CN109790163B - Carbazole compound and application thereof - Google Patents

Carbazole compound and application thereof Download PDF

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CN109790163B
CN109790163B CN201780059447.8A CN201780059447A CN109790163B CN 109790163 B CN109790163 B CN 109790163B CN 201780059447 A CN201780059447 A CN 201780059447A CN 109790163 B CN109790163 B CN 109790163B
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carbazole
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CN109790163A (en
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潘君友
胡光
杨曦
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Guangzhou Chinaray Optoelectronic Materials Ltd
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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Abstract

The invention relates to a carbazole compound and application thereof. The compound has the following structural formula:

Description

Carbazole compound and application thereof
Technical Field
The invention relates to the field of electronics, in particular to a carbazole compound and application thereof.
Background
Due to the characteristics of diversity of molecular structure design, relatively low manufacturing cost, excellent photoelectric performance and the like, the organic semiconductor material has great application potential in a plurality of photoelectric devices, such as Organic Light Emitting Diodes (OLEDs), organic photovoltaic cells (OPVs), Organic Field Effect Transistors (OFETs) and the like. Organic semiconductor materials have gained rapid development in the field of flat panel displays and lighting, since the bilayer OLED structure was reported in, inter alia, dun kun et al (c.w.tang and s.a.van Slyke, appl.phys.lett., 1987, 51, 913) in 1987.
The organic thin film light emitting element must satisfy enhancement of light emitting efficiency, reduction of driving voltage, enhancement of durability, and the like. However, there are still many technical issues, wherein the high efficiency and long lifetime of the device are one of the difficulties.
In order to accelerate the process of promoting the large-scale industrialization of the OLED and improve the photoelectric property of the OLED, various novel organic photoelectric material systems are widely designed, developed and produced. Among them, carbazole organic semiconductor materials have been widely used in optoelectronic devices due to their excellent photoelectric properties, redox properties, stability, etc. In addition, aromatic groups or heteroaromatic groups of condensed ring structures, such as fluoranthene, anthracene, pyrene, phenanthrene, phenanthroline, benzofluoranthene, and the like, generally have good carrier transport properties and photoelectric response due to the planar structure of their molecules. However, the currently reported carbazoles or organic semiconductor materials with condensed ring structures have certain limitations in carrier transport capability, stability, service life and the like in photoelectric devices.
CN 104350627 a discloses a compound in which a carbazole group substituted with a nitrogen atom on a benzene ring is linked to a fused ring group containing benzofluoranthene. The compound is used as an electron transport layer of a blue OLED device, so that the voltage of the device is reduced, and the service life of the device is prolonged. However, electron transport materials of this system of fused ring carbazoles have not been studied further.
CN 104768926 a discloses a compound in which triphenylamine is linked to a condensed ring group. The compound is used as an electron transport layer of a blue OLED device, so that the voltage of the device is reduced, and the service life of the device is prolonged. However, in analogy to triphenylamine, carbazole as a class of transport material unit with greater conjugation, combined with fused ring structure design, has not been further compared and studied for its impact on device performance and lifetime.
In order to further explore the photoelectric properties of the materials, materials with novel structures and combined carbazole condensed rings are still to be designed and developed. The carbazole and the condensed ring are endowed with excellent photoelectric properties by a novel design combination mode.
Disclosure of Invention
Accordingly, there is a need for providing carbazole-based compounds that can be used to fabricate electronic devices with high stability, high luminous efficiency, and long lifetime, and applications thereof.
A carbazole-based compound having the formula:
Figure GPA0000264356250000021
wherein Ar is1Is a fused aryl group having 13 to 60 ring atoms or a fused heteroaryl group having 13 to 60 ring atoms;
Ar2、Ar3is one of aryl with 6 to 60 carbon atoms, heteroaryl with 3 to 60 carbon atoms, condensed aryl with 7 to 60 carbon atoms, condensed heteroaryl with 4 to 60 carbon atoms or a combination group formed by connecting at least two of the above groups, wherein Ar is2Ar described in3At least one of which comprises a heteroaryl group having a N atom;
R1selected from H, D, F, CN, NO2、CF3One of alkenyl, alkynyl, amido, acyl, amido, cyano, isocyano, alkoxy, hydroxyl, carbonyl, sulfuryl, alkyl with the carbon number of 1-60, cycloalkyl with the carbon number of 3-60, aryl with the carbon number of 6-60, heteroaryl with the carbon number of 3-60, condensed aryl with the carbon number of 7-60, condensed heteroaryl with the carbon number of 4-60 and a combination group formed by connecting at least two of the above groups, wherein L is2And L3At least one of which comprises a heteroaryl group having a N atom;
n is an integer of 0 to 20;
p and q are independently selected from one of integers of 0-4, and p and q are not 0 at the same time.
The carbazole compound is beneficial to realizing better carrier transmission by directly connecting nitrogen atoms of carbazole with thick aryl or thick heteroaryl with a planar structureThe photoelectric response and the energy level matching improve the photoelectric property and the stability of the compound, so that a photoelectric device comprising the compound has higher stability, higher luminous efficiency and longer service life. Experiments prove that the difference between the energy levels of HOMO and LUMO of the materials comprising the carbazole compounds is small, which indicates that the carbazole compounds have good stability, and delta E of the carbazole compoundsSTAll of them are smaller, which indicates that the device lifetime of the material including the carbazole-based compound is longer, the device lifetime of the organic light-emitting diode including the carbazole-based compound is more than 2 times of that of the organic light-emitting diode not including the carbazole-based compound, and the light-emitting efficiency of the organic light-emitting diode including the carbazole-based compound is improved by at least 47.2% compared with that of the organic light-emitting diode not including the carbazole-based compound. The carbazole compound can be used for preparing electronic devices with high stability, high luminous efficiency and long service life.
Detailed Description
In order to facilitate an understanding of the present invention, a more complete description of the present invention is provided below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In the following embodiments, an aryl group means a hydrocarbon group containing at least one aromatic ring, unless otherwise specified. Heteroaryl refers to an aromatic hydrocarbon group containing at least one heteroatom. Among them, the hetero atom may be O, N or S, for example. Of course, it is to be noted that the aryl group or the heteroaryl group includes not only a group having an aromatic ring or a heteroaromatic ring but also a group having a non-aromatic ring, for example, a pyridyl group, a thienyl group, a pyrrolyl group, a pyrazolyl group, a triazolyl group, an imidazolyl group, an oxazolyl group, an oxadiazolyl group, a thiazolyl group, a tetrazolyl group, a pyrazinyl group, a pyridazinyl group, a pyrimidinyl group, a triazinyl group, a carbene group, or the like is also considered as the aryl group or the heteroaryl group. The aryl or heteroaryl group may further include a group in which at least two aromatic or heteroaromatic rings are linked by a non-aromatic cyclic group, wherein the number of atoms other than H in the non-aromatic cyclic group is less than 10%. In one embodiment, the number of atoms other than H in the non-aromatic ring group is less than 5%. In one embodiment, the non-aromatic cyclic group is a C atom, a N atom, or an O atom.
Specifically, aryl is phenyl, biphenylyl, terphenylyl, tolyl, chlorophenyl, or a derivative of the foregoing. Heteroaryl is pyridyl, thienyl, pyrrolyl, pyrazolyl, triazolyl, imidazolyl, oxazolyl, oxadiazolyl, thiazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, carbene or derivatives of the above.
