P-doped crosslinker, composition, polymer, film, and light emitting device

Abstract

The invention relates to the technical field of electroluminescence, in particular to a p-doped cross-linking agent, a composition, a polymer, a thin film and a light-emitting device. The p-doped cross-linking agent has a general formula structure as shown in a formula II. The material obtained by crosslinking the p-doped crosslinking agent and the host material has excellent solvent resistance, and can effectively solve the problem of intersolubility between layers, thereby improving the efficiency and prolonging the service life of the device prepared by the ink-jet printing process.

Description

Technical Field

[0001] The present application relates to the technical field of electroluminescence, and in particular to a p-doped crosslinking agent, a composition, a polymer, a film and a light-emitting device. Background Art

[0002] At present, there are two main production processes for display screens: evaporation and inkjet printing. The material utilization rate of inkjet printing technology is as high as 90%, while that of evaporation is only about 30% to 40%. Inkjet printing does not require a vacuum environment, and the cost of equipment and consumables is lower than that of panels prepared by evaporation. However, preparation by inkjet printing technology requires that the materials of each functional layer have good solvent resistance, otherwise it will cause inter-layer dissolution and affect device performance. However, the existing materials have poor solvent resistance and cannot effectively solve the problem of inter-layer dissolution. Summary of the invention

[0003] Based on this, it is necessary to provide a p-doped crosslinking agent, composition, polymer, film and light-emitting device for preparing a hole functional layer to solve the interlayer solubility problem and improve the efficiency and life of the device.

[0004] In a first aspect of the present application, a p-doped cross-linking agent is provided, having a general structure shown in Formula II:

[0005] Formula II;

[0006] Wherein, L1 and L2 are independently selected from -(CH2) q4 -(CH2O) q5 -(CH2) q6 -(CH=CH) q7 -P3-(CH2) q8 -;

[0007] P3 is selected from a single bond, -C(=CR5R6)-, substituted or unsubstituted C 6-60 Arylene, substituted or unsubstituted heteroarylene having 5 to 60 ring atoms, or one of the following groups:

[0008] ;

[0009] Ar5, Ar6 and Ar7, when present, are independently selected from substituted or unsubstituted C 6-60 Arylene, substituted or unsubstituted heteroarylene having 5 to 60 ring atoms; R5 and R6 are independently selected from H, C 1-20 Alkyl or cyano;

[0010] Each occurrence of q4, q5, q6, q7 and q8 is independently selected from any integer between 0 and 20;

[0011] W, at each occurrence, is independently selected from -H, -F, -Cl, -Br, -I, -CN, -NO2, C 1-20 Alkyl or C 1-20 Alkoxy;

[0012] The substituted substituents, each time they appear, are independently selected from D, amino, halogen, hydroxy, carboxyl, nitro, sulfonic acid, mercapto, cyano, C 1-20 Alkyl, C 1-20 A combination of one or more of an alkoxy group and an aryl group having 6 to 20 ring atoms.

[0013] In a second aspect of the present application, a composition is provided, comprising at least one main material and at least one of the above-mentioned p-doped cross-linking agents, wherein the main material has a general structure shown in Formula I:

[0014] Formula I;

[0015] Wherein, R1, R2, R3 and R4 are independently selected from -P1-(CH2) q1 -(CH2O) q2 -(CH2) q3 -P2;

[0016] P1 is selected from a single bond or C 6-60 arylene;

[0017] P2 is selected from H, -CH3, CH2=CH-, C 6-60 An aryl group or a heteroaryl group having 5 to 60 ring atoms;

[0018] Each occurrence of q1, q2 and q3 is independently selected from any integer between 0 and 20;

[0019] X is selected from O, S, -NR a , -PR a or CR a R b ;

[0020] Y single button, O, S, -NR a , -PR a or -CR a R b ;

[0021] Z selects single bond, O, S, -N-Ar1, -PR a or -CR a R b ;

[0022] R a and Rb Each occurrence is independently selected from H or C 1-3 alkyl;

[0023] Ar1 is selected from substituted or unsubstituted C 6-60 Aryl, substituted or unsubstituted heteroaryl having 5 to 60 ring atoms;

[0024] The substituted substituents, each time they appear, are independently selected from D, amino, halogen, hydroxy, carboxyl, nitro, sulfonic acid, mercapto, cyano, C 1-20 Alkyl, C 1-20 A combination of one or more of an alkoxy group and an aryl group having 6 to 20 ring atoms.

[0025] The third aspect of the present application provides a polymer, which is prepared by reacting the main material in the above-mentioned composition and the p-doped cross-linking agent.

[0026] A fourth aspect of the present application provides a thin film, wherein the material of the thin film is prepared by reacting the main material in the above-mentioned composition with the p-doped cross-linking agent.

[0027] In a fifth aspect of the present application, a light-emitting device is provided, comprising a first electrode, a functional layer and a second electrode stacked in sequence, wherein the material of the functional layer comprises a polymer prepared by reacting the main material in the above-mentioned composition and the p-doped crosslinking agent.

[0028] Compared with the traditional technology, this application has the following beneficial effects:

[0029] The material obtained by cross-linking the p-doped cross-linking agent and the main material provided in the present application has excellent solvent resistance, which can effectively solve the problem of interlayer miscibility, thereby improving the efficiency and life of the device prepared by the inkjet printing process. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 This is a schematic diagram of the structure of an OLED device according to an example of the present application;

[0031] Figure 2 The electron paramagnetic resonance test results of some embodiments are shown;

[0032] Figure 3 The conductive AFM morphology test results of some embodiments are shown. DETAILED DESCRIPTION

[0033] The organic compound, luminescent material, organic electroluminescent device and display panel of the present application are further described in detail below in conjunction with specific embodiments. The present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present application more thorough and comprehensive.

[0034] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the present invention belongs. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0035] In the present application, "*" represents a connecting site. When the connecting site is not specified in the group, it means that an optional connecting site in the group can be used as the connecting site.

[0036] In the present application, "substituted" means that the hydrogen atom in the substituted group is replaced by a substituent. In the present application, when the substitution of the group is not specifically specified, it means that the defined group may be substituted or not. When the defined group is substituted and it is not specified by which group it is substituted, it should be understood that it is optionally substituted by a group acceptable in the art, including but not limited to: an alkyl group containing 1 to 30 carbon atoms, a cycloalkyl group containing 3 to 20 carbon atoms, a heterocyclic group containing 3 to 20 carbon atoms, an aryl group containing 5 to 20 carbon atoms, a heteroaryl group containing 5 to 20 carbon atoms, a silane group, a carbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a haloformyl group, a formyl group, -NRR', a cyano group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a trifluoromethyl group, a nitro group or a halogen group, and the above groups may also be further substituted by substituents acceptable in the art; it is understandable that R and R' in -NRR' are each independently substituted by a group acceptable in the art, including but not limited to H, an alkyl group containing 1 to 6 carbon atoms, a cycloalkyl group containing 3 to 8 carbon atoms, a heterocyclyl group containing 3 to 8 carbon atoms, an aryl group containing 5 to 20 carbon atoms, or a heteroaryl group containing 5 to 10 carbon atoms; the alkyl group containing 1 to 6 carbon atoms, the cycloalkyl group containing 3 to 8 carbon atoms, the heterocyclyl group containing 3 to 8 carbon atoms, the aryl group containing 5 to 20 carbon atoms, or the heteroaryl group containing 5 to 10 carbon atoms are optionally further substituted by one or more of the following groups: an alkyl group containing 1 to 6 carbon atoms, a cycloalkyl group containing 3 to 8 ring atoms, a heterocyclyl group containing 3 to 8 ring atoms, halogen, hydroxyl, nitro or amino.

[0037] Currently reported technologies for solving the problem of interlayer miscibility include thermal or photochemical cross-linking of the previous functional layer before applying the hole injection layer material, forming a self-assembled layer on ITO, or utilizing the solubility difference between polar solvents and non-polar solvents to solve the problem of interlayer miscibility. However, the efficiency and lifespan of devices made with these related technical solutions still need to be further improved.

