Organic compound and preparation method thereof, composite material, photoelectric device and display device

Abstract

The invention discloses an organic compound and a preparation method thereof, a composite material, a photoelectric device and a display device. The compound provided by the invention takes a seven-parallel-ring structure with a large conjugate plane as a core, and modification groups such as alkoxy, R1, R2, D1 and D2 extend on four sides of the seven-parallel-ring structure, so that the compound has better hole mobility, a good hole transport channel can be formed, and hole transport is facilitated; in addition, the compound can have an adjustable energy level, so that different energy level requirements can be met; when the compound is doped in a P-type semiconductor material with hole transport and injection performance, hole transport channels of the P-type semiconductor material are increased, and the hole transport rate of the composite material is further improved.

Description

Technical Field

[0001] The present application relates to the field of semiconductor technology, and in particular to an organic compound and a preparation method thereof, a composite material, an optoelectronic device and a display device. Background Art

[0002] P-type semiconductor materials, also known as hole-type semiconductor materials, refer to semiconductor materials that can transport or inject holes. However, the hole mobility of such P-type semiconductor materials is relatively small, and the hole transport performance is poor, which limits their application. Summary of the invention

[0003] In view of this, the present application provides an organic compound and a preparation method thereof, a composite material, an optoelectronic device and a display device.

[0004] The embodiment of the present application is implemented as follows:

[0005] In a first aspect, the present application provides an organic compound having a structure shown in formula (1):

[0006]

[0007] Wherein, D1 and D2 are each independently selected from an aromatic group having 5 to 60 ring carbon atoms, which is substituted or unsubstituted by a first substituent, and the first substituent includes a combination of one or more of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a halogen group, and a cyano group;

[0008] R1 and R2 are each independently selected from

[0009] R3 is selected from any one of a C1-C30 alkyl group substituted or unsubstituted by a second substituent, and an aryl group having 6 to 30 ring carbon atoms substituted or unsubstituted by a third substituent, wherein the second substituent and the third substituent are each independently selected from a combination of one or more of a C1-C20 alkoxy group, a halogen group, and a cyano group;

[0010] R4 to R7 are each independently selected from C1-C20 alkyl groups.

[0011] In a second aspect, the present application also proposes a method for preparing an organic compound, comprising the following steps:

[0012] Mixing compound a with a halogenating agent to carry out a halogenation reaction to obtain compound b;

[0013] The compound b is mixed with the compound c, and subjected to a metal coupling reaction to obtain a compound d;

[0014] The compound d is mixed with the compound e, and a cyclization reaction is performed to obtain a compound f;

[0015] The compound f is mixed with the compound g to carry out an esterification reaction to obtain an organic compound;

[0016] Wherein, the organic compound has a structure shown in formula (1):

[0017]

[0018] wherein X is selected from Cl, Br or I;

[0019] D is selected from D1 or D2, R is selected from R1 or R2;

[0020] D1 and D2 are each independently selected from an aromatic group having 5 to 60 ring carbon atoms, which is substituted or unsubstituted by a first substituent, wherein the first substituent includes a combination of one or more of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a halogen group, and a cyano group;

[0021] R1 and R2 are each independently selected from

[0022] R3 is selected from any one of a C1-C30 alkyl group substituted or unsubstituted by a second substituent, and an aryl group having 6 to 30 ring carbon atoms substituted or unsubstituted by a third substituent, wherein the second substituent and the third substituent are each independently selected from a combination of one or more of a C1-C20 alkoxy group, a halogen group, and a cyano group;

[0023] R4 to R7 are each independently selected from C1-C20 alkyl groups.

[0024] In a third aspect, the present application further proposes a composite material, comprising a P-type semiconductor material and an additive, wherein the additive comprises the organic compound described above, or comprises an organic compound prepared by the preparation method described above.

[0025] In a fourth aspect, the present application further proposes a photoelectric device, comprising an anode, a hole functional layer and a cathode, wherein the material of the hole functional layer comprises the composite material described above.

[0026] In a fifth aspect, the present application also proposes a display device, which includes the optoelectronic device as described above.

[0027] The compound provided by the present application has a seven-ring structure with a large conjugated plane as the core, and extends alkoxy, R1, R2, D1, D2 and other modification groups on its four sides, so as to have a better hole mobility, can form a good hole transport channel, and help hole transport; in addition, the compound can have an adjustable energy level, thereby meeting different energy level requirements. When the compound is doped in a P-type semiconductor material with hole transport and injection properties, it helps to increase its hole transport channel, thereby improving the hole transport rate of the composite material. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without creative work.

[0029] Figure 1 is a schematic structural diagram of an optoelectronic device proposed in one embodiment of the present application;

[0030] Reference numerals:

[0031] 100 - photoelectric device; 10 - anode; 20 - light-emitting layer; 30 - electron transport layer; 40 - cathode; 50 - hole transport layer; 60 - hole injection layer. DETAILED DESCRIPTION

[0032] The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without making creative work belong to the scope of protection of the present application. In addition, it should be understood that the specific implementation methods described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0033] In this application, unless otherwise specified, the directional words used, such as "upper" and "lower", refer specifically to the directions of the drawings in the accompanying drawings. In addition, in the description of the specification of this application, the term "including" means "including but not limited to".

[0034] Various embodiments of the present application may be presented in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be understood as a rigid limitation on the scope of the present application; therefore, the range description should be considered to have specifically disclosed all possible sub-ranges and single numerical values ​​within the range. For example, the range description from 1 to 6 should be considered to have specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, which apply regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any cited number (fractional or integer) within the indicated range.

[0035] In this application, "and / or" describes the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural.

[0036] In the present application, "at least one" means one or more, and "plurality" means two or more. "At least one", "at least one of the following" or similar expressions refer to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, c can be single or multiple, respectively.

[0037] Explanation of terms

[0038] In the present application, "substituted or unsubstituted" means that the defined group may be substituted or unsubstituted. When the defined group is substituted, it is understood that the defined group may be substituted by one or more substituents. When substituted by multiple substituents, each substituent may be the same or different. Herein, "substituted by a first substituent" means that the group may be substituted by one or more first substituents, and when substituted by multiple first substituents, each first substituent may be the same or different.