Fused aryl refers to aryl groups having two or more rings, and wherein two carbon atoms are shared by two adjacent rings (i.e., fused rings). Fused heteroaryl refers to fused aryl groups containing at least one heteroatom. Among them, the hetero atom may be N, O or S, for example. Of course, the fused aryl or fused heteroaryl group includes not only a group having an aromatic ring or a heteroaromatic ring but also a group in which at least two aromatic rings or heteroaromatic rings are connected by a non-aromatic ring group in which the number of atoms other than H is less than 10%. In one embodiment, the number of atoms other than H in the non-aromatic ring group is less than 5%. In one embodiment, the non-aromatic cyclic group is a C atom, a N atom, or an O atom. In one embodiment, the 9, 9' -spirobifluorenyl, 9, 9-diarylfluorene, triarylamine, and diaryl ether groups are also considered to be fused aryl or fused heteroaryl groups.
Specifically, the fused aryl group is naphthyl, anthryl, fluoranthenyl, phenanthryl, benzophenanthryl, perylene, tetracenyl, pyrenyl, benzopyrenyl, acenaphthenyl, fluorenyl or derivatives of the above groups. Fused heteroaryl is benzofuranyl, benzothienyl, indolyl, carbazolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothienyl, furopyrrolyl, furofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, quinolyl, isoquinolyl, o-dinitronaphthyl, quinoxalyl, phenanthridinyl, primidinyl, quinazolinyl, quinazolinone, and derivatives of the foregoing.
One embodiment of the carbazole-based compound has the following structural formula:
Figure GPA0000264356250000041
wherein Ar is1Is a fused aryl group having 13 to 60 ring atoms or a fused heteroaryl group having 13 to 60 ring atoms;
Ar2、Ar3is one selected from aryl with 6-60 carbon atoms, heteroaryl with 3-60 carbon atoms, condensed aryl with 7-60 carbon atoms, condensed heteroaryl with 4-60 carbon atoms or a combination group formed by connecting at least two of the above groups independently, and Ar is2、Ar3At least one of which comprises a heteroaryl group having a N atom;
R1selected from H, D, F, CN, NO2、CF3One of alkenyl, alkynyl, amido, acyl, amido, cyano, isocyano, alkoxy, hydroxyl, carbonyl, sulfuryl, alkyl with the carbon number of 1-60, naphthenic base with the carbon number of 3-60, aryl with the carbon number of 6-60, heteroaryl with the carbon number of 3-60, condensed aryl with the carbon number of 7-60, condensed heteroaryl with the carbon number of 4-60 and a combination group formed by connecting at least two of the groups;
n is an integer of 0 to 20;
p and q are independently selected from one of integers of 0-4, and p and q are not 0 at the same time.
In one embodiment, Ar1Is a fused aryl group having 13 to 50 ring atoms or a fused heteroaryl group having 13 to 50 ring atoms.
In one embodiment, Ar1Is a fused aryl or ring having 13 to 40 ring atomsA fused heteroaryl group having 13 to 40 atoms.
In one embodiment, Ar1Is a fused aryl group having 13 to 30 ring atoms or a fused heteroaryl group having 13 to 30 ring atoms.
In one embodiment, Ar1Is a fused aryl group having 13 to 20 ring atoms or a fused heteroaryl group having 13 to 20 ring atoms.
In one embodiment, Ar1Is a condensed heteroaryl radical, Ar1Is Si, N, P, O, S or Ge.
In one embodiment, Ar1Is a condensed heteroaryl radical, Ar1The heteroatom of (A) is Si, N, P, O or S.
In one embodiment, Ar1Is a condensed heteroaryl radical, Ar1Is N, O or S.
In one embodiment, Ar1Is a condensed ring group with 3-20 ring atoms. Ar (Ar)1Is a ternary, quaternary, pentabasic or hexahydric ring group.
In one embodiment, Ar1Is a condensed ring group with 3-10 ring atoms.
In one embodiment, Ar1Is a condensed ring group with 3-5 ring atoms.
In one embodiment, Ar1The structural formula of (A) is selected from one of the following structural formulas:
Figure GPA0000264356250000051
wherein, X1Is C-R2Or N;
Y1is selected from C-R3-R4、Si-R5-R6、N-R7、C(＝O)、S(＝O)2One of O and S;
-R2、-R3、-R4、-R5、-R6and-R7Each independently selected from the group consisting of a single bond, -H, -D, -F, -CN and-NO2、-CF3One of alkenyl, alkynyl, amido, acyl, amido, cyano, isocyano, alkoxy, hydroxyl, carbonyl, sulfuryl, alkyl with the carbon number of 1-60, naphthenic base with the carbon number of 3-60, aryl with the carbon number of 6-60, heteroaryl with the carbon number of 3-60, condensed aryl with the carbon number of 7-60, condensed heteroaryl with the carbon number of 4-60 and a combination group formed by connecting at least two of the groups.
In one embodiment, Y1Is selected from C-R3-R4And O.
In one embodiment, -R2、-R3、-R4、-R5、-R6and-R7Each independently selected from a substituted alkyl group having 1 to 60 carbon atoms, a substituted cycloalkyl group having 3 to 60 carbon atoms, a substituted aryl group having 6 to 60 carbon atoms, a substituted heteroaryl group having 3 to 60 carbon atoms, a substituted fused aryl group having 7 to 60 carbon atoms and a substituted fused heteroaryl group having 4 to 60 carbon atoms.
In one embodiment, -R2、-R3、-R4、-R5、-R6and-R7Each independently selected from the group consisting of a single bond, -H, -D, -F, -CN and-NO2、-CF3One of alkenyl, alkynyl, amido, acyl, amido, cyano, isocyano, alkoxy, hydroxyl, carbonyl, sulfuryl, alkyl with the carbon number of 1-30, cycloalkyl with the carbon number of 3-30, aryl with the carbon number of 6-30, heteroaryl with the carbon number of 3-30, condensed aryl with the carbon number of 7-30, condensed heteroaryl with the carbon number of 4-30 and a combination group formed by connecting at least two of the above groups.
In one embodiment, -R2、-R3、-R4、-R5、-R6and-R7Each independently selected from the group consisting of a substituted alkyl group having 1 to 30 carbon atoms, a substituted cycloalkyl group having 3 to 30 carbon atoms, a substituted aryl group having 6 to 30 carbon atoms, a substituted heteroaryl group having 3 to 30 carbon atoms, and a substituted heteroaryl group having 3 to 30 carbon atoms7 to 30 thick aryl groups and substituted thick heteroaryl groups having 4 to 30 carbon atoms.
In one embodiment, -R2、-R3、-R4、-R5、-R6and-R7Can form a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aryl group or a polycyclic aryl group by themselves.
In one embodiment, -R2Can be reacted with-R3、-R4、-R5、-R6or-R7Form a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aryl group or a polycyclic aryl group.
In one embodiment, -R7Can be reacted with-R2、-R3、-R4、-R5or-R6Form a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aryl group or a polycyclic aryl group.
In one embodiment, -R3and-R4Can form a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aryl group or a polycyclic aryl group with each other.
In one embodiment, -R5and-R6Can form a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aryl group or a polycyclic aryl group with each other.
In one embodiment, Ar1Selected from one of anthryl, fluoranthenyl, phenanthryl, benzophenanthryl, perylene, tetracenyl, pyrenyl, benzopyrenyl, acenaphthenyl, fluorenyl, carbazolyl, dibenzofuranyl and dibenzothienyl.