[0038] Based on this, in the first aspect of the present application, a p-doped cross-linking agent is provided, having the general structure shown in Formula II:

[0039] Formula II;

[0040] Wherein, L1 and L2 are independently selected from -(CH2) q4 -(CH2O) q5 -(CH2) q6 -(CH=CH) q7 -P3-(CH2) q8 -;

[0041] P3 is selected from a single bond, -C(=CR5R6)-, substituted or unsubstituted C 6-60 Arylene, substituted or unsubstituted heteroarylene having 5 to 60 ring atoms, or one of the following groups: R5 and R6 are independently selected from H, C 1-20 Alkyl or cyano;

[0042] ;

[0043] Ar5, Ar6 and Ar7, when present, are independently selected from substituted or unsubstituted C 6-60 Arylene, substituted or unsubstituted heteroarylene having 5 to 60 ring atoms;

[0044] Each occurrence of q4, q5, q6, q7 and q8 is independently selected from any integer between 0 and 20;

[0045] W, at each occurrence, is independently selected from -H, -F, -Cl, -Br, -I, -CN, -NO2, C 1-20 Alkyl or C 1-20 Alkoxy;

[0046] The substituted substituents, each time they appear, are independently selected from D, amino, halogen, hydroxy, carboxyl, nitro, sulfonic acid, mercapto, cyano, C 1-20 Alkyl, C 1-20 A combination of one or more of an alkoxy group and an aryl group having 6 to 20 ring atoms.

[0047] Alkyl refers to an alkyl group containing several carbon atoms, which can be a straight chain alkyl group or a branched chain alkyl group. 1-8 Suitable examples of alkyl groups include, but are not limited to, methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, i-propyl, -CH(CH3)2), 1-butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, i-butyl, -CH2CH(CH3)2), 2-butyl (s-Bu, s-butyl, -CH(CH3)CH2CH3), 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH3)3), 1-pentyl (n-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl 1-butyl (-CH2CH2CH(CH3)2), 2-methyl-1-butyl (-CH2CH(CH3)CH2CH3), 1-hexyl (-CH2CH2CH2CH2CH2CH3), 2-hexyl (-CH(CH3)CH2CH2CH2CH3), 3-hexyl (-CH(CH2CH3)(CH2CH2CH3)), 2-methyl-2-pentyl (-C(CH3)2CH2CH2CH3), 3-methyl-2-pentyl (-CH(CH3)CH(CH3)CH2CH3), 4-methyl-2-pentyl (-CH(CH3)CH2CH(CH3)2), 3-methyl-3-pentyl (-C(CH3)(CH2CH3)2), 2-methyl-3-pentyl (-CH(CH2CH3)CH(CH3)2), 2,3-dimethyl-2-butyl (-C(CH3)2CH(CH3)2) and 3,3-dimethyl-2-butyl (-CH(CH3)C(CH3)3.

[0048] Aryl refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing a hydrogen atom. It can be a monocyclic aromatic group, a condensed aromatic group, or a polycyclic aromatic group. For polycyclic rings, at least one is an aromatic ring system. 6-60 Aryl refers to an aromatic group having 6 to 60 carbon atoms. Suitable examples include, but are not limited to, benzene, biphenyl, naphthalene, anthracene, phenanthrene, perylene, triphenylene and derivatives thereof. It is understood that multiple aromatic groups may also be interrupted by short non-aromatic units (e.g., <10% non-H atoms, such as C, N or O atoms), such as acenaphthene, fluorene, or 9,9-diarylfluorene, triarylamine, diaryl ether system should also be included in the definition of aromatic group.

[0049] Heteroaryl refers to an aryl or aromatic group in which at least one carbon atom is replaced by a non-carbon atom, and the non-carbon atom may be an N atom, an O atom, an S atom, an Si atom, a P atom, etc., and may further be an N atom, an O atom and an S atom. A 5- to 60-membered heteroaryl refers to a monocyclic or bicyclic heteroaryl having 5 to 10 ring atoms, of which 1, 2, 3 or 4 ring atoms are heteroatoms. Suitable examples include, but are not limited to, furan, benzofuran, thiophene, benzothiophene, pyrrole, benzopyrrole, pyrazole, benzopyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furanofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-naphthyridine, quinoxaline, phenanthridine, primary idine, quinazoline, and quinazolinone.

[0050] Optionally, the p-doped cross-linking agent has a general structure as shown in Formula II-a:

[0051] Formula II-a;

[0052] L1 and L2 are independently selected from one of the following groups:

[0053] ;

[0054] R5 and R6 are independently selected from H, C 1-10 Alkyl or cyano;

[0055] Ar4, at each occurrence, is independently selected from substituted or unsubstituted C 6-60 Arylene, substituted or unsubstituted heteroarylene having 5 to 60 ring atoms, or one of the following groups:

[0056] ;

[0057] Each occurrence of m is independently selected from any integer between 0 and 10.

[0058] Optionally, R5 and R6 are independently selected from H, C 1-6 Alkyl or cyano.

[0059] Optionally, Ar4, at each occurrence, is independently selected from C 6-30 Arylene or heteroaryl having 5 to 30 ring atoms. Optionally, each occurrence of Ar4 is independently selected from C 6-15 Arylene or heteroaryl having 5 to 15 ring atoms.

[0060] Optionally, Ar5, Ar6 and Ar7, when present at each time, are independently selected from C 6-30 Arylene or heteroaryl having 5 to 30 ring atoms. Optionally, Ar5, Ar6 and Ar7, when present each time, are independently selected from C 6-15 Arylene or heteroaryl having 5 to 15 ring atoms.

[0061] Optionally, m is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0062] In some preferred embodiments, L1 and L2 are the same.

[0063] Preferably, L1 and L2 are the same and are selected from .

[0064] Optionally, the Selected from one of the following groups:

[0065] ;

[0066] Each occurrence of m is independently selected from any integer between 0 and 6.

[0067] In some embodiments, the p-doped cross-linker has a symmetrical structure.

[0068] In some embodiments, the p-doping cross-linking agent includes at least one of the following compounds N1-N10:

[0069] .

[0070] The second aspect of the present application provides a composition for preparing a hole injection layer, comprising at least one main material and at least one p-doping crosslinking agent, wherein the main material has a general structure shown in Formula I:

[0071] Formula I;

[0072] Wherein, R1, R2, R3 and R4 are independently selected from -P1-(CH2) q1 -(CH2O) q2 -(CH2) q3 -P2;

[0073] P1 is selected from a single bond or C 6-60 arylene;

[0074] P2 is selected from H, -CH3, CH2=CH-, C 6-60 An aryl group or a heteroaryl group having 5 to 60 ring atoms;

[0075] Each occurrence of q1, q2 and q3 is independently selected from any integer between 0 and 20;

[0076] X is selected from O, S, -NR a , -PR a or CR a R b ;

[0077] Y single button, O, S, -NR a , -PR a or -CR a R b ;

[0078] Z selects single bond, O, S, -N-Ar1, -PR a or -CR a R b ;

[0079] R a and R b Each occurrence is independently selected from H or C 1-3 alkyl;

[0080] Ar1 is selected from substituted or unsubstituted C 6-60 Aryl, substituted or unsubstituted heteroaryl having 5 to 60 ring atoms;

[0081] The substituted substituents, each time they appear, are independently selected from D, amino, halogen, hydroxy, carboxyl, nitro, sulfonic acid, mercapto, cyano, C 1-20 Alkyl, C 1-20 A combination of one or more of an alkoxy group and an aryl group having 6 to 20 ring atoms.

[0082] Optionally, the host material has a general structure as shown in Formula Ia:

[0083] Formula Ia;

[0084] Wherein, R1, R2, R3 and R4 are independently selected from H, C 1-10 Alkyl, C 6-60 Aryl or one of the following substituents:

[0085] ;

[0086] Ar2, at each occurrence, is independently selected from C 6-60 arylene;

[0087] Ar3, when present, is independently selected from heteroaryl having 5 to 60 ring atoms;

[0088] Each occurrence of n is independently selected from any integer between 0 and 10, and n1 and n2 are any integers between 0 and 10.

[0089] Optionally, R1, R2, R3 and R4 are independently selected from H, C 1-6 Alkyl or C 6-30 Alternatively, R1, R2, R3 and R4 are independently selected from C 6-15 Aryl.

[0090] Optionally, Ar2, at each occurrence, is independently selected from C 6-30 Arylene. Optionally, each occurrence of Ar2 is independently selected from C 6-15 Arylene.

