WO2018113784A1 - 有机功能化合物、混合物、组合物、有机功能薄膜及其制备方法和有机电子器件 - Google Patents

有机功能化合物、混合物、组合物、有机功能薄膜及其制备方法和有机电子器件 Download PDF

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WO2018113784A1
WO2018113784A1 PCT/CN2017/118066 CN2017118066W WO2018113784A1 WO 2018113784 A1 WO2018113784 A1 WO 2018113784A1 CN 2017118066 W CN2017118066 W CN 2017118066W WO 2018113784 A1 WO2018113784 A1 WO 2018113784A1
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organic
aromatic
ring
organic functional
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French (fr)
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潘君友
于明泉
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广州华睿光电材料有限公司
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Priority to CN201780059504.2A priority Critical patent/CN109792000B/zh
Priority to US16/472,369 priority patent/US11404644B2/en
Publication of WO2018113784A1 publication Critical patent/WO2018113784A1/zh

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Definitions

  • the present invention relates to the field of organic electronic devices, and in particular to an organic functional compound, a mixture, a composition, an organic functional film, a method for preparing the same, and an organic electronic device.
  • OLEDs Organic light-emitting diodes
  • OLEDs have been invented since the invention (Appl. Phys. Lett. 1987, 51: 913-15.; Nature, 1990, 347: 539-541) due to the synthetic diversity of organic materials and relatively low manufacturing costs. And has excellent optical and electrical properties, making it a great potential for applications in optoelectronic devices such as flat panel displays and lighting (Chem Rev, 2009, 109: 897-1091; Chem Mater, 2011, 23: 326) -340).
  • OLED devices mostly use a multilayer device structure, that is, in addition to the light-emitting layer, one or more layers of hole transport/injection layers or electron transport/injection layers. Therefore, in addition to the development of excellent luminescent materials, the development of excellent electron transport/injection materials and hole transport/injection materials is also the key to achieving high performance OLEDs (J Mater Chem, 2008, 18: 4495-4509.; Acc Chem Res, 2005). , 38: 632-643.; Adv Mater, 2007, 19: 810-814).
  • OLEDs Although small molecules are easy to obtain multilayer, complex and highly efficient OLEDs by vacuum evaporation, vacuum evaporation methods have the disadvantages of being expensive, time consuming, wasteful of materials, and difficult to achieve large area applications. In contrast, solution-processed OLEDs have broad application prospects and commercial value because they have the advantages of being able to prepare large-area, flexible devices by low-cost inkjet printing, printing and other solution processing methods. Since general organic photoelectric materials have similar solubility, that is, organic/polymer luminescent materials, hole injection/transport materials, electron injection/transport materials in toluene, chloroform, chlorobenzene, o-dichlorobenzene, o-xylene, tetrahydrofuran, etc.
  • the organic solvent has good solubility, so that when the solution is processed to prepare a multi-layer, complex OLED, there are problems such as interface miscibility and interface erosion.
  • interface miscibility and interface erosion For example, when a solution is processed into a polymer or a small molecule light-emitting layer, the solvent used dissolves the underlying hole transport layer, causing problems such as interfacial miscibility and interface corrosion (J Mater Chem, 2008, 18: 4495-4509.; Chem Soc Rev, 2010, 39: 2500-2521).
  • the cross-linking cured polymer HTM has been used to solve the above problems.
  • a conventional cross-linking group such as a perfluorocyclobutane group, a styryl group, a butylene group, a silicone group, an acrylate group, a benzocyclobutane group, or the like, a modified conjugated polymer, a polymer
  • the above crosslinking group initiates perfluorocyclobutane (Adv. Funct. Mater., 2002, 12, 745), styrene (Adv. Mater., 2007, 19, 300), epoxy under conditions of illumination, heat, and the like. Butanyl (Nature, 2003, 421, 829.), silicone based (Acc. Chem.
  • the crosslinkable polymers reported so far are based on conjugated polymers.
  • Most conjugated polymers have lower triplet energy levels, which quench adjacent luminescent layers, such as excitons with higher triplet energy (relatively shorter wavelengths) in the green luminescent layer, and do not To the role of the exciton blocking layer. These all limit the performance improvement of solution processing OLED devices.
  • the materials of the light-emitting layer including soluble small molecules and light-emitting polymers, are mostly non-crosslinkable and solidified. Because cross-linking curing has a great influence on the performance of the luminescent layer. Therefore, the electron transport layer and/or the electron injection layer must also be prepared by a vacuum evaporation method.
  • organic functional compound capable of preparing a functional layer of an organic electronic device by a solution processing method, and the organic functional compound can avoid problems such as interfacial miscibility, interface corrosion, and the like.
  • A is an organic group having a photoelectric function
  • R 1 and R 2 are each independently selected from the group consisting of H, D, F, CN, alkyl, arylcyclo, aromatic heterocyclic, amino, silyl, decyl, alkoxy, aryloxy and siloxane
  • the alkyl group is selected from one of an unsubstituted alkyl group, a fluoroalkyl group, a halogenated alkyl group, and a halogenated fluoroalkyl group
  • the aromatic ring group is selected from the group consisting of unsubstituted aryl groups.
  • the alkoxy group is selected from the group consisting of an unsubstituted alkoxy group, a siloxy group, a fluoroalkoxy group, a deuterated alkoxy group, a deuterated fluoroalkoxy group, and a deuterated silyloxy group.
  • the aryloxy group is selected from one of an unsubstituted aryloxy group and a deuterated aryloxy group selected from the group consisting of unsubstituted siloxane groups and deuterated siloxanes.
  • p is an integer greater than or equal to 1.
  • a mixture comprising the above organic functional compound and an organic functional material selected from the group consisting of a hole injecting material, a hole transporting material, a hole blocking material, an electron injecting material, an electron transporting material, an electron blocking material, and an organic matrix. At least one of a material, a luminescent material, and an organic dye.
  • a composition comprising one of the above organic functional compound and the above mixture and an organic solvent.
  • An organic functional film prepared from the above organic functional compound, the above organic mixture, and one of the above compositions.
  • a method for preparing an organic functional film comprising the steps of:
  • the slurry is the above composition, or the slurry is prepared by dissolving one of the above organic functional compound and the above organic mixture in an organic solvent;
  • the film layer is subjected to a Bergman ring aromatization reaction at a temperature of 100 ° C or higher under anhydrous and anaerobic conditions to obtain an organic functional film.
  • An organic electronic device comprising a functional layer, wherein the material of the functional layer is the organic functional film, or the material of the functional layer is the organic functional film prepared by the method for preparing the organic functional film.
  • FIG. 1 is a schematic structural view of an organic light emitting diode according to an embodiment; wherein 101 is a substrate, 102 is an anode, 103 is a hole injection layer (HIL) or a hole transport layer (HTL), 104 is a light emitting layer, and 105 is an electron injection. Layer (EIL) or electron transport layer (ETL).
  • HIL hole injection layer
  • HTL hole transport layer
  • EIL electron transport layer
  • A is an organic group having a photoelectric function (hereinafter referred to as an electro-optic functional group);
  • X is selected from one of CR 13 and N; further, all X in the structural formula are CR 13 ;
  • R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are each independently selected from the group consisting of a single bond, 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 60 carbon atoms, a cycloalkyl group having 3 to 60 carbon atoms, and a carbon number It is 6 to 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 thick carbon number of 4 to 60 One of the heterocyclic aromatic groups.
  • R 1 and R 2 are each independently selected from the group consisting of H, D, F, CN, alkyl, arylcyclo, aromatic heterocyclic, amino, silyl, decyl, alkoxy, aryloxy and siloxane
  • the alkyl group being selected from the group consisting of an unsubstituted alkyl group, a fluoroalkyl group, a halogenated alkyl group, and a halogenated fluoroalkyl group
  • the aromatic ring group being selected from the group consisting of an unsubstituted aromatic ring group and an anthracene group.
  • the aromatic heterocyclic group is selected from the group consisting of an unsubstituted aromatic heterocyclic group and a deuterated aromatic heterocyclic group
  • the amino group is selected from the group consisting of an unsubstituted amino group and a halogenated amino group.
  • p is an integer greater than or equal to 1; further, p is any integer from 1 to 5; further, p is any integer from 1 to 3; and the dotted line in the formula (I) represents a bond to A.
  • the organic group having a photoelectric function is selected from an organic group having a hole (also called a hole) injection function, an organic group having a hole transporting function, and having a hole blocking function.
  • the group of the above photoelectric function may refer to a corresponding organic functional material containing the above photoelectric function, that is, the organic functional material is selected from a hole (also called a hole) injection material (HIM), a hole transport material (HTM), and an empty Hole blocking material (HBM), electron injecting material (EIM), electron transporting material (ETM), electron blocking material (EBM), organic matrix material (Host), singlet illuminant (fluorescent illuminant), triplet illuminant (phosphorescent emitter) and the like.
  • the above organic functional materials may be organic functional materials disclosed in WO2010135519A1, US20090134784A1 and WO2011110277A1.
  • the organic functional compound of the present embodiment is treated at 190 ° C for 2 hours in an environment of blocking water and oxygen, and a Bergman ring-forming aromatization reaction occurs to lower the solubility of the molecule, thereby curing the film.
  • reaction formula of the Bergman ring-forming aromatization reaction is as follows:
  • the structure b In the presence of a hydrogen donor, such as water in the air, other adjacent material molecules, a small amount of solvent molecules, the structure b further reacts as follows:
  • organic functional compound of the present embodiment can form a solvent-insoluble layer to cure the film, and the principle may be:
  • the above organic functional compound is capable of undergoing a cyclic aromatization reaction of Bergman to form a compound having the following formula (IV) or (IVa):
  • organic solvent S which is a good solvent of the organic functional compound represented by the general formula (I) and is a poor solvent having a compound represented by the general formula (IV) or (IVa).
  • n1 is an integer greater than or equal to 2; further, n1 is any integer from 2 to 50; further, n1 is any integer from 2 to 10; further, n1 is any integer from 2 to 5.
  • a in the general formula (IV) or (IVa) And the definition of p in the general formula (IV) is similar to A in the general formula (I), And the definition of p.
  • A has the following structural formula (III):
  • Ar 1 and Ar 2 are each independently selected from an unsubstituted aromatic hydrocarbon group, an unsubstituted aromatic heterocyclic hydrocarbon group, an R 11 -substituted aromatic hydrocarbon group, and an R 11 -substituted aromatic heterocyclic hydrocarbon group. One of them.
  • R 11 is selected from the group consisting of F, Cl, Br, I, D, CN, NO 2 , CF 3 , a linear alkane group, an alkane ether group, an alkane sulfide group having 1 to 10 carbon atoms, a branched alkane group and a cycloalkane group, or R 11 is a linear chain
  • the linear alkane group is selected from the group consisting of an unsubstituted linear alkane group and a linear alkane group substituted with at least one reactive group R 12 , or a linear alkane group is at least one H atom by D, F, Cl, Br, I , CN, an aromatic amine group containing a reactive group R 12 , an aromatic amine group containing an aromatic group, an aromatic amine group containing a heteroaromatic ring, and an alternate linear alkane group in the carbazole, the alkane ether group being selected from An unsubstituted alkane ether group and one of an alkane ether group substituted with at least one reactive group R 12 or an alkane ether group having at least one H atom by D, F, Cl, Br, I, CN, containing a reactive group An aromatic amine group of R 12 , an aromatic amine group containing an aromatic group, an aromatic amine group containing a heteroaromatic ring, and an substituted alkane
  • R 12 is independently selected from the group consisting of H and D, an aliphatic alkane group having 1 to 10 carbon atoms, an aromatic hydrocarbon, an aromatic ring group having 5 to 10 ring atoms, and a ring-constituting atomic number.
  • an aliphatic alkane group having 1 to 10 carbon atoms an aromatic hydrocarbon
  • an aromatic ring group having 5 to 10 ring atoms an aromatic ring group having 5 to 10 ring atoms
  • a ring-constituting atomic number One of 5 to 10 heteroaromatic groups
  • -Z- is a single bond, or Z is a two bridged group.
  • Z is selected from one of the structural formulae in Table 1:
  • R 4 ' , R 5 ' , R 6 ' and R 7 ' are each independently selected from the group consisting of H, D, F, CN, alkyl, arylcyclo, aromatic heterocyclic, amino, silicon.
  • R 4 ' , R 5 ' , R 6 ' and R 7 ' are each independently selected from the group consisting of H, D, F, CN, alkyl, arylcyclo, aromatic heterocyclic, amino, silicon.
  • An aromatic ring group selected from the group consisting of an unsubstituted aromatic ring group and a deuterated aromatic ring group
  • the aromatic heterocyclic group is selected from the group consisting of an unsubstituted aromatic heterocyclic group and a deuterated aromatic heterocyclic group.
  • the dotted line indicates two benzene rings in the formula (III) Together key.
  • Structural Formula (III), Structural Formula (IIIa), Structural Formula (IIIb), Structural Formula (IIIc), and Structural Formula (IIId) x is any integer from 0 to 4, and x1 is any integer from 0 to 3, and y is 0. Any integer of ⁇ 5, z is any integer from 0 to 5;
  • L is selected from the group consisting of 5 to 40 R 1 -substituted conjugated aryl groups and 5 to 40 carbon atoms in an unsubstituted conjugated aryl group.
  • L is selected from a group having the following structural formulas B1 and B2:
  • the dotted lines in the structural formulae (III) and (IIIa) indicate the bond of L to the group in the circle, and the position of the connection between L and the circle may be on the two benzene rings in the circle, or may be included in Ar 2 Any one of the possible positions on the aromatic or heteroaromatic ring.
  • L, Ar 1 and Ar 2 are each independently selected from one of an aryl group having 5 to 40 ring-forming atoms and a heteroaryl group having 5 to 40 ring-forming atoms; further, L, Ar 1 and Ar 2 are each independently selected from one of an aryl group having 5 to 30 ring-constituting atoms and a heteroaryl group having 5 to 30 ring-forming atoms; further, L, Ar 1 and Ar 2 Each of them is independently selected from the group consisting of an aryl group having 5 to 20 ring-forming atoms and a heteroaryl group having 5 to 20 ring-forming atoms; further, L, Ar 1 and Ar 2 are each independently selected from having One of 5 to 15 ring-constituting aryl groups and a heteroaryl group having 5 to 15 ring-forming atoms.
  • L, Ar 1 and Ar 2 are each independently selected from the group consisting of an aryl group having 6 to 15 ring-constituting carbon atoms and a heteroaryl group having 2 to 15 ring-forming carbon atoms and a hetero atom; Further, L, Ar 1 and Ar 2 are each independently selected from one of an aryl group having 6 to 10 ring-constituting carbon atoms and a heteroaryl group having 2 to 10 ring-forming carbon atoms and a hetero atom.
  • Ar 1 and Ar 2 are each a heteroaryl group having 2 to 15 ring-forming carbon atoms and a hetero atom, the sum of the number of carbon atoms and hetero atoms in L, Ar 1 and Ar 2 is at least 4 One.
  • the hetero atom is at least one selected from the group consisting of Si, N, P, O, S, and Ge; further, the hetero atom is selected from at least one of Si, N, P, O, and S; and the hetero atom is selected from N, At least one of O and S.
  • an aromatic group means a hydrocarbon group containing at least one aromatic ring. It includes a monocyclic group and a polycyclic group.
  • Heterocyclic aromatic group means an aromatic hydrocarbon group (containing a hetero atom) containing at least one hetero atom, and includes a monocyclic group and a polycyclic group.
  • the heteropolycyclic group may have more than two rings in which two carbon atoms are shared by two adjacent rings, a fused ring. And at least one of the polycyclic groups is an aromatic ring or a heteroaromatic ring.
  • the aromatic group and the heterocyclic aromatic group are not limited to a system including an aromatic ring or a heteroaromatic ring, and a non-aromatic ring system.
  • the plurality of aromatic or heterocyclic aromatic groups therein may also be interrupted by short non-aromatic units ( ⁇ 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 aromatic groups.
  • examples of the aromatic group are: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzopyrene, triphenylene, anthracene, anthracene, snail, and derivatives thereof.
  • heteroaryl groups are: furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, Thiazole, tetrazole, anthracene, oxazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrol, furanfuran, thienofuran, benzisoxazole, benzisothiazole, Benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-diazepine, quinoxaline, phenanthridine, pyridine, quinazoline, quinazolinone, and derivative.
  • both of Ar 1 and Ar 2 are aryl groups having 6 to 40 ring-constituting atoms; further, Ar 1 and Ar 2 are each an aryl group having 6 to 30 ring-constituting atoms; further, Ar 1 and Ar 2 are each an aryl group having 6 to 25 ring-constituting atoms.
  • L, Ar 1 and Ar 2 are each independently selected from one of the following groups:
  • X is selected from one of CR 13 and N; further, all X in the structural formula are CR 13 ;
  • R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are each independently selected from the group consisting of a single bond, 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 60 carbon atoms, a cycloalkyl group having 3 to 60 carbon atoms, and a carbon number It is 6 to 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 thick carbon number of 4 to 60 One of the heterocyclic aromatic groups.
  • Ar 1 and Ar 2 are each independently selected from one of the following general formulas C1 to C36:
  • R 3 is selected from the group consisting of H, F, Cl, Br, I, D, CN, NO 2 , CF 3 , B(OR 2 ) 2 , Si(R 2 ) 3 , and a linear chain.
  • the organic functional compound of the formula (I) or the compound of the formula (IV) of the present embodiment has a hole transporting function, it can be used in an organic electronic device, particularly a hole transport layer in an organic light emitting diode (OLED). .