[0039] In the present application, the "number of ring atoms" refers to the number of atoms among the atoms constituting the ring itself of a structural compound (for example, a monocyclic compound or a polycyclic compound) obtained by bonding atoms to form a ring. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring atoms. The same applies to the "number of ring atoms" described below unless otherwise specified. For example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, and the number of ring atoms of a thienyl group is 5. The "number of ring carbon atoms" refers to the number of atoms among the carbon atoms constituting the ring itself. For example, the number of ring carbon atoms of a benzene ring is 6, and the number of ring carbon atoms of a pyridine ring is 5.

[0040] In the present application, "alkyl" may represent a straight chain alkyl or a branched chain alkyl. C1-10 alkyl refers to an alkyl group containing 1 to 10 carbon atoms, and each occurrence may be independently C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl or C10 alkyl. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylpentyl, 3-methylpentyl, n-hexyl, etc.

[0041] In the present application, "aryl" refers to a group derived from an aromatic ring compound containing a benzene ring by removing one hydrogen. The aromatic ring compound can be a monocyclic aromatic ring, a condensed aromatic ring formed by multiple rings, or a non-condensed aromatic ring connected by multiple rings. For a polycyclic ring, at least one is an aromatic ring system. Suitable examples of aromatic ring compounds include, but are not limited to, benzene rings, naphthalene rings, biphenyl rings, anthracene rings, phenanthrene rings, tetraphenyl rings, fluorene rings, indene, etc. Correspondingly, the aryl groups corresponding to the above aromatic ring compounds are phenyl, naphthyl, biphenyl, anthracene, phenanthrene, tetraphenyl ring, fluorene, indenyl, etc. Further, "phenylene" refers to a group derived from phenyl by removing one more hydrogen; "arylene" refers to a group derived from aryl by removing one more hydrogen; "condensed aryl" refers to a group derived from condensed aryl by removing one more hydrogen.

[0042] In the present application, an alkoxy group has a structural feature of the formula -OR'; a cyano group refers to -CN; a halogen group refers to -F, -Br, -Cl or -I; wherein R' is selected from an alkyl group.

[0043] The technical solution of the embodiment of the present application is as follows:

[0044] In a first aspect, an embodiment of the present application provides an organic compound having a structure shown in formula (1):

[0045]

[0046] Wherein, D1 and D2 are each independently selected from an aromatic group having 5 to 60 ring carbon atoms, which is substituted or unsubstituted by a first substituent, wherein the first substituent includes a combination of one or more of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a halogen group, and a cyano group; R1 and R2 are each independently selected from

[0047] R3 is selected from any one of a C1-C30 alkyl group substituted or unsubstituted by a second substituent, and an aryl group having 6 to 30 ring carbon atoms substituted or unsubstituted by a third substituent, wherein the second substituent and the third substituent are each independently selected from a combination of one or more of a C1-C20 alkoxy group, a halogen group, and a cyano group;

[0048] R4 to R7 are each independently selected from C1-C20 alkyl groups.

[0049] The compound provided by the present application has a heptad ring structure with a large conjugated plane as the core, and alkoxy, R1, R2, D1, D2 and other modifying groups extending on its four sides. The obtained compound structure has a better planarity due to the core structure, and thus has a better hole mobility, can form a good hole transport channel, and is conducive to hole transport. When it is doped in a P-type semiconductor material with hole transport and injection properties, it can form a columnar stacking, which helps to increase its hole transport channel, thereby improving the hole transport rate of the composite material. In addition, by adjusting the type of modifying groups, the compound can have an adjustable energy level, thereby meeting different energy level requirements. Since the compound has suitable HOMO energy level and LUMO energy level, when doped in the hole transport layer 50, it helps to reduce the hole injection barrier between the hole injection layer 60 and the hole transport layer 50, and increase the rate of hole injection from the hole injection layer 60 to the hole transport layer 50. At the same time, it can also effectively block electrons from the light-emitting layer 20 to avoid the generation of leakage current; in addition, it can also improve the interface effect between the hole transport layer 50 and the light-emitting layer 20, balance the transmission of carriers, and improve the performance and life of the device.

[0050] In addition, D1 and D2 are connected at specific sites and are taken from aromatic groups, which helps to regulate the energy level of the compound and enhance the solubility of the compound, making the compound suitable for printing and film formation; the setting of R1 and R2 can also play a role in regulating the solubility, viscosity and surface tension of the compound, which helps to formulate a suitable hole functional layer ink.

[0051] In some embodiments, D1 and D2 are each independently selected from an aromatic group having 6 to 14 ring carbon atoms, which is substituted or unsubstituted by a first substituent; in other embodiments, the first substituent includes a combination of one or more of a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a halogen group, and a cyano group; this helps to more accurately control the energy level and solubility of the compound.

[0052] In some embodiments, D1 and D2 are the same. In this way, the synthesis route and synthesis complexity of the organic compound can be reduced, and the synthesis difficulty and cost of the organic compound can be reduced.

[0053] In some specific embodiments, D1 and D2 are each independently selected from one of the structures of Formula 1-1 to Formula 1-32:

[0054]

[0055]

[0056] R1 and R2 are each independently selected from In some embodiments, R3 is selected from a C1-C30 alkyl group which is substituted or unsubstituted by a second substituent; in other embodiments, the second substituent is selected from a combination of one or more of C1-C10 alkoxy and cyano; this helps to better regulate the properties of the compound so that it can better match the hole transport material and the hole transport layer 50 ink solvent.

[0057] In some embodiments, R1 and R2 are the same; thus, the synthesis route and complexity of the organic compound can be reduced, and the difficulty and cost of the synthesis of the organic compound can be reduced.

[0058] In some specific embodiments, R1 and R2 are each independently selected from one of the structures of Formula 2-1 to Formula 2-4:

[0059]

[0060] In some embodiments, R4 to R7 are each independently selected from C1-C6 alkyl, such as methyl, ethyl, isopropyl, n-propyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, etc. In some embodiments, R4 and R5 are the same; in other embodiments, R6 and R7 are the same. In some embodiments, R4 to R7 are pentyl.