In one embodiment, Ar1The structural formula of (A) is selected from one of the following structural formulas:
Figure GPA0000264356250000061
in one embodiment, the structural formula of the heteroaryl group having an N atom is selected from one of the following structural formulas:
Figure GPA0000264356250000071
wherein, X2Is C-R8Or N, and at least one X in the formula of a heteroaryl group having an N atom2Is N;
Y2is selected from C-R9-R10、Si-R11-R12、N-R13、C(＝O)、S(＝O)2One of O and S;
-R8、-R9、-R10、-R11、-R12and-R13Each independently selected from the group consisting of a single bond, -H, -D, -F, -CN and-NO2、-CF3One of alkenyl, alkynyl, amido, acyl, amido, cyano, isocyano, alkoxy, hydroxyl, carbonyl, sulfuryl, alkyl with the carbon number of 1-60, naphthenic base with the carbon number of 3-60, aryl with the carbon number of 6-60, heteroaryl with the carbon number of 3-60, condensed aryl with the carbon number of 7-60, condensed heteroaryl with the carbon number of 4-60 and a combination group formed by connecting at least two of the groups.
In one embodiment, -R8、-R9、-R10、-R11、-R12and-R13Each independently selected from a substituted alkyl group having 1 to 60 carbon atoms, a substituted cycloalkyl group having 3 to 60 carbon atoms, a substituted aryl group having 6 to 60 carbon atoms, a substituted heteroaryl group having 3 to 60 carbon atoms, a substituted fused aryl group having 7 to 60 carbon atoms and a substituted fused heteroaryl group having 4 to 60 carbon atoms.
In one embodiment, -R8、-R9、-R10、-R11、-R12and-R13Each independently selected from the group consisting of a single bond, -H, -D, -F, -CN and-NO2、-CF3Alkenyl, alkynyl, amino, acyl, amido, cyano, isocyano, alkoxy, hydroxyl, carbonyl, sulfone, C1-30 alkyl, C3-30 cycloalkyl, and CA sub-number of 6 to 30 aryl groups, a C3 to 30 heteroaryl group, a C7 to 30 fused aryl group, a C4 to 30 fused heteroaryl group, and a combination of at least two of the above groups.
In one embodiment, -R8、-R9、-R10、-R11、-R12and-R13Each independently selected from a substituted alkyl group having 1 to 30 carbon atoms, a substituted cycloalkyl group having 3 to 30 carbon atoms, a substituted aryl group having 6 to 30 carbon atoms, a substituted heteroaryl group having 3 to 30 carbon atoms, a substituted fused aryl group having 7 to 30 carbon atoms and a substituted fused heteroaryl group having 4 to 30 carbon atoms.
In one embodiment, -R8、-R9、-R10、-R11、-R12and-R13Can form a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aryl group or a polycyclic aryl group by themselves.
In one embodiment, -R8Can be reacted with-R9、-R10、-R11、-R12or-R13Form a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aryl group or a polycyclic aryl group.
In one embodiment, -R13Can be reacted with-R8、-R9、-R10、-R11or-R12Form a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aryl group or a polycyclic aryl group.
In one embodiment, -R9and-R10Can form a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aryl group or a polycyclic aryl group with each other.
In one embodiment, -R11and-R12Can form a monocyclic aliphatic ring group, a polycyclic aliphatic ring group, a monocyclic aryl group or a polycyclic aryl group with each other.
In one embodiment, the structural formula of the heteroaryl group having an N atom is selected from one of the following structural formulas:
Figure GPA0000264356250000081
in one embodiment, Ar2And Ar3Each independently comprises one of the following structural formulas or combination groups formed by at least two of the following structural formulas:
Figure GPA0000264356250000082
wherein n1 is an integer of 1-4.
In one embodiment, L2And L3At least one of which is a heteroaryl group having at least one N atom.
In one embodiment, n is an integer of 0 to 20.
In one embodiment, n is an integer of 0 to 10.
In one embodiment, n is an integer of 0 to 5.
In one embodiment, n is an integer of 0 to 3.
In one embodiment, p and q are each independently selected from one of integers from 0 to 4, and p and q are not 0 at the same time.
In one embodiment, p and q are each independently selected from one of integers from 0 to 3, and p and q are not 0 at the same time.
In one embodiment, p and q are each independently selected from one of integers from 0 to 2, and p and q are not 0 at the same time.
In one embodiment, p and q are each independently selected from one of integers from 0 to 1, and p and q are not 0 at the same time.
In one embodiment, the carbazole-based compound has an electron mobility of 10 or more-5cm2·V-1·S-1. The carbazole compound has high electron mobility, so that the lower the power consumption is, the lower the current bearing is when the same current is passedThe greater the load capacity.
In one embodiment, the carbazole-based compound has an electron mobility of 10 or more-4cm2·V-1·S-1。
In one embodiment, the carbazole-based compound has an electron mobility of 10 or more-3cm2·V-1·S-1。
In one embodiment, the carbazole-based compound has a glass transition temperature greater than or equal to 100 ℃. The carbazole compound has better stability and better service performance due to higher glass transition temperature, and is beneficial to wide application of the carbazole compound.
In one embodiment, the carbazole-based compound has a glass transition temperature greater than or equal to 110 ℃.
In one embodiment, the carbazole-based compound has a glass transition temperature greater than or equal to 120 ℃.
In one embodiment, the carbazole-based compound has a glass transition temperature greater than or equal to 140 ℃.
In one embodiment, the carbazole-based compound has a lowest unoccupied orbital Level (LUMO) of less than or equal to-2.7 eV.
In one embodiment, the LUMO of the carbazole-based compound is less than or equal to-2.8 eV.
In one embodiment, the LUMO of the carbazole-based compound is less than or equal to-2.9 eV.
In one embodiment, the LUMO of the carbazole-based compound is less than or equal to-3.0 eV.
In one embodiment, the carbazole-based compound has a highest occupied orbital level (HOMO) of less than or equal to-5.6 eV. In one embodiment, the HOMO of the carbazole-based compound is less than or equal to-5.65 eV.
In one embodiment, the HOMO of the carbazole-based compound is less than or equal to-5.7 eV.
In one embodiment, the triplet energy level (T) of the carbazole-based compound1) Greater than or equal to 1.7 eV.
In one embodiment, T of the carbazole-based compound1Greater than or equal to 1.9 eV.
In one embodiment, T of the carbazole-based compound1Greater than or equal to 2.15 eV.
In one embodiment, T of the carbazole-based compound1Greater than or equal to 2.4 eV.
In one embodiment, the lowest unoccupied orbital level and the highest occupied orbital level are both measured by the photoelectric effect, such as XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy), as well as by CV (cyclic voltammetry), and also by quantum chemical methods, such as DFT (density functional theory).
In one embodiment, the triplet level T1The measurement can be performed by low temperature Time-resolved luminescence spectroscopy, or can be obtained by quantum simulation calculation, such as Time-dependent DFT simulation calculation or commercial software Gaussian 03W (Gaussian Inc.). Specific simulation methods can be found in WO 2011141110.
Of course, HOMO, LUMO and T1The absolute value of (a) depends on the measurement method, calculation method or evaluation method used. Thus, a reasonably meaningful comparison should be made with the same measurement method and the same evaluation method. The energy level values determined by different methods should be calibrated with each other. In this embodiment, HOMO, LUMO and T1Is based on the simulation of the Time-dependent DFT but does not affect the application of other measurement methods or calculation methods.