  • OLED organic light emitting diode
  • the organic functional compound of the formula (I) or the compound of the formula (IV) of the present embodiment has a high LUMO, that is, has an electron blocking function, it can be used for electron blocking in organic electronic devices, particularly organic light emitting diodes.
  • the higher LUMO here means that the electron blocking layer has a higher LUMO than the adjacent functional layer (such as the luminescent layer in the organic light emitting diode).
  • the organic functional compound of the formula (I) or the compound of the formula (IV) of the present embodiment has a high triplet energy level T1, that is, has a triplet exciton blocking function, and can be used for organic electronic devices, particularly organic An exciton blocking layer in the light emitting diode.
  • T1 triplet energy level
  • the higher T1 here means that the exciton blocking layer has a higher T1 than the adjacent functional layer (such as the luminescent layer in the phosphorescent OLED).
  • the organic functional compound of the formula (I) or the compound of the formula (IV) of the present embodiment has a high singlet energy level S1, that is, it has a singlet exciton blocking function, and can be used for an organic electronic device, particularly a machine.
  • An exciton blocking layer in the light emitting diode It should be noted that the higher S1 here means that the exciton blocking layer has a higher S1 than the adjacent functional layer (such as the luminescent layer in the fluorescent OLED).
  • A when A is a group having a hole transporting function, A includes at least one of the following groups: a phthalocyanine group, a porphyrin group, an amine group, an aromatic amine group, a biphenyl triarylamine group, a thiophene group. And thiophenyl groups (such as dithienothiophenyl and thiophenyl), pyrrolyl, anilino, oxazolyl, azaindrazinyl, and derivatives thereof.
  • aromatic amine group having a hole transporting function is selected from one of the following structural formulas, but is not limited to the following structural formula:
  • Ar 3 , Ar 4 , Ar 5 , Ar 6 , Ar 6 , Ar 7 , Ar 8 , Ar 9 , Ar 10 and Ar 11 are each independently selected from a cyclic aromatic hydrocarbon group, an aromatic heterocyclic group and having 2 to 10 One of the groups of the ring;
  • the cyclic aromatic hydrocarbon group is selected from the group consisting of phenyl, biphenyl, triphenyl, benzo, naphthyl, anthryl, phenalkenyl, phenanthryl, anthryl, fluorenyl, fluorenyl One of a sulfhydryl group, a fluorenyl group, a fluorenyl group Pyrazolyl, imidazolyl, triazolyl, isoxazolyl, thiazolyl, oxadiazolyl, oxatriazole, oxazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyr
  • Ar 3 , Ar 4 , Ar 5 , Ar 6 , Ar 6 , Ar 7 , Ar 8 , Ar 9 , Ar 10 and Ar 11 may be further substituted, and the substituent is selected from hydrogen, alkyl, alkoxy, One of an amino group, an alkene group, an alkyne group, an aralkyl group, a heteroalkyl group, an aryl group, and a heteroaryl group.
  • Ar 3 , Ar 4 , Ar 5 , Ar 6 , Ar 6 , Ar 7 , Ar 8 , Ar 9 , Ar 10 and Ar 11 are each independently selected from one of the following groups:
  • a is any integer from 1 to 20; X 1 to X 8 are each independently selected from one of CH and N; and Ar 30 is the same as Ar 3 .
  • the compound corresponding to the aromatic amine group having a hole transporting function may also be a substance disclosed in US Pat. No. 3,567,450, US Pat. No. 4,724,432, US Pat. No. 5,061,569, US Pat.
  • organic functional compound of the formula (I) or the group A having a hole transporting function in the compound of the formula (IV) is selected from one of the following groups, but is not limited to the following groups:
  • a in the general formula (I) is a group having an organic main function (a fluorescent main body and a phosphorescent main body)
  • A contains the structural formula (1) Structural formula (2) Structural formula (3) Structural formula (4) Structural formula (5) And structural formula (6) One of them;
  • Ar 11 and Ar 12 are each independently selected from an aromatic group having 6 to 60 carbon atoms, an aromatic hetero group having 3 to 60 carbon atoms, and a carbon number. a fused ring aromatic group of 6 to 60 and a fused ring aromatic group having 3 to 60 carbon atoms;
  • each of them is independently selected from the group consisting of an aromatic group having 5 to 30 ring atoms and a aryl group having 5 to 30 ring atoms; further, and Each of them is independently selected from the group consisting of an aromatic group having 5 to 25 ring atoms and a aryl group having 5 to 25 ring atoms; further, and Each of them is independently selected from the group consisting of an aromatic group having 5 to 20 ring atoms and a aryl group having 5 to 20 ring atoms; further, and Each of them is independently selected from the group consisting of an aromatic group having 5 to 15 ring atoms and a aryl group having 5 to 15 ring atoms;
  • Ar 9 and Ar 10 are each independently selected from the group consisting of H, D, F, CN, NO 2 , CF 3 , alkenyl, alkynyl, amine, acyl, amide, and cyano. , isocyano 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 carbon atoms. 60 aromatic groups, heterocyclic aryl groups having 3 to 60 carbon atoms, fused ring aromatic groups having 7 to 60 carbon atoms, and fused heterocyclic aromatic groups having 4 to 60 carbon atoms One of the bases;
  • L 1 is one selected from the group consisting of an aromatic group having 5 to 60 ring atoms and a aryl group having 5 to 60 ring atoms; further , L 1 is selected from the group consisting of an aromatic group having 5 to 50 ring atoms and a aryl group having 5 to 50 ring atoms; further, L 1 is selected from ring atoms. 5 to 40 of an aromatic group and one of 5 to 40 aromatic groups; and further, L 1 is selected from the group consisting of 6 to 30 aromatic groups and One of the 6 to 30 aromatic hetero groups having a ring-forming atomic number.
  • -L 2 - is a single bond, or L 2 is selected from an aromatic group having 5 to 30 ring atoms and a ring-forming atomic number of 5 to 30
  • the linking position of L 2 may be any one of the carbon atoms on the ring; further, -L 2 - is a single bond, or L 2 is selected from 5 to 25 ring atoms.
  • One of the aromatic group and the number of ring-forming atoms is 5 to 25 aryl groups; further, -L 2 - is a single bond, or L 2 is selected from 5 to 20 ring atoms.
  • the aromatic group and the number of ring-forming atoms are one of 5 to 15 aromatic hetero groups.
  • R is selected from the group consisting of H, D, F, CN, alkenyl, alkynyl, nitrile, amine, nitro, acyl, alkoxy, carbonyl, sulfone, and an alkane having from 1 to 30 carbon atoms.
  • the group has 3 to 30 ring alkyl groups, 5 to 60 aromatic groups, and 5 to 60 aromatic heterocyclic groups.
  • R 1 and R 2 are the same as defined in the formula (II). Further, in the structural formulae (3) to (5), at least one of the carbon atoms substituted by R 1 and R 2 in the ring is at least one.
  • m is any integer of 0 to 4.
  • o is any integer from 0 to 4
  • q is any integer from 0 to 6.
  • s is any integer of 1 to 4. Further, s is any integer from 1 to 3; further, s is any integer from 1 to 2.
  • A is selected from one of the following structural formulas:
  • L 1 , R 1 , R 2 and R are the same as those in the structural formulae (1) to (6); a is any integer of 1 to 3; b 11 to b 13 are each independently selected from any integer of 0 to 6.
  • A is selected from one of the following structural formulas:
  • the group A having an organic main function in the general formula (I) and the general formula (IV) is selected from one of the following groups, but is not limited to the following Group:
  • A is a group having a singlet main function (fluorescent main function), and in this case, the core group of A is selected from a group containing a cyclic aromatic hydrocarbon, a group containing an aromatic heterocyclic ring, and having two ⁇ One of 10 ring groups; the group having a cyclic aromatic hydrocarbon is selected from the group consisting of biphenyl, triphenyl, benzo, naphthalene, anthracene, anthracene, phenanthrene, anthracene, anthracene, pyrene, anthracene and anthracene.
  • a group having an aromatic heterocyclic ring selected from the group consisting of dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, anthracene Azole, pyridinium, pyrrole dipyridine, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, triazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine , triazine, oxazine, oxazine, oxadiazine, hydrazine, benzimidazole, oxazole, pyridazine, benzoxazole, benzoisoxazole, benzothiazole, quinoline, isoquinoline, Por
  • the core group of A is selected from one of the following groups:
  • R 11 is selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, aryl and heteroaryl;
  • Ar 40 is selected from the group consisting of carbon atoms 6 to 60 aromatic groups, aryl groups having 3 to 60 carbon atoms, fused ring aromatic groups having 6 to 60 carbon atoms, and fused rings having 3 to 60 carbon atoms
  • One of the arylhetero groups; b is any integer from 0 to 20;
  • X 11 to X 18 are each independently selected from one of CH and N; and
  • X 19 and X 10 are independently selected from CR 1 R 2 and NR, respectively.
  • the definitions of R 1 and R 2 are the same as those in the structural formulae (1) to (6).
  • a in the formula (I) is a group having a function as a phosphorescent host, and in this case, A having a function as a phosphorescent host is selected from one of the above structural formulae (3) to (6).
  • A is structural formula (3)
  • the structural formula of A having a phosphorescent main function is selected from the group and One of them:
  • the structural formula of A having a phosphorescent main function is as follows:
  • R 1 , R 2 , L 1 and L 2 have the same meanings as in the structural formulae (3) to (6); and L 3 is selected from the group consisting of an aromatic group having 5 to 60 ring atoms and a ring-forming atom.
  • L 3 is selected from an aromatic group having 5 to 60 ring atoms and a ring-forming atom.
  • the group A having a function as a phosphorescent host in the general formula (I) and the general formula (IV) is selected from one of the following groups, but is not limited to the following groups:
  • the structural formula of the group A is selected from and One of the meanings of Ar 4 , Ar 5 , Ar 7 , Ar 8 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 , X 9 , R 1 , R 2 It is the same as structural formulae (1) to (6).
  • Ar 4 , Ar 7 , X 4 , X 5 , X 8 , X 9 , R 1 and R 2 have the same meanings as in the structural formulae (1) to (6).
  • the group A having a function as a phosphorescent host in the general formula (I) and the general formula (IV) is selected from one of the following groups, but is not limited to the following groups:
  • the structural formula of the group A is selected from and One of them; wherein Ar 3 , Ar 5 , X 1 , X 2 , X 3 , R 1 , R 2 , L 1 and s have the same meanings as in the structural formulae (1) to (6).
  • the group A having a function as a phosphorescent host in the general formula (I) and the general formula (IV) is selected from one of the following groups, but is not limited to the following groups:
  • the structural formula of the group A is selected from and One of them; wherein Ar 3 , Ar 4 , R 1 , R 2 , L 1 , and s have the same meanings as in the structural formulae (1) to (6).
  • R 1 , R 2 , L 1 and s are the same as those in the structural formulae (1) to (6).
  • a in the formula (I) is a functional group having a triplet main body, and a core group of A is selected from a group containing a cyclic aromatic hydrocarbon group, a group containing an aromatic heterocyclic group, and a package having 2 Groups of ⁇ 10 ring structures.
  • the group containing a cyclic aromatic hydrocarbon group is selected from the group consisting of a biphenyl group, a triphenyl group, a benzo group and a fluorenyl group; and the group containing the aromatic heterocyclic group is selected from the group consisting of dibenzothiophene group and diphenyl group.
  • furyl dibenzoselenophene, furyl, thienyl, benzofuranyl, benzothienyl, benzoseleno, carbazolyl, oxazolyl, pyridinyl, pyrrole Pyridyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, thiazolyl, oxadiazolyl, oxatriazole, oxazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl , pyrazinyl, triazinyl, oxazinyl, oxathiazinyl, oxadiazinyl, fluorenyl, benzimidazolyl, oxazolyl, oxazolyl, dibenzoxazolyl, benzoin Azolyl, benzothiazolyl, quinolyl, isoquinolin Az
  • It may also be linked together by at least one linking substance selected from one of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain aliphatic group, and an aliphatic ring group.
  • a in the formula (I) is a core group having a triplet main function selected from one of the following groups:
  • R 11 to R 17 are each independently selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkenyl, alkynyl, aralkyl, heteroalkyl, aryl and heteroaryl.
  • Ar 11 is selected from the group consisting of an aromatic group having 6 to 60 carbon atoms, an aromatic hetero group having 3 to 60 carbon atoms, a fused aromatic group having 6 to 60 carbon atoms, and a carbon atom number of One of three to 60 fused ring aryl groups; c is any integer from 0 to 20;
  • X 11 to X 18 are each independently selected from one of CH and N; and
  • X 19 is selected from CR 1 R 2 and one of NR 1 .
  • R 1 and R 2 are each independently selected from the group consisting of H, D, F, CN, alkenyl, alkynyl, nitrile, amine, nitro, acyl, alkoxy, carbonyl, sulfone, and one carbon atom.
  • Ar in the formula (II) may be none.
  • -SG is a group having the following structural formula:
  • solubilizing structural unit -SG is selected from one of the following structural formulae:
  • R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from the group consisting of H, respectively.
  • the aromatic heterocyclic group is selected from the group consisting of an unsubstituted aromatic heterocyclic group and a deuterated aromatic heterocyclic group
  • the amino group is selected from the group consisting of an unsubstituted amino group and a halogenated amino group.
  • the silicon group is selected from one of an unsubstituted silicon group and a deuterated silicon group
  • the formazan group is selected from one of an unsubstituted formazan group and a deuterated formazan group
  • the alkoxy group is selected from the group consisting of unsubstituted alkyl groups.
  • R 3 , R 4 , R 5 , R 6 and R 7 are each independently selected from the group consisting of hydrogen, a linear alkyl group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 20 carbon atoms. And one of a branched alkyl group having 3 to 20 carbon atoms and an alkoxy group having 3 to 20 carbon atoms.
  • n is an integer greater than 0; -L 1 - is a single bond, or L 1 is selected from one of an aryl group and a heteroaryl group; a dotted line indicates a functional structure The bond of the unit Ar bond.
  • L 1 is selected from the group consisting of one of the following single bonds and a structural formula:
  • R 1 , R 2 , R 3 and R 4 are each independently selected from the group consisting of F, Cl, Br, I, N(Ar) 2 , CN.
  • an alkyl group having 1 to 40 C atoms in which a single H atom or a CH 2 group may be substituted by the above-mentioned group or group R is selected from the following groups.
  • alkoxy group having 1 to 40 carbon atoms is selected from the group consisting of methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, One of sec-butoxy, tert-butoxy and methylbutoxy.
  • the glass transition temperature of the organic functional compound of the present embodiment is ⁇ 100 ° C; further, the glass transition temperature is ⁇ 120 ° C; further, the glass transition temperature is ⁇ 140 ° C; further, the glass transition temperature is ⁇ 160 ° C; further , glass transition temperature ⁇ 180 ° C.
  • the compound after the Bergman ring-forming reaction represented by the general formula (IV) is HTM, which has a high LUMO, generally LUMO ⁇ -2.7 eV; further, LUMO ⁇ -2.6 eV; further, LUMO ⁇ -2.5 eV; further, LUMO ⁇ -2.4 eV.
  • the compound after the Bergman ring-forming reaction represented by the general formula (IV) has hydrazine (HOMO-1)-HOMO ⁇ 0.3 eV; further, (HOMO-1)-HOMO ⁇ 0.35 eV; further, ( HOMO-1)-HOMO ⁇ 0.4 eV; further, (HOMO-1)-HOMO ⁇ 0.45 eV; further, (HOMO-1)-HOMO ⁇ 0.5 eV.
  • HOMO is the energy level of the highest occupied orbit
  • (HOMO-1) is the energy level of the second highest occupied orbit.
  • the compound after the Bergman ring-forming reaction represented by the general formula (IV) is HTM having a HOMO of ⁇ -5.0 eV; further, HOMO ⁇ -5.1 eV; further, HOMO ⁇ -5.2 eV.
  • the compound after the Bergman ring-forming reaction represented by the general formula (IV) is a phosphorescent host material having a triplet energy level E T ⁇ 2.5 eV, and further, a triplet energy level E T ⁇ 2.6 eV; further, a three-line The state level E T ⁇ 2.7 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 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.).
  • 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.
  • HOMO, LUMO is not an absolute value, it is a relative value to the standard material NPB (see the chemical formula below). It should be understood that the HOMO has a HOMO of -5.22 eV and a LUMO of -2.34 eV according to the method herein (see specific examples). Therefore, more accurate, this article on HOMO, LUMO requirements, when different methods are involved, the corresponding calibration should be made.
  • organic functional compound according to the general formula (I) is selected from one of the following compounds, but is not limited to the following compounds:
  • the method for synthesizing the above-described organic functional compound of the formula (I) is carried out by using a raw material containing a reactive group.
  • These active materials comprise at least one leaving group, for example, the leaving group is bromine, iodine, boric acid or a boronic ester.
  • Suitable reactions to form C-C linkages are well known in the art and are described in the literature, particularly suitable and preferred coupling reactions such as SUZUKI, STILLE and HECK coupling reactions.
  • the above organic functional compound contains an organic functional structural unit and a solubilizing group, and has good solubility and film forming properties. At the same time, the organic functional compound can form a larger conjugated group in the molecule through the reaction as needed, so that the solubility of the molecule is deteriorated, so that it has a characteristic of controlled irreversible solubility reduction as needed. In order to avoid problems such as interface miscibility and interface erosion.
  • the mixture of one embodiment comprises the organic functional compound represented by the above formula (I) and an organic functional material.
  • 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 is a fluorescent illuminant (single-state illuminant), in which case the organic functional compound represented by the general formula (I) is used as a host or a co-host, and in the mixture, the organic functional material
  • the weight percentage of the material is ⁇ 7 wt%.
  • the organic functional material is a TADF material.
  • the organic functional material is a phosphorescent emitter (or a triplet emitter).