[0061] Based on the above embodiments, the organic compound proposed in the embodiments of the present application has a suitable energy level. In some embodiments, the HOMO energy level of the organic compound is -5.3ev to -5.7ev; in other embodiments, the LUMO energy level of the organic compound is -2.0ev to -2.3ev; the organic compound can better match the conventional hole transport material, and when it is doped in the hole transport layer 50, it helps to reduce the hole injection barrier between the hole injection layer 60 and the hole transport layer 50, and increase the rate of hole injection from the hole injection layer 60 to the hole transport layer 50. At the same time, it can also effectively block electrons from the light-emitting layer 20 to avoid the generation of leakage current; in addition, it can also improve the interface effect between the hole transport layer 50 and the light-emitting layer 20, balance the transmission of carriers, and improve the performance and life of the device.

[0062] In some specific embodiments, the organic compound includes one or more compounds of the structures shown in Formula M1 to Formula M8:

[0063]

[0064]

[0065] In a second aspect, the present application also proposes a method for preparing an organic compound, the synthesis route of the organic compound is as follows:

[0066]

[0067] wherein X is selected from Cl, Br or I;

[0068] D is selected from D1 or D2, R is selected from R1 or R2;

[0069] D1 and D2 are each independently selected from an aromatic group having 5 to 60 ring carbon atoms, which is substituted or unsubstituted by a first substituent, wherein the first substituent includes a combination of one or more of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a halogen group, and a cyano group;

[0070] R1 and R2 are each independently selected from

[0071] R3 is selected from any one of a C1-C30 alkyl group substituted or unsubstituted by a second substituent, and an aryl group having 6 to 30 ring carbon atoms substituted or unsubstituted by a third substituent, wherein the second substituent and the third substituent are each independently selected from a combination of one or more of a C1-C20 alkoxy group, a halogen group, and a cyano group;

[0072] R4 to R7 are each independently selected from C1-C20 alkyl groups.

[0073] Accordingly, the preparation method comprises the following steps:

[0074] S10, mixing compound a with a halogenating agent to perform a halogenation reaction to obtain compound b;

[0075] S20, mixing the compound b and the compound c, and performing a metal coupling reaction to obtain a compound d;

[0076] S30, mixing the compound d with the compound e, and performing a cyclization reaction to obtain a compound f;

[0077] S40, mixing the compound f and the compound g, and performing an esterification reaction to obtain an organic compound, wherein the organic compound has a structure represented by formula (1).

[0078] In step S10:

[0079] The halogenating agent may be a halogenating agent commonly used in the art. A halogen atom is introduced into the benzene ring by subjecting compound a to a halogenating reaction with the halogenating agent. In some specific embodiments, the halogenating agent may be N-bromosuccinimide (NBS, CAS: 128-08-5), liquid bromine, 1,3-dibromo-5,5-dimethylhydantoin (DBH), N-iodosuccinimide (NIS), etc. When these halogenating agents are used, in the obtained compound b, X is Br.

[0080] In some embodiments, the molar ratio of the compound a to the halogenating agent is 1:(2.5-3.5); for example, it can be 1:2.5, 1:2.6, 1:2.8, 1:2.9, 1:3, 1:3.2, 1:3.4, 1:3.5 and values ​​between any two of the above values. Controlling the molar ratio of compound a to the halogenating agent within this range can promote the full reaction of the two to obtain compound b.

[0081] In some embodiments, the temperature of the halogenation reaction is 10°C to 25°C; for example, it can be 10°C, 12°C, 15°C, 18°C, 20°C, 23°C, 25°C, and values ​​between any two of the above values, so that the halogenation reaction of compound a and the halogenating agent can be promoted.

[0082] In some embodiments, the halogenation reaction time is 0.5 to 1.5 h (hours); for example, it can be 0.5 h, 0.6 h, 0.8 h, 1 h, 1.3 h, 1.5 h, and values ​​between any two of the above values, which helps to promote the full reaction of the two to obtain compound b.

[0083] Compound a can be purchased directly on the market or prepared by itself. In some embodiments, the synthesis route of compound a is as follows:

[0084]

[0085] In some specific embodiments, the compound a-1 can be selected from but not limited to any one of 1,2-dibromo-4,5-di(octyloxy)benzene (CAS: 118132-04-0; structural formula is shown in formula a-1-1 below), 4,5-dibromo-1,2-dimethoxybenzene (CAS: 37895-73-1; structural formula is shown in formula a-1-2 below), and 1,2-dibromo-4,5-di(octyloxy)benzene (CAS: 216485-86-8; structural formula is shown in formula a-1-3 below).

[0086]

[0087] In some embodiments, step S20 specifically includes: in an inert atmosphere, mixing the compound b, compound c, a base and a palladium catalyst, and performing a metal coupling reaction to obtain a compound d.

[0088] in:

[0089] The base can be an inorganic weak base commonly used in the art, including but not limited to one or more of alkali metal phosphates, alkali metal carbonates, and alkali metal bicarbonates. The alkali metal phosphates include one or more of potassium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium phosphate, sodium dihydrogen phosphate, and disodium hydrogen phosphate. The alkali metal carbonates include one or more of sodium carbonate and potassium carbonate. The alkali metal bicarbonates include one or more of sodium bicarbonate and potassium bicarbonate.

[0090] The palladium catalyst can be a palladium catalyst commonly used in the art, including but not limited to one or more of tris(dibenzylideneacetone)dipalladium (Pd2(dba)3), tetrakis(triphenylphosphine)palladium (pd(pph3)4).

[0091] In some embodiments, the molar ratio of the compound b and the compound c is 1:(2-5); for example, it can be 1:2, 1:2.5, 1:2.6, 1:2.8, 1:3, 1:3.2, 1:3.5, 1:4, 1:4.3, 1:4.5, 1:4.8, 1:5 and values ​​between any two of the above values, so that the compound b and compound c can be fully reacted to obtain compound d.

[0092] In some embodiments, the molar ratio of the compound b to the palladium catalyst is 1:(0.05-0.1); for example, it can be 1:0.05, 1:0.06, 1:0.08, 1:0.1, and values ​​between any two of the above values.

[0093] In some embodiments, the molar ratio of the compound b to the base is 1:(5-10); for example, it can be 1:5, 1:6, 1:8, 1:9, 1:10 and values ​​between any two of the above values.