In one embodiment, the carbazole-based compound can be applied to electronic devices as an Electron Transport Material (ETM), an Electron Injection Material (EIM), a Hole Blocking Material (HBM), and a Host material (Host).
In one embodiment, 10% to 40% of H in the carbazole-based compound is substituted with deuterium.
In one embodiment, 10% of the H in the carbazole-based compound is substituted with deuterium.
In one embodiment, 20% of the H in the carbazole-based compound is substituted with deuterium.
In one embodiment, 30% of the H in the carbazole-based compound is substituted with deuterium.
In one embodiment, 40% of the H in the carbazole-based compound is substituted with deuterium.
In one embodiment, the carbazole-based compound is a small molecule compound, i.e., a molecule that is not a polymer, oligomer, dendrimer, or copolymer.
In one embodiment, the molar mass of the carbazole-based compound is 700 g/mol to 3000 g/mol.
In one embodiment, the molar mass of the carbazole-based compound is less than or equal to 3000 g/mole.
In one embodiment, the molar mass of the carbazole-based compound is less than or equal to 2000 g/mole.
In one embodiment, the molar mass of the carbazole-based compound is less than or equal to 1500 g/mole.
In one embodiment, the molar mass of the carbazole-based compound is less than or equal to 1000 g/mole. The molar mass of the carbazole compound is less than or equal to 1000 g/mol, so that the carbazole compound can be used as a raw material of the evaporation type OLED.
In one embodiment, the molar mass of the carbazole-based compound is less than or equal to 900 g/mole.
In one embodiment, the molar mass of the carbazole-based compound is less than or equal to 850 g/mole.
In one embodiment, the molar mass of the carbazole-based compound is less than or equal to 800 g/mole.
In one embodiment, the molar mass of the carbazole-based compound is less than or equal to 700 g/mole.
In one embodiment, the molar mass of the carbazole-based compound is greater than or equal to 700 g/mole. The molar mass of the carbazole compound is more than or equal to 700 g/mol, so that the carbazole compound can be used as a raw material of the printing OLED.
In one embodiment, the molar mass of the carbazole-based compound is greater than or equal to 800 g/mole.
In one embodiment, the molar mass of the carbazole-based compound is greater than or equal to 900 g/mole.
In one embodiment, the molar mass of the carbazole-based compound is greater than or equal to 1000 g/mole.
In one embodiment, the molar mass of the carbazole-based compound is greater than or equal to 1100 g/mole.
In one embodiment, the carbazole-based compound is soluble in toluene, chlorobenzene, or xylene.
In one embodiment, the carbazole-based compound has a solubility in toluene of greater than or equal to 10mg/mL at 25 ℃. The high solubility of the carbazole compounds in toluene enables the compounds to be better widely used.
In one embodiment, the carbazole-based compound has a solubility in toluene of greater than or equal to 15mg/mL at 25 ℃.
In one embodiment, the carbazole-based compound has a solubility in toluene of greater than or equal to 20mg/mL at 25 ℃.
In one embodiment, the carbazole-based compound has a structural formula selected from one of the following structural formulas:
Figure GPA0000264356250000111
Figure GPA0000264356250000121
Figure GPA0000264356250000131
Figure GPA0000264356250000141
Figure GPA0000264356250000151
Figure GPA0000264356250000161
Figure GPA0000264356250000171
Figure GPA0000264356250000181
Figure GPA0000264356250000191
Figure GPA0000264356250000201
Figure GPA0000264356250000211
Figure GPA0000264356250000221
Figure GPA0000264356250000231
Figure GPA0000264356250000241
Figure GPA0000264356250000251
Figure GPA0000264356250000261
Figure GPA0000264356250000271
Figure GPA0000264356250000281
Figure GPA0000264356250000291
Figure GPA0000264356250000301
Figure GPA0000264356250000311
Figure GPA0000264356250000321
Figure GPA0000264356250000331
Figure GPA0000264356250000341
Figure GPA0000264356250000351
Figure GPA0000264356250000361
Figure GPA0000264356250000371
Figure GPA0000264356250000381
Figure GPA0000264356250000391
in the structural formulas, one structural formula represents a carbazole compound, and the staggering between adjacent structural formulas is only a problem of document typesetting and has no other significance.
The carbazole-based compound of one embodiment has at least the following advantages:
(1) the carbazole compound is beneficial to realizing better carrier transmission, photoelectric response and energy level matching by directly connecting the nitrogen atom of carbazole with the thick aryl or thick heteroaryl of a planar structure, improves the photoelectric property and stability of the compound, and further enables a photoelectric device comprising the compound to have devices with higher stability, higher luminous efficiency and longer service life. Experiments prove that the difference between the energy levels of HOMO and LUMO of the materials comprising the carbazole compounds is small, which indicates that the carbazole compounds have good stability, and delta E of the carbazole compoundsSTAll of them are smaller, indicating that the device life of the material including the carbazole-based compound is longer, the device life of the organic light-emitting diode including the carbazole-based compound is more than 2 times of that of the organic light-emitting diode not including the carbazole-based compound, and the light-emitting efficiency of the organic light-emitting diode including the carbazole-based compound is higher than that of the organic light-emitting diode not including the carbazole-based compoundThe luminous efficiency of the organic light-emitting diode of the azole compound is improved by at least 47.2 percent. The carbazole compound can be used for preparing electronic devices with high stability, high luminous efficiency and long service life.
(2) The Tg (glass transition temperature) of the carbazole compound is greater than or equal to 100 ℃, so that the carbazole compound has good stability and good service performance, and is beneficial to wide application of the carbazole compound.
(3) The carbazole compound can be used as an Electron Transport Material (ETM), an Electron Injection Material (EIM), a Hole Blocking Material (HBM) and a Host material (Host) to be applied to electronic devices.
(4) The high solubility of the carbazole compound in toluene enables the compound to be better widely applied.
The carbazole-based polymer of an embodiment includes a repeating unit formed of the above carbazole-based compound.
In one embodiment, the carbazole-based polymer is a homopolymer, i.e., the polymer is polymerized from only one type of repeating unit; that is, the carbazole-based polymer includes only the repeating unit formed by the above carbazole-based compound.
In one embodiment, the carbazole-based polymer is a copolymer (copolymer), i.e., the polymer is polymerized from two or more repeat units.
In one embodiment, the carbazole-based polymer is a copolymer obtained by polymerizing two monomers, and one of the two monomers is the carbazole-based compound or a derivative thereof. Preferably, the other of the two monomers is an aromatic amine compound.
In one embodiment, the carbazole-based polymer is a block copolymer (i.e., a polymer formed by linking two or more polymer segments having different properties. One of the polymer chain segments is a polymer chain segment formed by the carbazole compounds, and the other polymer chain segment is an arylamine structure.
In one embodiment, the carbazole-based polymer is a dendrimer (dendrimer). For the structure and application of Dendrimers, see [ Dendrimers and Dendrons, Wiley-VCH Verlag GmbH & Co. KGaA, 2002, Ed. George R. Newkome, Charles N. Moorefield, Fritz Vogtle ], which are not repeated herein.
In one embodiment, the number of the carbazole-based polymer repeating unit is 10 to 1000. Of course, it should be noted that the number of repeating units may be set as desired.