[0091] Optionally, each occurrence of Ar3 is independently selected from heteroaryl groups having 5 to 30 ring atoms. Optionally, each occurrence of Ar3 is independently selected from heteroaryl groups having 5 to 15 ring atoms.

[0092] Optionally, n is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0093] Optionally, n1 is 0, 1, 2, 3, 4 or 5.

[0094] Optionally, n2 is 0, 1, 2, 3, 4 or 5.

[0095] In some preferred embodiments, at least two of R1, R2, R3 and R4 are selected from or -(CH2) q1 -(CH2O) q2 -(CH2) q3 -CH=CH2, wherein q1, q2 and q3, when present, are independently selected from any integer between 0 and 10.

[0096] In some preferred embodiments, the host material has a structure shown in any one of Formula I-1 to Formula I-3:

[0097] Formula I-1;

[0098] Formula I-2;

[0099] Formula I-3.

[0100] Preferably, R1 and R4 are independently selected from H or phenyl; R2 and R3 are independently selected from C 1-8 Alkyl or one of the following substituents:

[0101]

[0102] Optionally, Ar1 is selected from any one of the following formulae (i) to (xii):

[0103] ;

[0104] Wherein R7 is selected from C 1-8 alkyl.

[0105] Further optionally, formula (xiii) may include one or more of the following formulae:

[0106] .

[0107] In some specific embodiments, Ar1 is selected from formula (ii), formula (iii), formula (vii), formula (xi) or formula (xiii).

[0108] Optionally, Ar1 is selected from any one of the following groups:

[0109] .

[0110] In some embodiments, the host material has a symmetrical structure. In some embodiments, both the host material and the p-doped cross-linking agent have a symmetrical structure.

[0111] In some embodiments, the host material includes at least one of the following compounds M1 to M10:

[0112] ,

[0113] .

[0114] In some embodiments, the host material includes at least one of the above compounds M1-M11, and the p-doping cross-linking agent includes at least one of the above compounds N1-N10.

[0115] In some embodiments, the mass percentage of the p-doped crosslinking agent in the composition is 0.1% to 50%, for example, 0.1%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, or a value between any two of the above values.

[0116] The above-mentioned host material can be prepared or obtained by commercial purchase or methods known in the art.

[0117] In a third aspect of the present application, a polymer is provided, wherein the polymer is prepared by reacting the main material in the above-mentioned composition with the p-doped cross-linking agent.

[0118] Optionally, the reaction conditions are: heating by a hot plate, the temperature range is 100°C to 250°C, and the heating time is 0.1h to 24h.

[0119] In a fourth aspect of the present application, a thin film is provided, wherein the material of the thin film is prepared by reacting the main material in the above-mentioned composition and the p-doped cross-linking agent.

[0120] In a fifth aspect of the present application, a light-emitting device is provided, comprising a first electrode, a functional layer and a second electrode stacked in sequence, wherein the material of the functional layer comprises a polymer prepared by reacting the main material in the above-mentioned composition and the p-doped crosslinking agent.

[0121] Optionally, the functional layer includes a hole injection layer, and the material of the hole injection layer includes a polymer prepared by reacting the main material in the above composition and the p-doped cross-linking agent.

[0122] Optionally, the functional layer further comprises a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer which are stacked in sequence; wherein the hole injection layer is located on a side of the hole transport layer away from the light emitting layer.

[0123] In addition, the light emitting device of the present application is described.

[0124] The light-emitting device comprises a cathode, an anode and one or more organic functional layers between the cathode and the anode. The organic functional layer is selected from one or more layers of an electron injection layer, an electron transport layer, a hole blocking layer, a hole injection layer, a hole transport layer, an electron blocking layer and a light-emitting layer, wherein at least one light-emitting layer is included. Typically, the organic functional layer comprises a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer and an electron injection layer.

[0125] This application has no particular restrictions on other aspects of the light-emitting device. Figure 1 : is a schematic diagram of the structure of an organic electroluminescent device as an example. The organic electroluminescent device includes an anode 2, a cathode 4, and an organic functional layer 3 located between the anode 2 and the cathode 4, which are stacked in sequence, including a hole injection layer (HIL) 3a, a hole transport layer (HTL) 3b, a light emitting layer (EML) 3c, an electron transport layer (ETL) 3d, and an electron injection layer (EIL) 3e. Further, the organic electroluminescent device also includes a substrate 1.

[0126] The cathode, anode and organic functional layer of the light emitting device structure are further described below, but are not limited thereto.

[0127] Optionally, the materials of the first electrode and the second electrode independently include a doped metal oxide particle electrode, a composite electrode, a graphene electrode, a carbon nanotube electrode, a metal element electrode or an alloy electrode, the material of the doped metal oxide particle electrode includes one or more of indium-doped tin oxide, fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide and aluminum-doped magnesium oxide, the composite electrode includes one or more of AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO2 / Ag / TiO2, TiO2 / Al / TiO2, ZnS / Ag / ZnS or ZnS / Al / ZnS, and the material of the metal element electrode includes one or more of Ag, Al, Cu, Mo, Au, Pt, Ca, Mg and Ba.

[0128] Optionally, the material of the hole transport layer includes poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-(4,4'-(N-(4-n-butyl)phenyl)-diphenylamine)], polyvinylcarbazole, [N,N'-(4-n-butylphenyl)-N,N'-diphenyl-p-phenylenediamine]-[9,9-dioctylfluorenyl-2,7-diyl] copolymer, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-1,1'-biphenyl-4,4'-diamine, 4,4',4''-tri(carbazole-9-yl)triphenylamine, 4,4'-cyclohexylbis[N,N-di(4-methylphenyl)aniline], Poly-T BP, Poly-TPD, N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine, 4,4'-bis(9-carbazole)biphenyl), 4,4'-N,N'-dicarbazolyl-biphenyl, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4''-diamine, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine, poly(N, N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine), N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-spiro, N,N'-bis(4-(N,N'-diphenyl-amino)phenyl)-N,N'-diphenylbenzidine, 4,4',4'-tri(N-carbazolyl)-triphenylamine, 4,4',4'-tri(N-3-methylphenyl-N-phenylamino)triphenylamine, poly[(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))], poly(N-vinylcarbazole) and its derivatives, N,N'-di(1-naphthyl)-N,N'-diphenyl-1,1'-biphenyl-4-4'-diamine, Spiro NPB, poly(phenylene vinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene], poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene], 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene, 1,3-di(carbazol-9-yl)benzene, polyaniline, polypyrrole, poly(p-phenylene vinylene), aromatic tertiary amine, polynuclear aromatic tertiary amine, 4,4'-bis(p-carbazolyl)-1,1'-biphenyl compound, N,N,N',N'-tetraarylbenzidine, PEDOT:PSS and its derivatives, polymethacrylate and its derivatives, poly(9,9-octylfluorene) and its derivatives, poly (spirofluorene) and its derivatives, doped graphene, undoped graphene, C60, doped or undoped NiO, doped or undoped MoO3, doped or undoped WO3, doped or undoped V2O5, doped or undoped P-type gallium nitride, doped or undoped CrO3, doped or undoped CuO.

[0129] Optionally, the material of the light-emitting layer includes one or more of organic light-emitting materials and quantum dots;

[0130] Wherein, the organic light-emitting material is selected from trihydroxyquinoline (Alq3), 4,4'-bis(N-carbazole)-1,1'-biphenyl:tri[2-(p-tolyl)pyridine iridium(III) (BD01), 4,4',4''-tri(carbazole-9-yl)triphenylamine:tri[2-(p-tolyl)pyridine iridium, diaromatic anthracene derivatives, distilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials, DBP fluorescent materials, delayed fluorescent materials, TTA materials, thermally activated delayed materials, polymers containing BN covalent bonds, hybrid localized charge transfer excited state materials and exciplex luminescent materials.