[0094] In some embodiments, the temperature of the metal coupling reaction is 75°C to 90°C; for example, it can be 75°C, 80°C, 85°C, 90°C, and values ​​between any two of the above values, which helps promote the metal coupling reaction.

[0095] In some embodiments, the metal coupling reaction time is 12 to 24 hours; for example, it can be 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours, and values ​​between any two of the above values.

[0096] Wherein, compound c is used to introduce D1 and D2 groups, which can be a boronic acid compound containing D1 or D2. The compound c can be purchased on the market, or can be synthesized by referring to the conventional synthesis method of aryl boronic acid compounds in the art.

[0097] In some embodiments, step S30 may specifically include: mixing the compound d, the compound e and a Lewis acid catalyst in air to perform a cyclization reaction to obtain a compound f.

[0098] in:

[0099] Compound e can be purchased on the market, or prepared by referring to the following synthetic route: 2,3-dihydroxynaphthalene (CAS: 92-44-4) is used as a starting material, and it is reacted with a brominated alkane in an alkaline environment to prepare compound e.

[0100]

[0101] Specifically, taking compound e as 2,3-bis(pentyloxy)naphthalene (CAS: 861333-71-3) as an example, it can be purchased on the market or synthesized according to the following synthesis method: add compound 2,3-dihydroxynaphthalene (10 mmol, 1.6 g), 1-bromopentane (25 mmol, 3.77 g, CAS: 110-53-2), NaOH (40 mmol, 1.6 g) and add 100 mL DMSO to a 250 mL two-necked bottle and place in an 85 ° C oil bath for reaction for 24 hours, then extract the reaction solution, select dichloromethane (500 mL) and water (200 mL) for repeated washing 3 to 4 times, mix the crude product with 300 to 400 mesh silica gel, and perform column chromatography separation, eluent PE: Ea = 25:1, and separate the compound 2,3-bis(pentyloxy)naphthalene as a colorless liquid with a weight of 2.7 g and a yield of 90%.

[0102] The Lewis acid catalyst may include, but is not limited to, one or more of ferric chloride and aluminum chloride.

[0103] In some embodiments, the molar ratio of the compound d to the compound e is 1:(1.5-3); for example, it can be 1:1.5, 1:2, 1:2.5, 1:3, and values ​​between any two of the above values, which can promote the full reaction of the compound d and the compound e.

[0104] In some embodiments, the molar ratio of the compound d to the Lewis acid catalyst is 1:(3-6); for example, it can be 1:3, 1:4, 1:5, 1:6, and values ​​between any two of the above values.

[0105] In some embodiments, the temperature of the cyclization reaction is 25°C to 40°C; for example, it can be 25°C, 26°C, 28°C, 30°C, 33°C, 35°C, 37°C, 40°C, and values ​​between any two of the above values. Controlling the reaction temperature within this range can promote the cyclization reaction of compound d and compound e.

[0106] In some embodiments, the cyclization reaction time is 1 to 3 hours; for example, it can be 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, and values ​​between any two of the above values.

[0107] In some embodiments, step S40 may specifically include: in an inert atmosphere, mixing the compound f, the compound g, N,N'-dicyclohexylcarbodiimide and 4-dimethylaminopyridine, and performing an esterification reaction to obtain an organic compound.

[0108] in:

[0109] The compound g is used to introduce R1 and R2 groups, which can be an organic acid R1H or R2H containing R1 or R2. The compound g can be purchased on the market. In some specific embodiments, the compound g can include but is not limited to any one of 3-ethoxypropionic acid and trimethylacetic acid.

[0110] In some embodiments, the molar ratio of the compound f to the compound g is 1:(2-4); for example, it can be 1:1, 1:2, 1:3, 1:4, and values ​​between any two of the above values. Controlling the reaction temperature within this range can promote the full reaction of the compound f and the compound g to generate an organic compound.

[0111] In some embodiments, the molar ratio of the compound f to N,N'-dicyclohexylcarbodiimide is 1:(3-5); for example, it can be 1:3, 1:4, 1:5, and values ​​between any two of the above values.

[0112] In some embodiments, the molar ratio of the compound f to 4-dimethylaminopyridine is 1:(1.5-2.5); for example, it can be 1:1.5, 1:2, 1:2.5, and values ​​between any two of the above values.

[0113] In some embodiments, the temperature of the esterification reaction is 25°C to 50°C; for example, it can be 25°C, 26°C, 28°C, 30°C, 33°C, 35°C, 37°C, 40°C, 45°C, 50°C, and values ​​between any two of the above values. Controlling the reaction temperature within this range can promote the esterification reaction of compound f and compound g.

[0114] In some embodiments, the esterification reaction time is 12 to 24 hours; for example, it can be 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours, and values ​​between any two of the above values.

[0115] In a third aspect, based on the above embodiments, the present application further proposes a composite material, which includes a P-type semiconductor material and an additive, wherein the additive includes the organic compound described above, or includes an organic compound prepared by the preparation method described above, and the P-type semiconductor material refers to a semiconductor material with hole transport or injection properties, and the HOMO energy level of the P-type semiconductor material is in the range of -5.3eV to -5.9ev. In this way, the organic compound and the P-type semiconductor material can be better matched to make it suitable for the hole functional layer of the optoelectronic device 100.

[0116] In some embodiments, in the composite material, the mass percentage of the additive is 5% to 30%; for example, it can be 5%, 10%, 15%, 20%, 25%, 30% and a value between any two of the above values.

[0117] In some embodiments, the P-type semiconductor material includes polyvinyl carbazole (PVK, CAS: 25067-59-8), 4,4'-di(9-carbazole)biphenyl (CBP, CAS: 58328-31-7), 4,4',4"-tri(carbazole-9-yl)triphenylamine (TCTA, CAS: 139092-78-7), poly(9,9-dioctylfluorene-CO-N-(4-butylphenyl)diphenylamine) (TFB, CAS :223569-31-1), N,N'-diphenyl-N,N'-di(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD, CAS: 122738-21-0), N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine (NPB, CAS: 123847-85-8), CBP-V (derived from the document "Inkjet-Printed High-Efficiency Multilayer QLEDs Based on a NovelCrosslinkable Small-Molecule Hole Transport Material").