In one embodiment, the carbazole-based polymer is a conjugated polymer, i.e., the backbone of the polymer is composed primarily of sp2 hybridized orbitals of C atoms. Of course, it should be noted that when the C atom on the backbone of the polymer is replaced by another non-C atom or the sp2 hybridization on the backbone is interrupted by some natural defect, the polymer is still considered to be a conjugated polymer. Meanwhile, when the main chain of the polymer includes aromatic amine (aryl amine), aryl phosphine (aryl phosphine), other heterocyclic aromatic hydrocarbon (heterocyclic aromatic) and organic metal complex (organometallic complexes), the polymer is still considered to be a conjugated polymer.
In one embodiment, the carbazole-based polymer is a non-conjugated polymer, and the above carbazole-based compound is located on a side chain of the polymer.
The carbazole-based polymer of one embodiment has at least the following advantages:
the carbazole polymer comprises the carbazole compound, so that the carbazole polymer has good solubility, stability and photoelectric properties, can be used as a Hole Injection Material (HIM), a Hole Transport Material (HTM), an Electron Transport Material (ETM), an Electron Injection Material (EIM), an Electron Blocking Material (EBM), a Hole Blocking Material (HBM), a light emitting body (Emitter) and a main body material (Host) to be applied to an electronic device, and has wide application range, good stability, high luminous efficiency and long service life.
The organic electroluminescent material according to the first embodiment includes an organic functional material and at least one of the carbazole-based compound and the carbazole-based polymer.
In one embodiment, the organic functional material is selected from at least one of a Hole Injection Material (HIM), a Hole Transport Material (HTM), an Electron Injection Material (EIM), an Electron Transport Material (ETM), a Hole Blocking Material (HBM), an Electron Blocking Material (EBM), a Host material (Host), a singlet emitter, a thermally activated delayed fluorescence emission material (TADF), a triplet emitter, a Host material, and an organic dye. Various organic functional materials are described in detail in WO2010135519a1, US20090134784a1 and WO 2011110277a1, and the organic functional materials in these three patents can be used as organic functional materials in the organic electroluminescent material in this embodiment mode, and are not described herein again.
The invention further relates to a mixture comprising at least one carbazole-based compound or polymer according to the invention and at least one organic functional material.
The organic functional material is a hole (also called hole) injection or transport material (HIM/HTM), a Hole Blocking Material (HBM), an electron injection or transport material (EIM/ETM), an Electron Blocking Material (EBM), an organic Host material (Host), a singlet emitter (fluorescent emitter), a thermally activated delayed fluorescent emitter (TADF), a triplet emitter (phosphorescent emitter), or an organic dye. Further, the triplet emitter is a light-emitting organometallic complex. Various organic functional materials are described in detail, for example, in WO2010135519a1, US20090134784a1 and WO 2011110277a1, the entire contents of this 3 patent document being hereby incorporated by reference.
The organic functional material may be a small molecule material or a polymer material.
In certain embodiments, the carbazole-based compound is present in the mixture according to the present invention in an amount of 50 to 99 wt%. In the mixture according to the invention, the content of the carbazole compound is 60 wt% -97 wt%. In the mixture according to the invention, the content of the carbazole compound is 60 wt% -95 wt%. . In the mixture according to the invention, the content of the carbazole compound is 70 wt% -90 wt%.
In one embodiment, the mixtures according to the invention comprise a compound or polymer according to the invention and a fluorescent light-emitting material (singlet emitter).
In a further embodiment, the mixtures according to the invention comprise a compound or polymer according to the invention and a thermally activated delayed fluorescence phosphor (TADF).
In a further embodiment, the mixtures according to the invention comprise a compound or polymer according to the invention, a fluorescent light-emitting material and a TADF material.
Some more detailed descriptions (but not limited to) of the fluorescent or singlet emitters (fluorescent emitters) and TADF materials are provided below.
1. Singlet state luminophor (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 at least one of the group consisting of monostyrenes, distyrenes, tristyrenes, tetrastyrenes, styrylphosphines, styryl ethers, and aromatic amines.
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. In one embodiment, the aromatic amine Wie is an aromatic anthracylamine, an aromatic anthracenediamine, an aromatic pyreneamine, an aromatic pyrenediamine, an aromatic chrysylamine or an aromatic chrysenediamine. 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 chrysophamines and aromatic chrysophanylamines 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: WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007/115610, US 7250532B 2, DE 102005058557 a1, CN 1583691 a, JP 08053397 a, US 6251531B 1, US 2006/210830 a, EP 1957606A 1 and US 2008/0113101 a1 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 US5121029 a.
Further preferred singlet emitters may be selected from indenofluorene-amines and indenofluorene-diamines, as disclosed in WO 2006/122630, 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. US5121029A, US5130603A), cyclopentadienes such as tetraphenylcyclopentadiene, rubrene, coumarin, rhodamine, quinacridones, pyrans such as 4 (dicyanomethylene) -6- (4-p-dimethylaminostyryl-2-methyl) -4H-pyran (DCM), thiopyrans, bis (azinyl) boron compounds (US 2007/0092753A 1), 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 4769292a, US 6020078a, 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:
Figure GPA0000264356250000421
Figure GPA0000264356250000431
2. thermally activated delayed fluorescence luminescent material (TADF):
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%.
TADF materials need to have a small singlet-triplet energy level difference, typically Δ Est < 0.3eV for TADF materials. Further, the Δ Est of the TADF material is < 0.2 eV. Further, the Δ Est of the TADF material is < 0.1 eV. Further, the Δ Est of the TADF material is < 0.05 eV. In one embodiment, the TADF material has better fluorescence quantum efficiency. Some TADF materials can be found in the following patent documents: CN103483332(a), TW201309696(a), TW201309778(a), TW201343874(a), TW201350558(a), US20120217869(a1), WO2013133359(a1), WO2013154064(a1), Adachi, et.al.adv.mater, 21, 2009, 4802, Adachi, et.al.appl.phys.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, addi.c. et 3, addi.7, addi.et 3, addi.7.
Some examples of suitable TADF phosphors are listed in the following table:
Figure GPA0000264356250000432
Figure GPA0000264356250000441
Figure GPA0000264356250000451
the above-identified publications of organic functional materials are incorporated by reference into this application for disclosure purposes.
The invention relates to a composition or ink comprising a compound or polymer or mixture according to the invention and at least one organic solvent. The composition and the ink in the present embodiment have the same meaning. Further, the present invention provides a method for preparing a film comprising a compound or polymer according to the present invention from a solution.
For the printing process, viscosity and surface tension of the ink are important parameters. Suitable inks have surface tension parameters suitable for a particular substrate and a particular printing process.
In one embodiment, the ink according to the present invention has a surface tension of 19dyne/cm to 50dyne/cm at 25 ℃ to 300 ℃. Further, the ink according to the present invention has a surface tension in the range of 22dyne/cm to 35dyne/cm at 25 ℃ to 300 ℃. Further, the ink according to the present invention has a surface tension in the range of 25dyne/cm to 33dyne/cm at 25 ℃ to 300 ℃.
In one embodiment, the viscosity of the ink according to the present invention is 1cps to 100cps at 25 ℃ to 300 ℃. Further, the viscosity of the ink according to the present invention is 1cps to 50cps at 25 ℃ to 300 ℃. Further, the viscosity of the ink according to the present invention is 1.5cps to 20cps at 25 ℃ to 300 ℃. Further, the viscosity of the ink according to the present invention is 4.0cps to 20cps at 25 ℃ to 300 ℃. The composition so formulated will be suitable for 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 said compounds or polymers facilitate the adjustment of the printing inks to the appropriate range according to the printing process used. Generally, the composition according to the invention comprises 0.3 to 30 wt% of organic functional material. The composition according to the present invention comprises 0.5 wt% to 20 wt% of the organic functional material and the composition according to the present invention comprises 0.5 wt% to 15 wt% of the organic functional material. The composition according to the present invention comprises the organic functional material in a weight ratio of 0.5 wt% to 10 wt%. The composition according to the present invention comprises the organic functional material in a weight ratio of 1 wt% to 5 wt%.