[0131] The quantum dots are selected from one or more of single-component quantum dots, core-shell quantum dots, inorganic perovskite quantum dots, organic perovskite quantum dots and organic-inorganic hybrid perovskite quantum dots; the material of the single-component quantum dots, the material of the core of the core-shell quantum dots and the material of the shell of the core-shell quantum dots are independently selected from at least one of II-VI compounds, III-V compounds, IV-VI compounds or I−III−VI compounds, wherein the II-VI compounds are selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, Cd One or more of CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe and HgZnSTe, wherein the III-V group compound is selected from GaN, GaP, GaAs, Ga Sb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb , InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb , InAlPAs and InAlPSb, the IV-VI group compound is selected from one or more of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe and SnPbSTe, the I-III-VI group compound is selected from one or more of CuInS, CuInSe and AgInS; the general structural formula of the inorganic perovskite quantum dot is AMX3, wherein A is C s+ ion, M is a divalent metal cation, M is selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ and Eu 2+ One or more of, X is a halogen anion; the general structural formula of the organic perovskite quantum dots is CMX3, C is a carboxamidine group; the general structural formula of the organic-inorganic hybrid perovskite quantum dots is BMX3, and B is selected from organic amine cations.

[0132] Optionally, the material of the electron transport layer includes one or more of an inorganic electron transport material and an organic electron transport material, the inorganic electron transport material includes but is not limited to one or more of doped metal oxide particles, undoped metal oxide particles, ceramic semiconductor materials, IIB-VIA semiconductor materials, IIIA-VA semiconductor materials and IB-IIIA-VIA semiconductor materials, the metal oxide in the undoped metal oxide particles includes one or more of ZnO, TiO2, SnO2, ZrO2, Ta2O5, the metal oxide in the doped metal oxide includes one or more of ZnO, TiO2, SnO2, ZrO2, Ta2O5, Al2O3, the doping elements in the doped metal oxide include Al, Mg, Li, Mn, The invention relates to a semiconductor material comprising one or more of Y, La, Cu, Ni, Zr, Ce, In, Ga and Sn, the semiconductor material of Group IIB-VIA comprises one or more of ZnS, ZnSe and CdS, the semiconductor material of Group IIIA-VA comprises one or more of InP and GaP, the semiconductor material of Group IB-IIIA-VIA comprises one or more of CuInS and CuGaS, the organic electron transport material comprises one or more of quinoxaline compounds, imidazole compounds, triazine compounds, fluorene-containing compounds and hydroxyquinoline compounds; the hydroxyquinoline compound comprises one or more of 8-hydroxyquinoline lithium (LiQ) and metal chelates of 8-hydroxyquinoline; the imidazole compound comprises 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl) (TPBi).

[0133] Optionally, the material of the electron injection layer is selected from one or more of Yb, MgF2, LiF, lithium oxide, cesium carbonate, and cesium fluoride.

[0134] Other organic materials involved in this application, such as PSS is polystyrene sulfonate, and PEDOT is a polymer of EDOT (3,4-ethylenedioxythiophene monomer).

[0135] The organic electroluminescent device described in the present application can be selected from, but not limited to, organic light emitting diodes (OLEDs), organic photovoltaic cells, organic light emitting cells, organic field effect transistors, organic light emitting field effect transistors, organic lasers, organic spin electronic devices, organic sensors and organic plasmon emission diodes, etc., and OLEDs are particularly preferred.

[0136] Example

[0137] The embodiments described below are exemplary and are only used to explain the present application, and should not be construed as limiting the present application. Where the techniques or conditions are not specified in the embodiments, the techniques or conditions described in the literature in the art or the product specifications are used. The reagents or instruments used are conventional products that can be obtained commercially if the manufacturer is not specified.

[0138] The synthesis method of the organic compound of the present application is exemplified, but the present application is not limited to the following examples.

[0139] 1. Preparation of main materials

[0140] 1.1 Preparation of compound M1

[0141]

[0142]

[0143] (1) Preparation of compound 1

[0144] Under nitrogen protection, 5,10-dihydrophenoxazine (20 mmol), N-bromosuccinimide (80 mmol) and 100 ml dichloromethane were added to a 250 ml reaction bottle and stirred at room temperature for 24 hours in the dark. After the reaction was completed, the product was extracted with dichloromethane, the organic phase was washed with saturated sodium chloride aqueous solution, the solvent was evaporated under reduced pressure, and the crude product was purified by column chromatography using a mixed solvent of petroleum ether: dichloromethane = 6:1 (v / v) as the eluent to obtain a white solid with a yield of 52%.

[0145] (2) Preparation of Compound 2

[0146] Under nitrogen protection, compound 1 (20 mmol), 1-thiophene tributyltin (40 mmol), tetrakistriphenylphosphine palladium (1 mmol) and 200 ml of anhydrous tetrahydrofuran were added to the reaction flask, and the temperature was raised and refluxed for 12 hours. After the reaction was completed, the product was extracted with dichloromethane, and the organic phase was washed 5 times with saturated sodium chloride aqueous solution until the water layer was clear, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography using a mixed solvent of petroleum ether: dichloromethane = 7:1 (v / v) as the eluent to obtain a white solid with a yield of 54%.

[0147] (3) Preparation of compound 3

[0148] Under nitrogen protection, compound 2 (20 mmol) and catalyst COPC (CAS No.: 91443-37-7) (8%) were added to the reaction flask, dissolved and stirred with 50 ml acetonitrile at room temperature, and irradiated with 254 nm ultraviolet light for 24 hours. After the reaction was completed, the product was extracted with dichloromethane, and the organic phase was washed 5 times with saturated sodium chloride aqueous solution until the water layer was clear. The solvent was removed under reduced pressure, and the crude product was purified by column chromatography using a mixed solvent of petroleum ether: dichloromethane = 7:1 (v / v) as the eluent to obtain a white solid with a yield of 63%.

[0149] (4) Preparation of Compound 2-1

[0150] Add compound 3 (20 mmol) and N-4-bromophenyl diphenylamine into a 300 ml two-necked flask. (40 mmol), potassium carbonate (40 mmol) and tetrakistriphenylphosphine palladium (0.4 mmol) were added, 20 ml of water and 40 ml of 1,4-dioxane were added, and the temperature was raised to 85°C and stirred for 12 hours. After the reaction was completed, the product was extracted with dichloromethane, washed with saturated sodium chloride aqueous solution, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography using a mixed solvent of petroleum ether: dichloromethane = 3:1 (v / v) as the eluent to obtain a white solid with a yield of 61%.

[0151] (5) Preparation of compound 2-2

[0152] Under nitrogen protection, add 2-1 (20 mmol), N-bromosuccinimide (80 mmol) and 200 ml of dichloromethane to a 250 ml two-necked flask and stir at room temperature for 24 hours in the dark. After the reaction is completed, extract the product with dichloromethane, wash the organic phase with saturated sodium chloride aqueous solution, evaporate the solvent under reduced pressure, and purify the crude product by column chromatography using a mixed solvent of petroleum ether: dichloromethane = 6:1 (v / v) as the eluent to obtain a white solid with a yield of 49%.

[0153] (6) Preparation of Compound M1

[0154] Add compound 2-2 (10 mmol), p-vinylbenzeneboronic acid into a 300 ml two-necked flask. (40mmol), potassium carbonate (20 mmol) and tetrakistriphenylphosphine palladium (0.25 mmol) were added, 15 ml of water and 60 ml of 1,4-dioxane were added, and the temperature was raised to 85°C and stirred for 12 hours. After the reaction was completed, the product was extracted with dichloromethane, washed with saturated sodium chloride aqueous solution, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography using a mixed solvent of petroleum ether: dichloromethane = 3:1 (v / v) as the eluent to obtain a white solid with a yield of 54%.

[0155] The characterization results of compound M1 are: 1 H NMR (400 MHz, CDCl3), δ (ppm): 7.72 (m, J=7.7Hz,.10H), 7.62-7.57 (d, J=7.7Hz, 12H), 7.54-7.47 (dd, J=9.7, 5.6 Hz, 4H), 7.46-7.41 (m, J=8.2 Hz, 12H), 7.25-7.30 (m, J=5.0Hz 4H), 7.03-7.09 (t, J=7.7Hz,4H), 5.03-5.09 (t, J=7.7Hz,4H).

[0156] 1.2 Preparation of Compound M2

[0157] (1)-(4), referring to steps (1)-(4) of the preparation of compound M1, compound 2-1 was prepared.

[0158] (5) Preparation of Compound 2-3

[0159] Under nitrogen protection, add 2-1 (20 mmol), N-bromosuccinimide (40 mmol) and 200 ml of dichloromethane to a 250 ml two-necked flask and stir at room temperature for 24 hours in the dark. After the reaction is completed, extract the product with dichloromethane, wash the organic phase with saturated sodium chloride aqueous solution, evaporate the solvent under reduced pressure, and purify the crude product by column chromatography using a mixed solvent of petroleum ether: dichloromethane = 6:1 (v / v) as the eluent to obtain compound 2-3, with the structural formula: , yield 52%.