  • the organofunctional compound represented by the formula (I) is used as a host or a co-host, and in the mixture, an organic functional material
  • the weight percentage is ⁇ 30% by weight; further, the weight percentage of the organic functional material is ⁇ 25 wt%; further, the weight percentage of the organic functional material is ⁇ 20 wt%; further, the weight percentage of the organic functional material ⁇ 18wt%.
  • the organic functional material is an HTM material.
  • the composition of one embodiment is a solvent-based mixture, 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.
  • OLED organic light emitting diode
  • OCV organic photovoltaic cell
  • OFET organic field effect transistor
  • OFET organic light emitting field effect transistor
  • organic laser an organic spintronic device.
  • organic spintronic device One of an organic sensor and an organic plasmon emitting diode (Organic Plasmon Emitting Diode).
  • the mixture may be a solution or a suspension.
  • the composition includes one of an organic functional compound and a mixture and an organic solvent.
  • the organic functional compound is an organic functional compound represented by the above formula (1)
  • the mixture is the above mixture.
  • the molar mass of the organic functional compound is ⁇ 700 g/mol, further, the molar mass of the organic functional compound is ⁇ 800 g/mol; the molar mass of the organic functional compound is ⁇ 900 g/mol; further, the molar of the organic functional compound The mass is ⁇ 1000 g/mol; further, the molar mass of the organic functional compound is ⁇ 1100 g/mol.
  • the solubility of the organic functional compound in toluene is ⁇ 10 mg/ml at 25 ° C; further, the solubility of the organic functional compound in toluene is ⁇ 15 mg/ml; further, the solubility of the organic functional compound in toluene ⁇ 20mg/ml.
  • 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.
  • the composition has a surface tension at an operating temperature or at 25 ° C of from about 19 dyne/cm to 50 dyne/cm; further from 22 dyne/cm to 35 dyne/cm; and further from 25 dyne/cm to 33 dyne/cm.
  • the viscosity of the composition at an operating temperature or 25 ° C is in the range 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 of the composition can be adjusted by different methods, such as by selecting a suitable solvent, organic functional compound or concentration of the mixture.
  • the printing is carried out by a usual printing method by the viscosity of a mixture containing an organic functional compound or a mixture.
  • the composition of the organic functional compound or mixture is from 0.3% to 30% by weight; further, the weight percent of the organic functional compound or mixture is from 0.5% to 20%; further, the organic functional compound Or the weight percentage of the mixture is 0.5% to 1%; further, the weight percentage of the organic functional compound or mixture is 0.5% to 10%; further, the weight percentage of the organic functional compound or mixture is 1% ⁇ 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 "Handbook of Print Media: Technologies and Production Methods” edited by Helmut Kipphan, ISBN 3-540-67326-1 for printing techniques and solvents, concentrations, and viscosities in mixtures. Wait for adjustments.
  • the above has good printability and film-forming property, and is convenient for realizing high-performance small-molecule organic electronic devices, especially organic electroluminescent devices, through solution processing, especially printing process, thereby providing a low cost and high cost. Efficient manufacturing technology solutions.
  • the organic functional film of one embodiment is prepared from a total of one of the organic functional compound, the mixture and the composition represented by the above formula (I).
  • the organic functional film can be used in an organic electronic device.
  • Step S1 Providing a slurry.
  • the slurry is the above composition, or the slurry is obtained by dissolving one of the organic functional compound of the above formula (I) and the above organic mixture in an organic solvent.
  • Step S2 forming a film layer on the substrate using the slurry.
  • the slurry is applied to a substrate by a printing or coating method to form a film layer.
  • 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.
  • Step S3 The Bergman ring-forming aromatization reaction is carried out under the conditions of 100 ° C or higher under anhydrous and anaerobic conditions to obtain an organic functional film.
  • the film layer was treated at 190 ° C in an environment of isolating water and oxygen for 2 hours to cause a Bergman ring-forming aromatization reaction.
  • the thickness of the resulting organic functional film is at least 50% of the thickness of the film layer, further, at least 60%; further, at least 70%; further, at least 85%.
  • the above organic functional film can be applied to an organic electronic device 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), and an organic light emitting device.
  • OLED organic light emitting diode
  • OLED organic photovoltaic cell
  • OEEC organic light emitting cell
  • OFET organic field effect transistor
  • a field effect transistor an organic laser, an organic spintronic device, an organic sensor, and an organic plasmon emitting diode (Organic Plasmon Emitting Diode).
  • the organic functional film is used in a hole transport layer, a hole injection layer or a light-emitting layer of an OLED device; further, the organic functional film is used for a hole transport layer of an OLED device.
  • An organic electronic device includes a functional layer, and the material of the functional layer is the above organic functional film.
  • such an organic electronic device further comprises at least one cathode and one anode, the functional layer being located between the cathode and the anode.
  • 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.
  • OLED organic light emitting diode
  • OCV organic photovoltaic cell
  • OEEC organic light emitting cell
  • OFET organic field effect transistor
  • organic light emitting field effect transistor an organic laser
  • organic spintronic device One of an organic sensor and an organic plasmon emitting diode (Organic Plasmon Emitting Diode).
  • the structure shown in FIG. 1 is an organic light emitting diode 100.
  • the organic electronic device 100 includes a substrate 101, an anode 102, at least one light emitting layer 104, and a cathode 106.
  • the substrate 101 may be opaque or transparent.
  • Transparent substrates can be used to make transparent light-emitting components.
  • the transparent substrate 101 may be the substrate 101 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 101 may be a rigid substrate 101 or an elastic substrate 101.
  • the substrate 101 is a plastic, metal, semiconductor wafer or glass. Further, the substrate 101 has a smooth surface. No surface defects are ideal for the substrate 101.
  • the substrate 101 is flexible.
  • the substrate 101 is a polymer film or plastic; the substrate 101 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 101 is selected from one of poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).
  • the material of the anode 102 includes one of a conductive metal, a metal oxide, and a conductive polymer.
  • the anode 102 can easily inject holes into the light-emitting layer, the hole injection layer, or the hole transport layer.
  • the work function of the anode 102 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 The absolute value of the difference of the HOMO level (or valence band) level is less than 0.5 eV; further, less than 0.3 eV; and further, less than 0.2 eV.
  • the material of the anode 102 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 102 material can be prepared by physical vapor deposition.
  • the physical vapor deposition method is specifically RF magnetron sputtering, vacuum thermal evaporation or electron beam (e-beam) evaporation.
  • the material of the anode 102 is not limited to the above materials, and the material of the anode 102 may also be patterned ITO.
  • the material of the light-emitting layer 104 is the above-described organic functional film.
  • the material of the cathode 106 is selected from one of a conductive metal and a metal oxide.