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 aromatic solvents substituted by aliphatic chains, aromatic solvents substituted by aliphatic rings, aromatic ketone solvents or aromatic ether solvents.
Examples of organic 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 one embodiment, the composition according to the invention is a suspension.
The solution or suspension may additionally contain one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, etc., for adjusting viscosity, film-forming properties, improving adhesion, etc. For details on printing techniques and their requirements relating to the solutions, such as solvents, concentrations and viscosities, see the printed media handbook, master record of Helmut Kipphan: techniques and Production Methods (Handbook of Print Media: Technologies and Production Methods), ISBN 3-540 and 67326-1.
The invention also relates to the use of said composition as an ink for the production of organic electronic devices, particularly preferably by printing or coating.
Suitable Printing or coating techniques include, but are not limited to, ink jet Printing, jet Printing (Nozzle Printing), letterpress Printing, screen Printing, dip coating, spin coating, doctor blade coating, roll Printing, twist roll Printing, offset Printing, flexographic Printing, rotary Printing, spray coating, brush or pad Printing, jet Printing (Nozzle Printing), slot die coating, and the like. Further, suitable printing or coating techniques are inkjet printing, slot die coating, spray printing or gravure printing.
Based on the compound, the invention also provides application of the compound or the polymer in organic electronic devices. 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 (efets), Organic lasers, Organic spintronic devices, Organic sensors, Organic Plasmon Emitting diodes (Organic plasma Emitting diodes), and the like, particularly OLEDs. In the embodiment of the invention, the organic compound is used in an electron transport layer or a light emitting layer of an OLED device.
Further, the present invention relates to an organic electronic device comprising at least one compound or polymer as described above. Generally, such an organic electronic device comprises at least a cathode, an anode and a functional layer located between the cathode and the anode, wherein the functional layer comprises at least one compound or polymer as described above. The Organic electronic device may be selected from, but not limited to, an Organic Light Emitting Diode (OLED), an Organic photovoltaic cell (OPV), an Organic light Emitting cell (OLEEC), an Organic Field Effect Transistor (OFET), an Organic light Emitting field effect transistor (fet), an Organic laser, an Organic spintronic device, an Organic sensor, or an Organic Plasmon Emitting Diode (Organic plasma Emitting Diode).
In one embodiment, the organic electronic device is an electroluminescent device, such as an OLED, comprising a substrate, an anode, a cathode, and a light-emitting layer disposed at least between the anode and the cathode. The organic electronic device may further include a hole transport layer or an electron transport layer. In one embodiment, the organic electronic device comprises an electron transport layer or an electron injection layer comprising a compound or polymer according to the present invention. In one embodiment, the organic electronic device comprises a light-emitting layer comprising a compound or polymer according to the present invention. The luminescent layer further comprises a compound or polymer according to the invention and at least one luminescent material, wherein the luminescent material is a fluorescent light emitter or a TADF material.
The device structure of the electroluminescent device is described below, but not limited thereto.
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. Further, the substrate has a smooth surface. A substrate free of surface defects is a particularly desirable choice. In one embodiment, the substrate is flexible, and may be selected from a polymer film or plastic. The glass transition temperature Tg of the substrate is greater than or equal to 150 ℃. The glass transition temperature of the substrate is greater than or equal to 200 ℃. The glass transition temperature of the substrate is greater than or equal to 250 ℃. The glass transition temperature of the substrate is greater than or equal to 300 ℃. Examples of materials suitable as 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 as HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5 eV. 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 as HIL or HTL or Electron Blocking Layer (EBL) is less than 0.3 eV. 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 as HIL or HTL or Electron Blocking Layer (EBL) is 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. The cathode can easily inject electrons into the EIL, ETL, or light emitting layer. In one embodiment, an absolute value of a difference between a work function of the cathode and a LUMO level or a conduction band level of an emitter or an n-type semiconductor material as an Electron Injection Layer (EIL) or an Electron Transport Layer (ETL) or a Hole Blocking Layer (HBL) in the light emitting layer is less than 0.5 eV. In one embodiment, an absolute value of a difference between a work function of the cathode and a LUMO level or a conduction band level of an emitter or an n-type semiconductor material as an Electron Injection Layer (EIL) or an Electron Transport Layer (ETL) or a Hole Blocking Layer (HBL) in the light emitting layer is less than 0.3 eV. In one embodiment, an absolute value of a difference between a work function of the cathode and a LUMO level or a conduction band level of an emitter or an n-type semiconductor material as an Electron Injection Layer (EIL) or an Electron Transport Layer (ETL) or a Hole Blocking Layer (HBL) in the light emitting layer is 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, BaF2/Al, 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 well known to those skilled in the art and are readily found in the literature.
In a preferred embodiment, in the light emitting device according to the present invention, the electron transporting layer or the electron injecting layer comprises the compound or the polymer of the present invention.
The light emitting device according to the present invention emits light at a wavelength of 300nm to 1000 nm. The light emitting device according to the present invention emits light at a wavelength of 350nm to 900 nm. The light emitting device according to the present invention emits light at a wavelength of 400nm to 800 nm.
The invention also relates to the use of the organic electronic device according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.
The following are specific examples.
Example 1
The synthesis process of the carbazole compound N- (3-fluoranthene) -3, 6-bis (4- (3-pyridine) phenyl) carbazole of the present embodiment is as follows:
Figure GPA0000264356250000481
n- (3-fluoranthene) -3, 6-dibromo-carbazole (10g, 19.04mmol) and 4- (3-pyridine) phenylboronic acid (9.47g, 47.6mmol) were placed in a 500mL two-necked round-bottomed flask, 250mL of toluene (i.e., solvent) was added, potassium carbonate (10.51g, 76.16mmol) was completely dissolved in 30mL of water, and the mixture was added to the round-bottomed flask, followed by addition of Pd (PPh)3)4(1.32g, 1.14mmol), pumping off the air in the bottle by an oil pump, introducing nitrogen, heating at constant temperature under reflux for 12 hours, and cooling. Transferring the reaction solution into a rotary evaporation bottle, carrying out rotary evaporation on most of the solvent, extracting with dichloromethane, washing with water for three times, drying with anhydrous magnesium sulfate, filtering, carrying out rotary drying, and purifying to obtain the N- (3-fluoranthene) -3, 6-bis (4- (3-pyridine) phenyl) carbazole with the yield of 78%.
Example 2
The synthesis process of the carbazole compound N- (3-fluoranthene) -3- (4- (3-pyridine) phenyl) carbazole of the present embodiment is as follows:
Figure GPA0000264356250000491
n- (3-fluoranthene) -3-bromocarbazole (10g, 22.40mmol) and 4- (3-pyridine) phenylboronic acid (5.35g, 26.88mmol) were placed in a 500mL two-neck round-bottom flask, 250mL of toluene (i.e., solvent) was added, potassium carbonate (7.42g, 53.76mmol) was dissolved completely with 30mL of water, the flask was charged, Pd (PPh3)4(0.78g, 0.67mmol) was added, the air in the flask was removed by an oil pump, nitrogen was introduced, and the flask was heated at constant temperature under reflux for 12 hours and cooled. Transferring the reaction solution into a rotary evaporation bottle, carrying out rotary evaporation on most of the solvent, extracting with dichloromethane, washing with water for three times, drying with anhydrous magnesium sulfate, filtering, carrying out rotary drying, and purifying to obtain the N- (3-fluoranthene) -3- (4- (3-pyridine) phenyl) carbazole, wherein the yield is 80%.