[0160] (6) Preparation of Compound 2-4

[0161] Add compound 2-3 (10 mmol), p-vinylbenzeneboronic acid into a 300 ml two-necked flask. (20mmol), potassium carbonate (20 mmol) and tetrakistriphenylphosphine palladium (0.25 mmol) were added and 15 ml of water and 60 ml of 1,4-dioxane were added and the temperature was raised to 85°C and stirred for 12 hours. After the reaction was completed, the product was extracted with dichloromethane, washed with saturated sodium chloride aqueous solution, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography using a mixed solvent of petroleum ether: dichloromethane = 3:1 (v / v) as an eluent to obtain compound 2-4, with the structural formula: , yield 54%.

[0162] (7) Preparation of Compound 2-5

[0163] Under nitrogen protection, 2-4 (20 mmol), N-bromosuccinimide (20 mmol) and 200 ml of dichloromethane were added to a 250 ml two-necked flask and stirred at room temperature for 24 hours in the dark. After the reaction was completed, the product was extracted with dichloromethane, the organic phase was washed with a saturated sodium chloride aqueous solution, the solvent was evaporated under reduced pressure, and the crude product was purified by column chromatography using a mixed solvent of petroleum ether: dichloromethane = 6:1 (v / v) as the eluent to obtain compound 2-5, the structural formula of which is , yield 49%.

[0164] (8) Add compound 2-5 (10 mmol), (10 mmol), potassium carbonate (20 mmol) and tetrakistriphenylphosphine palladium (0.25 mmol) were added, 15 ml of water and 60 ml of 1,4-dioxane were added, and the temperature was raised to 85°C and stirred for 12 hours. After the reaction was completed, the product was extracted with dichloromethane, washed with saturated sodium chloride aqueous solution, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography using a mixed solvent of petroleum ether: dichloromethane = 3:1 (v / v) as an eluent to obtain compound M2 with a yield of 53%.

[0165] The characterization results of compound M2 are: 1 H NMR (400 MHz, CDCl3), δ (ppm): 7.76-7.78 (m, J=7.7Hz, 10H), 7.53-7.59 (d, J=7.7Hz, 10H), 7.54-7.47 (m, J=9.7, 5.6 Hz, 16H), 6.72-6.74 (m, J=8.2 Hz, 2H), 5.76-5.78 (dd, J=5.0Hz 2H), 5.25-5.30 (m, J=7.7Hz, 2H)

[0166] 1.3 Preparation of Compound M3

[0167] (1)-(5), refer to steps (1)-(5) of the preparation of compound M2 to prepare compound 2-3.

[0168] (6) is basically the same as step (6) of compound M2, except that vinylbenzene boronic acid Replace with , prepare compound 2-6, the structural formula is: , yield 48%.

[0169] (7) Preparation of Compound 2-7

[0170] Under nitrogen protection, add 2-6 (20 mmol), N-bromosuccinimide (40 mmol) and 200 ml dichloromethane to a 250 ml two-necked bottle and stir at room temperature for 24 hours in the dark. After the reaction is completed, extract the product with dichloromethane, wash the organic phase with saturated sodium chloride aqueous solution, evaporate the solvent under reduced pressure, and purify the crude product by column chromatography using a mixed solvent of petroleum ether: dichloromethane = 6:1 (v / v) as the eluent to obtain compound 2-7, the structure of which is: , with a yield of 56%.

[0171] (8) Add compound 2-7 (10 mmol), (20 mmol), potassium carbonate (20 mmol) and tetrakistriphenylphosphine palladium (0.25 mmol) were added, 15 ml of water and 60 ml of 1,4-dioxane were added, and the temperature was raised to 85°C and stirred for 12 hours. After the reaction was completed, the product was extracted with dichloromethane, washed with saturated sodium chloride aqueous solution, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography using a mixed solvent of petroleum ether: dichloromethane = 3:1 (v / v) as an eluent to obtain compound M3 with a yield of 50%.

[0172] The characterization results of compound M3 are: 1 H NMR (400 MHz, CDCl3), δ (ppm): 7.76-7.78 (m, J=7.7Hz, 4H), 7.53-7.59 (d, J=7.7Hz, 14H), 7.40-7.46 (s, J=9.7, 5.6 Hz, 2H), 7.24-7.28 (m, , 2.78-2.81 (m,J=5.0Hz 4H),1.60-1.68 (m, J=8.2 Hz, 4H), 1.29-1.30 (m, J=5.0Hz 6H), 0.88-0.92(m, J=7.7Hz,6H)

[0173] 1.4 Preparation of Compound M4

[0174] (1)-(8), refer to steps (1)-(8) of the preparation of compound M3, the main difference is that in step (6), Replace with , compound M4 was prepared with a yield of 49%.

[0175] The characterization results of compound M4 are: 1 H NMR (400 MHz, CDCl3), δ (ppm): 8.34-8.38 (m, J=7.7Hz, 10H), 7.96-7.80 (d, J=7.7Hz, 12H), 7.08-7.33 (m, J=9.7, 24H), 6.72-6.74 (m, J=8.2 Hz, 2H), 5.76-5.78 (dd, J=5.0Hz 2H), 5.25-5.30 (m, J=7.7Hz,2H), 4.16-4.18 (t, J=5.0Hz 4H), 2.80-2.82 (m, J=8.2 Hz, 4H), 1.68-1.74 (m, J=5.0Hz 8H), 1.26-1.29 (m, J=7.7Hz,4H)

[0176] 1.5 Preparation of Compound M5

[0177] (1)-(8), refer to steps (1)-(8) of the preparation of compound M3, the main difference is that in step (6), Replace with , compound M5 was prepared with a yield of 47%.

[0178] The characterization results of compound M5 are: 1 H NMR (400 MHz, CDCl3), δ (ppm): 7.76-7.78 (m, J=7.7Hz, 6H), 7.48-7.82 (m, J=7.7Hz, 8H), 7.24-7.28 (m, J=9.7, 5.6 Hz, 4H), 6.96-7.24 (m, , 3.35-3.38(m, J=8.2 Hz, 4H), 1.68-1.74 (m, J=5.0Hz 8H), 0.96-1.00 (m, J=7.7Hz, 6H)

[0179] 1.6 Preparation of Compound M6

[0180] (1)-(8), refer to steps (1)-(8) of the preparation of compound M3, the main difference is that in step (6), Replace with , compound M6 was prepared with a yield of 51%.

[0181] The characterization results of compound M6 are: 1 H NMR (400 MHz, CDCl3), δ (ppm): 7.76-7.78 (m, J=7.7Hz, 6H), 7.48-7.82 (m, J=7.7Hz, 8H), 7.24-7.28 (m, J=9.7, 5.6 Hz, 4H), 6.96-7.24 (m, , 2.81-2.85(m, J=8.2 Hz, 4H), 2.13-2.16 (m, J=8.2 Hz, 4H), 1.50-1.55 (m, J=5.0Hz 4H), 1.29-1.1.35 (m, J=7.7Hz, 4H)

[0182] 1.7 Preparation of Compound M7

[0183] (1)-(3), Compound 3 was prepared by referring to steps (1)-(3) of the preparation of Compound M1.

[0184] (4) Preparation of Compound 2-8

[0185] Add compound 3 (20 mmol), (40 mmol), potassium carbonate (40 mmol) and tetrakistriphenylphosphine palladium (0.4 mmol) were added and 20 ml of water and 40 ml of 1,4-dioxane were added and the temperature was raised to 85°C and stirred for 12 hours. After the reaction was completed, the product was extracted with dichloromethane, washed with saturated sodium chloride aqueous solution, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography using a mixed solvent of petroleum ether: dichloromethane = 3:1 (v / v) as an eluent to obtain compound 2-8, with the structural formula: , yield 45%.

