WO2018103746A1 - Dérivé cyclique fusionné de carbazole benzène, polymère, mélange, composition, dispositif électronique organique et son procédé de préparation - Google Patents

Dérivé cyclique fusionné de carbazole benzène, polymère, mélange, composition, dispositif électronique organique et son procédé de préparation Download PDF

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WO2018103746A1
WO2018103746A1 PCT/CN2017/115310 CN2017115310W WO2018103746A1 WO 2018103746 A1 WO2018103746 A1 WO 2018103746A1 CN 2017115310 W CN2017115310 W CN 2017115310W WO 2018103746 A1 WO2018103746 A1 WO 2018103746A1
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group
carbon atoms
aromatic
fused ring
organic
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Chinese (zh)
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胡光
潘君友
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广州华睿光电材料有限公司
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Priority to CN201780059472.6A priority Critical patent/CN109790117A/zh
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the invention relates to the field of organic electronic devices, in particular to a carbazole benzene fused ring derivative, a polymer, a mixture, a composition, an organic electronic device and a preparation method thereof.
  • organic semiconductor materials Due to the diversity of molecular structure design, relatively low manufacturing cost, and superior optoelectronic performance, organic semiconductor materials have great potential applications in many optoelectronic devices, such as organic light-emitting diodes (OLEDs) and organic photovoltaic cells (OPVs). There are airport effect tubes (OFETs) and so on. Especially since the double-layer OLED structure was reported by Deng Qingyun et al. (C.W. Tang and S.A. Van Slyke, Appl. Phys. Lett., 1987, 51, 913), organic semiconductor materials have been rapidly developed in the field of flat panel display and illumination.
  • the organic thin film light-emitting element must satisfy an improvement in luminous efficiency, a reduction in driving voltage, and an improvement in durability.
  • an improvement in luminous efficiency a reduction in driving voltage
  • an improvement in durability a reduction in durability
  • carbazole organic semiconductor materials have a wide range of applications in optoelectronic devices due to their superior optoelectronic properties, redox properties, and stability.
  • aromatic group or the aromatic hetero group of the fused ring structure such as fluoranthene, fluorene, fluorene, phenanthrene, phenanthroline, benzofluoranthene, etc., generally has good carrier transport due to the planar structure of the molecule. Performance and photoelectric response.
  • the currently reported carbazoles or organic semiconductor materials having a fused ring structure have certain limitations in carrier transport capability, stability, and lifetime of photovoltaic devices.
  • CN 104768926 A discloses compounds in which triphenylamine is attached to a fused ring group. Such compounds are used as electron transport layers for blue OLED devices, resulting in a certain improvement in device performance.
  • carbazole as a class of transporting materials with a greater conjugate, its effect on the performance and lifetime of the device combined with the design of the fused ring structure has not been further studied.
  • CN 102372694 A discloses a class of compounds in which a carbazole benzene unit is attached to an aromatic group containing a pyridine unit. Such compounds are used as electron transport layers for blue OLED devices, which reduce the voltage of the device and increase the efficiency.
  • the large planar conjugated fused ring structure with high electron mobility and photoelectric efficiency, combined with the design of carbazole benzene and aromatic groups containing nitrogen atoms, has not been further developed for device performance and lifetime.
  • KR 20130059802 discloses a class of compounds in which a carbazole benzene unit is attached to a pyridine, quinoline or isoquinoline. Such compounds employ an aromatic group of a pyridine, quinoline or isoquinoline containing a nitrogen atom, and the number of ring atoms is less than 10.
  • the influence of the design of the fused ring structure of the larger conjugate plane and the design of the carbazole benzene unit on the performance and lifetime of the device has not been systematically compared and studied.
  • a polymer, a mixture, a composition, an organic electronic device, and a method of preparing the same are also provided.
  • a carbazole benzene fused ring derivative having the following formula:
  • Ar 1 and Ar 2 are each independently selected from the group consisting of an aromatic group and an aromatic hetero group, and at least one of the Ar 1 and the Ar 2 is selected from a thick group having 13 to 60 ring atoms. a ring aromatic group and one of 13 to 60 fused ring aromatic groups;
  • R 1 and R 2 are each independently selected from the group consisting of H, D, F, CN, NO 2 , CF 3 , alkenyl, alkynyl, amine, acyl, amide, cyano, isocyano, alkoxy, hydroxy, a carbonyl group, a sulfone group, an alkyl group having 1 to 60 carbon atoms, a cycloalkyl group having 3 to 60 carbon atoms, an aromatic group having 6 to 60 carbon atoms, and 3 carbon atoms One to 60 heterocyclic aryl groups, one having 7 to 60 fused ring aromatic groups, and one of 4 to 60 fused heterocyclic aryl groups;
  • Ar 3 and Ar 4 are each independently selected from an aromatic group having 6 to 60 carbon atoms, a heterocyclic aromatic group having 3 to 60 carbon atoms, and a condensed aromatic ring having 7 to 60 carbon atoms. a group of one or more fused heterocyclic aryl groups having 4 to 60 carbon atoms;
  • At least one of Ar 3 and Ar 4 contains an aromatic hetero ring having an N atom
  • a polymer comprising repeating structural units of the above formula oxazobenzene fused ring derivatives.
  • a mixture comprising the above carbazole benzene fused ring derivative and one of the above polymers and an organic functional material selected from the group consisting of a hole injecting material, a hole transporting material, a hole blocking material, and an electron At least one of an injection material, an electron transport material, an electron blocking material, an organic matrix material, a luminescent material, and an organic dye.
  • a composition comprising a main ingredient and an organic solvent, the main material comprising one of the above-mentioned carbazole benzene fused ring derivatives, the above polymer and the above mixture, the organic solvent comprising a first solvent,
  • the first solvent is at least one of an aromatic solvent, a heteroaromatic solvent, a ketone solvent, an ether solvent, and an ester solvent.
  • An organic electronic device comprising a functional layer, the material of which comprises one of the above carbazole benzene fused ring derivatives, the above polymer, the above mixture, and one of the above compositions.
  • a method of producing an organic electronic device comprising the step of forming a functional layer by vapor deposition using one of the above carbazole benzene fused ring derivatives, the above polymer, and the above mixture.