  • the material of the cathode 106 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 106 and the organic functional material (light-emitting material) of the light-emitting layer 104, the n-type semiconductor material of the electron injection layer, the n-type semiconductor material of the electron transport layer or the LUMO of the n-type semiconductor material of the hole blocking layer The absolute value of the difference of the energy level (or conduction band) energy level is less than 0.5 eV; further, less than 0.3 eV, and further, less than 0.2 eV. In principle, all materials that can be used as the cathode 106 of the OLED are possible as the material of the cathode 106 of the present embodiment.
  • the cathode 106 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 106 material can be prepared 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 light emitting diode 100 further includes other functional layers such as a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an electron injection layer (EIL), and an electron transport layer (ETL). And at least one of a hole blocking layer (HBL).
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • ETL electron injection layer
  • ETL electron transport layer
  • HBL hole blocking layer
  • Suitable materials for use in these functional layers may be the materials disclosed in WO2010135519A1, US20090134784A1 and WO2011110277A1.
  • the organic light emitting diode 100 further includes a hole injection layer or a hole transport layer 103.
  • the material of the hole injection layer or the hole transport layer 103 is the above-described organic functional film.
  • the organic light emitting diode 100 further includes an electron injection layer or an electron transport layer 105.
  • the organic light emitting diode 100 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.
  • 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:
  • Example 1 The organic functional compounds of Examples 1 to 5 were respectively dissolved in toluene at a concentration of 20 mg/mL, and the solution was spin-coated on a glass substrate in a nitrogen glove box to obtain a 60 nm film; 6 is the organic functional compound of Example 1, Example 7 is the organic functional compound of Example 2, Example 8 is the organic functional compound of Example 3, and Example 9 is the use of Example 4.
  • the organic functional film of Examples 6 to 10 was obtained by annealing at 190 ° C for 10 minutes, and the thickness and surface roughness of the organic functional films of Examples 6 to 10 were respectively measured;

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Abstract

一种有机功能化合物，具有如下通式（E）：其中，A为具有光电功能的有机基团；SG的结构式选自式（F）及式（G）中的一个，其中，式（H）选自具有5个～40个成环原子的芳基及具有5个～40个成环原子的杂芳基中的一种；R1和R2分别独立选自H、D、F、CN、烷基、芳环基、芳香性杂环基、氨基、硅基、甲锗基、烷氧基、芳氧基及硅氧烷基中的一种，p为大于或等于1的整数。

Description

有机功能化合物、混合物、组合物、有机功能薄膜及其制备方法和有机电子器件 技术领域
本发明涉及有机电子器件领域，特别是涉及一种有机功能化合物、混合物、组合物、有机功能薄膜及其制备方法和有机电子器件。
背景技术
有机发光二极管(OLEDs)自发明以来(Appl.Phys.Lett.1987,51:913-15.；Nature,1990,347:539-541)，由于有机材料具有合成上多样性、制造成本相对较低，且具有优良的光学与电学性能，使得其在光电器件(例如平板显示器和照明)的应用方面具有很大的潜力(Chem Rev,2009,109:897-1091；Chem Mater,2011,23:326-340)。
OLED器件大多采用多层器件结构，即除了发光层外，还含有一层或多层空穴传输/注入层或电子传输/注入层。因此，除了开发优异的发光材料，开发优异的电子传输/注入材料和空穴传输/注入材料也是实现高性能OLED的关键(J Mater Chem,2008,18:4495-4509.；Acc Chem Res,2005,38:632-643.；Adv Mater,2007,19:810-814)。
虽然小分子很容易通过真空蒸镀方法获得多层、复杂的高效OLEDs器件，但是真空蒸镀方法具有价格昂贵、耗时、浪费材料、难以实现大面积应用等缺点。相比而言，由于溶液加工型OLEDs具有能够通过低廉的喷墨打印、印刷等溶液加工方法制备大面积、柔性器件等优点，使其具有广泛的应用前景和商业价值。由于一般有机光电材料具有相似的溶解性，即有机/聚合物发光材料、空穴注入/传输材料、电子注入/传输材料在甲苯、氯仿、氯苯、邻二氯苯、邻二甲苯、四氢呋喃等有机溶剂中具有良好的溶解性，使得在溶液加工制备多层、复杂的OLED时，会存在界面混溶、界面侵蚀等问题。例如溶液加工聚合物或小分子发光层时，所使用的溶剂会溶解下面的空穴传输层，造成界面混溶、界面侵蚀等问题(J Mater Chem,2008,18:4495-4509.；Chem Soc Rev,2010,39:2500-2521)。
一直以来人们都采用可交联固化的聚合物HTM来解决上述问题。常规的交联基团，如全氟环丁烷基、苯乙烯基、环氧丁烷基、硅酮基、丙烯酸酯基、苯并环丁烷基等修饰的共轭聚合物时，聚合物上的交联基团在光照、加热等条件下会引发全氟环丁烷基(Adv.Funct.Mater.,2002,12,745)、苯乙烯基(Adv.Mater.,2007,19,300)、环氧丁烷基(Nature,2003,421,829.)、硅酮基(Acc.Chem.Res.,2005,38,632)、丙烯酸酯基(Chem.Mater.,2003,15,1491)及苯并环丁烷基(Chem.Mater.,2007,19,4827.)等可交联基团发生交联反应，形成不溶不熔的互穿网络聚合物膜，具有优异的抗溶剂性能，可以避免界面混溶、界面侵蚀等问题(TW201406810A,US7592414B2)。
但迄今为止报道的可交联高聚物都是基于共轭聚合物。共轭聚合物大多具有较低的三线态能级，会淬灭相邻发光层，如绿光发光层中具有更高三线态能量(相对更短的波长)的激子，同时也不会起到激子阻挡层的作用。这些都制约了溶液加工OLED器件的性能的提高。
另外，到目前为止，发光层的材料，包括可溶性小分子和发光聚合物，大多是不可交联固化的。因为交联固化对发光层的性能影响极大。因此电子传输层和/或电子注入层还必须通过真空蒸镀的方法制备。
因此，急需开发一种能够通过溶液加工的方法制备功能层的有机化合物，且该有机化合物能够避免界面混溶、界面侵蚀等问题。
发明内容
基于此，有必要提供一种能够通过溶液加工的方法制备有机电子器件的功能层的有机功能化合物，且该有机功能化合物能够避免界面混溶、界面侵蚀等问题。
此外，还提供一种含有该有机功能化合物的混合物、组合物、有机功能薄膜及其制备方法和有机电子器件。
一种有机功能化合物，具有如下通式：
Figure PCTCN2017118066-appb-000001
其中，A为具有光电功能的有机基团；
-SG的结构式选自
Figure PCTCN2017118066-appb-000002
及
Figure PCTCN2017118066-appb-000003
中的一个；
Figure PCTCN2017118066-appb-000004
选自具有5个～40个成环原子的芳基及具有5个～40个成环原子的杂芳基中的一种；
R 1和R 2分别独立选自H、D、F、CN、烷基、芳环基、芳香性杂环基、氨基、硅基、甲锗基、烷氧基、芳氧基及硅氧烷基中的一种，所述烷基选自未取代的烷基、氟代烷基、氘代烷基及氘代氟代烷基中的一种，所述芳环基选自未取代的芳环基及氘代芳环基中的一种，所述芳香性杂环基选自未取代的芳香性杂环基及氘代芳香性杂环基中的一种，所述氨基选自未取代的氨基及氘代氨基中的一种，所述硅基选自未取代的硅基及氘代硅基中的一种，所述甲锗基选自未取代的甲锗基及氘代甲锗基中的一种，所述烷氧基选自未取代的烷氧基、甲硅烷氧基、氟代烷氧基、氘代烷氧基、氘代氟代烷氧基及氘代甲硅烷氧基中的一种，所述芳氧基选自未取代的芳氧基及氘代芳氧基中的一种，所述硅氧烷基选自未取代的硅氧烷基及氘代硅氧烷基中的一种；
p为大于或等于1的整数。
一种混合物，包括上述有机功能化合物和有机功能材料，所述有机功能材料选自空穴注入材料、空穴传输材料、空穴阻挡材料、电子注入材料、电子传输材料、电子阻挡材料、有机基质材料、发光材料及有机染料中的至少一种。
一种组合物，包括上述有机功能化合物及上述混合物中的一种和有机溶剂。
一种有机功能薄膜，由上述有机功能化合物、上述有机混合物及上述组合物中的一种制备得到。
一种有机功能薄膜的制备方法，包括如下步骤：
采用浆料在基板上形成膜层，其中，所述浆料为上述组合物，或者，所述浆料由上述有机功能化合物及上述有机混合物中的一种溶解在有机溶剂中制备获得；
将所述膜层在100℃以上的温度下，在无水和无氧的条件下发生Bergman成环芳构化反应，得到有机功能薄膜。
一种有机电子器件，包括功能层，所述功能层的材料为上述有机功能薄膜，或者，所述功能层的材料为上述有机功能薄膜的制备方法制备得到的所述有机功能薄膜。
本发明的一个或多个实施例的细节在下面的附图和描述中提出。本发明的其它特征、目的和优点将从说明书、附图以及权利要求书变得明显。
说明书附图
图1为一实施方式的有机发光二极管的结构示意图；其中101是基板，102是阳极，103是空穴注入层(HIL)或空穴传输层(HTL)，104是发光层，105是电子注入层(EIL)或电子传输层(ETL)。
具体实施方式
为了便于理解本发明，下面将参照相关附图对本发明进行更全面的描述。
一实施方式的有机功能化合物，具有如下通式(I)：
Figure PCTCN2017118066-appb-000005
其中，A为具有光电功能的有机基团(以下简称光电功能基团)；
-SG的结构式为(II)所示：
Figure PCTCN2017118066-appb-000006
其中，通式(II)中，
Figure PCTCN2017118066-appb-000007
选自具有5个～40个成环原子的芳基及具有5个～40个成环原子的杂芳基中的一种；进一步地，
Figure PCTCN2017118066-appb-000008
选自具有5个～20个成环原子的芳基及具有5个～20个成环原子的杂芳基中的一种；进一步地，
Figure PCTCN2017118066-appb-000009
选自具有5个～16个成环原子的芳基及具有5个～16个成环原子的杂芳基中的一种；进一步地，
Figure PCTCN2017118066-appb-000010
选自具有5个～12个成环原子的芳基及具有5个～12个成环原子的杂芳基中的一种；进一步地，
Figure PCTCN2017118066-appb-000011
选自具有5个～9个成环原子的芳基及具有5个～9个成环原子的杂芳基中的一种。
进一步地，
Figure PCTCN2017118066-appb-000012
包括如下基团中的至少一个：
Figure PCTCN2017118066-appb-000013
其中，X选自CR 13及N中的一种；进一步地，结构式中的所有X均为CR 13；
Y选自CR 14R 15、SiR 16R 17、NR 18、C(＝O)、S(＝O) 2、O及S中的一种；
R 13、R 14、R 15、R 16、R 17及R 18分别独立选自单键、H、D、F、CN、NO 2、CF 3、烯基、炔基、胺基、酰基、酰胺基、氰基、异氰基、烷氧基、羟基、羰基、砜基、碳原子数为1个～60个的烷基、碳原子数为3个～60个的环烷基、碳原子数为6个～60个芳香基、碳原子数为3个～60个的杂环芳香基、碳原子数为7个～60个的稠环芳香基及碳原子数为4个～60个的稠杂环芳香基中的一个。
更进一步地，
Figure PCTCN2017118066-appb-000014
选自如下基团及环上氢被取代的如下基团中的一种：
Figure PCTCN2017118066-appb-000015
具体地，
Figure PCTCN2017118066-appb-000016
选自苯基及奈基中的一种。
R 1和R 2分别独立选自H、D、F、CN、烷基、芳环基、芳香性杂环基、氨基、硅基、甲锗基、烷氧基、芳氧基及硅氧烷基中的一种，烷基选自未取代的烷基、氟代烷基、氘代烷基及氘代氟代烷基中的一种，芳环基选自未取代的芳环基及氘代芳环基中的一种，芳香性杂环基选自未取代的芳香性杂环基及氘代芳香性杂环基中的一种，氨基选自未取代的氨基及氘代氨基中的一种，硅基选自未取代的硅基及氘代硅基中的一种，甲锗基选自未取代的甲锗基及氘代甲锗基中的一种，烷氧基选自未取代的烷氧基、甲硅烷氧基、氟代烷氧基、氘代烷氧基、氘代氟代烷氧基及氘代甲硅烷氧基中的一种，芳氧基选自未取代的芳氧基及氘代芳氧基中的一种，硅氧烷基选自未取代的硅氧烷基及氘代硅氧烷基中的一种；
p为大于或等于1的整数；进一步地，p为1～5的任一整数；更进一步地，p为1～3的任一整数；通式(I)中虚线表示与A相连的键。
具体地，通式(I)中，具有光电功能的有机基团选自具有空穴(也称电洞)注入功能的有机基团、具有空穴传输功能的有机基团、具有空穴阻挡功能的有机基团、具有电子注入功能的有机基团、具有电子传输功能的有机基团、具有电子阻挡功能的有机基团、具有有机主体功能的有机基团、具有单重态发光功能(荧光发光功能)的有机基团、具有三重态发光功能(磷光发光功能)的有机基团及具有热激发延迟荧光功能的有机基团中的一种。其中，上述光电功能的基团可以参照含有上述光电功能的相应的有机功能材料，即有机功能材料选自空穴(也称电洞)注入材料(HIM)、空穴传输材料(HTM)、空穴阻挡材料(HBM)、电子注入材料(EIM)、电子传输材料(ETM)、电子阻挡材料(EBM)、有机基质材料(Host)、单重态发光体(荧光发光体)、三重态发光体(磷光发光体)等。且上述有机功能材料可以为WO2010135519A1、US20090134784A1和WO 2011110277A1中公开的有机功能材料。
进一步地，本实施方式的有机功能化合物在190℃下，在隔绝水和氧气的环境下处理2小时，会发生Bergman成环芳构化反应，使分子溶解性下降，从而使薄膜固化。
具体地，Bergman成环芳构化反应的反应式如下：
Figure PCTCN2017118066-appb-000017
结构如a所示的小分子，在加热的条件下(180℃～200℃)，会发生关环反应，形成一个新的共轭6元环自由基。
在存在氢给体的情况下，如空气中的水，其它相邻材料分子、少量溶剂分子，会使结构b进一步发生如下反应：
Figure PCTCN2017118066-appb-000018
在隔绝水和氧气，且非常纯净(指只含有邻双炔键小分子和极少的杂质)的惰性环境中，苯环自由基之间会形成新的共价键，形成一种共轭的交联结构，具体反应式如下：
Figure PCTCN2017118066-appb-000019
此反应最早由Bergman,R.G.报道，具体可参考文献J.Am.Chem.Soc.1972,94,660-661。
进一步地，本实施方式的有机功能化合物能够形成溶剂难溶层，从而使薄膜固化，其原理可能为：
上述有机功能化合物能够发生Bergman成环芳构化反应生成具有如下通式(IV)或(IVa)所示的化合物：
且存在一种有机溶剂S，该有机溶剂S是通式(I)所示的有机功能化合物的良溶剂，是具有通式(IV)或(IVa)所示的化合物的不良溶剂。
其中，-SG 1为结构式为
Figure PCTCN2017118066-appb-000021
的基团；
且在通式(IVa)所示的化合物中，-SG 1的连接位点如下式中*号所示：
Figure PCTCN2017118066-appb-000022
其中，n1为大于或等于2的整数；进一步地，n1为2～50的任一整数；进一步地，n1为2～10的任一整数；进一步地，n1为2～5的任一整数。且通式(IV)或(IVa)中的A和
Figure PCTCN2017118066-appb-000023
以及通式(IV)中的p的定义分别类似于通式(I)中A、
Figure PCTCN2017118066-appb-000024
和p的定义。
进一步地，A具有如下结构式(III)：
Figure PCTCN2017118066-appb-000025
其中，Ar 0的结构式选自
Figure PCTCN2017118066-appb-000026
Figure PCTCN2017118066-appb-000027
及
Figure PCTCN2017118066-appb-000028
(IIId)中的一种；
在结构式(III)和结构式(IIIa)中，Ar 1和Ar 2分别独立选自未取代的芳烃基、未取代的芳杂环烃基、R 11取代的芳烃基及R 11取代的芳杂环烃基中的一种。