[0186] (5) Preparation of Compound 2-9

[0187] Under nitrogen protection, add 2-8 (20 mmol), N-bromosuccinimide (40 mmol) and 200 ml of dichloromethane to a 250 ml two-necked flask and stir at room temperature for 24 hours in the dark. After the reaction is completed, extract the product with dichloromethane, wash the organic phase with saturated sodium chloride aqueous solution, evaporate the solvent under reduced pressure, and purify the crude product by column chromatography using a mixed solvent of petroleum ether: dichloromethane = 6:1 (v / v) as the eluent to obtain compound 2-9, with the structural formula: , yield 50%.

[0188] (6) Preparation of Compound 2-10

[0189] Add compound 2-9 (10 mmol), p-vinylbenzeneboronic acid into a 300 ml two-necked flask. (20mmol), potassium carbonate (20 mmol) and tetrakistriphenylphosphine palladium (0.25 mmol) were added and 15 ml of water and 60 ml of 1,4-dioxane were added and the temperature was raised to 85°C and stirred for 12 hours. After the reaction was completed, the product was extracted with dichloromethane, washed with a saturated sodium chloride aqueous solution, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography using a mixed solvent of petroleum ether: dichloromethane = 3:1 (v / v) as an eluent to obtain compound 2-10, with the structural formula: , yield 56%.

[0190] (7) Preparation of Compound 2-11

[0191] Under nitrogen protection, 2-10 (20 mmol), N-bromosuccinimide (20 mmol) and 200 ml of dichloromethane were added to a 250 ml two-necked bottle and stirred at room temperature for 24 hours in the dark. After the reaction was completed, the product was extracted with dichloromethane, the organic phase was washed with a saturated sodium chloride aqueous solution, the solvent was evaporated under reduced pressure, and the crude product was purified by column chromatography using a mixed solvent of petroleum ether: dichloromethane = 6:1 (v / v) as the eluent to obtain compound 2-11, the structural formula of which is , yield 62%.

[0192] (8) Add compound 2-11 (10 mmol), (10 mmol), potassium carbonate (20 mmol) and tetrakistriphenylphosphine palladium (0.25 mmol) were added, 15 ml of water and 60 ml of 1,4-dioxane were added, and the temperature was raised to 85°C and stirred for 12 hours. After the reaction was completed, the product was extracted with dichloromethane, washed with saturated sodium chloride aqueous solution, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography using a mixed solvent of petroleum ether: dichloromethane = 3:1 (v / v) as an eluent to obtain compound M7 with a yield of 51%.

[0193] The characterization results of compound M7 are:1 H NMR (400 MHz, CDCl3), δ (ppm): 8.39-8.42 (dd,J=7.7Hz, 2H), 7.48-7.82 (m, J=7.7Hz, 27H), 6.89-6.96 (s, J=9.7, Hz, 4H), 6.72-6.74 (m, J=8.2 Hz, 4H), 5.76-5.78 (dd, J=5.0Hz 4H), 5.25-5.30 (m, J=7.7Hz,4H), 4.16-4.18 (t, J=5.0Hz 4H), 1.26-1.29 (m, J=8.2 Hz, 2H), 0.86-0.92(m, J=5.0Hz 3H)

[0194] 2. Preparation of p-doped crosslinker

[0195] 2.1 Preparation of compound N1

[0196]

[0197] (1) Preparation of compound 3-3

[0198] Under nitrogen protection, 4,8-dibromo-1,2,3,6,7,8-hexafluoronaphthalene (20 mmol), compound 3-2 (80 mmol) and 100 ml dichloromethane were added to a 250 ml reaction bottle and stirred at room temperature for 24 hours in the dark. After the reaction was completed, the product was extracted with dichloromethane, the organic phase was washed with a saturated sodium chloride aqueous solution, the solvent was evaporated under reduced pressure, and the crude product was purified by column chromatography using a mixed solvent of petroleum ether: dichloromethane = 6:1 (v / v) as the eluent to obtain a white solid with a yield of 50%.

[0199] (2) Preparation of compound N1

[0200] Under nitrogen protection, compound 3-2 (20 mmol), 1-vinylpropyltributyltin (40 mmol), tetrakistriphenylphosphine palladium (1 mmol) and 200 ml of anhydrous tetrahydrofuran were added to the reaction flask, and the temperature was raised and refluxed for 12 hours. After the reaction was completed, the product was extracted with dichloromethane, and the organic phase was washed 5 times with saturated sodium chloride aqueous solution until the water layer was clear, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography using a mixed solvent of petroleum ether: dichloromethane = 7:1 (v / v) as the eluent to obtain a white solid with a yield of 50%.

[0201] The characterization results of compound N1 are: 1H NMR (400 MHz, CDCl3), δ (ppm): 5.85-5.90 (m, J=7.7Hz, 2H), 5.03-5.08 (m, J=7.7Hz, 4H), 2.63-2.68 (t, J=9.7, 4H)

[0202] 2.1 Preparation of compound N7

[0203]

[0204] (3) Preparation of compound 4-3

[0205] Under nitrogen protection, 4,8-dibromo-1,2,3,6,7,8-hexafluoronaphthalene (20 mmol), compound 4-2 (80 mmol) and 100 ml dichloromethane were added to a 250 ml reaction bottle and stirred at room temperature for 24 hours in the dark. After the reaction was completed, the product was extracted with dichloromethane, the organic phase was washed with a saturated sodium chloride aqueous solution, the solvent was evaporated under reduced pressure, and the crude product was purified by column chromatography using a mixed solvent of petroleum ether: dichloromethane = 6:1 (v / v) as the eluent to obtain a white solid with a yield of 50%.

[0206] (4) Preparation of Compound 4-5

[0207] Under nitrogen protection, compound 4-3 (20 mmol), compound 4-4 (20 mmol), potassium carbonate (40 mmol) and tetrakistriphenylphosphine palladium (0.4 mmol) were added to a 250 ml two-necked bottle, and 20 ml of water and 40 ml of 1,4-dioxane were added, and the temperature was raised to 85°C and stirred for 12 hours. After the reaction was completed, the product was extracted with dichloromethane, washed with saturated sodium chloride aqueous solution, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography using a mixed solvent of petroleum ether: dichloromethane = 3:1 (v / v) as the eluent to obtain a white solid with a yield of 60%.

[0208] (5) Preparation of compound N7

[0209] Under nitrogen protection, compound 4-5 (20 mmol), compound 4-2 (25 mmol), potassium carbonate (40 mmol) and tetrakistriphenylphosphine palladium (0.4 mmol) were added to a 250 ml two-necked bottle, and 20 ml of water and 40 ml of 1,4-dioxane were added, and the temperature was raised to 85°C and stirred for 12 hours. After the reaction was completed, the product was extracted with dichloromethane, washed with saturated sodium chloride aqueous solution, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography using a mixed solvent of petroleum ether: dichloromethane = 3:1 (v / v) as the eluent to obtain a white solid with a yield of 60%.

[0210] The characterization results of compound N7 are:1 H NMR (400 MHz, CDCl3), δ (ppm): 7.78-7.82 (m, J=7.7Hz, 4H), 7.00-7.24 (m, J=7.7Hz, 22H), 6.72-6.76 (m, J=9.7, 2H), 5.85-5.90(m, J=7.7Hz, 2H), 5.03-5.08 (m, J=7.7Hz, 2H), 2.63-2.68 (t, J=9.7, 8H), 1.59-1.62 (m, J=8.2 Hz, 4H), 0.86-0.92 (m, J=5.0Hz 8H)

[0211] 2. Application Examples

[0212] Example 1

[0213] Device structure: IZO / HIL (35 nm) / HTL (40 nm) / EML (45 nm) / ETL (25 nm) / EIL (1 nm) / Ag (100 nm). Among them, HIL is a hole injection layer, which is cross-linked and polymerized by the main material M1 and the p-doped cross-linking agent N7 with a mass ratio of 98:2, the HTL layer material is Poly-TFB film (CAS: 223569-31-1, purchased from Lumtec.Corp; 5 mg / mL xylene solution), EML is a light-emitting layer, and the material is Alq3 and BD01, wherein the mass ratio of Alq3 and BD01 is 7:3; ETL is an electron transport layer, and the material is LiQ (8-hydroxy lithium phosphate), EIL is an electron injection layer, and the material is Yb, and Ag is a cathode material.