  • a method of preparing an organic electronic device comprising the step of forming a functional layer by one of printing and coating using the above composition.
  • an aromatic group means a hydrocarbon group containing at least one aromatic ring.
  • Heterocyclic aromatic group means an aromatic hydrocarbon group containing at least one hetero atom.
  • a fused ring aromatic group means that the ring of the aryl group may have two or more rings in which two carbon atoms are shared by two adjacent rings, that is, a fused ring.
  • a fused heterocyclic aryl group refers to a fused ring aromatic hydrocarbon group containing at least one hetero atom.
  • the aryl group contains a fused ring aromatic group
  • the heterocyclic aryl group contains a fused heterocyclic aryl group.
  • the aromatic group and the heterocyclic aromatic group are not limited to a system including an aromatic ring, and a non-aromatic ring system is also included.
  • a non-aromatic ring system is also included.
  • the system is also considered to be an aromatic or heterocyclic aromatic group as referred to herein.
  • the fused ring aromatic group is not limited to a system including an aromatic group
  • the fused heterocyclic aryl group is not limited to a system including a heteroaromatic group
  • a plurality of aromatic or heterocyclic aromatic groups may also be short non-
  • the aromatic unit is interrupted ( ⁇ 10% non-H atoms, further less than 5% non-H atoms, such as C, N or O atoms).
  • systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether, etc., are also considered to be fused ring aromatic groups.
  • examples of the aromatic group are: benzene, biphenyl, terphenyl, toluene, chlorobenzene, and derivatives thereof.
  • fused ring aromatic group examples include: naphthalene, anthracene, fluoranthene, phenanthrene, triphenylene, perylene, tetracene, anthracene, benzopyrene, anthracene, anthracene, and derivatives thereof.
  • heterocyclic aromatic groups are: pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, carbene And its derivatives.
  • fused heterocyclic aromatic group examples include: benzofuran, benzothiophene, anthracene, oxazole, pyrroloimidazole, pyrrolopyrrol, thienopyrrole, thienothiophene, furopyrrol, furanfuran , thienofuran, benzisoxazole, benzisothiazole, benzimidazole, quinoline, isoquinoline, o-diazepine, quinoxaline, phenanthridine, pyridine, quinazoline, quinazolinone And its derivatives.
  • R 1 and R 2 are each independently selected from the group consisting of H, D, F, CN, NO 2 , CF 3 , alkenyl, alkynyl, amine, acyl, amide, cyano, Isocyanato group, alkoxy group, hydroxyl group, carbonyl group, sulfone group, alkyl group having 1 to 60 carbon atoms, cycloalkyl group having 3 to 60 carbon atoms, and 6 to 60 carbon atoms Aromatic group, a heterocyclic aryl group having 3 to 60 carbon atoms, a fused ring aromatic group having 7 to 60 carbon atoms, and a fused heterocyclic aryl group having 4 to 60 carbon atoms One of them.
  • n is any integer from 0 to 20; further, n is any integer from 0 to 10; further, n is any integer from 0 to 5; further, n is any of 0 to 3 An integer.
  • n is any integer from 0 to 20.
  • p is any integer from 0 to 4; further, p is any integer from 0 to 3; further, p is any integer from 0 to 2; further, p is any integer from 0 to 1.
  • q is any integer from 0 to 4, and at most one of p and q is 0. Further, q is any integer from 0 to 3; further, q is any integer from 0 to 2; further, q is any integer from 0 to 1.
  • Ar 3 and Ar 4 are each independently selected from an aromatic group having 6 to 60 carbon atoms, a heterocyclic aromatic group having 3 to 60 carbon atoms, and 7 carbon atoms. One to 60 fused ring aromatic groups and one of 4 to 60 fused heterocyclic aryl groups. And at least one of Ar 3 and Ar 4 contains an aromatic heterocyclic ring having an N atom.
  • the aromatic heterocyclic rings having N atoms are each independently selected from and one of the;
  • hydrogen on the ring may be optionally substituted.
  • the hydrogen on the ring may be optionally substituted means that the aromatic heterocyclic ring having an N atom may be selected not only from one of the above structures but also one selected from the above structures in which a hydrogen atom is substituted.
  • all X in each of the above structures is selected from one of CR 3 , N and C, and at least one X in each structure is N, and in two adjacent X At most one is N.
  • one to five X are N; further, in each structure, one to three X are N; further, one to two X are N.
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently selected from the group consisting of H, D, F, CN, NO 2 , CF 3 , alkenyl, alkynyl, amine, acyl, amide, cyanide a group, an isocyano group, an alkoxy group, a hydroxyl group, a carbonyl group, a sulfone group, an alkyl group having 1 to 60 carbon atoms, a cycloalkyl group having 3 to 60 carbon atoms, and 6 carbon atoms ⁇ 60 aromatic groups, a heterocyclic aryl group having 3 to 60 carbon atoms, a fused ring aromatic group having 7 to 60 carbon atoms, and a fused heterocyclic ring having 4 to 60 carbon atoms One of the aromatic bases.
  • R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently selected from the group consisting of H, D, F, CN, NO 2 , CF 3 , alkenyl, alkynyl, amine, acyl, amide a group, a cyano group, an isocyano group, an alkoxy group, a hydroxyl group, a carbonyl group, a sulfone group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, and a carbon number 6 to 30 aromatic groups, 3 to 30 heterocyclic aryl groups, 7 to 30 fused ring aromatic groups, and 4 to 30 carbon atoms One of the fused heterocyclic aryl groups.
  • the aromatic heterocyclic ring having an N atom is each selected from the group consisting of and one of the.
  • Ar 3 and Ar 4 contain an aromatic heterocyclic ring having an N atom.
  • Ar 1 and Ar 2 are each independently selected from one of an aromatic group and an aromatic hetero group, and at least one of Ar 1 and Ar 2 is selected from the group consisting of 13 to 60 ring atoms.
  • Ar 1 and Ar 2 are each independently selected from the group consisting of a fused ring aromatic group having 13 to 50 ring atoms and a fused ring aromatic group having 13 to 50 ring atoms; , Ar 1 and Ar 2 are each independently selected from the group consisting of a fused ring aromatic group having 13 to 40 ring atoms and a fused ring aromatic group having 13 to 40 ring atoms; further , Ar 1 and Ar 2 are each independently selected from the group consisting of a fused ring aromatic group having 13 to 30 ring atoms and a fused ring aromatic group having 13 to 30 ring atoms; further, Ar 1 and Ar 2 are each independently selected from the group consisting of a fused ring aromatic group having 13 to 20 ring atoms and a fused ring aromatic group having 13 to 20 ring atoms.