[0118] In a fourth aspect, the present application provides an optoelectronic device 100, which may be, for example, an OLED, a QLED, a solar cell, etc. Figure 1 The photoelectric device 100 includes an anode 10, a hole functional layer and a cathode 40, and the material of the hole functional layer includes the composite material described above.

[0119] The composite material has a higher hole transport rate because the organic compound having the structure shown in formula (1) is added to increase its hole transport channel. When the composite material is used to prepare a hole functional layer, it helps to reduce the hole injection barrier between the hole injection layer 60 and the hole transport layer 50, and increase the rate of hole injection from the hole injection layer 60 to the hole transport layer 50. At the same time, it can also effectively block electrons from the light-emitting layer 20 to avoid the generation of leakage current. In addition, it can also improve the interface effect between the hole transport layer 50 and the light-emitting layer 20, balance the transmission of carriers, and improve the performance and life of the device.

[0120] In some embodiments, the anode 10 may be an anode 10 known in the art for use in a photoelectric device 100, for example, may be selected from but not limited to a doped metal oxide particle electrode, a composite electrode of a metal and a metal oxide, a graphene electrode, a carbon nanotube electrode, a metal electrode or an alloy electrode, the material of the doped metal oxide particle electrode is selected from 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 of a metal and a metal oxide is selected from 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, ZnS / Al / ZnS, the material of the metal electrode is selected from one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg and Ba. Here, “ / ” represents a stacked structure. For example, the composite electrode AZO / Ag / AZO represents an electrode with a composite structure of three stacked layers consisting of an AZO layer, an Ag layer and an AZO layer.

[0121] The cathode 40 can be a cathode 40 for the optoelectronic device 100 known in the art, for example, can be selected from but not limited to a doped metal oxide particle electrode, a composite electrode of metal and metal oxide, a graphene electrode, a carbon nanotube electrode, a metal electrode or an alloy electrode, the material of the doped metal oxide particle electrode is selected from 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 of metal and metal oxide is selected from 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, ZnS / Al / ZnS, and the material of the metal electrode is selected from one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg and Ba.

[0122] In some embodiments, the hole functional layer includes a hole transport layer 50 , and the material of the hole transport layer 50 includes the composite material described above.

[0123] In some other embodiments, the hole functional layer further includes a hole injection layer 60, and the hole injection layer 60 is disposed between the hole transport layer 50 and the anode 10. The material of the hole injection layer 60 may include, but is not limited to, one or more of PEDOT:PSS (poly (3,4-ethylenedioxythiophene) -polystyrene sulfonic acid), CuPc, TiOPc (phthalocyanine titanium oxide), mMTDATA (CAS: 124729-98-2), 2-TNATA (4,4',4"-tri (2-naphthylphenylaminotriphenylamine)), transition metal oxides, and transition metal sulfur compounds. Among them, the transition metal oxide includes NiO x 、MoO x , WO x CrO x , CuO; the metal sulfide compound includes MoS x 、MoSe x , WS x ,WSe x , CuS or more.

[0124] In some embodiments, the optoelectronic device 100 further includes a light-emitting layer 20, and the light-emitting layer 20 is disposed between the cathode 40 and the hole functional layer. The material of the light-emitting layer 20 includes one or more of an organic light-emitting material and a quantum dot light-emitting material. When the material of the light-emitting layer 20 is an organic light-emitting material, the optoelectronic device 100 is an organic light-emitting device. When the material of the light-emitting layer 20 is a quantum dot light-emitting material, the optoelectronic device 100 is a quantum dot light-emitting device.

[0125] The organic light-emitting material is selected from one or more of 4,4'-bis(N-carbazole)-1,1'-biphenyl:tris[2-(p-tolyl)pyridine iridium(III), 4,4',4"-tris(carbazole-9-yl)triphenylamine:tris[2-(p-tolyl)pyridine iridium, poly[(9,9-dioctylfluorene-2,7-diyl)-alternate-(2,1,3-benzothiadiazole-4,7-diyl)], 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.

[0126] The quantum dot luminescent material is selected from at least one of single structure quantum dots, core-shell structure quantum dots and perovskite semiconductor materials; the material of the single structure quantum dots, the core material of the core-shell structure quantum dots and the shell material of the core-shell structure quantum dots are respectively selected from at least one of II-VI group compounds, IV-VI group compounds, III-V group compounds and I-III-VI group compounds; the II-VI group compounds are selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, 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; the IV-VI group compound is selected from SnS, SnSe, SnTe, PbS , PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, SnPbSTe; the III-V group compound is selected from GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlN At least one of Sb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs and InAlPSb; the I-III-VI group compound is selected from at least one of CuInS2, CuInSe2 and AgInS2.

[0127] As an example, the core-shell structured quantum dots may be selected from but not limited to at least one of CdZnSe / CdZnSe / ZnSe / CdZnS / ZnS, CdZnSe / CdZnSe / CdZnS / ZnS, CdSe / CdSeS / CdS, InP / ZnSeS / ZnS, CdZnSe / ZnSe / ZnS, CdSeS / ZnSeS / ZnS, CdSe / ZnS, CdSe / ZnSe / ZnS, ZnSe / ZnS, ZnSeTe / ZnS, CdSe / CdZnSeS / ZnS and InP / ZnSe / ZnS.

[0128] It should be noted that, for the material of the aforementioned single structure quantum dot, or the material of the core of the core-shell structure quantum dot, or the material of the shell of the core-shell structure quantum dot, the chemical formula provided only indicates the elemental composition, but does not indicate the content of each element. For example, CdZnSe only indicates that it is composed of three elements, Cd, Zn and Se. If the content of each element is indicated, it corresponds to Cd x Zn 1-x Se,0 <x<1。

[0129] The perovskite semiconductor material is selected from doped or undoped inorganic perovskite semiconductors, or organic-inorganic hybrid perovskite semiconductors; the inorganic perovskite semiconductor has a general structural formula of AMX3, wherein A is Cs + ion, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - At least one of the following; the general structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX3, wherein B is an organic amine cation selected from CH3(CH2) n-2 NH 3+ or [NH3(CH2) n NH3] 2+ , where n≥2, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - At least one of .