Example 3
The synthesis process of the carbazole compound N- (1-anthracene) -3, 6-bis (4- (3-pyridine) phenyl) carbazole of the present embodiment is as follows:
Figure GPA0000264356250000492
n- (1-anthracene) -3, 6-dibromocarbazole (10g, 19.95mmol) and 4- (3-pyridine) phenylboronic acid (9.93g, 49.88mmol) are placed in a 500mL two-neck round-bottom flask, 250mL of toluene (i.e., solvent) is added, potassium carbonate (11.01g, 79.80mmol) is completely dissolved in 30mL of water, the round-bottom flask is added, Pd (PPh3)4(1.38g, 1.19mmol) is added, the air in the flask is pumped out by an oil pump, nitrogen is introduced, and the flask is heated at constant temperature and refluxed for 12 hours and cooled. Transferring the reaction solution into a rotary evaporation bottle, carrying out rotary evaporation on most of the solvent, extracting with dichloromethane, washing with water for three times, drying with anhydrous magnesium sulfate, filtering, carrying out rotary drying, and purifying to obtain Xg of N- (1-anthracene) -3, 6-bis (4- (3-pyridine) phenyl) carbazole with the yield of 83%.
Example 4
The synthesis process of the carbazole compound N- (2-anthracene) -3, 6-bis (4- (3-pyridine) phenyl) carbazole of the present embodiment is as follows:
Figure GPA0000264356250000501
n- (2-fluoranthene) -3, 6-dibromocarbazole (10g, 19.95mmol) and 4- (3-pyridine) phenylboronic acid (9.93g, 49.88mmol) are taken, 250mL of toluene (i.e., solvent) is added into a 500mL double-neck round-bottom flask, potassium carbonate (11.01g, 79.80mmol) is taken and completely dissolved with 30mL of water, the round-bottom flask is added, Pd (PPh3)4(1.38g, 1.19mmol) is added, the air in the flask is pumped by an oil pump, nitrogen is introduced, and the mixture is heated and refluxed for 12 hours at constant temperature and cooled. Transferring the reaction solution into a rotary evaporation bottle, carrying out rotary evaporation on most of the solvent, extracting with dichloromethane, washing with water for three times, drying with anhydrous magnesium sulfate, filtering, carrying out rotary drying, and purifying to obtain the N- (2-anthracene) -3, 6-bis (4- (3-pyridine) phenyl) carbazole with the yield of 80%.
Example 5
The synthesis process of the carbazole compound N- (1-pyrene) -3, 6-bis (4- (3-pyridine) phenyl) carbazole of the present embodiment is as follows:
Figure GPA0000264356250000502
n- (1-pyrene) -3, 6-dibromocarbazole (10g, 19.04mmol) and 4- (3-pyridine) phenylboronic acid (9.47g, 47.6mmol) are placed in a 500mL two-neck round-bottom flask, 250mL of toluene (i.e., solvent) are added, potassium carbonate (10.51g, 76.16mmol) is then completely dissolved in 30mL of water, the round-bottom flask is added, Pd (PPh3)4(1.32g, 1.14mmol) is added, the air in the flask is pumped out by an oil pump, nitrogen is introduced, and the flask is heated at constant temperature and refluxed for 12 hours and cooled. Transferring the reaction solution into a rotary evaporation bottle, carrying out rotary evaporation on most of the solvent, extracting with dichloromethane, washing with water for three times, drying with anhydrous magnesium sulfate, filtering, carrying out rotary drying, and purifying to obtain the N- (1-pyrene) -3, 6-bis (4- (3-pyridine) phenyl) carbazole with the yield of 82%.
Example 6
The synthesis process of the carbazole compound 2- (4- (9, 10-bis (2-naphthalene) anthracene-2-) phenyl) -1-phenyl-1-H-benzimidazole of this example is as follows:
Figure GPA0000264356250000503
9, 10-bis (2-naphthalene) anthracene-2-boronic acid (47.4g, 0.1mol) and 2- (4-bromobenzene) -1-phenyl-1-H-benzimidazole (34.9g, 0.1mol) were taken and placed in a 1L two-neck round-bottom flask, 500mL of toluene (i.e., solvent) was added, then potassium carbonate (20.7g, 0.15mol) was taken and dissolved completely with 100mL of water, the above round-bottom flask was added, Pd (PPh3)4(3.4g, 0.003mol) was added, the air in the flask was evacuated with an oil pump, nitrogen was introduced, the flask was heated at constant temperature under reflux for 12 hours, and cooled. Transferring the reaction solution into a rotary evaporation bottle, performing rotary evaporation on most of the solvent, extracting with dichloromethane, washing with water for three times, drying with anhydrous magnesium sulfate, filtering, performing rotary drying, and purifying to obtain 2- (4- (9, 10-di (2-naphthalene) anthracene-2-) phenyl) -1-phenyl-1-H-benzimidazole with the yield of 74%.
And (3) detection:
1. the energy structures of the compounds of examples 1 to 6 were measured
The energy levels of the compounds are determined by Gaussian09W (Gaussian Inc.) using TD-DFT (including time density functional theory), and a specific simulation method can be found in WO 2011141110. Specifically, the geometric structure of the compound is optimized by using a density function method of 'group State/DFT/Default Spin/B3 LYP' and a base group of '6-31G (d)' (Charge 0/Spin Singlet), and the energy structure of the compound 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). HOMO and LUMO energy levels were calculated according to the following calibration formulas (1) and (2), S1And T1Can be used directly.
Homo (ev) [ (homo (g) x 27.212) -0.9899]/1.1206 calibrates formula (1),
wherein, HOMO (G) is directly calculated by Gaussian 03W, and the unit is Hartree;
formula (2) was calibrated with lumo (ev) ═ ((lumo (g) x 27.212) -2.0041)/1.385,
wherein, LUMO (G) is directly calculated by Gaussian 03W, and the unit is Hartree.
Table 1 shows the HOMO level, LUMO level, and T level of the compounds of examples 1-61Energy level and S1Energy level.
TABLE 1
HOMO[eV] LUMO[eV] T1[eV] S1[eV]
Example 1 -5.73 -3.03 2.19 2.75
Example 2 -5.75 -2.99 2.19 2.80
Example 3 -5.69 -2.94 1.72 2.86
Example 4 -5.63 -2.92 1.74 2.89
Example 5 -5.68 -2.83 2.03 3.04
Example 6 -5.56 -2.83 1.66 2.83
As can be seen from Table 1, the energy level differences between the HOMO and LUMO of the compounds of examples 1-5 are small, indicating that the stability of the compounds of examples 1-5 is good, and the Δ E of the compounds of examples 1-5 is smallST[ namely, [ Delta (S) ]1-T1) Energy level difference between singlet level and triplet level]All are smaller, indicating that the materials comprising the compounds of examples 1-5 have higher luminous efficiency.