  • the hetero atom in the fused ring arehetero group is at least one selected from the group consisting of Si, N, P, O, S, and Ge; further, in Ar 1 and Ar 2 , The hetero atom in the fused ring arehetero group is at least one selected from the group consisting of Si, N, P, O and S; further, in Ar 1 and Ar 2 , the hetero atom in the fused ring aryl group is selected from N, One of O and S.
  • Ar 1 and Ar 2 are each independently selected from the group consisting of a fused ring having 3 to 30 ring atoms, wherein the ring is selected from the group consisting of a three-membered ring and a four-membered ring.
  • the ring is selected from the group consisting of a three-membered ring and a four-membered ring.
  • the number of ring atoms of Ar 1 and Ar 2 is 3 to 20 fused rings; further, the number of ring atoms of Ar 1 and Ar 2 is a fused ring having 3 to 10 ring atoms. Further, the number of ring atoms is from 3 to 5 fused rings.
  • Ar 1 and Ar 2 are each independently selected from the group consisting of one of the;
  • H may be optionally substituted on the ring means that Ar 1 and Ar 2 may be selected not only from one of the above structures but also one selected from the above structures in which the H atom is substituted.
  • X is selected from one of CR 9 and N, and at most one of two adjacent X is N; further, X in each of the above structural formulas is CR 9 .
  • R 9 is selected from the group consisting of H, D, F, CN, NO 2 , CF 3 , alkenyl, alkynyl, amine, acyl, amide, cyano, isocyano, alkoxy, hydroxy, carbonyl, sulfone,
  • R 9 is a site attached to other groups, or R 9 is selected from the group consisting of H, D, F, CN, NO 2 , CF 3 , alkenyl, alkynyl, amine, acyl, amide, cyanide a group, an isocyano group, an alkoxy group, a hydroxyl group, a carbonyl group, a sulfone group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, and 6 carbon atoms ⁇ 30 aromatic groups, a heterocyclic aryl group having 3 to 30 carbon atoms, a fused ring aromatic group having 7 to 30 carbon atoms, and a fused heterocyclic ring having 4 to 30 carbon atoms One of the aromatic bases. Further, R 9 is selected from one of H and D.
  • R 10 , R 11 , R 12 , R 13 and R 14 are each independently selected from the group consisting of H, D, F, CN, NO 2 , CF 3 , alkenyl, alkynyl, amine, acyl, amide, cyano, Isocyanato group, alkoxy group, hydroxyl group, carbonyl group, sulfone group, alkyl group having 1 to 60 carbon atoms, cycloalkyl group having 3 to 60 carbon atoms, and 6 to 60 carbon atoms a aryl group, a heterocyclic aryl group having 3 to 60 carbon atoms, a fused ring aromatic group having 7 to 60 carbon atoms, and a fused heterocyclic aryl group having 4 to 60 carbon atoms One of them.
  • R 10 , R 11 , R 12 , R 13 and R 14 are each independently selected from the group consisting of H, D, F, CN, NO 2 , CF 3 , alkenyl, alkynyl, amine, acyl, amide, cyanide a group, an isocyano group, an alkoxy group, a hydroxyl group, a carbonyl group, a sulfone group, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, and 6 carbon atoms ⁇ 30 aromatic groups, a heterocyclic aryl group having 3 to 30 carbon atoms, a fused ring aromatic group having 7 to 30 carbon atoms, and a fused heterocyclic ring having 4 to 30 carbon atoms One of the aromatic bases.
  • Ar 1 and Ar 2 are each independently selected from the group consisting of fluorene, fluoranthene, phenanthrene, benzophenanthrene, perylene, tetracene, anthracene, benzopyrene, anthracene, anthracene, oxazole, dibenzofuran and One of the dibenzothiophenes.
  • Ar 1 and Ar 2 are each independently selected from the group consisting of and one of the.
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 each independently comprise a structural unit At least one of them, wherein s is any integer from 1 to 4.
  • the carbazole benzene fused ring derivative has a high electron mobility, and the electron mobility of the above carbazole benzene fused ring derivative is ⁇ 10 -5 cm 2 /Vs; further, the electron mobility is ⁇ 10 -4 cm 2 / Vs; further, the electron mobility is optimal ⁇ 10 -3 cm 2 / Vs.
  • the glass transition temperature of the carbazole benzene fused ring derivative is ⁇ 100 ° C; further, the glass transition temperature is ⁇ 110 ° C; further, the glass transition temperature is ⁇ 120 ° C; further, the glass transition temperature is ⁇ 140 ° C.
  • the lowest unoccupied orbital energy level LUMO ⁇ -2.7 eV of the carbazole benzene fused ring derivative further, LUMO ⁇ -2.8 eV; further, LUMO ⁇ -2.9 eV; further, LUMO ⁇ -3.0 eV.
  • the highest occupied orbital energy level HOMO ⁇ -5.6 eV of the carbazole benzene fused ring derivative further, HOMO ⁇ -5.7 eV; further, HOMO ⁇ -5.8 eV; further, HOMO ⁇ -5.9 eV.
  • the triplet level of the carbazole benzene fused ring derivative is T1 ⁇ 1.7 eV; further, T1 ⁇ 1.9 eV; further, T1 ⁇ 2.2 eV; further, T1 ⁇ 2.4 eV.
  • the triplet levels E T , HOMO, and LUMO play a key role. The following is an introduction to the determination of these energy levels.
  • the HOMO and LUMO levels can be measured by photoelectric effect, for example, XPS (X-ray photoelectron spectroscopy), UPS (UV photoelectron spectroscopy), etc., and can also pass cyclic voltammetry (hereinafter referred to as CV).
  • XPS X-ray photoelectron spectroscopy
  • UPS UV photoelectron spectroscopy
  • CV cyclic voltammetry
  • quantum chemical methods such as density functional theory (hereinafter referred to as DFT) have also become effective methods for calculating molecular orbital energy levels.