[0130] In some embodiments, the optoelectronic device 100 further includes an electron transport layer 30, and the electron transport layer 30 is disposed between the cathode 40 and the hole functional layer. When the device also includes a light-emitting layer 20, the electron transport layer 30 is located between the light-emitting layer 20 and the cathode 40. The material of the electron transport layer 30 may include, but is not limited to, one or more of N-type metal oxides or doped N-type metal oxides, the N-type metal oxides including one or more of ZnO, TiO2, SnO2, and ZrO2; the N-type metal oxides in the doped N-type metal oxides include one or more of ZnO, TiO2, SnO2, and ZrO2, and the doping elements include one or more of Al, Mg, Li, In, and Ga.

[0131] It is understandable that the optoelectronic device 100 may also be provided with some functional layers conventionally used in optoelectronic devices 100 that help improve the performance of the optoelectronic device 100, such as an electron blocking layer, a hole blocking layer, etc.

[0132] It can be understood that the materials of each layer of the optoelectronic device 100 can be adjusted according to the actual requirements of the optoelectronic device 100 .

[0133] When there are multiple film layers between the anode 10 and the cathode 40, and the multiple film layers are selected from the light-emitting layer 20, the electron transport layer 30, the hole transport layer 50, and the hole injection layer 60, the film layer stacking order of the photoelectric device 100 is the anode 10, the hole injection layer 60, the hole transport layer 50, the light-emitting layer 20, the electron transport layer 30 and the cathode 40; it can be understood that the photoelectric device 100 can be a positive device or an inverted device. In some embodiments, the photoelectric device 100 is a positive device, and accordingly, the photoelectric device 100 includes the anode 10, the hole injection layer 60, the hole transport layer 50, the light-emitting layer 20, the electron transport layer 30 and the cathode 40 stacked in sequence from bottom to top; in other embodiments, the photoelectric device 100 is an inverted device, and accordingly, the photoelectric device 100 includes the cathode 40, the electron transport layer 30, the light-emitting layer 20, the hole transport layer 50, the hole injection layer 60 and the anode 10 stacked in sequence from bottom to top.

[0134] Based on the above-mentioned embodiment of the optoelectronic device 100, the present application further proposes a method for preparing the optoelectronic device 100, the method comprising the following steps: preparing a plurality of film layers in sequence according to a preset film layer sequence to obtain the optoelectronic device 100; wherein the plurality of film layers include an anode 10, a cathode 40, and at least one functional layer disposed between the anode 10 and the cathode 40, wherein the at least one functional layer includes at least one of a light-emitting layer 20, an electron transport layer 30, a hole transport layer 50, and a hole injection layer 60. The preset film layer sequence refers to the order in which the optoelectronic device 100 is stacked from bottom to top.

[0135] In the optoelectronic device 100 provided in the present application, the functional layer, the anode 10, and the cathode 40 can also be prepared by conventional preparation methods. Specifically, the conventional preparation method can be a chemical method or a physical method. Among them, the chemical method includes chemical vapor deposition, continuous ion layer adsorption and reaction method, anode 10 oxidation method, electrolytic deposition method, and coprecipitation method. The physical method includes physical plating method and solution method, among which the physical plating method includes: thermal evaporation coating method, electron beam evaporation coating method, magnetron sputtering method, multi-arc ion plating method, physical vapor deposition method, atomic layer deposition method, pulsed laser deposition method, etc.; the solution method can be spin coating, printing method, inkjet printing method, blade coating method, printing method, dip pulling method, immersion method, spraying method, roll coating method, casting method, slit coating method and strip coating method, etc.

[0136] In some embodiments, after the photoelectric device 100 is prepared, the step of packaging the photoelectric device 100 is further included. The packaging process can be performed by a common machine packaging or by manual packaging. Preferably, in the packaging process environment, the oxygen content and the water content are both less than 0.1 ppm to ensure the stability of the photoelectric device 100.

[0137] In addition, the present application also relates to a display device, which includes the optoelectronic device 100 described above. The display device can be any electronic product with a display function, including but not limited to smart phones, tablet computers, laptops, digital cameras, digital video cameras, smart wearable devices, smart weighing electronic scales, car displays, televisions or e-book readers, wherein the smart wearable device can be, for example, a smart bracelet, a smart watch, a virtual reality (VR) helmet, etc.

[0138] The technical scheme and technical effects of the present application are described in detail below through specific embodiments and comparative examples. The following embodiments are only some embodiments of the present application and do not specifically limit the present application.

[0139] Material Example 1

[0140] The synthesis steps of the organic compound M1 in this example are as follows:

[0141]

[0142]

[0143] (1) Compound a-1 (10 mmol, 4.8 g), (3-isopropoxyphenyl)boric acid (25 mmol, 5.4 g), Pd(PPh3)4 (1.25 mmol, 1440 mg) and sodium carbonate (40 mmol, 4200 mg) were added to a 250 mL two-necked flask, and then 50 mL of redistilled tetrahydrofuran was added. Nitrogen was introduced and vacuum pumped for 20 min. The reaction solution was stirred and heated to 80° C. for 24 h. The reaction was stopped and cooled to room temperature. The reaction solution was extracted and repeatedly washed with dichloromethane (800 mL) and water (250 mL) for 3 to 4 times. The obtained organic phase was dried with anhydrous magnesium sulfate, filtered, concentrated, and separated by column chromatography. The eluent PE / DCM / EA = 20:1:1. A beige liquid, i.e., compound a-2, was separated. The weight was 4403 mg and the yield was 85%.

[0144] Compound a-2 (10 mmol, 5.18 g) and (NH4)2[Ce(NO3)6] (20 mmol, 10.96 g) were added to a 250 mL two-necked flask, and then 100 mL of anhydrous acetonitrile in tetrahydrofuran was added. Nitrogen was introduced and a vacuum pump was used to evacuate and ventilate for 20 min. The reaction solution was stirred and heated to reflux for 24 h. The reaction was stopped and cooled to room temperature. The reaction solution was extracted and repeatedly washed with dichloromethane (800 mL) and water (250 mL) for 3 to 4 times. The obtained organic phase was dried over anhydrous magnesium sulfate, filtered, concentrated, and separated by column chromatography. The eluent was PE / DCM / EA=30:1:1. A colorless liquid, i.e., compound a, was separated. The weight was 3.87 g and the yield was 75%.