[0214] The preparation steps of OLED devices are as follows:

[0215] 1. Indium zinc oxide (IZO) coated glass (Specifications: thickness 75 nm, sheet resistance 10 Ω m -2 , surface size 30 mm × 30 mm) pre-processed

[0216] The cleaning machine was used for program cleaning in sequence, with each cleaning step lasting 120 seconds. The stains and dust on the surface of the ITO glass substrate were thoroughly cleaned and placed on a hot plate at 230°C for 30 minutes. Then, the substrate was placed in an electric blast drying oven for 24 hours for drying. The dried glass substrate was then exposed to UV light and treated with O2 plasma for 15 minutes to reduce the surface work enthalpy.

[0217] 2. The pretreated ITO glass substrate was used as the device anode. Then, the main material M1, p-doped crosslinker N7 and toluene were poured into the inkjet printer cartridge in a nitrogen glove box. 9 pL of HIL ink was injected into each pixel luminous point, and VD was performed for 3 min (vacuum degree was 1×10 -4 mPa) to form a 35nm thick HIL layer and anneal it at 230℃ for 30 minutes. Then, the hole transport layer material (concentration of 30 mg / ml) dissolved in a mixed solution of xylene and cyclohexylbenzene was filtered and poured into the inkjet printer cartridge. 12 pL of HTL layer ink was injected into each pixel luminous point and VD was performed for 7min (vacuum degree of 1×10 -4 mPa) to form a 40nm thick HTL layer, which was annealed at 230℃ for 30 minutes. Then, the dissolved luminescent layer material (concentration 20 mg / ml) was prepared into ink and poured into the inkjet printer cartridge. 10 pL of EML layer ink was injected into each pixel of the HTL layer, and VD was performed for 5min (vacuum degree 1×10 -4 mPa), forming an EML layer, annealing at 140 °C for 20 min, with a thickness of 35 nm, and then transferring the substrate to a vacuum evaporation chamber (vacuum degree of 5×10 -7 Pa), vacuum evaporation is performed to evaporate 25 nm of ETL material onto the EML layer, then 1 nm of Yb is evaporated onto the surface of the ETL layer to form an EIL layer, and finally 100 nm thick Ag is evaporated onto the EIL, and finally UV curing and packaging are performed, and heating and baking are performed for 20 minutes.

[0218] Example 2-Example 12 and Comparative Example 1

[0219] The preparation methods of Examples 2 to 12 and Comparative Example 1 refer to Example 1, with the main difference being that the main material and the p-doped cross-linking agent in the hole injection layer are of different types or have different mass ratios. For details, see Table 1.

[0220] Comparative Example 2

[0221] Comparative Example 2: A HIL layer was prepared in the same manner as in Example 1, except that no p-doping crosslinking agent N7 was added.

[0222] The current-voltage (JV) characteristics of each OLED device were characterized by a characterization device, and the lifetime (LT90@1000nits) and the relative value of the external quantum efficiency EQE were recorded at the same time. The results are shown in Table 1. The lifetime LT90@1000nits refers to the time it takes for the brightness of the device to drop from an initial brightness of 1000nits to 90% of the initial brightness under a constant current.

[0223] The weight average molecular weight of the polymers of the HIL layers of Examples 1 to 12 after annealing is shown in Table 1. Electron paramagnetic resonance tests were performed on the annealed HIL layers of Examples 1, 8 to 10, 12 and Comparative Example 2, and the results are shown in Table 1. Figure 2 The conductive AFM morphology test was performed on Example 1 and Example 9, and the results are shown in Figure 3 .

[0224] Table 1

[0225]

[0226] It can be seen from Table 1 that each embodiment can significantly improve the lifespan and efficiency of the OLED device.

[0227] Depend on Figure 2 It can be seen that compared with the undoped p-doped cross-linker, after doping, the hole carriers increase, which is beneficial to the hole injection of the device.

[0228] Depend on Figure 3 It can be seen that after doping with the p-doping crosslinker, the current morphology shows better doping uniformity.

[0229] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0230] The above-mentioned embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application shall be subject to the attached claims.

Claims

1. A p-doped crosslinking agent, characterized in that It has the general structure shown in formula II: Formula II; Wherein, L1 and L2 are independently selected from -(CH2) q4 -(CH2O) q5 -(CH2) q6 -(CH=CH) q7 -P3-(CH2) q8 -; P3 is selected from a single bond, -C(=CR5R6)-, substituted or unsubstituted C 6-60 Arylene, substituted or unsubstituted heteroarylene having 5 to 60 ring atoms, or one of the following groups: ； Ar5, Ar6 and Ar7, when present, are independently selected from substituted or unsubstituted C 6-60 Arylene, substituted or unsubstituted heteroarylene having 5 to 60 ring atoms; R5 and R6 are independently selected from H, C 1-20 Alkyl or cyano; Each occurrence of q4, q5, q6, q7 and q8 is independently selected from any integer between 0 and 20; W, at each occurrence, is independently selected from -H, -F, -Cl, -Br, -I, -CN, -NO2, C 1-20 Alkyl or C 1-20 Alkoxy; The substituted substituents, each time they appear, are independently selected from D, amino, halogen, hydroxy, carboxyl, nitro, sulfonic acid, mercapto, cyano, C 1-20 Alkyl, C 1-20 A combination of one or more of an alkoxy group and an aryl group having 6 to 20 ring atoms.

2. The p-doped crosslinking agent according to claim 1, characterized in that The p-doped cross-linking agent has a general structure shown in Formula II-a: Formula II-a; L1 and L2 are independently selected from one of the following groups: ； R5 and R6 are independently selected from H, C 1-10 Alkyl or cyano; Ar4, at each occurrence, is independently selected from substituted or unsubstituted C 6-60 Arylene, substituted or unsubstituted heteroarylene having 5 to 60 ring atoms, or one of the following groups: ； Each occurrence of m is independently selected from any integer between 0 and 10.

3. The p-doped crosslinking agent according to claim 1, characterized in that Said Selected from one of the following groups: ； Each occurrence of m is independently selected from any integer between 0 and 6.

4. The p-doped crosslinking agent according to any one of claims 1 to 3, characterized in that The p-doping cross-linking agent includes at least one of the following compounds N1 to N10: 。 5. A composition, characterized in that The invention comprises at least one main material and at least one p-doped cross-linking agent according to any one of claims 1 to 4, wherein the main material has a general structure shown in Formula I: Formula I; Wherein, R1, R2, R3 and R4 are independently selected from -P1-(CH2) q1 -(CH2O) q2 -(CH2) q3 -P2; P1 is selected from a single bond or C 6-60 arylene; P2 is selected from H, -CH3, CH2=CH-, C 6-60 An aryl group or a heteroaryl group having 5 to 60 ring atoms; Each occurrence of q1, q2 and q3 is independently selected from any integer between 0 and 20; X is selected from O, S, -NR a , -PR a or CR a R b ; Y single button, O, S, -NR a , -PR a or -CR a R b ; Z selects single bond, O, S, -N-Ar1, -PR a or -CR a R b ; R a and R b Each occurrence is independently selected from H or C 1-3 alkyl; Ar1 is selected from substituted or unsubstituted C 6-60 Aryl, substituted or unsubstituted heteroaryl having 5 to 60 ring atoms; The substituted substituents, each time they appear, are independently selected from D, amino, halogen, hydroxy, carboxyl, nitro, sulfonic acid, mercapto, cyano, C 1-20 Alkyl, C 1-20 A combination of one or more of an alkoxy group and an aryl group having 6 to 20 ring atoms.

6. The composition according to claim 5, characterized in that The host material has a general structure shown in Formula Ia: Formula Ia; Wherein, R1, R2, R3 and R4 are independently selected from H, C 1-10 Alkyl, C 6-60 Aryl or one of the following substituents: ； Ar2, at each occurrence, is independently selected from C 6-60 arylene; Ar3, when present, is independently selected from heteroaryl having 5 to 60 ring atoms; Each occurrence of n is independently selected from any integer between 0 and 10, and n1 and n2 are any integers between 0 and 10.

7. The composition according to claim 5, characterized in that At least two of R1, R2, R3 and R4 are selected from or -(CH2) q1 -(CH2O) q2 -(CH2) q3 -CH=CH2, wherein q1, q2 and q3, when present, are independently selected from any integer between 0 and 10.