在结构式(III)、结构式(IIIa)、结构式(IIIb)、结构式(IIIc)和结构式(IIId)以及上述Ar 1和Ar 2中，R 11选自F、Cl、Br、I、D、CN、NO 2、CF 3、直链烷烃基、烷烃醚基、碳原子数为1个～10个的烷烃硫醚基、支链烷烃基及环烷烃基中的一种，或者，R 11为直链烷烃基中的一个或多个非相邻的亚甲基被R 12C＝CR 12、C＝C、Si(R 12) 2、Ge(R 12) 2、Sn(R 12) 2、C＝O、C＝S、C＝Se、C＝N(R 12)、O、S、酯基及CONR 12中的一个替换后的基团，或者，R 11为烷烃醚基中的一个或多个非相邻的亚甲基被R 12C＝CR 12、C＝C、Si(R 12) 2、Ge(R 12) 2、Sn(R 12) 2、C＝O、C＝S、C＝Se、C＝N(R 12)、O、S、酯基及CONR 12中的一个替换后的基团，或者，R 11为碳原子数为1个～10个的烷烃硫醚基中的一个或多个非相邻的亚甲基被R 12C＝CR 12、C＝C、Si(R 12) 2、Ge(R 12) 2、Sn(R 12) 2、C＝O、C＝S、C＝Se、C＝N(R 12)、O、S、酯基及CONR 12中的一个替换后的基团，或者，R 11为支链烷烃基中的一个或多个非相邻的亚甲基被R 12C＝CR 12、C＝C、Si(R 12) 2、Ge(R 12) 2、Sn(R 12) 2、C＝O、C＝S、C＝Se、C＝N(R 12)、O、S、酯基及CONR 12中的一个替换后的基团，或者，R 11为环烷烃基中的一个或多个非相邻的亚甲基被R 12C＝CR 12、C＝C、Si(R 12) 2、Ge(R 12) 2、Sn(R 12) 2、C＝O、C＝S、C＝Se、C＝N(R 12)、O、S、酯基及CONR 12中的一个替换后的基团；
直链烷烃基选自未取代的直链烷烃基及被至少一个活性基团R 12取代的直链烷烃基，或者，直链烷烃基为至少一个H原子被D、F、Cl、Br、I、CN、包含活性基团R 12的芳香胺基、包含一个芳香基团的芳香胺基、包含杂芳香环的芳香胺基及咔唑中的一个替换的直链烷烃基，烷烃醚基选自未取代的烷烃醚基及被至少一个活性基团R 12取代的烷烃醚基中的一个，或者烷烃醚基为至少一个H原子被D、F、Cl、Br、I、CN、包含活性基团R 12的芳香胺基、包含一个芳香基团的芳香胺基、包含杂芳香环的芳香胺基及咔唑中的一个替换的烷烃醚基，所述碳原子数为1个～10个的烷烃硫醚基选自未取代的碳原子数为1个～10个的烷烃硫醚基及被至少一个活性基团R 12取代的碳原子数为1个～10个的烷烃硫醚基中的一个，或者，所述烷烃硫醚基为至少一个H原子被D、F、Cl、Br、I、CN、包含活性基团R 12的芳香胺基、包含一个芳香基团的芳香胺基、包含杂芳香环的芳香胺基及咔唑中的一个替换的烷烃硫醚基，支链烷烃基选自未取代的碳原子数为1个～10个的支链烷烃基及被至少一个活性基团R 12取代的支链烷烃基中的一个，或者，支链烷烃基为至少一个H原子被D、F、Cl、Br、I、CN、包含活性基团R 12的芳香胺基、包含一个芳香基团的芳香胺基、包含杂芳香环的芳香胺基及咔唑中的一个替换的支链烷烃基，环烷烃基选自未取代的环烷烃基及被至少一个活性基团R 12取代的环烷烃基中的一个，或者，环烷烃基为至少一个H原子被D、F、Cl、Br、I、CN、包含活性基团R 12的芳香胺基、包含一个芳香基团的芳香胺基、包含杂芳香环的芳香胺基及咔唑中的一个替换的环烷烃基；
R 12分别独立选自H、D、碳原子数为1个～10个的脂肪族烷烃基、芳香碳氢化合物、成环原子数为5个～10个的芳香环基及成环原子数为5个～10个的杂芳香基中的一种；
-Z-为单键，或者，Z为二桥联基。
当Z为二桥联基时，Z选自表1中的结构式中的一个：
表1
Figure PCTCN2017118066-appb-000029
在表1中，符号R 4’、R 5’、R 6’与R 7’分别独立选自H、D、F、CN、烷基、芳环基、芳香性杂环基、氨基、硅基、甲锗基、烷氧基、芳氧基及硅氧烷基中的一种，烷基选自未取代的烷基、氟代烷基、氘代烷基及氘代氟代烷基中的一种，芳环基选自未取代的芳环基及氘代芳环基中的一种，芳香性杂环基选自未取代的芳香性杂环基及氘代芳香性杂环基中的一种，氨基选自未取代的氨基及氘代氨基中的一种，硅基选自未取代的硅基及氘代硅基中的一种，甲锗基选自未取代的甲锗基及氘代甲锗基中的一种，烷氧基选自未取代的烷氧基、甲硅烷氧基、氟代烷氧基、氘代烷氧基、氘代氟代烷氧基及氘代甲硅烷氧基中的一种，芳氧基选自未取代的芳氧基及氘代芳氧基中的一种，硅氧烷基选自未取代的硅氧烷基及氘代硅氧烷基中的一种；虚线键表示与通式(III)中两个苯环键合的键。
在结构式(III)、结构式(IIIa)、结构式(IIIb)、结构式(IIIc)和结构式(IIId)中，x为0～4的任一整数，x1为0～3的任一整数，y为0～5的任一整数，z为0～5的任一整数；
-L-为单键，或者，L选自碳原子数为5个～40个的R 1取代的共轭芳香基及碳原子数为5个～40个的未取代的共轭芳香基中的一种。
进一步地，L选自具有如下结构式B1及B2中的一种基团：
Figure PCTCN2017118066-appb-000030
其中，在结构式B1和B2中，虚线表示与相邻基团的连接的键；
在结构式(III)和(IIIa)中的虚线表示L与圆圈内基团的连接的键，L与圆圈内的连接位置可以在圆圈内的两个苯环上，也可以为Ar 2所包含的芳香族环或杂芳族环上的任意一个可能的位置。
进一步地，L、Ar 1和Ar 2分别独立选自具有5个～40个成环原子的芳基及具有5个～40个成环原子的杂芳基中的一种；进一步地，L、Ar 1和Ar 2分别独立选自具有5个～30个成环原子的芳基及具有5个～30个成环原子的杂芳基中的一种；进一步地，L、Ar 1和Ar 2分别独立选自具有5个～20个成环原子的芳基及具有5个～20个成环原子的杂芳基中的一种；进一步地，L、Ar 1和Ar 2分别独立选自具有5个～15个成环原子的芳基及具有5个～15个成环原子的杂芳基中的一种。
进一步地，L、Ar 1和Ar 2分别独立选自具有6个～15个成环碳原子的芳基及具有2个～15个成环碳原子和杂原子的杂芳基中的一种；进一步地，L、Ar 1和Ar 2分别独立选自具有6个～10个成环碳原子的芳基及具有2个～10个成环碳原子和杂原子的杂芳基中的一种。当L、Ar 1和Ar 2均为具有2个～15个成环碳原子和杂原子的杂芳基时，L、Ar 1和Ar 2中的碳原子和杂原子的数量的总和至少为4个。且杂原子选自Si、N、P、O、S及Ge中的至少一种；进一步地，杂原子选自Si、N、P、O及S中的至少一种；杂原子选自N、O及S中的至少一种。
需要说明的是，在本文中，芳香基指至少包含一个芳环的烃基。包括单环基团和多环基团。杂环芳香基指包含至少一个杂原子的芳香烃基(含有杂原子)，包括单环基团和多环基团。杂多环的基团可以为具有两个以上的环，其中两个碳原子被两个相邻的环共用，即稠环。且多环基团中至少一个环是芳族环或杂芳族环。在本文中，芳香基和杂环芳香基均不限于包括芳香环或杂芳环的体系，还包含非芳香族的环系。其中的多个芳香基或杂环芳香基也可以被短的非芳族单元间断(<10％的非H原子，进一步为小于5％的非H原子，比如C、N或O原子)。因此，比如9,9'-螺二芴，9,9-二芳基芴，三芳胺，二芳基醚等体系，同样认为是芳香基。
具体地，芳族基团的例子有：苯、萘、蒽、菲、二萘嵌苯、并四苯、芘、苯并芘、三亚苯、苊、芴、螺芴及其衍生物。
具体地，杂芳基团的例子有：呋喃、苯并呋喃、二苯并呋喃、噻吩、苯并噻吩、二苯并噻吩、吡咯、吡唑、三唑、咪唑、噁唑、噁二唑、噻唑、四唑、吲哚、咔唑、吡咯并咪唑、吡咯并吡咯、噻吩并吡咯、噻吩并噻吩、呋喃并吡咯、呋喃并呋喃、噻吩并呋喃、苯并异噁唑、苯并异噻唑、苯并咪唑、吡啶、吡嗪、哒嗪、嘧啶、三嗪、喹啉、异喹啉、邻二氮萘、喹喔啉、菲啶、伯啶、喹唑啉、喹唑啉酮、及其衍生物。
或者，Ar 1和Ar 2均为具有6个～40个成环原子的芳基；进一步地，Ar 1和Ar 2均为具有6个～30个成环原子的的芳基；更进一步地，Ar 1和Ar 2均为具有6个～25个成环原子的芳基。
具体地，在通式(III)和(IIIa)中，L、Ar 1、Ar 2分别独立选自如下基团中的一个：
Figure PCTCN2017118066-appb-000031
其中，X选自CR 13及N中的一种；进一步地，结构式中的所有X均为CR 13；
Y选自CR 14R 15、SiR 16R 17、NR 18、C(＝O)、S(＝O) 2、O及S中的一种；
R 13、R 14、R 15、R 16、R 17及R 18分别独立选自单键、H、D、F、CN、NO 2、CF 3、烯基、炔基、胺基、酰基、酰胺基、氰基、异氰基、烷氧基、羟基、羰基、砜基、碳原子数为1个～60个的烷基、碳原子数为3个～60个的环烷基、碳原子数为6个～60个芳香基、碳原子数为3个～60个的杂环芳香基、碳原子数为7个～60个的稠环芳香基及碳原子数为4个～60个的稠杂环芳香基中的一个。
进一步地，Ar 1和Ar 2分别独立选自如下通式C1～C36中的一个：
Figure PCTCN2017118066-appb-000032
Figure PCTCN2017118066-appb-000033
其中，在通式C1～C36中，R 3选自H、F、Cl、Br、I、D、CN、NO 2、CF 3、B(OR 2) 2、Si(R 2) 3、直链烷烃基、烷烃醚基、具有1个～10个碳原子的烷烃硫醚基、具有1个～10个碳原子的支链烷烃基、环烷烃基、具有3个～10个碳原子的烷烃醚基、具有3个～10个碳原子的烷烃硫醚基团氢及具有6个～10个碳原子的芳基中的一个；u为0～2的任一整数，v为0～3的任一整数，w为0～4的任一整数，t为0～5的任一整数。
当本实施方式的通式(I)的有机功能化合物或通式(IV)的化合物具有空穴传输功能，其可用于有机电子器件中，特别是有机发光二极管(OLED)中的空穴传输层。
当本实施方式的通式(I)的有机功能化合物或通式(IV)的化合物具有较高的LUMO，即具有电子阻挡功能，其可用于有机电子器件，特别是有机发光二极管中的电子阻挡层。需要说明的是，此处较高的LUMO是指相比相邻的功能层(如有机发光二极管中的发光层)，电子阻挡层具有更高的LUMO。
当本实施方式的通式(I)的有机功能化合物或通式(IV)的化合物具有较高的三线态能级T1，即具有三线态激子阻挡功能，可用于有机电子器件，特别是有机发光二极管中的激子阻挡层。需要说明的是，此处较高的T1是指相比相邻的功能层(如磷光OLED中的发光层)，激子阻挡层具有更高的T1。
当本实施方式的通式(I)的有机功能化合物或通式(IV)的化合物具有较高的单线态能级S1，即具有单线态激子阻挡功能，可用于有机电子器件，特别是机发光二极管中的激子阻挡层。需要说明的是，此处较高的S1是指相比相邻的功能层(如荧光OLED中的发光层)，激子阻挡层具有更高的S1。
进一步地，当A为具有空穴传输功能的基团时，A包括如下基团中的至少一种：酞菁基、卟啉基、胺基、芳香胺基、联苯类三芳胺基、噻吩基、并噻吩基(如二噻吩并噻吩基和并噻吩基等)、吡咯基、苯胺基、咔唑基、氮茚并氮芴基、及它们的衍生物。
更进一步地，具有空穴传输功能的芳香胺基选自以下结构式中的一种，但不限于为以下结构式：
Figure PCTCN2017118066-appb-000034
其中，Ar 3、Ar 4、Ar 5、Ar 6、Ar 6、Ar 7、Ar 8、Ar 9、Ar 10及Ar 11分别独立选自环芳香烃基、芳香杂环基及具有2个～10个环的基团中的一种；环芳香烃基选自苯基、联苯基、三苯基、苯并基、萘基、蒽基、非那烯基、菲基、芴基、芘基、屈基、苝基及薁基中的一种；芳香杂环基选自二苯并噻吩基、二苯并呋喃基、呋喃基、噻吩基、苯并呋喃基、苯并噻吩基、咔唑基、吡唑基、咪唑基、三氮唑基、异恶唑基、噻唑基、恶二唑基、恶三唑基、二恶唑基、噻二唑基、吡啶基、哒嗪基、嘧啶基、吡嗪基、三嗪基、恶嗪基、恶噻嗪基、恶二嗪基、吲哚基、苯并咪唑基、吲唑基、吲哚嗪基、苯并恶唑基、苯异恶唑基、苯并噻唑基、喹啉基、异喹啉基、邻二氮(杂)萘基、喹唑啉基、喹喔啉基、萘基、酞基、蝶啶基、氧杂蒽基、吖啶基、吩嗪基、吩噻嗪基、吩恶嗪基、二苯并硒吩基、苯并硒吩基、苯并呋喃吡啶基、吲哚咔唑基、吡啶吲哚基、吡咯二吡啶基、呋喃二吡啶基、苯并噻吩吡啶基、噻吩吡啶基、苯并硒吩吡啶基及硒吩二吡啶基中的一种；具有2个～10个环的基团中的每个环可以是环芳香烃基或芳香杂环基，且环与环可以直接连接在一起，也可以通过至少一个以下的物质连接在一起：氧原子、氮原子、硫原子、硅原子、磷原子、硼原子、链状脂肪基和脂肪环基。其中，Ar 3、Ar 4、Ar 5、Ar 6、Ar 6、Ar 7、Ar 8、Ar 9、Ar 10及Ar 11可以进一步被取代，且取代基选自氢、烷基、烷氧基、氨基、烯、炔、芳烷基、杂烷基、芳基及杂芳基中的一种。
进一步地，Ar 3、Ar 4、Ar 5、Ar 6、Ar 6、Ar 7、Ar 8、Ar 9、Ar 10及Ar 11分别独立选自如下基团中的一个:
Figure PCTCN2017118066-appb-000035
a为1～20的任一整数；X 1～X 8分别独立选自CH及N中的一种；Ar 30定义同Ar 3。
具体地，具有空穴传输功能的芳香胺基对应的化合物还可以为US3567450、US4720432、US5061569、US3615404及US5061569中公开的物质。
具体地，通式(I)的有机功能化合物或通式(IV)的化合物中的具有空穴传输功能的基团A选自如下基团中的一种，但不限于为如下基团：
Figure PCTCN2017118066-appb-000036
当通式(I)中的A为具有有机主体功能(荧光主体和磷光主体)的基团时，A包含结构式(1)
Figure PCTCN2017118066-appb-000037
结构式(2)
Figure PCTCN2017118066-appb-000038
结构式(3)
Figure PCTCN2017118066-appb-000039
结构式(4)
Figure PCTCN2017118066-appb-000040
结构式(5)
Figure PCTCN2017118066-appb-000041
及结构式(6)
Figure PCTCN2017118066-appb-000042
中的一种；
在结构式(1)和(2)中，Ar 11和Ar 12分别独立选自碳原子数为6个～60个的芳香基、碳原子数为3个～60个的芳杂基、碳原子数为6个～60个的稠环芳香基及碳原子数为3个～60个的稠环芳杂基中的一种；
在结构式(3)～(6)中，
Figure PCTCN2017118066-appb-000043
及
Figure PCTCN2017118066-appb-000044
分别独立选自成环原子数为5个～30个的芳香基及成环原子数为5个～30个的芳杂基中的一种；进一步地，
Figure PCTCN2017118066-appb-000045
Figure PCTCN2017118066-appb-000046
及
Figure PCTCN2017118066-appb-000047
分别独立选自成环原子数为5个～25个的芳香基及成环原子数为5个～25个的芳杂基中的一种；进一步地，
Figure PCTCN2017118066-appb-000048
及
Figure PCTCN2017118066-appb-000049
分别独立选自成环原子数为5个～20个的芳香基及成环原子数为5个～20个的芳杂基中的一种；进一步地，
Figure PCTCN2017118066-appb-000050
及
Figure PCTCN2017118066-appb-000051
分别独立选自成环原子数为5个～15个的芳香基及成环原子数为5个～15个的芳杂基中的一种；
在结构式(1)和(2)中，Ar 9和Ar 10分别独立选自H、D、F、CN、NO 2、CF 3、烯基、炔基、胺基、酰基、酰胺基、氰基、异氰基、烷氧基、羟基、羰基、砜基、碳原子数为1个～60个的烷基、碳原子数为3个～60个的环烷基、碳原子数为6个～60个的芳香基、碳原子数为3个～60个的杂环芳香基、碳原子数为7个～60个的稠环芳香基及碳原子数为4个～60个的稠杂环芳香基中的一种；
在结构式(1)和(2)中，L 1选自成环原子数为5个～60个的芳香基及成环原子数为5个～60个的芳杂基中的一种；进一步地，L 1选自成环原子数为5个～50个的芳香基及成环原子数为5个～50个的芳杂基中的一种；进一步地，L 1选自成环原子数为5个～40个的芳香基及成环原子数为5个～40个的芳杂基中的一种；更进一步地，L 1选自成环原子数为6个～30个的芳香基及成环原子数为6个～30个的芳杂基中的一种。
在结构式(3)和(4)中，-L 2-为单键，或者，L 2选自成环原子数为5个～30个的芳香基及成环原子数为5个～30个的芳杂基中的一种，L 2的连接位置可以是环上任意一碳原子上；进一步地，-L 2-为单键，或者，L 2选自成环原子数为5个～25个的芳香基及成环原子数为5个～25个的芳杂基中的一种；进一步地，-L 2-为单键，或者，L 2选自成环原子数为5个～20个的芳香基及成环原子数为5个～20个的芳杂基中的一种；进一步地，-L 2-为单键，或者，L 2选自成环原子数为5个～15个的芳香基及成环原子数为5个～15个的芳杂基中的一种。
在结构式(5)和结构式(6)中，-X 1-为单键，或者，X 1选自N(R)、C(R) 2、Si(R) 2、O、C＝N(R)、C＝C(R) 2、P(R)、P(＝O)R、S、S＝O及SO 2中的一种；进一步地，-X 1-为单键，或者，X 1选自N(R)、C(R) 2、O及S中的一种。
在结构式(3)和(4)中，-X 2-、-X 3-、-X 4-、-X 5-、-X 6-、-X 7-、-X 8-及-X 9-分别独立选自单键、-N(R)-、-C(R) 2-、-Si(R) 2-、-O-、-(C＝N(R))-、-(C＝C(R) 2)、-P(R)-、-(P(＝O)R)-、-S-、-(S＝O)-及-(SO 2)-，且-X 2-及-X 3-中最多一个为单键，-X 4-和-X 5-中最多一个单键，-X 6-和-X 7-中最多一个单键，-X 8-和-X 9-中最多一个单键；进一步地，-X 2-、-X 3-、-X 4-、-X 5-、-X 6-、-X 7-、-X 8-及-X 9-分别独立选自单键、-N(R)-、-C(R) 2-、-O-及-S-中的一种。
其中，R选自H、D、F、CN、烯基、炔基、腈基、胺基、硝基、酰基、烷氧基、羰基、 砜基、碳原子数为1个～30个的烷基、碳原子数为3个～30个的环烷基、成环原子数为5个～60个的芳烃基及成环原子数为5个～60个的芳香杂环基中的一种。
在结构式(3)～(5)中，R 1和R 2的定义与通式(II)中定义相同。而且在结构式(3)～(5)中，环上被R 1、R 2取代的碳原子至少为一个。
在结构式(1)中，m为0～4的任一整数。
在结构式(2)中，o为0～4的任一整数，q为0～6的的任一整数。
在结构式(5)和(6)中，s为1～4的任一整数。进一步地，s为1～3的任一整数；进一步地，s为1～2的任一整数。
进一步地，结构式(1)～(2)中的Ar 11、Ar 12、Ar 9及Ar 10和结构式(3)～(6)中的
Figure PCTCN2017118066-appb-000052
Figure PCTCN2017118066-appb-000053
及
Figure PCTCN2017118066-appb-000054
分别独立选自如下基团及环上氢被取代的如下基团中的一种：
Figure PCTCN2017118066-appb-000055
具体地，按照结构式(1)，A选自如下结构式中的一种：
Figure PCTCN2017118066-appb-000056
在结构式(1-1)和结构式(1-2)中，L 1、R 1、R 2及R的定义与结构式(1)～(6)中相同；a为1～3的任一整数；b 11～b 13分别独立选自0～6的任一整数。
进一步地，按照结构式(1)，A选自如下结构式中的一种：
Figure PCTCN2017118066-appb-000057
在结构式(1-1a)和结构式(1-2a)中，L 1、R 1、R 2、a、R、b 11及b 12的定义与结构式(1-1)和结构式(1-2)中的相同。
具体地，按照结构式(1)和结构式(2)，通式(I)及通式(IV)中的具有有机主体功能的基团A选自如下基团中的一种，但不限于为如下基团：
Figure PCTCN2017118066-appb-000058
Figure PCTCN2017118066-appb-000059
Figure PCTCN2017118066-appb-000060