[0145] (2) Compound a (5 mmol, 2.58 g) was added to a 250 mL two-necked flask, and 100 mL of chloroform was added and placed in an ice bath. NBS (15 mmol, 2.67 g) was dissolved in 50 mL of chloroform and slowly added dropwise to the reaction device. After the addition was completed, the mixture was stirred for 10 min in an ice bath, and the mixture was heated to room temperature for reaction for 1 h. The reaction was quenched with 50 mL of 1 mol / mL sodium thiosulfate aqueous solution, and the reaction solution was extracted. Dichloromethane (500 mL) and water (200 mL) were used for repeated washing 3 to 4 times. The crude product was mixed with 300 to 400 mesh silica gel and separated by column chromatography. The eluent was PE (petroleum ether) / dichloromethane = 5:2. Compound b was separated as a colorless liquid with a weight of 3.037 g and a yield of 90%. The mass spectrometry result was m / z = 675.51 [M+H] + .

[0146] (3) Compound 1-1 (10 mmol, 2.18 g; CAS: 71521-89-6) was added to a 250 mL two-necked bottle, and 100 mL of chloroform was added and placed in an ice bath. NIS (15 mmol, 3.37 g) was dissolved in 50 mL of chloroform and slowly added dropwise to the reaction device. After the addition was completed, the mixture was stirred for 10 min in an ice bath, and the mixture was heated to room temperature for 1 h. The reaction was quenched with 50 mL of 1 mol / mL sodium thiosulfate aqueous solution, and the reaction solution was extracted and repeatedly washed with dichloromethane (500 mL) and water (200 mL) for 3 to 4 times. The crude product was mixed with 300 to 400 mesh silica gel and separated by column chromatography using PE as the eluent to obtain a colorless liquid, namely compound 1-2. Compound 1-2 (1 mmol, 344 mg), K4Fe(CN)6 (0.6 mmol, 220 mg), K2CO3 (1.5 mmol, 207 mg), C 30 H 24N3OPPd (0.017mmol, 10mg), and add 10mlDMF, stir, and react at 120℃ under nitrogen atmosphere for 24h, then extract the reaction solution, select dichloromethane (500mL) and water (200mL) for repeated washing 3 to 4 times, mix the crude product with 300 to 400 mesh silica gel, and separate by column chromatography, using PE as eluent to obtain a colorless liquid - compound 1-3. Compound 1-3 (10 mmol) was added to a 250 mL two-necked bottle, and 100 mL of chloroform was added and placed in an ice bath. NBS (15 mmol, 3.37 g) was dissolved in 50 mL of chloroform and slowly added dropwise to the reaction device. After the addition was completed, the mixture was stirred for 10 min in an ice bath, warmed to room temperature and reacted for 1 h. The reaction was quenched with 50 mL of 1 mol / mL sodium thiosulfate aqueous solution, and then the reaction solution was extracted. Dichloromethane (500 mL) and water (200 mL) were used for repeated washing 3 to 4 times. The crude product was mixed with 300 to 400 mesh silica gel and separated by column chromatography using PE as the eluent to obtain compound 1-4. Compound 1-4 (0.2 mmol, 64.4 mg) was added to a 100 ml two-necked bottle, and the mixture was combined with 1% ethyl acetate and 1% ethanol. Boric acid pinacol ester (0.8 mg, 202 mg; CAS: 73183-34-3), Pd(dppf)Cl2 (0.04 mmol, 30 mg) and potassium acetate (1 mmol, 98 mg), then add 40 ml of redistilled 1,4-dioxane, pass nitrogen, use a vacuum pump to evacuate for 15 minutes, place the reaction bottle in an oil bath and heat to 100 ° C with tin foil to avoid light for 24 hours, stop the reaction, and cool to room temperature. The reaction solution is extracted and repeatedly washed with dichloromethane (1000 ml) and water (250 ml) for 3-4 times, and the organic phase is dried with anhydrous magnesium sulfate. The filtrate is collected and crudely separated by column chromatography, and the developing agent is petroleum ether: dichloromethane (volume ratio is 20:1) to obtain colorless oily compound c-1.

[0147] Compound b (2.5 mmol, 1685 mg), compound c-1 (7.5 mmol, 2152 mg), Pd(PPh3)4 (0.125 mmol, 144 mg) and potassium phosphate (12.5 mmol, 1060 mg) were added to a 250 mL two-necked flask, and then 100 mL of redistilled tetrahydrofuran was added, nitrogen was introduced, and a vacuum pump was used to evacuate and ventilate for 20 min. The reaction solution was stirred and heated to 85 ° C for 24 h, the reaction was stopped, and the temperature was reduced. The reaction mixture was cooled to room temperature, and the reaction solution was extracted. Dichloromethane (800 mL) and water (250 mL) were used for repeated washing 3 to 4 times. The obtained organic phase was dried over anhydrous magnesium sulfate, filtered, concentrated, and separated by column chromatography. The eluent was PE / DCM / EA=10:3:2. Compound d-1 was separated as a white solid with a weight of 1998 mg, a yield of 80%, a melting point of 111.2°C to 112.2°C, and a mass spectrometry result of m / z=999.69 [M+H] + .

[0148] (4) Compound d-1 (2.5 mmol, 2497 mg), compound e (3.75 mmol, 1125 mg), and FeCl3 (8.75 mmol, 1417 mg) were added to a 200 ml two-necked bottle, and then 100 ml of dichloromethane was added. Stirring was started and the temperature was controlled at 30°C. After reacting for 2 h, the degree of reaction was monitored. After the reaction was complete, 50 ml of icy methanol was injected into the reaction device to quench the reaction. The mixture was stirred for 10 min and filtered under reduced pressure using a Buchner funnel. The filtrate was mixed with 300-400 mesh silica gel and filled into a column chromatography for purification. The eluent was petroleum ether: dichloromethane: acetone = 10:2:1. The crude product was recrystallized from ethanol to obtain compound f-1, which was a white solid of 2329 mg with a yield of 77%. The melting point was 121.2°C to 122.9°C and the mass spectrometry result was m / z = 1211.77 [M+H]. + .