  • the triplet energy level E T of organic materials can be measured by low temperature time-resolved luminescence spectroscopy, or can also be obtained by quantum simulation calculations (eg by Time-dependent DFT), as by the commercial software Gaussian 09W (Gaussian Inc.), specific
  • the simulation method can be referred to the method in the patent document WO2011141110, or can also be obtained by the method described later in the embodiment.
  • HOMO, LUMO and E T depend on the measurement method or calculation method used. Even for the same method, different evaluation methods may lead to different results, for example, the starting point and the peak point on the CV curve. Different HOMO/LUMO values are given. Therefore, a reasonable and meaningful comparison should use the same measurement method and the same evaluation method.
  • the values of HOMO, LUMO, and E T in the present embodiment are obtained based on the simulation of Time-dependent DFT. It should be noted that the acquisition of HOMO, LUMO, and E T is not limited to the method, and they may also pass other measurements. The method or calculation method is obtained, but the energy level values determined by different methods should be mutually calibrated.
  • a part of the hydrogen atom of the structural formula of the carbazole benzene fused ring derivative is substituted by hydrazine; further, the structural formula of the carbazole benzene fused ring derivative has a hydrogen atom number of 10% substituted by hydrazine; further The number of hydrogen atoms substituted by deuterium is 20%; further, the number of hydrogen atoms substituted by deuterium is 30%; further, the number of hydrogen atoms substituted by deuterium is 40%.
  • carbazole benzene fused ring derivative is selected from one of the following compounds, but is not limited to the following compounds:
  • the above carbazole benzene fused ring derivative has at least the following advantages: the nitrogen atom on the carbazole of the above carbazole benzene fused ring derivative is linked to a large plane conjugated fused ring aromatic structure, which is advantageous for achieving better current carrying current. Sub-transmission and photoelectric response, better energy level matching, improve the photoelectric performance and stability of such compounds and optoelectronic devices, thereby providing a material solution for a light-emitting device with high manufacturing efficiency and long life.
  • the polymer of one embodiment comprises a repeating structural unit of a carbazole benzene fused ring derivative of the formula (1).
  • the polymer is a non-conjugated polymer in which a structural unit of a carbazole benzene fused ring derivative represented by the formula (1) is on a side chain.
  • the polymer may also be a conjugated polymer.
  • the polymer that is, the polymer, includes a homopolymer, a copolymer, and a block copolymer.
  • the polymer also includes a dendrimer, wherein the dendrimer can be the literature [Dendrimers and Dendrons, Wiley-VCH Ver lag GmbH & Co. KGaA, 2002, Dendrites disclosed in Ed. George R. Newkome, Charles N. Moorefield, Fritz Vogtle., or synthetically synthesized by the synthetic methods described above.
  • a conjugated polymer is a polymer whose backbone backbone is mainly composed of sp 2 hybrid orbitals of C atoms, such as polyacetylene polyacetylene and poly(phenylene vinylene), and C atoms in its main chain. It can also be substituted by other non-C atoms, and is still considered to be a conjugated polymer when the sp 2 hybrid on the backbone is interrupted by some natural defects. And herein, the conjugated polymer also includes an aryl amine, an aryl phosphine and other heteroarmotics, and an organometallic complexes in the main chain. )Wait.
  • the carbazole benzene fused ring derivative is a small molecule material.
  • the "small molecule” referred to herein it is not a polymer, an oligomer, a dendrimer, and a blend; and the molecular mass is ⁇ 3000 g/mmol; further, a small molecule The molecular mass is ⁇ 2000 g / mmol; further, the molecular mass of the small molecule is ⁇ 1500 g / mmol.
  • the polymer herein is a polymer comprising the above-mentioned repeating structural unit of the carbazole benzene fused ring derivative represented by the formula (1).
  • the relative molar mass of the carbazole benzene fused ring derivative is 1000 g/mol; further, the relative molar mass of the carbazole benzene fused ring derivative is 900 g/mol; further The relative molar mass of the carbazole benzene fused ring derivative is 850 g/mol; further, the relative molar mass of the carbazole benzene fused ring derivative is 800 g/mol; further, the carbazole benzene fused ring The relative molar mass of the derivatives was 700 g/mol.
  • the organic functional material is selected from the group consisting of a hole (also called a hole) injection material (HIM), a hole transport material (HTM), a hole blocking material (HBM), an electron injection material (EIM), an electron transport material (ETM), and an electron.
  • a hole also called a hole
  • HIM hole injection material
  • HTM hole transport material
  • HBM hole blocking material
  • EIM electron injection material
  • ETM electron transport material
  • ETM electron transport material
  • ETM electron transport material
  • ETM electron transport material
  • ETM electron transport material
  • EBM electron injection material
  • ETM electron transport material
  • ETM electron transport material
  • ETM electron transport material
  • ETM electron transport material
  • ETM electron transport material
  • an electron At least one of a barrier material (EBM), an organic host material (Host), a luminescent material, and an organic dye.
  • the luminescent material is selected from at least one of a singlet illuminant (fluorescent illuminant), a triplet
  • the organic functional material may be a small molecule material or a high polymer material.
  • the organic functional material may be an organic functional material as disclosed in WO2010135519A1, US20090134784A1 and WO2011110277A1.
  • the carbazole benzene fused ring derivative or the above polymer is 50% by weight to 99.9% by weight; further, the carbazole benzene fused ring derivative or the above polymer
  • the weight percentage of the carbazole benzene fused ring derivative or the above polymer is 60% to 95%; further, the carbazole benzene fused ring derivative Or the above polymer has a weight percentage of 70% to 90%.
  • the mixture comprises a carbazole benzene fused ring derivative and one of the above polymers, and further comprises a fluorescent luminescent material (singlet light illuminant).
  • the mixture comprises a carbazole benzene fused ring derivative and one of the above polymers, and further comprises a thermally activated delayed fluorescent luminescent material (TADF).
  • TADF thermally activated delayed fluorescent luminescent material
  • the mixture includes a carbazole benzene fused ring derivative and one of the above polymers, and further includes a fluorescent luminescent material and a TADF material.
  • fluorescent luminescent materials single-state illuminants
  • phosphorescent luminescent materials single-state illuminants
  • TADF materials TADF materials
  • Singlet emitters tend to have longer conjugated pi-electron systems.