2. When the compounds of examples 1 to 6 were used as materials for ETLs of organic electroluminescent devices (OLEDs), the OLEDs were measured for luminous efficiency, lifetime, and emission color. Wherein the luminous efficiency was measured by the XX method. The luminescence color was measured by the XX method. The current-voltage (J-V) characteristic of the OLED device is characterized by a characterization device, and the life of the OLED device is recorded and is represented by T951000nits, and the lifetimes of examples 1-5 are relative values to the lifetime of example 6. The results are detailed in table 2. The specific process is as follows:
test example 1
The structure of the OLED is as follows:
ITO/HIL (50nm)/HTL (35 nm)/light-emitting layer (20nm)/ETL (28nm)/LiQ (1nm)/Al (150 nm)/cathode, ("/" in the above structure represents a lamination).
Wherein the content of the first and second substances,
the material of HIL is 4, 4', 4 "-tris [ 2-naphthylphenylamino ] triphenylamine (2-TNATA);
the material of the HTL is N, N ' -bis (1-naphthyl) -N, N ' -diphenyl-4, 4 ' -diamine (NPD);
the luminescent layer is prepared by mixing a main material and an auxiliary material according to the mass ratio of 95: 5,
the main material is
Figure GPA0000264356250000521
The auxiliary material is
Figure GPA0000264356250000522
The material of the ETL was selected from the example 1 compounds.
The preparation process of the OLED is as follows:
(1) 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;
(2) by thermal evaporation in a 1X 10 manner-6HIL, HTL, light emitting layer, ETL, cathode, LiQ, and Al were sequentially formed on a conductive glass substrate in mbar, and encapsulated with ultraviolet hardening resin in a nitrogen glove box to obtain an OLED.
Test example 2
The structure of the OLED is as follows: ITO/HIL (50nm)/HTL (35 nm)/light-emitting layer (20nm)/ETL (28nm)/LiQ (1nm)/Al (150 nm)/cathode (in the above structure, "/" represents a lamination). Wherein the compound of example 2 is used as the material of ETL. The rest was the same as in test example 1.
Test example 3
The structure of the OLED is as follows: TO/HIL (50nm)/HTL (35 nm)/light-emitting layer (20nm)/ETL (28nm)/LiQ (1nm)/Al (150 nm)/cathode (in the above structure, "/" represents a stack). Wherein the compound of example 3 is used as the material of ETL. The rest was the same as in test example 1.
Test example 4
The structure of the OLED is as follows: TO/HIL (50nm)/HTL (35 nm)/light-emitting layer (20nm)/ETL (28nm)/LiQ (1nm)/Al (150 nm)/cathode (in the above structure, "/" represents a stack). Wherein the compound of example 4 is used as the material of ETL. The rest was the same as in test example 1.
Test example 5
The structure of the OLED is as follows: TO/HIL (50nm)/HTL (35 nm)/light-emitting layer (20nm)/ETL (28nm)/LiQ (1nm)/Al (150 nm)/cathode (in the above structure, "/" represents a stack). Wherein the compound of example 5 is used as the material of ETL. The rest was the same as in test example 1.
Test example 6
The structure of the OLED is as follows: TO/HIL (50nm)/HTL (35 nm)/light-emitting layer (20nm)/ETL (28nm)/LiQ (1nm)/Al (150 nm)/cathode (in the above structure, "/" represents a stack). Wherein the compound of example 6 is used as the material of ETL. The rest was the same as in test example 1.
TABLE 2
Luminous efficiency (cd/A) Lifetime (T)95，1000nits) Color of light emission
Test example 1 6.2 4.00 Blue color
Test example 2 6.5 3.75 Blue color
Test example 3 6.0 3.45 Blue color
Test example 4 5.7 3.125 Blue color
Test example 5 5.3 2.75 Blue color
Test example 6 3.6 1 Blue color
As can be seen from Table 2, the color coordinates (X < 0.15, Y < 0.10) of the OLEDs obtained using the compounds of examples 1-5 as the material of ETL are all better than the color coordinates of the OLEDs obtained using the compound of example 6 as the material of ETL. The luminous efficiency of the OLED obtained by using the compounds in the embodiments 1-5 as the ETL material is 5.3 cd/A-6.2 cd/A, which is at least 47.2% higher than that of the OLED obtained by using the compound in the embodiment 6 as the ETL material, and is obviously better than that of the OLED obtained by using the compound in the embodiment 6 as the ETL material, thereby indicating that the compounds in the embodiments 1-5 are more favorable for preparing electronic devices with higher luminous efficiency. Meanwhile, the OLED obtained by using the compounds of examples 1-5 as ETL material has T value under 1000nits95The ratio of the compound to the compound is more than 2 times that of the compound in example 6, which shows that the compounds in examples 1 to 5 are more favorable for preparing electronic devices with longer service life.
In summary, the structure of the carbazole compound enables the compound to have better carrier transmission, photoelectric response and energy level matching, so that the compound has better photoelectric properties and stability, and finally, an electronic device containing the compound has higher luminous efficiency, longer service life and better blue coordinate.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (8)

1. A carbazole-based compound used as an electron transport layer material is characterized by having the following structural formula:
Figure 660296DEST_PATH_IMAGE001
；
wherein Ar is1One selected from the following structural formulas:
Figure 207952DEST_PATH_IMAGE002
；
Ar2、Ar3are respectively and independently selected from
Figure 971508DEST_PATH_IMAGE003
；
R1Independently selected from H, D, F, CN, NO2、CF3Alkenyl, alkynyl, cyano, isocyano, alkoxy, hydroxyl, carbonyl, sulfonyl and alkyl with 1-60 carbon atoms; n is 0;
p and q are independently selected from one of integers of 0-1, and p and q are not 0 at the same time.
2. The carbazole-based compound according to claim 1, wherein the carbazole-based compound is selected from the following structures:
Figure 211997DEST_PATH_IMAGE004
。
3. a carbazole-based polymer comprising a repeating unit formed of the carbazole-based compound according to any one of claims 1 to 2.
4. A mixture comprising the carbazole-based compound according to any one of claims 1 to 2 or the carbazole-based polymer according to claim 3 and at least one other organic functional material selected from a hole injection material, a hole transport material, an electron injection material, an electron transport material, a hole blocking material, an electron blocking material, a light emitting material, an organic matrix material, or an organic dye, wherein the mass ratio of the organic functional material to the carbazole-based compound according to any one of claims 1 to 2 or the carbazole-based polymer according to claim 3 is 0.01: 99.9-50: 50.
5. a composition comprising an organic solvent, at least one of the carbazole-based compound according to any one of claims 1 to 2, the carbazole-based polymer according to claim 3, and the mixture according to claim 4, wherein the mass ratio of the organic solvent to at least one of the carbazole-based compound according to any one of claims 1 to 2, the polymer according to claim 3, and the mixture according to claim 4 is 70: 30-99.7: 0.3, the organic solvent is selected from at least one of aromatic solvents, aromatic and hetero solvents, ester solvents, ketone solvents and ether solvents.
6. An electronic device comprising a functional layer comprising at least one of the carbazole-based compound according to any one of claims 1 to 2, the polymer according to claim 3, and the mixture according to claim 4.
7. The electronic device of claim 6, wherein the electronic device is an organic electroluminescent device, an organic photovoltaic cell, an organic light-emitting cell, an organic field-effect transistor, an organic light-emitting field-effect transistor, an organic laser, an organic spintronic device, an organic sensor, or an organic plasmon emitting diode.
8. Electronic device according to claim 6, characterized in that the functional layer is an electron injection layer, an electron transport layer or a light emitting layer.
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