8. The composition according to claim 5, characterized in that The main material has a structure shown in any one of Formula I-1 to Formula I-3: Formula I-1; Formula I-2; Formula I-3; Optionally, R1 and R4 are independently selected from H or phenyl; R2 and R3 are independently selected from C 1-8 Alkyl or one of the following substituents: 。 9. The composition according to any one of claims 5 to 8, characterized in that The Ar1 is selected from any one of the following formulas (i) to (xii): ； Wherein R7 is selected from C 1-8 alkyl.

10. The composition according to claim 5, characterized in that The main material includes at least one of the following compounds M1 to M10: 。 11. The composition according to any one of claims 5 to 8 and 10, characterized in that The mass percentage of the p-doped crosslinking agent in the composition is 0.1% to 50%.

12. A polymer, characterized in that The polymer is prepared by reacting the main material in the composition according to any one of claims 5 to 11 and the p-doped cross-linking agent.

13. A film, characterized in that: The material of the film is prepared by reacting the main material in the composition according to any one of claims 5 to 11 and the p-doped cross-linking agent.

14. A light-emitting device, comprising a first electrode, a functional layer and a second electrode stacked in sequence, characterized in that: The material of the functional layer includes a polymer prepared by reacting the main material in the composition according to any one of claims 5 to 11 and the p-doped cross-linking agent.

15. The light emitting device according to claim 14, characterized in that: The functional layer comprises a hole injection layer, and the material of the hole injection layer comprises a polymer prepared by reacting the main material in the composition according to any one of claims 1 to 7 and the p-doped cross-linking agent.

16. The light emitting device according to claim 15, characterized in that: The functional layer further comprises a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer which are stacked in sequence; wherein the hole injection layer is located on a side of the hole transport layer away from the light emitting layer; Optionally, the materials of the first electrode and the second electrode independently include a doped metal oxide particle electrode, a composite electrode, a graphene electrode, a carbon nanotube electrode, a metal single substance electrode or an alloy electrode, the material of the doped metal oxide particle electrode includes one or more of indium-doped tin oxide, fluorine-doped tin oxide, antimony-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, indium-doped zinc oxide, magnesium-doped zinc oxide and aluminum-doped magnesium oxide, the composite electrode includes one or more of AZO / Ag / AZO, AZO / Al / AZO, ITO / Ag / ITO, ITO / Al / ITO, ZnO / Ag / ZnO, ZnO / Al / ZnO, TiO2 / Ag / TiO2, TiO2 / Al / TiO2, ZnS / Ag / ZnS or ZnS / Al / ZnS, and the material of the metal single substance electrode includes one or more of Ag, Al, Cu, Mo, Au, Pt, Ca, Mg and Ba; Optionally, the material of the hole transport layer includes poly[(9,9-di-n-octylfluorenyl-2,7-diyl)-alt-(4,4'-(N-(4-n-butyl)phenyl)-diphenylamine)], polyvinyl carbazole, [N,N'-(4-n-butylphenyl)-N,N'-diphenyl-p-phenylenediamine]-[9,9-di-n-octylfluorenyl-2,7-diyl] copolymer, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-1,1'-biphenyl-4,4'-diamine, 4,4',4''-tri(carbazole-9-yl)triphenylamine, 4,4'-cyclohexylbis[N,N- Bis(4-methylphenyl)aniline], Poly-TBP, Poly-TPD, N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine, 4,4'-di(9-carbazole)biphenyl, 4,4'-N,N'-dicarbazolyl-biphenyl, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'-biphenyl-4,4''-diamine, N,N'-diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine, poly(N, N'bis(4-butylphenyl)-N,N'-bis(phenyl)benzidine), N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-spiro, N,N'-bis(4-(N,N'-diphenyl-amino)phenyl)-N,N'-diphenylbenzidine, 4,4',4'-tri(N-carbazolyl)-triphenylamine, 4,4',4'-tri(N-3-methylphenyl-N-phenylamino)triphenylamine, poly[(9,9'-dioctylfluorene-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl)diphenylamine))], poly(N-vinylcarbazole) and its derivatives, N,N'-di(1-naphthyl)-N,N'-diphenyl-1,1'-biphenyl-4-4'-diamine, Spiro NPB, poly(phenylene vinylene), poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene vinylene], poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene], 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene, 1,3-di(carbazol-9-yl)benzene, polyaniline, polypyrrole, poly(p-phenylene vinylene), aromatic tertiary amine, polynuclear aromatic tertiary amine, 4,4'-bis(p-carbazolyl)-1,1'-biphenyl compound, N,N,N',N'-tetraarylbenzidine, PEDOT:PSS and its derivatives, polymethacrylate and its derivatives, poly(9,9-octylfluorene) and its derivatives, poly (spirofluorene) and its derivatives, doped graphene, undoped graphene, C60, doped or undoped NiO, doped or undoped MoO3, doped or undoped WO3, doped or undoped V2O5, doped or undoped P-type gallium nitride, doped or undoped CrO3, doped or undoped CuO; one or more thereof; Optionally, the material of the light-emitting layer includes one or more of organic light-emitting materials and quantum dots; Wherein, the organic light-emitting material is selected from trihydroxyquinoline, 4,4'-bis(N-carbazole)-1,1'-biphenyl:tri[2-(p-tolyl)pyridine iridium(III), 4,4',4''-tri(carbazole-9-yl)triphenylamine:tri[2-(p-tolyl)pyridine iridium, diaromatic anthracene derivatives, distilbene aromatic derivatives, pyrene derivatives, fluorene derivatives, TBPe fluorescent materials, TTPX fluorescent materials, TBRb fluorescent materials, DBP fluorescent materials, delayed fluorescent materials, TTA materials, thermally activated delayed materials, polymers containing BN covalent bonds, hybrid localized charge transfer excited state materials and exciplex light-emitting materials. The quantum dots are selected from one or more of single-component quantum dots, core-shell quantum dots, inorganic perovskite quantum dots, organic perovskite quantum dots and organic-inorganic hybrid perovskite quantum dots; the material of the single-component quantum dots, the material of the core of the core-shell quantum dots and the material of the shell of the core-shell quantum dots are independently selected from at least one of II-VI compounds, III-V compounds, IV-VI compounds or I−III−VI compounds, wherein the II-VI compounds are selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, Cd One or more of CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe and HgZnSTe, wherein the III-V group compound is selected from GaN, GaP, GaAs, Ga Sb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb , InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb , InAlPAs and InAlPSb, the IV-VI group compound is selected from one or more of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe and SnPbSTe, the I-III-VI group compound is selected from one or more of CuInS, CuInSe and AgInS; the general structural formula of the inorganic perovskite quantum dot is AMX3, wherein A is C s+ ion, M is a divalent metal cation, M is selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ and Eu 2+ One or more of, X is a halogen anion; the general structural formula of the organic perovskite quantum dot is CMX3, C is a carboxamidine group; the general structural formula of the organic-inorganic hybrid perovskite quantum dot is BMX3, B is selected from an organic amine cation; Optionally, the material of the electron transport layer includes one or more of an inorganic electron transport material and an organic electron transport material, the inorganic electron transport material includes but is not limited to one or more of doped metal oxide particles, undoped metal oxide particles, ceramic semiconductor materials, IIB-VIA semiconductor materials, IIIA-VA semiconductor materials and IB-IIIA-VIA semiconductor materials, the metal oxide in the undoped metal oxide particles includes one or more of ZnO, TiO2, SnO2, ZrO2, Ta2O5, the metal oxide in the doped metal oxide includes one or more of ZnO, TiO2, SnO2, ZrO2, Ta2O5, Al2O3, the doping elements in the doped metal oxide include Al, Mg, One or more of Li, Mn, Y, La, Cu, Ni, Zr, Ce, In, Ga, and Sn, the IIB-VIA semiconductor material includes one or more of ZnS, ZnSe, and CdS, the IIIA-VA semiconductor material includes one or more of InP and GaP, the IB-IIIA-VIA semiconductor material includes one or more of CuInS and CuGaS, the organic electron transport material includes one or more of quinoxaline compounds, imidazole compounds, triazine compounds, fluorene-containing compounds, and hydroxyquinoline compounds; the hydroxyquinoline compound includes one or more of 8-hydroxyquinoline lithium and metal chelates of 8-hydroxyquinoline; the imidazole compound includes 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl); Optionally, the material of the electron injection layer is selected from one or more of Yb, MgF2, LiF, lithium oxide, cesium carbonate, and cesium fluoride.

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