  • styrylamine and its derivatives disclosed in JP 2913116 B and WO 2001021729 A1
  • indenoindenes and derivatives thereof disclosed in WO 2008/006449 and WO 2007/140847.
  • the singlet emitter is one selected from the group consisting of monostyrylamine, dibasic styrylamine, ternary styrylamine, quaternary styrylamine, styrenephosphine, styrene ether, and aromatic amine.
  • the monostyrylamine refers to a compound comprising an unsubstituted or substituted styryl group and at least one amine; wherein the amine is preferably an aromatic amine.
  • the dibasic styrylamine is a compound comprising two unsubstituted or substituted styryl groups and at least one amine; wherein the amine is preferably an aromatic amine.
  • the ternary styrylamine refers to a compound comprising three unsubstituted or substituted styryl groups and at least one amine; wherein the amine is preferably an aromatic amine.
  • the tetrabasic styrene amine refers to a compound comprising four unsubstituted or substituted styryl groups and at least one; wherein the amine is preferably an aromatic amine.
  • styrene is stilbene, which may be further substituted.
  • styrene phosphine and styrene ether are similar to those of the above amines and will not be described herein.
  • An arylamine refers to a compound comprising three unsubstituted or substituted aromatic ring or heterocyclic systems directly bonded to a nitrogen. At least one of these aromatic or heterocyclic ring systems is a fused ring system, and preferably the total number of carbon atoms is greater than or equal to 14.
  • the aromatic amine is selected from one of aromatic amide, aromatic guanidine diamine, aromatic guanamine, aromatic guanidine diamine, aromatic thiamine, and aromatic quinone diamine.
  • the aromatic decylamine refers to a compound in which one of the diarylamine groups is directly bonded to the oxime; further, the diarylamine group is at the position of 9 of oxime.
  • the aromatic oxime diamine refers to a compound in which two diaryl arylamine groups are directly bonded to the oxime; further, the two diaryl arylamine groups are attached to the oxime 9,10, respectively.
  • the singlet emitters based on styrylamine and arylamine may be WO2006/000388, WO2006/058737, WO2006/000389, WO2007/065549, WO2007/115610, US7250532B2, DE102005058557A1, CN1583691A, JP 08053397A, US6251531 B1, US2006 Singlet illuminators as disclosed in EP 1 957 606 A1 and US 2008/0113101 A1.
  • Singlet emitters based on styrylamine and its derivatives are singlet emitters as disclosed in U.S. Patent 5,212,029.
  • the singlet emitter is one selected from the group consisting of an indeno-amine and an indeno-diamine, such as the benzoindole-amine or benzoindole-diamine disclosed in WO2006/122630 , a dibenzoindolo-amine or a dibenzoindeno-diamine as disclosed in WO 2008/006449, and an indeno-amine or an indeno-diamine disclosed in WO2007/140847.
  • an indeno-amine and an indeno-diamine such as the benzoindole-amine or benzoindole-diamine disclosed in WO2006/122630 , a dibenzoindolo-amine or a dibenzoindeno-diamine as disclosed in WO 2008/006449, and an indeno-amine or an indeno-diamine disclosed in WO2007/140847.
  • the singlet illuminant may also be a polycyclic aromatic hydrocarbon compound, such as the following compounds and derivatives thereof: such as 9,10-bis(2-naphthoquinone), naphthalene, tetraphenyl, xanthene, phenanthrene, anthracene (eg 2,5,8,11-tetra-t-butylindole), indenoindole, phenylene such as (4,4'-bis(9-ethyl-3-carbazolevinyl)-1,1 '-Biphenyl), indenyl hydrazine, decacycloolefin, hexacene benzene, anthracene, spirobifluorene, aryl hydrazine (such as the aryl fluorene disclosed in US20060222886), arylene vinyl (such as US5121029 and US5130603) Disclosed subaromatic vinyl), cyclopenta
  • the singlet illuminant is the following compound, but is not limited to the following compounds:
  • TDF Thermally activated delayed fluorescent luminescent material
  • the thermally activated delayed fluorescent luminescent material is a third generation organic luminescent material developed after organic fluorescent materials and organic phosphorescent materials.
  • the TADF material needs to have a small singlet-triplet energy level difference, typically ⁇ E st ⁇ 0.3 eV, further ⁇ E st ⁇ 0.2 eV; further, ⁇ E st ⁇ 0.1 eV; further, ⁇ E st ⁇ 0.05 eV. And TADF materials have better fluorescence quantum efficiency.
  • the TADF material may be CN103483332 (A), TW201309696 (A), TW201309778 (A), TW201343874 (A), TW201350558 (A), US20120217869 (A1), WO2013133359 (A1), WO2013154064 (A1), and literature (Adachi, et. Al. Adv.
  • the TADF luminescent material is the following compound, but is not limited to the following compounds:
  • Triplet emitters are also known as phosphorescent emitters.
  • the triplet emitter is a metal complex having the formula M(L)n.
  • M is a metal atom; L may be the same or different at each occurrence; L is an organic ligand which is bonded to the metal atom M by one or more positional bonds or coordination; n is a value greater than one. Integer; further, n is 1, 2, 3, 4, 5 or 6.
  • the metal complex is attached to the polymer through one or more positions; further, the metal complex is linked to the polymer via an organic ligand.
  • the metal atom M is selected from one of a transition metal element, a lanthanoid element, and a lanthanoid element; further, the metal atom M is selected from the group consisting of Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, One of Gd, Tb, Dy, Re, Cu, and Ag; further, the metal atom M is selected from one of Os, Ir, Ru, Rh, Re, Pd, and Pt.
  • L is a chelating ligand, ie, a ligand, coordinated to the metal through at least two binding sites; further, L has two bidentate ligands, three bidentate ligands, and two multidentate Ligand or three multidentate ligands.
  • the bidentate ligands may be the same or the same; the multidentate ligands may be the same or different.
  • Chelating ligands are beneficial for increasing the stability of metal complexes.
  • the organic ligand is selected from the group consisting of a phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2(2-thienyl)pyridine derivative, a 2(1-naphthyl)pyridine derivative, and a 2 phenyl group.
