example 2, a 250ml three-necked flask was charged with 4.11g, 10mmol of (7-phenyl-7H-phenanthro [1, 9-bc)]Carbazole-10-yl) boronic acid, 3.0g, 11mmol of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine, 6.9g, 50mmol of potassium carbonate, 0.58g, 0.5mmol of Pd (PPh)₃)₄100ml of toluene, 25ml of water and 25ml of ethanol in N₂Reacting at 110 ℃ in the atmosphere, tracking the reaction process by TLC, and cooling to room temperature after the reaction is finished. Pouring the reaction solution into water, washing to remove K₂CO₃Then, the solid product was obtained by suction filtration, and washed with dichloromethane. Recrystallizing with dioxane and ethanol to obtain solid powder 10- (4, 6-diphenyl-1, 3, 5-triazine-2-yl) -7-phenyl-7H-phenanthro [1, 9-bc ] of product]4.8g of carbazole. Ms (asap) ═ 598.2.

Example 6

14- (3- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) -3b, 14-dihydropyrazine [2 ', 3': the preparation of 5, 6] phenanthro [1, 8-ab ] carbazole, which has the structural formula shown in the following (6):

synthesis procedure analogously to example 1, 3.19g, 10mmol of azaphenanthrocarbazole, 4.3g, 11mmol of 2- (3-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine, 6.9g, 50mmol of potassium carbonate, 0.26g, 1mmol of 18-crown-6, 3.0g, 15mmol of cuprous iodide and 150ml of o-dichlorobenzene are placed in a 250ml three-necked flask₂Reacting at 160 ℃ in the atmosphere, tracking the reaction process by TLC, and cooling to room temperature after the reaction is finished. Pouring the reaction solution into water, washing to remove K₂CO₃Then, the solid product was obtained by suction filtration, and washed with dichloromethane. Recrystallizing by using a toluene/petroleum ether mixed solvent to obtain a white solid powder product, namely 14- (3- (4, 6-diphenyl-1, 3, 5-triazine-2-yl) phenyl) -3b, 14-dihydropyrazine [2 ', 3': 5,6]Phenanthro [1, 8-ab]4.5g of carbazole. Ms (asap) ═ 613.3.

The energy level of the organic compound material can be obtained by quantum calculation, for example, by using TD-DFT (including time density functional theory) through Gaussian09W (Gaussian Inc.), and a specific simulation method can be seen in WO 2011141110. Firstly, a Semi-empirical method of 'group State/Semi-empirical/Default Spin/AM 1' (Charge 0/Spin Singlet) is used for optimizing the molecular geometrical structure, and then the energy structure of the organic molecules is calculated by a TD-DFT (including time density functional theory) method to obtain 'TD-SCF/DFT/Default Spin/B3PW 91' and a base group of '6-31G (d)' (Charge 0/Spin Singlet). The HOMO and LUMO energy levels are calculated according to the following calibration equation, S₁，T₁And resonance factor f (S)₁) Can be used directly.

HOMO(eV)＝((HOMO(G)×27.212)-0.9899)/1.1206

LUMO(eV)＝((LUMO(G)×27.212)-2.0041)/1.385

Where HOMO (G) and LUMO (G) are direct calculations of Gaussian09W in Hartree. The results of calculations for the materials prepared in examples 1-6 are shown in Table 1:

TABLE 1

Material	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

The materials (1) and (2) can be applied to green phosphorescent host materials, and the materials (3) to (6) can be applied to blue fluorescent host materials or luminescent materials, so that various conditions of luminescent layer materials are met.

Compared with the phosphorescent host material, the host material of the carbazole material system structure commonly used at present is marked by Ref 1:

preparing an OLED device:

has the following composition of ITO/HATCN (10nm)/NPB (35nm)/TCTA (5nm)/(1) - (2): 5% Ir (ppy)₃The preparation method of the OLED device comprises the following steps of/B3 PYMPM (40nm)/LiF (1nm)/Al (150 nm):

a. cleaning the conductive glass substrate: for the first time, the cleaning agent can be cleaned by various solvents, such as chloroform, ketone and isopropanol, and then ultraviolet ozone plasma treatment is carried out;

b. HTL (35nm), EML (15nm), ETL (65 nm): under high vacuum (1X 10)^-6Mbar, mbar) by thermal evaporation;

c. cathode: LiF/Al (1nm/150nm) in high vacuum (1X 10)^-6Millibar) hot evaporation;

d. packaging: the devices were encapsulated with uv curable resin in a nitrogen glove box.

The current-voltage (J-V) characteristics of each OLED device were characterized by a characterization device, while recording important parameters such as efficiency, lifetime, and external quantum efficiency. It is detected that the luminous efficiency and the lifetime of the OLED1 (corresponding to the material (1)) are both more than 3 times of those of the OLED Ref1 (corresponding to the material (Ref1)), the luminous efficiency of the OLED2 (corresponding to the material (2)) is more than 4 times of that of the OLED Ref1, and the lifetime is more than 5 times, especially the maximum external quantum efficiency of the OLED2 reaches more than 19%. Therefore, the OLED device prepared by the organic mixture has greatly improved luminous efficiency and service life, and the external quantum efficiency is obviously improved.

It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims

1. A carbazole derivative having the following structural formula:

2. a polymer comprising a compound corresponding to a repeating unit of the polymer, wherein the carbazole derivative according to claim 1 is contained in the compound.

3. The polymer according to claim 2, wherein the polymer is a nonconjugated polymer, and the carbazole derivative according to claim 1 is located in a side chain of the polymer.

4. The polymer of claim 2, wherein the polymer is a conjugated polymer.

5. A mixture comprising the carbazole derivative according to claim 1 and an organic functional material, or a mixture comprising the high polymer according to any one of claims 2 to 4 and an organic functional material;

6. A composition comprising the carbazole derivative of claim 1 and at least one organic solvent;

alternatively, the composition comprises the polymer as claimed in any one of claims 2 to 4 and at least one organic solvent;

alternatively, the composition comprises the mixture of claim 5 and at least one organic solvent.

7. Use of a carbazole derivative as claimed in claim 1 or a high polymer as claimed in any one of claims 2 to 4 in an organic electronic device.

8. An organic electronic device comprising the carbazole derivative according to claim 1, the high polymer according to any one of claims 2 to 4, or the mixture according to claim 5.

9. The organic electronic device according to claim 8, wherein the organic electronic device is selected from at least one of an organic light emitting diode, an organic photovoltaic cell, an organic light emitting cell, an organic field effect transistor, an organic light emitting field effect transistor, and an organic sensor.

10. The organic electronic device according to claim 8, wherein the organic electronic device is an electroluminescent device, and a light-emitting layer of the electroluminescent device comprises at least one carbazole derivative according to claim 1;

alternatively, the light-emitting layer comprises at least one polymer as defined in any one of claims 2 to 4.

11. The organic electronic device according to claim 10, wherein the light-emitting layer of the electroluminescent device comprises at least one carbazole derivative according to claim 1 and a phosphorescent emitter, a fluorescent emitter or a host material;

alternatively, the light-emitting layer comprises at least one polymer as claimed in any one of claims 2 to 4 and a phosphorescent emitter, a fluorescent emitter or a host material.