进一步地，A为具有单重态主体功能(荧光主体功能)的基团，此时，A的核心基团选自含有环芳香烃的基团、含有芳香杂环的基团及具有2个～10个环的基团中的一种；具有环芳香烃的基团选自联苯、三苯基、苯并、萘、蒽、萉、菲、芴、芘、屈、苝及薁中的一种；具有芳香杂环的基团选自二苯并噻吩、二苯并呋喃、二苯并硒吩、呋喃、噻吩、苯并呋喃、苯并噻吩、苯并硒吩、咔唑、吲哚咔唑、吡啶吲哚、吡咯二吡啶、吡唑、咪唑、三氮唑、异恶唑、噻唑、恶二唑、恶三唑、二恶唑、噻二唑、吡啶、哒嗪、嘧啶、吡嗪、三嗪、恶嗪、恶噻嗪、恶二嗪、吲哚、苯并咪唑、吲唑、吲哚嗪、苯并恶唑、苯异恶唑、苯并噻唑、喹啉、异喹啉、噌啉、喹唑啉、喹喔啉、萘、酞、蝶啶、氧杂蒽、吖啶、吩嗪、吩噻嗪、吩恶嗪、苯并呋喃吡啶、呋喃二吡啶、苯并噻吩吡啶、噻吩二吡啶、苯并硒吩吡啶及硒吩二吡啶中的一种；具有2个～10个环的基团中的每个环可以是环芳香烃基或芳香杂环基，且环与环可以直接连接在一起，也可以通过至少一个以下的物质连接在一起：氧原子、氮原子、硫原子、硅原子、磷原子、硼原子、链状脂肪基和脂肪环基。
进一步地，A为具有单重态主体功能的基团时，A的核心基团选自如下基团中的一个：
Figure PCTCN2017118066-appb-000061
其中，R 11选自氢、烷基、烷氧基、氨基、烯基、炔基、芳烷基、杂烷基、芳基及杂芳基中的一种；Ar 40选自碳原子数为6个～60个的芳香基、碳原子数为3个～60个的芳杂基、碳原子数为6个～60个的稠环芳香基及碳原子数为3个～60个的稠环芳杂基中的一种；b为0～20的任一整数；X 11～X 18分别独立选自CH及N中的一种；X 19和X 10分别独立选自CR 1R 2及NR 1中的一种，R 1和R 2的定义与结构式(1)～(6)中相同。
进一步地，通式(I)中的A为具有磷光主体功能的基团，此时，具有磷光主体功能的A选自上述结构式(3)～(6)中的一种。
进一步地，当A为结构式(3)时，具有磷光主体功能的A的结构式选自基团
Figure PCTCN2017118066-appb-000062
及
Figure PCTCN2017118066-appb-000063
中的一种：
其中，Ar 3、Ar 6、X 2、X 3、X 4、X 5、R 1、R 2的含义与结构式(3)中的含义相同。
更进一步地，按照结构式(3)时，具有磷光主体功能的A的结构式如下：
Figure PCTCN2017118066-appb-000064
其中，R 1、R 2、L 1及L 2的含义与结构式(3)～(6)中的含义相同；L 3选自成环原子数为5个～60个的芳香基及成环原子数为5个～60个的芳杂基中的一种；进一步地，L 3选自成环原子数为5个～50个的芳香基及成环原子数为5个～50个的芳杂基中的一种；进一步地，L 3选自成环原子数为5个～40个的芳香基及成环原子数为5个～40个的芳杂基中的一种；更进一步地，L 3选自成环原子数为6个～30个的芳香基及成环原子数为6个～30个的芳杂基中的一种。
具体地，按照结构式(3)时，通式(I)及通式(IV)中的具有磷光主体功能的基团A选自如下基团中的一种，但不限于为如下基团：
Figure PCTCN2017118066-appb-000065
Figure PCTCN2017118066-appb-000066
Figure PCTCN2017118066-appb-000067
Figure PCTCN2017118066-appb-000068
Figure PCTCN2017118066-appb-000069
Figure PCTCN2017118066-appb-000070
Figure PCTCN2017118066-appb-000071
Figure PCTCN2017118066-appb-000072
具体地，按照基团A的结构式(4)，基团A的结构式选自
Figure PCTCN2017118066-appb-000073
Figure PCTCN2017118066-appb-000074
及
Figure PCTCN2017118066-appb-000075
中的一 种；其中，Ar 4、Ar 5、Ar 7、Ar 8、X 2、X 3、X 4、X 5、X 6、X 7、X 8、X 9、R 1、R 2的含义与结构式(1)～(6)相同。
进一步地，按照基团A的结构式(4)，基团A的结构式如下：
Figure PCTCN2017118066-appb-000076
其中，Ar 4、Ar 7、X 4、X 5、X 8、X 9、R 1、R 2的含义与结构式(1)～(6)相同。
具体地，按照结构式(4)，通式(I)及通式(IV)中的具有磷光主体功能的基团A选自如下基团中的一种，但不限于为如下基团：
Figure PCTCN2017118066-appb-000077
具体地，按照基团A的结构式(5)，基团A的结构式选自
Figure PCTCN2017118066-appb-000078
Figure PCTCN2017118066-appb-000079
及
Figure PCTCN2017118066-appb-000080
中的一种；其中，Ar 3、Ar 5、X 1、X 2、X 3、R 1、R 2、L 1、s的含义与结构式(1)～(6)相同。
进一步地，按照基团A的结构式(5)，基团A的结构式如下：
Figure PCTCN2017118066-appb-000081
其中，X 2、X 3、R 1、R 2、L 1、s的含义与结构式(1)～(6)相同。
具体地，按照结构式(5)，通式(I)及通式(IV)中的具有磷光主体功能的基团A选自如下基团中的一种，但不限于为如下基团：
Figure PCTCN2017118066-appb-000082
Figure PCTCN2017118066-appb-000083
Figure PCTCN2017118066-appb-000084
Figure PCTCN2017118066-appb-000085
Figure PCTCN2017118066-appb-000086
具体地，按照基团A的结构式(6)，基团A的结构式选自
Figure PCTCN2017118066-appb-000087
Figure PCTCN2017118066-appb-000088
及
Figure PCTCN2017118066-appb-000089
中的一种；其中，Ar 3、Ar 4、R 1、R 2、L 1、s的含义与结构式(1)～(6)中的相同。
进一步地，按照基团A的结构式(6)，基团A的结构式如下：
Figure PCTCN2017118066-appb-000090
其中，R 1、R 2、L 1、s的含义与结构式(1)～(6)中的相同。
进一步地，通式(I)中的A为具有三重态主体功能基团，且A的核心基团选自包含有环芳香烃基的基团、包含有芳香杂环基的基团及包具有2个～10个环结构的基团。其中，包含有环芳香烃基的基团选自联苯基、三苯基、苯并基及芴基中的一种；包含有芳香杂环基的基团选自二苯并噻吩基、二苯并呋喃基、二苯并硒吩基、呋喃基、噻吩基、苯并呋喃基、苯并噻吩基、苯并硒吩基、咔唑基、吲哚咔唑基、吡啶吲哚基、吡咯二吡啶基、吡唑基、咪唑基、三唑基、恶唑基、噻唑基、恶二唑基、恶三唑基、二恶唑基、噻二唑基、吡啶基、哒嗪基、嘧啶基、吡嗪基、三嗪基、恶嗪基、恶噻嗪基、恶二嗪基、吲哚基、苯并咪唑基、吲唑基、恶唑基、二苯并恶唑基、苯异恶唑基、苯并噻唑基、喹啉基、异喹啉基、邻二氮杂萘基、喹唑啉基、喹喔啉基、萘基、酞基、蝶啶基、氧杂蒽基、吖啶基、吩嗪基、吩噻嗪基、吩恶嗪基、苯并呋喃吡啶基、呋喃并吡啶基、苯并噻吩吡啶基、噻吩吡啶基、苯并硒吩吡啶基及硒吩苯并二吡啶基中的一种；具有2个～10个环结构的基团中的环可以是相同的，也可以是不同类型的环芳香烃基团或芳香杂环基团，且环与环之间可以直接连接，也可以通过至少一个连接物质连接在一起，连结物质选自氧原子、氮原子、硫原子、硅原子、磷原子、硼原子、链状脂肪基及脂肪环基团中的一种。
进一步地，通式(I)中的A为具有三重态主体功能的核心基团选自如下基团中的一种：
Figure PCTCN2017118066-appb-000091
其中，R 11～R 17分别独立的选自氢、烷基、烷氧基、氨基、烯基、炔基、芳烷基、杂烷基、芳基及杂芳基中的一种。Ar 11选自碳原子数为6个～60个的芳香基、碳原子数为3个～60个的芳杂基、碳原子数为6个～60个的稠环芳香基及碳原子数为3个～60个的稠环芳杂基中的一种；c为0～20的任一整数；X 11～X 18分别独立选自CH及N中的一种；X 19选自CR 1R 2及NR 1中的一种。R 1和R 2分别独立选自H、D、F、CN、烯基、炔基、腈基、胺基、硝基、酰基、烷氧基、羰基、砜基、碳原子数为1个～30个的烷基、碳原子数为3个～30个的环烷基、成环原子数为5个～60个的芳烃基及成环原子数为5个～60个的芳香杂环基中的一种。
或者，通式(II)中的Ar可以为无，此时，-SG为具有如下结构式的基团：
Figure PCTCN2017118066-appb-000092
进一步地，按照通式(II)，增溶性结构单元-SG选自如下结构通式中的一种：
Figure PCTCN2017118066-appb-000093
Figure PCTCN2017118066-appb-000094
在其中一个实施例中，在增溶性结构单元SG的结构通式SG-01～SG-27中，R 3、R 4、R 5、R 6及R 7分别独立选自分别独立选自H、D、F、CN、烷基链、芳环基、芳香性杂环基、氨基、硅基、甲锗基、烷氧基、芳氧基及硅氧烷基中的一种，烷基链选自未取代的烷基链、氟代烷基链、氘代烷基链及氘代部分氟代的烷基链中的一种，芳环基选自未取代的芳环基及氘代芳环基中的一种，芳香性杂环基选自未取代的芳香性杂环基及氘代芳香性杂环基中的一种，氨基选自未取代的氨基及氘代氨基中的一种，硅基选自未取代的硅基及氘代硅基中的一种，甲锗基选自未取代的甲锗基及氘代甲锗基中的一种，烷氧基选自未取代的烷氧基、甲硅烷氧基、氟代烷氧基、氘代烷氧基、氘代氟代烷氧基及氘代甲硅烷氧基中的一种，芳氧基选自未取代的芳氧基及氘代芳氧基中的一种，硅氧烷基选自未取代的硅氧烷基及氘代硅氧烷基中的一种。进一步地，R 3、R 4、R 5、R 6及R 7分别独立选自是氢、具有1个～20个碳原子的直链烷基、具有1个～20个碳原子的烷氧基、具有3个～20个碳原子的支链的烷基及具有3个～20个碳原子的烷氧基中的一种。
在增溶性结构单元SG的结构通式中，n为大于0的整数；-L 1-为单键，或者，L 1选自芳基及杂芳基中的一种；虚线键表示与功能结构单元Ar键合的键。
进一步地，L 1选自以下单键及结构式的一种：
Figure PCTCN2017118066-appb-000095
Figure PCTCN2017118066-appb-000096
或者，在另一个实施例中，上述结构式SG-01～SG-27中，R 1、R 2、R 3及R 4分别独立选自F、Cl、Br、I、N(Ar) 2、CN、NO 2、Si(R’) 3,、B(OR’) 2、C(＝O)Ar、C(＝O)R’、P(＝O)(Ar) 2、P(＝O)(R’) 2、S(＝O)Ar、S(＝O)R’、S(＝O) 2Ar、S(＝O) 2R’、-CR’＝CR’Ar、OSO 2R’、具有1～40个碳原子的直链烷基(进一步为具有1个～20个碳原子的直链烷基)、烷氧基(进一步为3个～20个碳原子的烷氧基)、硫代烷氧基(进一步为3个～20个碳原子的硫代烷氧基)、具有3个～40个碳原子的支链烷基(进一步为具有3个～20个碳原子的支链烷基)及具有3个～40个碳原子的环烷基(进一步为具有3个～20个碳原子的环烷基)中一种；R 1、R 2、R 3及R 4可被一个或多个基团R’取代，其中一个或多个非相邻的CH 2基团可被R’C＝CR’、C≡C、Si(R’) 2、Ge(R’) 2、Sn(R’) 2、C＝O、C＝S、C＝Se、C＝NR’、P(＝O)(R’)、SO、SO 2、NR’、O、S或CONR’代替，和其中一个或多个H原子可被F，Cl，Br，I，CN或NO 2代替。
需要说明的是，在本文中，单独的H原子或CH 2基团可被上述提到的基团或基团R取代的、具有1～40个C原子的烷基选自如下基团中的一种：甲基、乙基、正丙基、异丙基、环丙基、正丁基、异丁基、仲丁基、叔丁基、环丁基、甲基丁基、正戊基、仲戊基、环戊基、正己基、环己基、正庚基、环庚基、正辛基、环辛基、乙基己基、三氟甲基、五氟乙基、三氟乙基、乙烯基、丙烯基、丁烯基、戊烯基、环戊烯基、己烯基、环己烯基、庚烯基、环庚烯基、辛烯基、环辛烯基、乙炔基、丙炔基、丁炔基、戊炔基、己炔基及辛炔基中的一种。其中，具有1个～40个碳原子的烷氧基选自甲氧基、三氟甲氧基、乙氧基、正丙氧基、异丙氧基、正丁氧基、异丁氧基、仲丁氧基、叔丁氧基及甲基丁氧基中的一种。
具体地，本实施方式的有机功能化合物的玻璃化温度≥100℃；进一步地，玻璃化温度≥120℃；进一步地，玻璃化温度≥140℃；进一步地，玻璃化温度≥160℃；进一步地，玻璃化温度≥180℃。
进一步地，通式(IV)所示的Bergman成环反应后的化合物是HTM，具有较高的LUMO，一般是LUMO≥-2.7eV；进一步地，LUMO≥-2.6eV；更进一步地，LUMO≥-2.5eV；进一步地，LUMO≥-2.4eV。
进一步地，通式(IV)所示的Bergman成环反应后的化合物，其∣(HOMO-1)-HOMO≥0.3eV；进一步地，(HOMO-1)-HOMO≥0.35eV；进一步地，(HOMO-1)-HOMO≥0.4eV；进一步地，(HOMO-1)-HOMO≥0.45eV；进一步地，(HOMO-1)-HOMO≥0.5eV。其中，HOMO是最高被占据轨道的能级，(HOMO-1)是第二高的被占据轨道的能级。
或者，通式(IV)所示的Bergman成环反应后的化合物是HTM，其HOMO≤-5.0eV；进一步地，HOMO≤-5.1eV；进一步地，HOMO≤-5.2eV。
或者，通式(IV)所示的Bergman成环反应后的化合物是磷光主体材料，其三线态能级E T≥2.5eV，进一步地，三线态能级E T≥2.6eV；进一步地，三线态能级E T≥2.7eV。
有机材料的能级结构中，三线态能级E T、HOMO、LUMO起着关键的作用。以下对这些能级的确定做一介绍。
HOMO和LUMO能级能够通过光电效应进行测量，例如，XPS(X射线光电子光谱法)、UPS(紫外光电子能谱)等，还能够通过循环伏安法(以下简称CV)。最近，量子化学方法，例如密度泛函理论(以下简称DFT)，也成为行之有效的计算分子轨道能级的方法。
有机材料的三线态能级E T能够通过低温时间分辨发光光谱来测量，或者，还能够通过量子模拟计算(如通过Time-dependent DFT)得到，如通过商业软件Gaussian 09W(Gaussian Inc.)，具体的模拟方法可以参考专利文件WO2011141110中的方法，或者也可以本实施方式后面介绍的方法获得。
应该注意，HOMO、LUMO和E T的绝对值取决于所用的测量方法或计算方法，甚至对于相同的方法，不同的评价方法也会导致结果的不同，例如在CV曲线上起始点和峰点会给出不同的HOMO/LUMO值。因此，合理有意义的比较应该用相同的测量方法和相同的评价方法。本实施方式中的HOMO、LUMO、E T的值是基于Time-dependent DFT的模拟获得的，需要说明的是，HOMO、LUMO、E T的获得也不限于采用该方法，它们也可以通过其它测量方法或计算方法获得，然而不同方法确定的能级值应进行相互标定。
在本文中，HOMO、LUMO不是一个绝对的值，它是一个相对与标准材料NPB(见如下化学式)的值。应作如下理解：按照本文的方法(见具体实施例)，NPB的HOMO为-5.22eV，LUMO为-2.34eV。因此，较为准确的，本文对HOMO、LUMO要求，当涉及不同方法时，要作相应的校准。
Figure PCTCN2017118066-appb-000097
具体地，按照通式(I)的有机功能化合物选自如下化合物中的一种，但是不限于为如下化合物：
Figure PCTCN2017118066-appb-000098
Figure PCTCN2017118066-appb-000099
Figure PCTCN2017118066-appb-000100
Figure PCTCN2017118066-appb-000101
Figure PCTCN2017118066-appb-000102
Figure PCTCN2017118066-appb-000103
Figure PCTCN2017118066-appb-000104
上述的通式(I)的有机功能化合物的合成方法，通过使用含有活性基团的原料进行反应。这些活性原料包含至少一种离去基团，例如，离去基团为溴，碘，硼酸或硼酸酯。形成C-C连接的适当的反应是本领域熟知的、并描述于文献中，特别适当和优选的偶联反应例如SUZUKI，STILLE和HECK偶联反应。
上述有机功能化合物至少有以下优点：
上述有机功能化合物包含一个有机功能结构单元和增溶性基团，具有较好的溶解性和成膜性。同时，该有机功能化合物可以根据需要，经过反应在分子内形成更大的共轭基团，使分子的溶解性变差，以使其具有能够根据需要发生受控的不可逆的溶解性降低的特性，从而避免界面混溶、界面侵蚀等问题。
一实施方式的混合物，包含上述通式(I)所示的有机功能化合物和有机功能材料。
有机功能材料选自空穴(也称电洞)注入材料(HIM)、空穴传输材料(HTM)、空穴阻挡材料(HBM)、电子注入材料(EIM)、电子传输材料(ETM)、电子阻挡材料(EBM)、有机基质材料(Host)、发光材料及有机染料中的至少一种。其中，发光材料选自单重态发光体(荧光发光体)、三重态发光体(磷光发光体)及有机热激发延迟荧光材料(TADF材料)中的至少一种。这些有机功能材料在上文已有所描述。有机功能材料可以为WO2010135519A1、US20090134784A1和WO2011110277A1中公开的有机功能材料。
在其中一个实施例中，有机功能材料为荧光发光体(单重态发光体)，此时，通式(I)所示的有机功能化合物作为主体或共主体，且在混合物中，有机功能材料的重量百分含量≤15wt％；进一步地，有机功能材料的重量百分含量≤12wt％；有机功能材料的重量百分含量≤9wt％；有机功能材料的重量百分含量≤8wt％；有机功能材料的重量百分含量≤7wt％。
在另一个实施例中，有机功能材料为TADF材料。
在另一个实施例中，有机功能材料为磷光发光体(或三重态发光体)此时，通式(I)所示的有机功能化合物作为主体或共主体，且在混合物中，有机功能材料的重量百分含量≤30wt％；进一步地，有机功能材料的重量百分含量≤25wt％；进一步地，有机功能材料的重量百分含量≤20wt％；进一步地，有机功能材料的重量百分含量≤18wt％。
在另一个实施例中，有机功能材料为HTM材料。
一实施方式的组合物，为有溶剂型的混合物，能够作为涂料或油墨，并且能够应用在有机电子器件中，作为功能层的材料。其中，有机电子器件选自有机发光二极管(OLED)、有机光伏电池(OPV)、有机发光电池(OLEEC)、有机场效应管(OFET)、有机发光场效应管、有机激光器、有机自旋电子器件、有机传感器及有机等离激元发射二极管(Organic Plasmon Emitting Diode)中的一种。该混合物可以为溶液，也可以为悬浮液。
该组合物包括有机功能化合物及混合物中的一种和有机溶剂。其中，有机功能化合物为上述通式(1)所示的有机功能化合物，混合物为上述混合物。
在本实施方式中，有机功能化合物的摩尔质量≥700g/mol，进一步地，有机功能化合物的摩尔质量≥800g/mol；有机功能化合物的摩尔质量≥900g/mol；进一步地，有机功能化合物的摩尔质量≥1000g/mol；进一步地，有机功能化合物的摩尔质量≥1100g/mol。
进一步地，在25℃时，有机功能化合物在甲苯中的溶解度≥10mg/ml；进一步地，有机功能化合物在甲苯中的溶解度≥15mg/ml；更进一步地，有机功能化合物在甲苯中的溶解度≥20mg/ml。
由于本实施方式的混合物用作印刷材料，因此，组合物的粘度、表面张力是重要的参数。 只有合适的参数的组合物才能适合于特定的基板和特定的印刷方法。
具体地，组合物在工作温度或在25℃下的表面张力约为19dyne/cm～50dyne/cm；进一步为22dyne/cm～35dyne/cm；更进一步为25dyne/cm～33dyne/cm。
具体地，组合物在工作温度或25℃下的粘度约为1cps～100cps范围；进一步为1cps～50cps；进一步为1.5cps～20cps；进一步为4.0cps～20cps范围。此时，该组合物能够用于喷墨印刷。
其中，组合物的粘度可以通过不同的方法调节，如通过选取合适的溶剂、有机功能化合物或混合物的浓度。通过对包含有机功能化合物或混合物的混合物的粘度，以便于按照通常的印刷方法进行印刷。