  • a phenylpyridine derivative a 7,8-benzoquinoline derivative
  • a 2(2-thienyl)pyridine derivative a 2(1-naphthyl)pyridine derivative
  • a 2 phenyl group One of the quinoline derivatives.
  • the organic ligand may be substituted, for example by fluorine or trifluoromethyl.
  • the ancillary ligand may preferably be derived from acetone acetate or picric acid.
  • M is as defined above; each of Ar 1 may be the same or different, Ar 1 is a cyclic group, and each Ar 1 contains at least one donor atom, that is, a lone pair An atom of an electron, such as nitrogen or phosphorus, is coordinated to the metal through its cyclic group; each occurrence of Ar 2 may be the same or different, a cyclic group, and each Ar 2 contains at least one C atom , through which a cyclic group is attached to a metal; Ar 1 and Ar 2 are linked together by a covalent bond, each of which may carry one or more substituent groups, which may also be linked together by a substituent group; When present, may be the same or different, is an ancillary ligand, preferably a bidentate chelate ligand, further a monoanionic bidentate chelate ligand; m is selected from one of 1, 2 and 3, further, m 2 or 3, further, m is 3; n is selected from one of 0, 1, and
  • the triplet emitters can be patented WO 200070655, WO 200141512, WO 200202714, WO 200215645, EP 1191613, EP 1191612, EP 1191614, WO 2005033244, WO 2005019373, US 2005/0258742, WO 2009146770, WO 2010015307, WO 2010031485 , US Pat.
  • the triplet emitters disclosed in 2012004407A1, WO 2012007088A1, WO2012007087A1, WO 2012007086A1, US 2008027220A1, WO 2011157339A1, CN 102282150A and WO 2009118087A1 may also be in the literature (Baldo, Thompson et al.
  • the triplet emitter is the following compound, but is not limited to the following compounds:
  • the composition of one embodiment is a solvent-based composition, can be used as a coating or ink, and can be applied to an organic electronic device as a material of a functional layer.
  • the organic electronic device is selected from the group consisting of an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, an organic laser, and an organic spintronic device. , organic sensors and organic plasmon emission diodes (Organic One of the Plasmon Emitting Diodes.
  • the composition may be a solution or a suspension.
  • the composition comprises a main ingredient and an organic solvent, and the main ingredient comprises one of the above carbazole benzene fused ring derivatives, the above polymer and the above mixture.
  • the polymer herein is a polymer comprising the above-mentioned repeating structural unit of the carbazole benzene fused ring derivative represented by the formula (1).
  • the mixture herein is the mixture described above and will not be described again here.
  • the molar mass of the carbazole benzene fused ring derivative and the polymer are both ⁇ 700 g/mol, and further, the molar mass of the carbazole benzene fused ring derivative and the polymer are both ⁇ 800 g/mol;
  • the molar mass of the oxazobenzene fused ring derivative and the polymer are both ⁇ 900 g/mol;
  • the molar mass of the carbazole benzene fused ring derivative and the polymer are both ⁇ 1000 g/mol; further, the carbazole benzene is thick
  • the molar mass of the cyclic derivative and the polymer are both ⁇ 1100 g/mol.
  • the solubility of the carbazole benzene fused ring derivative and the polymer in toluene is ⁇ 10 mg/ml at 25 ° C; further, the carbazole benzene fused ring derivative and the polymer in toluene Solubility ⁇ 15 mg / ml; further, the solubility of the carbazole benzene fused ring derivative and the polymer in toluene ⁇ 20 mg / ml.
  • the composition of the present embodiment has a surface tension of about 19 dyne/cm to 50 dyne/cm at an operating temperature or at 25 ° C; further 22 dyne/cm to 35 dyne/cm; and further 25 dyne/cm to 33 dyne/cm. .
  • the composition of the present embodiment has a viscosity at an operating temperature or 25 ° C of about 1 cps to 100 cps; further from 1 cps to 50 cps; further from 1.5 cps to 20 cps; further from 4.0 cps to 20 cps.
  • the composition can be used for inkjet printing.
  • the viscosity and surface tension of the composition are important parameters. Only compositions with suitable parameters can be adapted to a particular substrate and to a particular printing method. Among them, the viscosity of the composition can be adjusted by different methods, such as by selecting a suitable solvent and the concentration of the main ingredient. The viscosity of the composition is adjusted so as to facilitate printing in accordance with a usual printing method.
  • the weight percentage of the main material is 0.3% to 30%; further 0.5% to 20%; further 0.5% to 1%; further 0.5% to 10%; further It is 1% to 5%.
  • the organic solvent includes a first solvent.
  • the first solvent is at least one selected from the group consisting of an aromatic solvent, a heteroaromatic solvent, a ketone solvent, an ether solvent, and an ester solvent.
  • the aromatic solvent is selected from at least one of a chain aliphatic substituted aromatic compound and a cyclic aliphatic substituted aromatic compound.
  • the aromatic solvent and the heteroaromatic solvent are selected from the group consisting of p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, and 3-isopropylbiphenyl.
  • p-Methyl cumene dipentylbenzene, triphenylbenzene, 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-pair Isopropylbenzene, 1-methoxynaphthalene, cyclohexylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2,4-trichloro Benzene
  • the ketone solvent is selected from the group consisting of 1-tetralone, 2-tetralone, 2-(phenyl epoxy)tetralone, 6-(methoxy)tetralone, acetophenone , a derivative of propiophenone, benzophenone, 1-tetralone, a derivative of 2-tetralone, a derivative of 2-(phenyl epoxy)tetralone, 6-(methoxy At least one of a derivative of a tetralone, a derivative of acetophenone, a derivative of propiophenone, and a derivative of benzophenone.
  • the derivative, the derivative of acetophenone, the derivative of propiophenone, and the derivative of benzophenone may be 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4 -methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, isophorone, 2,6,8-trimethyl-4-indolone, anthrone, 2-nonanone, 3- Anthrone, 5-fluorenone, 2-nonanone, 2,5-hexanedione, phorone, di-n-pentyl ketone, and the like.
  • the ether solvent is selected from the group consisting of 3-phenoxytoluene, butoxybenzene, benzylbutylbenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1,2-dimethoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxytoluene, 4- Ethyl phenethyl ether, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethoxybenzene, glycidylphenyl Ether, dibenzyl ether, 4-tert-butyl anisole, trans-p-propenyl anisole, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-
  • the ester solvent is selected from the group consisting of alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenyl acetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkane At least one of a lactone and an alkyl oleate.
  • the first solvent is at least one selected from the group consisting of an aliphatic ketone and an aliphatic ether.
  • the aliphatic ketone is selected from the group consisting of 2-nonanone, 3-fluorenone, 5-nonanone, 2-nonanone, 2,5-hexanedione, 2,6,8-trimethyl-4-indanone At least one of phorone and di-n-pentyl ketone.
  • the aliphatic ether is selected from the group consisting of pentyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, and triethylene glycol diethylene glycol. At least one of ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
  • the organic solvent further includes a second solvent, wherein the second solvent is selected from the group consisting of methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole , morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4 dioxane, acetone, methyl ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide At least one of tetrahydronaphthalene, decalin and hydrazine.
  • the second solvent is selected from the group consisting of methanol, ethanol, 2-
  • the mixture of the present embodiment is capable of producing an organic electronic device by printing or coating.
  • the printing method may be inkjet printing or Nozzle Printing.
  • the coating method can be typography, screen printing, dip coating, spin coating, blade coating, roller printing, torsion roll printing, lithography, flexographic printing, rotary printing, spraying, brushing, pad printing, Slit type extrusion coating, etc. Further, the coating method is gravure printing; the printing method is jet printing or inkjet printing.
  • the mixture further includes at least one of a surfactant, a lubricant, a wetting agent, a dispersing agent, a hydrophobic agent, and a binder. It is used to adjust the viscosity of the mixture, film forming properties, adhesion, and the like. According to Helmut Kipphan, "Handbook of Print Media: Techno logies and Production Methods", ISBN 3-540-67326-1, for printing techniques and solvents, concentrations, Adjust the viscosity and so on.
  • An organic electronic device of an embodiment is an organic light emitting diode comprising a substrate, an anode, a functional layer, and a cathode.
  • the functional layer comprises a light-emitting layer
  • the material of the light-emitting layer comprises one of the above carbazole benzene fused ring derivatives, the above polymer, the above mixture and the above composition.
  • the polymer herein is a polymer comprising the above-mentioned repeating structural unit of the carbazole benzene fused ring derivative represented by the formula (1).
  • the organic functional material in the mixture includes the luminescent material, that is, the luminescent material is the self-fluorescent illuminant, phosphorescent illuminant or TADF material described above. Further, the luminescent material is a fluorescent illuminant or a TADF material.
  • the functional layer may further include a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer. At least one of (HBL).
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • EIL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • HBL hole blocking layer
  • the substrate may be opaque or transparent.
  • Transparent substrates can be used to make transparent light-emitting components.
  • the transparent substrate may be a substrate disclosed in the literature (Bulovic et al. Nature 1996, 380, p29) and the literature (Gu et al., Appl. Phys. Lett. 1996, 68, p2606).
  • the substrate may be a rigid substrate or an elastic substrate.
  • the substrate is a plastic, metal, semiconductor wafer or glass. Further, the substrate has a smooth surface. No surface defects are ideal for substrates.
  • the substrate is flexible.
  • the substrate is a polymer film or plastic; the substrate has a glass transition temperature Tg of 150 ° C or more; further, more than 200 ° C; further, more than 250 ° C; further, more than 300 ° C.
  • the substrate is selected from one of poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).
  • the material of the anode includes one of a conductive metal, a metal oxide, and a conductive polymer.
  • the anode can easily inject holes into the light-emitting layer, the hole injection layer, or the hole transport layer.
  • the work function of the anode and the organic functional material (luminescent material) in the light-emitting layer, the p-type semiconductor material of the hole injection layer, the p-type semiconductor material of the hole transport layer, or the p-type semiconductor material of the electron blocking layer is less than 0.5 eV; further, less than 0.3 eV; and further, less than 0.2 eV.
  • the anode material is selected from one of Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, and aluminum-doped zinc oxide (AZO).
  • the anode material can be obtained by physical vapor deposition.
  • the physical vapor deposition method is specifically RF magnetron sputtering, vacuum thermal evaporation or electron beam (e-beam) evaporation.
  • anode material is not limited to the above materials, and the anode material may also be patterned ITO.
  • the material of the cathode is selected from one of a conductive metal and a metal oxide.
  • the material of the cathode is such that electrons can be easily injected into the electron injecting layer, the electron transporting layer or the light emitting layer.
  • the work function of the cathode and the LUMO level of the organic functional material (luminescent material) of the light-emitting layer, the n-type semiconductor material of the electron injecting layer, the n-type semiconductor material of the electron transporting layer or the n-type semiconductor material of the hole blocking layer The absolute value of the difference in the (or conduction band) energy level is less than 0.5 eV; further, less than 0.3 eV, and further, less than 0.2 eV.
  • all materials which can be used as cathodes of OLEDs are possible as cathode materials for the organic electronic devices of the present embodiment.
  • the cathode material is selected from the group consisting of Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF 2 /Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, and ITO. .
  • the cathode material can be obtained by physical vapor deposition.
  • the physical vapor deposition method is specifically RF magnetron sputtering, vacuum thermal evaporation or electron beam (e-beam) evaporation.
  • the organic electronic device of the present embodiment has an emission wavelength of 300 nm to 1000 nm, further, an emission wavelength of 350 to 900 nm, and further, an emission wavelength of 400 to 800 nm.
  • the above organic electronic device can be applied to various electronic devices.
  • display devices for example, display devices, lighting devices, light sources or sensors, and the like.
  • a method of producing an organic electronic device includes the step of forming a functional layer by vapor deposition using the above carbazole benzene fused ring derivative, the above polymer, and the above mixture.
  • the mixture of the present embodiment is a solventless type mixture as described above.
  • a method of producing an organic electronic device comprising the step of forming a functional layer by printing or coating using the above composition.
  • the composition is a solvent-based composition as described above.
  • the printing method may be inkjet printing or Nozzle Printing.
  • the coating method can be typography, screen printing, dip coating, spin coating, blade coating, roller printing, torsion roll printing, lithography, flexographic printing, rotary printing, spraying, brushing, pad printing, Slit type extrusion coating, etc.