具体地，组合物中，有机功能化合物或混合物的重量百分含量为0.3％～30％；进一步地，有机功能化合物或混合物的重量百分含量为0.5％～20％；进一步地，有机功能化合物或混合物的重量百分含量为0.5％～1％；进一步地，有机功能化合物或混合物的重量百分含量为0.5％～10％；进一步地，有机功能化合物或混合物的重量百分含量为1％～5％。
具体地，有机溶剂包括第一溶剂。其中，第一溶剂选自芳族溶剂、杂芳族溶剂、酮类溶剂、醚类溶剂及酯类溶剂中的至少一种。
进一步地，芳族溶剂选自链式脂肪族取代的芳族化合物及环式脂肪族取代的芳族化合物中的至少一种。
具体地，芳族溶剂及杂芳族溶剂选自对二异丙基苯、戊苯、四氢萘、环己基苯、氯萘、1,4-二甲基萘、3-异丙基联苯、对甲基异丙苯、二戊苯、三戊苯、戊基甲苯、邻二甲苯、间二甲苯、对二甲苯、邻二乙苯、间二乙苯、对二乙苯、1,2,3,4-四甲苯、1,2,3,5-四甲苯、1,2,4,5-四甲苯、丁苯、十二烷基苯、二己基苯、二丁基苯、对二异丙基苯、1-甲氧基萘、环己基苯、二甲基萘、3-异丙基联苯、对甲基异丙苯、1-甲基萘、1,2,4-三氯苯、1,3-二丙氧基苯、4,4-二氟二苯甲烷、1,2-二甲氧基-4-(1-丙烯基)苯、二苯甲烷、2-苯基吡啶、3-苯基吡啶、N-甲基二苯胺、4-异丙基联苯、α,α-二氯二苯甲烷、4-(3-苯基丙基)吡啶、苯甲酸苄酯、1,1-双(3,4-二甲基苯基)乙烷、2-异丙基萘及二苄醚中的至少一种。
具体地，酮类溶剂选自1-四氢萘酮、2-四氢萘酮、2-(苯基环氧)四氢萘酮、6-(甲氧基)四氢萘酮、苯乙酮、苯丙酮、二苯甲酮、1-四氢萘酮的衍生物、2-四氢萘酮的衍生物、2-(苯基环氧)四氢萘酮的衍生物、6-(甲氧基)四氢萘酮的衍生物、苯乙酮的衍生物、苯丙酮的衍生物及二苯甲酮的衍生物中的至少一种。其中，1-四氢萘酮的衍生物、2-四氢萘酮的衍生物、2-(苯基环氧)四氢萘酮的衍生物、6-(甲氧基)四氢萘酮的衍生物、苯乙酮的衍生物、苯丙酮的衍生物及二苯甲酮的衍生物可以为4-甲基苯乙酮、3-甲基苯乙酮、2-甲基苯乙酮、4-甲基苯丙酮、3-甲基苯丙酮、2-甲基苯丙酮，异佛尔酮、2,6,8-三甲基-4-壬酮、葑酮、2-壬酮、3-壬酮、5-壬酮、2-癸酮、2,5-己二酮、佛尔酮、二正戊基酮等。
具体地，醚类溶剂选自3-苯氧基甲苯、丁氧基苯、苄基丁基苯、对茴香醛二甲基乙缩醛、四氢-2-苯氧基-2H-吡喃、1,2-二甲氧基-4-(1-丙烯基)苯、1,4-苯并二噁烷、1,3-二丙基苯、2,5-二甲氧基甲苯、4-乙基苯乙醚、1,2,4-三甲氧基苯、4-(1-丙烯基)-1,2-二甲氧基苯、1,3-二甲氧基苯、缩水甘油基苯基醚、二苄基醚、4-叔丁基茴香醚、反式-对丙烯基茴香醚、1,2-二甲氧基苯、1-甲氧基萘、二苯醚、2-苯氧基甲醚、2-苯氧基四氢呋喃、乙基-2-萘基醚、戊醚c己醚、二辛醚、乙二醇二丁醚、二乙二醇二乙醚、二乙二醇丁基甲醚、二乙二醇二丁醚、三乙二醇二甲醚、三乙二醇乙基甲醚、三乙二醇丁基甲醚、三丙二醇二甲醚及四乙二醇二甲醚中的至少一种。
具体地，酯类溶剂选自辛酸烷酯、癸二酸烷酯、硬脂酸烷酯、苯甲酸烷酯、苯乙酸烷酯、肉桂酸烷酯、草酸烷酯、马来酸烷酯、烷内酯及油酸烷酯中的至少一种。
进一步，第一溶剂选自脂肪族酮及脂肪族醚中的至少一种。具体地，脂肪族酮选自2-壬酮、3-壬酮、5-壬酮、2-癸酮、2,5-己二酮、2,6,8-三甲基-4-壬酮、佛尔酮及二正戊基酮中的至少一种。脂肪族醚选自戊醚、己醚、二辛醚、乙二醇二丁醚、二乙二醇二乙醚、二乙二醇丁基甲醚、二乙二醇二丁醚、三乙二醇二甲醚、三乙二醇乙基甲醚、三乙二醇丁基甲醚、三丙二醇二甲醚及四乙二醇二甲醚中的至少一种。
进一步地，有机溶剂还包括第二溶剂，其中，第二溶剂选自甲醇、乙醇、2-甲氧基乙醇、 二氯甲烷、三氯甲烷、氯苯、邻二氯苯、四氢呋喃、苯甲醚、吗啉、甲苯、邻二甲苯、间二甲苯、对二甲苯、1,4二氧杂环己烷、丙酮、甲基乙基酮、1,2二氯乙烷、3-苯氧基甲苯、1,1,1-三氯乙烷、1,1,2,2-四氯乙烷、醋酸乙酯、醋酸丁酯、二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、四氢萘、萘烷及茚中的至少一种。
本实施方式的混合物能够通过印刷或涂布的方式制备有机电子器件。
其中，印刷方法可以为喷墨打印或喷印(Nozzle Printing)。涂布的方法可以为活版印刷、丝网印刷、浸涂、旋转涂布、刮刀涂布、辊筒印花、扭转辊印刷、平版印刷、柔版印刷、轮转印刷、喷涂、刷涂、移印、狭缝型挤压式涂布等。进一步地，涂布的方法凹版印刷；打印方法为喷印或喷墨印刷。
进一步地，混合物还包括表面活性剂、润滑剂、润湿剂、分散剂、疏水剂及粘接剂中的至少一种。以用于调节混合物的粘度、成膜性能、提高附着性等。可以根据Helmut Kipphan主编的《印刷媒体手册:技术和生产方法》(Handbook of Print Media:Technologies and Production Methods)，ISBN 3-540-67326-1对打印技术及对混合物的中的溶剂、浓度、粘度等进行调整。
上述组合物至少有以下优点：
上述具有较好的印刷性及成膜性能，便于通过溶液加工，特别是印刷工艺，便于实现高性能的小分子有机电子器件，特别是有机电致发光器件，从而提供了一种成本低、高效率的制造技术方案。
一实施方式的有机功能薄膜，由上述通式(I)所示的有机功能化合物、混合物及组合物中共的一种制备得到。该有机功能薄膜能够用于有机电子器件中。
一实施方式的有机功能薄膜的制备方法，至少包含如下步骤：
步骤S1：提供浆料。
其中，浆料为上述组合物，或者，浆料为上述通式(I)的有机功能化合物及上述有机混合物中的一种溶解在有机溶剂中制备获得。
步骤S2：采用浆料在基板上形成膜层。
具体地，用印刷或涂布的方法将浆料涂布于一基板上形成一膜层。
其中，印刷方法可以为喷墨打印或喷印(Nozzle Printing)。涂布的方法可以为活版印刷、丝网印刷、浸涂、旋转涂布、刮刀涂布、辊筒印花、扭转辊印刷、平版印刷、柔版印刷、轮转印刷、喷涂、刷涂、移印、狭缝型挤压式涂布等。
步骤S3：将膜层在100℃以上的温度下，在无水和无氧的条件下发生Bergman成环芳构化反应，得到有机功能薄膜。
进一步地，将膜层在190℃、隔绝水和氧气的环境下处理2小时，使之发生Bergman成环芳构化反应。
在某些实施例中，所得的有机功能薄膜(即膜层Bergman成环芳构化反应后)的厚度是膜层的厚度的至少50％，进一步地，至少为60％；进一步地，至少为70％；进一步地，至少为85％。
上述有机功能薄膜能够应用在有机电子器件中，其中，有机电子器件选自有机发光二极管(OLED)、有机光伏电池(OPV)、有机发光电池(OLEEC)、有机场效应管(OFET)、有机发光场效应管、有机激光器、有机自旋电子器件、有机传感器及有机等离激元发射二极管(Organic Plasmon Emitting Diode)中的一种。进一步地，该有机功能薄膜用于OLED器件的空穴传输层、空穴注入层或发光层中；进一步地，该有机功能薄膜用于OLED器件的空穴传输层。
一实施方式的有机电子器件，包括功能层，功能层的材料为上述有机功能薄膜。一般地，此种有机电子器件至少还包含一个阴极和一个阳极，功能层位于阴极和阳极之间。
其中，有机电子器件选自有机发光二极管(OLED)、有机光伏电池(OPV)、有机发光电池(OLEEC)、有机场效应管(OFET)、有机发光场效应管、有机激光器、有机自旋电子器件、有机传感器及有机等离激元发射二极管(Organic Plasmon Emitting Diode)中的一种。
如图1所示，图1所示的结构为一有机发光二极管100，该有机电子器件100包含基片101、阳极102、至少一发光层104和阴极106。
具体地，基片101可以是不透明或透明。透明的基板可以用来制造透明的发光元器件。例如透明的基片101可以为文献(Bulovic等Nature 1996，380，p29)和文献(Gu等，Appl.Phys.Lett.1996，68，p2606)中公开的基片101。基片101可以是刚性基片101或弹性基片101。
具体地，基片101为塑料、金属、半导体晶片或玻璃。进一步地，基片101具有有一个平滑的表面。无表面缺陷是基片101的理想选择。
进一步地，基片101是柔性的。基片101为聚合物薄膜或塑料；基片101的玻璃化温度Tg为150℃以上；进一步地，超过200℃；进一步地，超过250℃；进一步地，超过300℃。具体地，基片101选自聚(对苯二甲酸乙二醇酯)(PET)及聚乙二醇(2,6-萘)(PEN)中的一种。
阳极102的材料包括导电金属、金属氧化物及导电聚合物中的一种。阳极102能够很容易地将空穴注入到发光层、空穴注入层或空穴传输层中。
具体地，阳极102的功函数和发光层中的有机功能材料(发光材料)、空穴注入层的p型半导体材料、空穴传输层的p型半导体材料、或电子阻挡层的p型半导体材料的HOMO能级(或价带)能级的差的绝对值小于0.5eV；进一步地，小于0.3eV；更进一步地，小于0.2eV。
具体地，阳极102材料选自Al、Cu、Au、Ag、Mg、Fe、Co、Ni、Mn、Pd、Pt、ITO及铝掺杂氧化锌(AZO)中的一种。阳极102材料可以采用物理气相沉积法制备获得。其中，物理气相沉积法具体为射频磁控溅射、真空热蒸发或电子束(e-beam)蒸发等。
需要说明的是，阳极102材料不限于于为上述材料，阳极102材料还可以为图案化的ITO。
发光层104的材料为上述有机功能薄膜。
阴极106的材料选自导电金属及金属氧化物中的一种。阴极106的材料为能够容易地将电子注入到电子注入层、电子传输层或发光层中。
进一步地，阴极106的功函数和发光层104的有机功能材料(发光材料)、电子注入层的n型半导体材料、电子传输层的n型半导体材料或空穴阻挡层的n型半导体材料的LUMO能级(或导带)能级的差的绝对值小于0.5eV；进一步地，小于0.3eV，更进一步地，小于0.2eV。原则上，所有能够用作OLED的阴极106的材料都可能作为本实施方式的阴极106材料。
进一步地，阴极106材料选自Al、Au、Ag、Ca、Ba、Mg、LiF/Al、MgAg合金、BaF 2/Al、Cu、Fe、Co、Ni、Mn、Pd、Pt及ITO中的一种。阴极106材料可以采用物理气相沉积法制备获得。其中，物理气相沉积法具体为射频磁控溅射、真空热蒸发或电子束(e-beam)蒸发等。
进一步地，有机发光二极管100还包括其它功能层，例如空穴注入层(HIL)、空穴传输层(HTL)、电子阻挡层(EBL)、电子注入层(EIL)、电子传输层(ETL)及空穴阻挡层(HBL)中的至少一种。适合用于这些功能层中的材料可以为WO2010135519A1、US20090134784A1和WO2011110277A1中公开的材料。
具体在图示的实施例中，有机发光二极管100还包括空穴注入层或空穴传输层103。其中，空穴注入层或空穴传输层103的材料为上述有机功能薄膜。
进一步地，有机发光二极管100还包括电子注入层或电子传输层105。
其中，本实施方式的有机发光二极管100的发光波长为300nm～1000nm；进一步地，发光波长为350～900nm；进一步地，发光波长为400～800nm。
上述有机电子器件能够在各种电子设备中的应用。例如，显示设备、照明设备、光源或传感器等等。
以下为实施例部分：
实施例1
本实施例的有机功能材料的合成如下：
在室温条件下，依次将13.6g(0.018mol)中间体a和9.51g(0.018mol)中间体b溶于300ml甲苯中，然后依次加入四三苯基膦钯1.2g、碳酸钾10g(0.74mol)、水60ml及乙醇60ml， 加热到110℃反应15小时，TLC板显示反应完全。将反应液加入到水中后用二氯甲烷提取三次，然后将有机相干燥浓缩得到粗品，经层析柱的固体为化合物1，为12.6g，收率为65％。
合成路线如下：
Figure PCTCN2017118066-appb-000105
实施例2
本实施例的有机功能材料的合成如下：
在室温条件下，依次将13.6 g(0.018mol)中间体a和13.6 g(0.018 mol)中间体b溶于300ml甲苯中，依次四三苯基膦钯1.2 g、碳酸钾9.7 g(0.074mol)、水60 ml和乙醇60 ml，加热到110℃反应15小时，TLC板显示反应完全。将反应液加入到水中后用二氯甲烷提取三次，然后有机相干燥浓缩得到粗品，经层析柱的固体为化合物2，为15.3g(收率65％)。
合成路线如下：
Figure PCTCN2017118066-appb-000106
实施例3
本实施例的有机功能材料的合成如下：
在室温条件下，依次将10.54g(0.018mol)中间体a和8.14g(0.018mol)中间体b溶于300ml甲苯中，然后依次加入四三苯基膦钯1.2g、碳酸钾9.7g(0.074mol)、水60ml和乙醇60ml，加热到110℃反应15小时，TLC板显示反应完全。将反应液加入到水中后用二氯甲烷提取三次，然后有机相干燥浓缩得到粗品，经层析柱的固体为化合物3，为8.98g(收率为60％)。
合成路线如下：
Figure PCTCN2017118066-appb-000107
实施例4
本实施例的有机功能材料的合成如下：
在室温下，依次将10.54g(0.018mol)中间体a和8.14g(0.018mol)中间体b溶于300ml甲苯中，依次四三苯基膦钯1.2g、碳酸钾9.7g(0.074mol)、水60ml和乙醇60ml，然后加热到110℃反应15小时，TLC板显示反应完全。将反应液加入到水中后用二氯甲烷提取三次，然后有机相干燥浓缩得到粗品，经层析柱的固体为化合物4，为8.98g(收率为60％)。
合成路线如下：
Figure PCTCN2017118066-appb-000108
实施例5
本实施例的有机功能材料的合成如下：
在室温条件下，依次将10.54g(0.018mol)中间体a和9.51g(0.018mol)中间体b溶于300ml甲苯中，然后依次加入四三苯基膦钯1.2g、碳酸钾9.7g(0.074mol)、水60ml和乙醇60ml，加热到110℃反应15小时，TLC板显示反应完全。将反应液加入到水中后用二氯甲烷提取三次，然后有机相干燥浓缩得到粗品，经层析柱的固体为化合物5，为9.79g(收率60％)。
合成路线如下：
Figure PCTCN2017118066-appb-000109
实施例6～实施例10
实施例6～实施例10的有机功能薄膜的制备过程如下：
(1)玻璃衬底的清洗：使用5％Decon90清洗液的水溶液超声处理30分钟，之后去离子水超声清洗数次，然后异丙醇超声清洗，氮气吹干；在氧气等离子下处理5分钟；
(2)分别将实施例1～5的有机功能化合物溶于甲苯中，溶液的浓度为20mg/mL，将此溶液在氮气手套箱中旋涂于玻璃衬底上得到60nm薄膜；其中，实施例6使用的为实施例1的有机功能化合物，实施例7使用的是实施例2的有机功能化合物，实施例8使用的为实施例3的有机功能化合物，实施例9使用的是实施例4的有机功能化合物，实施例10使用的为实施例5的有机功能化合物；
(3)然后在190℃退火下10分钟，分别得到实施例6～实施例10的有机功能薄膜，分别测实施例6～实施例10的有机功能薄膜的厚度及表面粗糙度；
(4)在薄膜上滴加甲苯，烘干，再次测实施例6～实施例10的有机功能薄膜的厚度及表面粗糙度。
经测试显示，实施例6～实施例10的有机功能薄膜两次测试的厚度及表面粗糙度的数值基本不变，即实施例6～实施例10的有机功能薄膜在经过步骤(4)滴加甲苯前后的厚度及表面粗糙度的数值都基本上不变，说明实施例1～实施例5的有机功能化合物在经过转换后生成的有机功能化合物在甲苯中溶解度很低。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (20)

  1. 一种有机功能化合物，具有如下通式：
    Figure PCTCN2017118066-appb-100001
    其中，A为具有光电功能的有机基团；
    -SG的结构式选自
    Figure PCTCN2017118066-appb-100002
    及
    Figure PCTCN2017118066-appb-100003
    中的一个；
    Figure PCTCN2017118066-appb-100004
    选自具有5个～40个成环原子的芳基及具有5个～40个成环原子的杂芳基中的一种；
    R 1和R 2分别独立选自H、D、F、CN、烷基、芳环基、芳香性杂环基、氨基、硅基、甲锗基、烷氧基、芳氧基及硅氧烷基中的一种，所述烷基选自未取代的烷基、氟代烷基、氘代烷基及氘代氟代烷基中的一种，所述芳环基选自未取代的芳环基及氘代芳环基中的一种，所述芳香性杂环基选自未取代的芳香性杂环基及氘代芳香性杂环基中的一种，所述氨基选自未取代的氨基及氘代氨基中的一种，所述硅基选自未取代的硅基及氘代硅基中的一种，所述甲锗基选自未取代的甲锗基及氘代甲锗基中的一种，所述烷氧基选自未取代的烷氧基、甲硅烷氧基、氟代烷氧基、氘代烷氧基、氘代氟代烷氧基及氘代甲硅烷氧基中的一种，所述芳氧基选自未取代的芳氧基及氘代芳氧基中的一种，所述硅氧烷基选自未取代的硅氧烷基及氘代硅氧烷基中的一种；
    p为大于或等于1的整数。
  2. 根据权利要求1所述的有机功能化合物，其特征在于，所述具有光电功能的有机基团选自具有空穴注入功能的有机基团、具有空穴传输功能的有机基团、具有空穴阻挡功能的有机基团、具有电子注入功能的有机基团、具有电子传输功能的有机基团、具有电子阻挡功能的有机基团、具有有机主体功能的有机基团、具有单重态发光功能的有机基团、具有三重态发光功能的有机基团及具有热激发延迟荧光功能的有机基团中的一种。
  3. 根据权利要求1所述的有机功能化合物，其特征在于，所述A具有如下结构式：
    Figure PCTCN2017118066-appb-100005
    其中，Ar 0的结构式选自
    Figure PCTCN2017118066-appb-100006
    Figure PCTCN2017118066-appb-100007
    及
    Figure PCTCN2017118066-appb-100008
    中的一种；
    Ar 1和Ar 2分别独立选自未取代的芳烃基、未取代的芳杂环烃基、R 11取代的芳烃基及R 11取代的芳杂环烃基中的一种；
    R 11选自F、Cl、Br、I、D、CN、NO 2、CF 3、直链烷烃基、烷烃醚基、碳原子数为1个～10个的烷烃硫醚基、支链烷烃基及环烷烃基中的一种，或者，所述R 11为直链烷烃基中的一个或多个非相邻的亚甲基被R 12C＝CR 12、C＝C、Si(R 12) 2、Ge(R 12) 2、Sn(R 12) 2、C＝O、C＝S、C＝Se、C＝N(R 12)、O、S、酯基及CONR 12中的一个替换后的基团，或者，所述R 11为烷烃醚 基中的一个或多个非相邻的亚甲基被R 12C＝CR 12、C＝C、Si(R 12) 2、Ge(R 12) 2、Sn(R 12) 2、C＝O、C＝S、C＝Se、C＝N(R 12)、O、S、酯基及CONR 12中的一个替换后的基团，或者，所述R 11为碳原子数为1个～10个的烷烃硫醚基中的一个或多个非相邻的亚甲基被R 12C＝CR 12、C＝C、Si(R 12) 2、Ge(R 12) 2、Sn(R 12) 2、C＝O、C＝S、C＝Se、C＝N(R 12)、O、S、酯基及CONR 12中的一个替换后的基团，或者，所述R 11为支链烷烃基中的一个或多个非相邻的亚甲基被R 12C＝CR 12、C＝C、Si(R 12) 2、Ge(R 12) 2、Sn(R 12) 2、C＝O、C＝S、C＝Se、C＝N(R 12)、O、S、酯基及CONR 12中的一个替换后的基团，或者，所述R 11为环烷烃基中的一个或多个非相邻的亚甲基被R 12C＝CR 12、C＝C、Si(R 12) 2、Ge(R 12) 2、Sn(R 12) 2、C＝O、C＝S、C＝Se、C＝N(R 12)、O、S、酯基及CONR 12中的一个替换后的基团；