  • the synthetic route is as follows:
  • the synthetic route is as follows:
  • the synthetic route is as follows:
  • the synthetic route is as follows:
  • the synthetic route is as follows:
  • the synthetic route is as follows:
  • the synthetic route is as follows:
  • the energy level of the organic material can be obtained by quantum calculation, for example, by using TD-DFT (time-dependent density functional theory) by Gaussian 03W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110.
  • TD-DFT time-dependent density functional theory
  • Gaussian 03W Gaussian Inc.
  • the specific simulation method can be found in WO2011141110.
  • the semi-empirical method “Ground State/Semi-empirical/Default Spin/AM1" (Charge 0/Spin Singlet) is used to optimize the molecular geometry, and then the energy structure of the organic molecule is determined by TD-DFT (time-dependent density functional theory) method.
  • TD-SCF/DFT/Default Spin/B3PW91 and the base group "6-31G(d)” (Charge 0/Spin Singlet).
  • the HOMO and LUMO levels are calculated according to the following calibration formula, and S1 and T1 are used directly.
  • HOMO(eV) ((HOMO(G) ⁇ 27.212)-0.9899)/1.1206
  • HOMO(G) and LUMO(G) are direct calculation results of Gaussian 03W, and the unit is Hartree.
  • the results of the compounds of Examples 1 to 6 and Comparative Example 1 are shown in Table 1:
  • the structures of the organic light emitting diodes (OLED devices) of Examples 7 to 12 and Comparative Example 2 were all ITO/HIL (50 nm) / HTL (35 nm) / Host: 5% Dopant (25 nm) / ETL (28 nm) / LiQ (1 nm) ) / Al (150 nm) / cathode. "/" indicates the layer.
  • the compound prepared in Example 1 is the material of the electron transport layer (ETL) of Example 7 and the compound prepared in Example 2 is the material of the electron transport layer (ETL) of Example 8, prepared in Example 3.
  • the compound was the material of the electron transport layer (ETL) of Example 9
  • the compound prepared in Example 4 was the material of the electron transport layer (ETL) of Example 10
  • the compound prepared in Example 5 was the electron transport of Example 11.
  • the material of the layer (ETL), the compound prepared in Example 6 was the material of the electron transport layer (ETL) of Example 12
  • the compound prepared in Comparative Example 1 was the material of the electron transport layer (ETL) of Comparative Example 2.
  • the materials of the hole injection layer (HIL), the material of the hole transport layer (HTL), and the material of the host of Examples 7 to 12 and Comparative Example 2 were the same as those of the anthracene derivative and the Dopant.
  • the material of the hole injection layer is a triarylamine derivative
  • the material of the hole transport layer is a triarylamine derivative
  • the material of Host is an anthracene derivative
  • the material of Dopant is a triarylamine derivative.
  • ITO indium tin oxide
  • a conductive glass substrate cleaning using a variety of solvents (such as one or several of chloroform, acetone or isopropanol) cleaning, and then UV ozone treatment;
  • HIL 50 nm
  • HTL 35 nm
  • EML 25 nm
  • ETL 28 nm
  • cathode LiQ / Al (1nm / 150nm) in a high vacuum (1 ⁇ 10 -6 mbar) in the thermal evaporation;
  • the device is encapsulated in a nitrogen glove box with an ultraviolet curable resin.
  • the current-voltage (J-V) characteristics of the organic light-emitting diodes of Examples 7 to 12 and Comparative Example 2 were tested using a characterization apparatus, Also record important parameters such as luminous efficiency, lifetime and color coordinates (see Table 2).
  • the device X of Comparative Example 2 which was a material of the electron transport layer, was 0.18 and Y was 0.15. Obviously, the color coordinates of the devices of Examples 7 to 12 were more superior than those of Comparative Example 2.
  • the luminous efficiency of Examples 7 to 12 using the compounds prepared in Examples 1 to 6 as the material of the electron transporting layer was at least 4.8 cd/A, and the device of Comparative Example 2 was only 3.6 cd/A, that is, the examples were employed.
  • the devices of Examples 7 to 12 in which the obtained compound was used as a material of the electron transport layer had more excellent luminous efficiency.
  • T 95 1000 nits represents the initial luminance at 1000, and the luminance is attenuated to 95% of the time), and the lifetimes of the organic light-emitting diodes of Examples 7 to 12 recorded in Table 2 are relative to the organic ratio of Comparative Example 2
  • the multiple of the light emitting diode for example, the lifetime of the organic light emitting diode of Comparative Example 2 is 1, and the lifetime of Example 7 in Table 2 is 3.7, which is 3.7 times the lifetime of the organic light emitting diode of Embodiment 7, Example 8 The same is true for ⁇ 12, which is not described here.
  • the lifetime of the devices of Examples 7 to 12 is more than twice the life of Comparative Example 2, and has a long life.

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Abstract

L'invention concerne un dérivé cyclique fusionné de carbazole benzène ayant la formule générale suivante : Ar1 et Ar2 sont indépendamment choisis parmi un groupe aryle et un groupe hétéroaryle ; R1 et R2 sont indépendamment choisis parmi H, D, F, CN, NO2、CF3, alcényle, alcynyle, groupe amine, acyle, groupe amide, groupe cyano, groupe isocyano, alcoxyle, hydroxyle, carbonyle, sulfuryle, alkyle ayant 1 à 60 atomes de carbone, et un cycloalkyle ayant 3 à 60 atomes de carbone, un aryle ayant 6 à 60 atomes de carbone, un hétéroaryle ayant 3 à 60 atomes de carbone, un aryle fusionné ayant de 7 à 60 atomes de carbone, et un hétéroaryle fusionné ayant de 4 à 60 atomes de carbone ; Ar3 et Ar4 sont choisis indépendamment l'un de l'autre parmi un aryle ayant 6 à 60 atomes de carbone, un hétéroaryle ayant de 3 à 60 atomes de carbone, un aryle fusionné ayant de 7 à 60 atomes de carbone, et un hétéroaryle fusionné ayant de 4 à 60 atomes de carbone.
PCT/CN2017/115310 2016-12-08 2017-12-08 Dérivé cyclique fusionné de carbazole benzène, polymère, mélange, composition, dispositif électronique organique et son procédé de préparation WO2018103746A1 (fr)

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