    所述直链烷烃基选自未取代的直链烷烃基及被至少一个活性基团R 12取代的直链烷烃基，或者，所述直链烷烃基为至少一个H原子被D、F、Cl、Br、I、CN、包含活性基团R 12的芳香胺基、包含一个芳香基团的芳香胺基、包含杂芳香环的芳香胺基及咔唑中的一个替换的直链烷烃基，所述烷烃醚基选自未取代的烷烃醚基及被至少一个活性基团R 12取代的烷烃醚基中的一个，或者所述烷烃醚基为至少一个H原子被D、F、Cl、Br、I、CN、包含活性基团R 12的芳香胺基、包含一个芳香基团的芳香胺基、包含杂芳香环的芳香胺基及咔唑中的一个替换的烷烃醚基，所述碳原子数为1个～10个的烷烃硫醚基选自未取代的碳原子数为1个～10个的烷烃硫醚基及被至少一个活性基团R 12取代的碳原子数为1个～10个的烷烃硫醚基中的一个，或者，所述烷烃硫醚基为至少一个H原子被D、F、Cl、Br、I、CN、包含活性基团R 12的芳香胺基、包含一个芳香基团的芳香胺基、包含杂芳香环的芳香胺基及咔唑中的一个替换的烷烃硫醚基，所述支链烷烃基选自未取代的碳原子数为1个～10个的支链烷烃基及被至少一个活性基团R 12取代的支链烷烃基中的一个，或者，所述支链烷烃基为至少一个H原子被D、F、Cl、Br、I、CN、包含活性基团R 12的芳香胺基、包含一个芳香基团的芳香胺基、包含杂芳香环的芳香胺基及咔唑中的一个替换的支链烷烃基，所述环烷烃基选自未取代的环烷烃基及被至少一个活性基团R 12取代的环烷烃基中的一个，或者，所述环烷烃基为至少一个H原子被D、F、Cl、Br、I、CN、包含活性基团R 12的芳香胺基、包含一个芳香基团的芳香胺基、包含杂芳香环的芳香胺基及咔唑中的一个替换的环烷烃基；
    R 12选自H、D、碳原子数为1个～10个的脂肪族烷烃基、成环原子数为5个～10个的芳香环基及成环原子数为5个～10个的杂芳香基中的一种；
    -Z-为单键，或者，Z为二桥联基；
    x为0～4的任一整数，x1为0～3的任一整数，y为0～5的任一整数，z为0～5的任一整数；
    -L-为单键，或者，L选自碳原子数为5个～40个的R 1取代的共轭芳香基及碳原子数为5个～40个的未取代的共轭芳香基中的一种。
  4. 根据权利要求1所述的有机功能化合物，其特征在于，所述A包含结构式
    Figure PCTCN2017118066-appb-100009
    Figure PCTCN2017118066-appb-100010
    及
    Figure PCTCN2017118066-appb-100011
    中的一种；
    其中，Ar 11和Ar 12分别独立选自碳原子数为6个～60个的芳香基、碳原子数为3个～60个的芳杂基、碳原子数为6个～60个的稠环芳香基及碳原子数为3个～60个的稠环芳杂基中的一种；
    Figure PCTCN2017118066-appb-100012
    及
    Figure PCTCN2017118066-appb-100013
    分别独立选自成环原子数为5个～30个的芳香基及成环原子数为5个～30个的芳杂基中的一种；
    Ar 9和Ar 10分别独立选自H、D、F、CN、NO 2、CF 3、烯基、炔基、胺基、酰基、酰胺基、氰基、异氰基、烷氧基、羟基、羰基、砜基、碳原子数为1个～60个的烷基、碳原子数为3个～60个的环烷基、碳原子数为6个～60个的芳香基、碳原子数为3个～60个的杂环芳香基、碳原子数为7个～60个的稠环芳香基及碳原子数为4个～60个的稠杂环芳香基中的一种；
    L 1选自成环原子数为5个～60个的芳香基及成环原子数为5个～60个的芳杂基中的一种；
    -L 2-为单键，或者，L 2选自成环原子数为5个～30个的芳香基及成环原子数为5个～30个的芳杂基中的一种；
    -X 1-为单键，或者，X 1选自N(R)、C(R) 2、Si(R) 2、O、C＝N(R)、C＝C(R) 2、P(R)、P(＝O)R、S、S＝O及SO 2中的一种；
    -X 2-、-X 3-、-X 4-、-X 5-、-X 6-、-X 7-、-X 8-、-X 9-分别独立选自单键、-N(R)-、-C(R) 2-、-Si(R) 2-、-O-、-(C＝N(R))-、-(C＝C(R) 2)、-P(R)-、-(P(＝O)R)-、-S-、-(S＝O)-及-(SO 2)-，且-X 2-及-X 3-中最多一个为单键，-X 4-和-X 5-中最多一个单键，-X 6-和-X 7-中最多一个单键，-X 8-和-X 9-中最多一个单键；
    而且，在所述A包含的所述结构式中，环上与R 1、R 2连接的碳原子至少为一个；
    R独立选自H、D、F、CN、烯基、炔基、腈基、胺基、硝基、酰基、烷氧基、羰基、砜基、碳原子数为1个～30个的烷基、碳原子数为3个～30个的环烷基、成环原子数为5个～60个的芳烃基及成环原子数为5个～60个的芳香杂环基中的一种；
    m为0～4的任一整数，o为0～4的任一整数，q为0～6的的任一整数，s为1～4的任一整数。
  5. 根据权利要求1所述的有机功能化合物，其特征在于，所述
    Figure PCTCN2017118066-appb-100014
    包括如下基团中的至少一个：
    Figure PCTCN2017118066-appb-100015
    其中，X选自CR 13及N中的一种；
    Y选自CR 14R 15、SiR 16R 17、NR 18、C(＝O)、S(＝O) 2、O及S中的一种；
    R 13、R 14、R 15、R 16、R 17及R 18分别独立选自单键、H、D、F、CN、NO 2、CF 3、烯基、炔基、胺基、酰基、酰胺基、氰基、异氰基、烷氧基、羟基、羰基、砜基、碳原子数为1个～60个的烷基、碳原子数为3个～60个的环烷基、碳原子数为6个～60个芳香基、碳原子数为3个～60个的杂环芳香基、碳原子数为7个～60个的稠环芳香基及碳原子数为4个～60个的稠杂环芳香基中的一个。
  6. 根据权利要求1所述的有机功能化合物，其特征在于，所述
    Figure PCTCN2017118066-appb-100016
    选自如下基团及环上氢被取代的如下基团中的一种：
    Figure PCTCN2017118066-appb-100017
  7. 根据权利要求1所述的有机功能化合物，其特征在于，所述-SG选自如下结构式中的一种：
    Figure PCTCN2017118066-appb-100018
    Figure PCTCN2017118066-appb-100019
    其中，R 3、R 4、R 5、R 6和R 7分别独立选自H、D、F、CN、烷基、芳环基、芳香性杂环基、氨基、硅基、甲锗基、烷氧基、芳氧基及硅氧烷基中的一种，所述烷基选自未取代的烷基、氟代烷基、氘代烷基及氘代氟代烷基中的一种，所述芳环基选自未取代的芳环基及氘代芳环基中的一种，所述芳香性杂环基选自未取代的芳香性杂环基及氘代芳香性杂环基中的一种，所述氨基选自未取代的氨基及氘代氨基中的一种，所述硅基选自未取代的硅基及氘代硅基中的一种，所述甲锗基选自未取代的甲锗基及氘代甲锗基中的一种，所述烷氧基选自未取代的烷氧基、甲硅烷氧基、氟代烷氧基、氘代烷氧基、氘代氟代烷氧基及氘代甲硅烷氧基中的一种，所述芳氧基选自未取代的芳氧基及氘代芳氧基中的一种，所述硅氧烷基选自未取代的硅氧烷基及氘代硅氧烷基中的一种；
    n为大于0的整数；
    -L 1-为单键，或者，L 1选自芳基及杂芳基中一种。
  8. 根据权利要求1所述的有机功能化合物，其特征在于，所述有机功能化合物能够发生Bergman成环芳构化反应生成具有通式
    Figure PCTCN2017118066-appb-100020
    及
    Figure PCTCN2017118066-appb-100021
    中的一种的化合物，且存在一种有机溶剂S，所述有机溶剂S是所述有机功能化合物的良溶剂，是所述具有通式
    Figure PCTCN2017118066-appb-100022
    的化合物及具有通式 的化合物的不良溶剂；
    其中，-SG1为结构式为
    Figure PCTCN2017118066-appb-100024
    的基团；
    且所述
    Figure PCTCN2017118066-appb-100025
    中，-SG 1之间的连接位点如下式中*号所示：
    Figure PCTCN2017118066-appb-100026
    n1为大于或等于2的整数。
  9. 根据权利要求1所述的有机功能化合物，其特征在于，所述有机功能化合物的玻璃化温度在100℃以上。
  10. 一种混合物，包括权利要求1～9任一项所述的有机功能化合物和有机功能材料，所述有机功能材料选自空穴注入材料、空穴传输材料、空穴阻挡材料、电子注入材料、电子传输材料、电子阻挡材料、有机基质材料、发光材料及有机染料中的至少一种。
  11. 一种组合物，包括权利要求1～9任一项所述的有机功能化合物及权利要求10所述的混合物中的一种和有机溶剂。
  12. 根据权利要求11所述的组合物，其特征在于，所述有机溶剂包括第一溶剂，所述第一溶剂选自芳族溶剂、杂芳族溶剂、酮类溶剂、醚类溶剂及酯类溶剂中的至少一种。
  13. 根据权利要求11所述的组合物，其特征在于，所述有机功能化合物的摩尔质量在700g/mol以上。
  14. 一种有机功能薄膜，由权利要求1～9任一项所述的有机功能化合物、权利要求10所述的有机混合物及权利要求11～13任一项所述的组合物中的一种制备得到。
  15. 一种有机功能薄膜的制备方法，包括如下步骤：
    采用浆料在基板上形成膜层，其中，所述浆料为权利要求11～13任一项所述的组合物，或者，所述浆料由权利要求1～9任一项所述的有机功能化合物及权利要求10所述的有机混合物中的一种溶解在有机溶剂中制备获得；
    将所述膜层在100℃以上的温度下，在无水和无氧的条件下发生Bergman成环芳构化反应，得到有机功能薄膜。
  16. 根据权利要求15所述的有机功能薄膜的制备方法，其特征在于，所述有机功能薄膜的厚度是所述膜层厚度的50％以上。
  17. 一种有机电子器件，包括功能层，所述功能层的材料为权利要求14所述的有机功能薄膜，或者，所述功能层的材料为权利要求15和16任一项所述的有机功能薄膜的制备方法制备得到的所述有机功能薄膜。
  18. 根据权利要求17所述的有机电子器件，其特征在于，所述功能层包括空穴传输层，所述空穴传输层的材料为权利要求14所述的有机功能薄膜，或者，所述功能层的材料为权利要求15和16任一项所述的有机功能薄膜的制备方法制备得到的所述有机功能薄膜。
  19. 根据权利要求17所述的有机电子器件，其特征在于，所述功能层包括发光层，所述发光层的材料为权利要求14所述的有机功能薄膜，或者，所述功能层的材料为权利要求15和16任一项所述的有机功能薄膜的制备方法制备得到的所述有机功能薄膜。
  20. 根据权利要求17所述的有机电子器件，其特征在于，所述有机电子器件选自有机发光二极管、有机光伏电池、有机发光电池、有机场效应管、有机发光场效应管、有机激光器、有机自旋电子器件、有机传感器及有机等离激元发射二极管中的一种。
PCT/CN2017/118066 2016-12-22 2017-12-22 有机功能化合物、混合物、组合物、有机功能薄膜及其制备方法和有机电子器件 WO2018113784A1 (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110698475A (zh) * 2018-12-10 2020-01-17 广州华睿光电材料有限公司 稠环有机化合物及其应用
US11289654B2 (en) 2016-12-22 2022-03-29 Guangzhou Chinaray Optoelectronic Materials Ltd. Polymers containing furanyl crosslinkable groups and uses thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1009043A2 (en) * 1998-12-09 2000-06-14 Eastman Kodak Company Electroluminescent device with polyphenyl hydrocarbon hole transport layer
CN1947274A (zh) * 2004-04-26 2007-04-11 默克专利有限公司 包含平面芳基胺单元的电致发光聚合物，其制备和用途
CN102449796A (zh) * 2009-05-29 2012-05-09 默克专利有限公司 包含至少一种发光体化合物和至少一种具有共轭间断单元的聚合物的组合物

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3567450A (en) 1968-02-20 1971-03-02 Eastman Kodak Co Photoconductive elements containing substituted triarylamine photoconductors
US3615404A (en) 1968-04-25 1971-10-26 Scott Paper Co 1 3-phenylenediamine containing photoconductive materials
US6252001B1 (en) * 1986-09-12 2001-06-26 The Dow Chemical Company Ethynyl substituted aromatic compounds, synthesis, polymers and uses thereof
US4720432A (en) 1987-02-11 1988-01-19 Eastman Kodak Company Electroluminescent device with organic luminescent medium
US5061569A (en) 1990-07-26 1991-10-29 Eastman Kodak Company Electroluminescent device with organic electroluminescent medium
WO1997010193A1 (en) * 1995-09-12 1997-03-20 The Dow Chemical Company Ethynyl substituted aromatic compounds, synthesis, polymers and uses thereof
DE10037391A1 (de) 2000-08-01 2002-02-14 Covion Organic Semiconductors Strukturierbare Materialien, Verfahren zu deren Herstellung und deren Verwendung
JP4345298B2 (ja) * 2002-12-25 2009-10-14 住友ベークライト株式会社 芳香族カルボン酸誘導体及びその酸塩化物誘導体
KR101139055B1 (ko) 2005-11-25 2012-04-30 삼성전자주식회사 신규한 방향족 엔다이인 유도체, 이를 이용한 유기 반도체및 전자소자
JP2007287354A (ja) 2006-04-12 2007-11-01 Hitachi Displays Ltd 有機ｅｌ表示装置
CN101220112B (zh) 2007-12-07 2011-05-04 华南理工大学 含芳基二乙炔类共轭聚合物及其合成方法
US8221905B2 (en) 2007-12-28 2012-07-17 Universal Display Corporation Carbazole-containing materials in phosphorescent light emitting diodes
US8586203B2 (en) 2009-05-20 2013-11-19 Universal Display Corporation Metal complexes with boron-nitrogen heterocycle containing ligands
JP6246468B2 (ja) 2010-03-11 2017-12-13 メルク パテント ゲーエムベーハー 治療および化粧品におけるファイバー
WO2011141110A2 (de) 2010-05-12 2011-11-17 Merck Patent Gmbh Photostabilisatoren
US9644070B2 (en) 2012-04-17 2017-05-09 Merck Patent Gmbh Cross-linkable and cross-linked polymers, process for the preparation thereof, and the use thereof
US20180354934A1 (en) 2015-12-04 2018-12-13 Guangzhou Chinaray Optoelectronic Materials Ltd. Terbenzocyclopentadiene compound, high polymer, mixture, composition and organic electronic device
WO2017118174A1 (zh) 2016-01-07 2017-07-13 广州华睿光电材料有限公司 用于制备有机电子器件的有机功能化合物及其应用
EP3401317B1 (en) 2016-01-07 2022-05-04 Guangzhou Chinaray Optoelectronic Materials Ltd. Sulfone-containing fused heterocyclic compounds and applications thereof
CN108137622B (zh) 2016-01-07 2021-07-23 广州华睿光电材料有限公司 含硅的有机化合物及其应用
US11453745B2 (en) * 2016-11-23 2022-09-27 Guangzhou Chinaray Optoelectronic Materials Ltd. High polymer, mixture containing same, composition, organic electronic component, and monomer for polymerization
EP3560917B1 (en) 2016-12-22 2023-12-20 Guangzhou Chinaray Optoelectronic Materials Ltd. Polymer containing furan crosslinking group and use thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1009043A2 (en) * 1998-12-09 2000-06-14 Eastman Kodak Company Electroluminescent device with polyphenyl hydrocarbon hole transport layer
CN1947274A (zh) * 2004-04-26 2007-04-11 默克专利有限公司 包含平面芳基胺单元的电致发光聚合物，其制备和用途
CN102449796A (zh) * 2009-05-29 2012-05-09 默克专利有限公司 包含至少一种发光体化合物和至少一种具有共轭间断单元的聚合物的组合物

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11289654B2 (en) 2016-12-22 2022-03-29 Guangzhou Chinaray Optoelectronic Materials Ltd. Polymers containing furanyl crosslinkable groups and uses thereof
CN110698475A (zh) * 2018-12-10 2020-01-17 广州华睿光电材料有限公司 稠环有机化合物及其应用

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