[0149] (5) In a 100 ml two-necked bottle, compound f-1 (1 mmol, 1210 mg), compound g-1 (3-ethoxypropionic acid, 2.5 mmol, 295 mg), N,N'-dicyclohexylcarbodiimide (3 mmol, 62 mg), 4-dimethylaminopyridine (1 mmol, 120 mg) were added, and then 50 ml of ultra-dry dichloromethane was added, argon was introduced, and a vacuum pump was used to evacuate and ventilate for 15 min. Stirring was started and the temperature was controlled at 40°C. The reaction was carried out for 12 h. The reaction liquid was filtered using a Buchner funnel, and the filtrate was mixed with silica gel for column chromatography purification. The eluent used petroleum ether: ethyl acetate = 20:1. The crude product was recrystallized using ethanol to obtain 1057 mg of M1 as a white solid with a yield of 75% and a melting point of 128°C to 129.9°C. The mass spectrometry result was m / z = 1411.87 [M+H] + ; 1 The HNMR spectrum is shown in Table 1.

[0150] (6) Compound M1 obtained in step (5) was mixed with TFB at a mass ratio of 1:5 to obtain a composite material. The composite material was dispersed in a mixed solution of xylene and cyclohexylbenzene to form a HT solution with a concentration of 30 mg / ml for later use.

[0151] The HT solution was printed on a substrate to form a thin film; the cyclic voltammetry method was used to test the cyclic voltammetry curve and HOMO energy level: the test selected Shanghai CHI 660E electrochemical workstation, using a three-electrode system, that is, the titanium dioxide FTO conductive glass loaded with the above film was used as the working electrode, the Ag / AgCl electrode was used as the reference electrode, and the platinum wire electrode was used as the counter electrode; the electrolyte was 0.1 mol / L tetrabutylammonium hexafluorophosphate (TBAPF6) in acetonitrile, and 0.1 mol / L ferrocene was added as an external standard, and the scanning speed was 0.05 V / s. After testing, the HOMO energy level of the M1 compound was -5.3 ev, and the LUMO energy level was -2.1 ev.

[0152] Material Example 2

[0153] The synthesis steps of the organic compound M2 in this embodiment are as follows:

[0154]

[0155] The scheme of this material example is basically the same as that of material example 1, except that the compound prepared in this material example is M2, and correspondingly, in the synthesis steps:

[0156] In step (3), compound c-1 is changed to compound c-2, and the preparation steps of compound c-2 are:

[0157] According to the preparation steps of compound 1-2, the raw material compound 1-1 was changed to compound 2-1 (CAS: 324-42-5), NIS was changed to NBS, and compound 2-2 was prepared; compound 2-2 (0.3mmol, 95.4mg), NiCl2(H2O) 1.5 0.0075mmol was added to a 100ml two-necked bottle, and 30ml of anhydrous THF was added, and then nitrogen was pumped for 15min. The reaction device was placed in an ice bath at -10°C, and an anhydrous ether solution (0.3mmol, 1mol / l) containing tert-butylmagnesium chloride was slowly injected into the reaction device using a syringe. The reaction was allowed to react for 12h. 10ml of methanol was used to quench the reaction, and then an aqueous solution of ammonium chloride (1mol / l, 10ml) and 20ml of an aqueous solution of ethyl acetate were used for extraction, and the organic phase was dried over anhydrous magnesium sulfate. The filtrate was collected and crudely separated using column chromatography, and the developing agent was petroleum ether: dichloromethane (volume ratio of 50:1) to obtain a colorless liquid compound 2-3; according to the steps of synthesizing compound c-1 from compound 1-4, compound 1-4 was changed to compound 2-3 to obtain compound c-2.

[0158] In step (5), compound g-1 was changed to compound g-2 to obtain compound M2 (1072 mg, yield 80%), melting point 138°C to 139.9°C, mass spectrometry result m / z = 1341.78 [M+H] + .

[0159] After testing, the HOMO energy level of the M2 compound is -5.35ev and the LUMO energy level is -2.15ev.

[0160] Material Example 3

[0161] The synthesis steps of the organic compound M3 in this example are as follows:

[0162]

[0163]

[0164] The scheme of this material example is basically the same as that of material example 1, except that the compound prepared in this material example is M3, and correspondingly, in the synthesis steps:

[0165] In step (3), compound c-1 is replaced by compound c-3. The preparation steps of compound c-3 are basically the same as those of compound c-1, except that:

[0166] Synthesis of compound 3-2: The synthesis method of compound 3-2 is the same as that of compound 1-2, except that compound 1-1 is replaced by compound 3-1 (CAS: 62375-59-1); Synthesis of compound 3-3: The synthesis method of compound 3-3 is the same as that of compound 1-3, except that compound 1-2 is replaced by compound 3-2; Synthesis of compound 3-4: The synthesis method of compound 3-4 is the same as that of compound 1-4, except that compound 1-4 is replaced by compound 3-3 and NIS is replaced by NBS; Synthesis of compound c-3: The synthesis method of compound c-3 is the same as that of compound c-1, except that compound 1-4 is replaced by compound 3-4;

[0167] In step (5), compound g-1 was changed to compound g-2 to obtain compound M3 (1121 mg, yield 78%), melting point 140°C to 141°C, mass spectrometry result m / z = 1439.79 [M+H] + .

[0168] After testing, the HOMO energy level of the M3 compound is -5.43ev and the LUMO energy level is -2.2ev.

[0169] Material Example 4

[0170] The synthesis steps of organic compound M4 in this example are as follows:

[0171]

[0172] The scheme of this material example is basically the same as that of material example 1, except that the compound prepared in this material example is M4, and correspondingly, in the synthesis steps:

[0173] In step (3), compound c-1 is replaced by compound c-4; the preparation steps of compound c-4 are basically the same as those of compound c-1, except that:

[0174] Synthesis of compound 4-2: The synthesis method of compound 4-2 is the same as that of compound 1-2, except that compound 1-1 is replaced by compound 4-1 (CAS: 613-12-7); Synthesis of compound 4-3: The synthesis method of compound 4-3 is the same as that of compound 2-3, except that compound 2-2 is replaced by compound 4-2; Synthesis of compound 4-4: The synthesis method of compound 4-4 is the same as that of compound 1-3, except that compound 1-2 is replaced by compound 4-3; Synthesis of compound 4-5: The synthesis method of compound 4-5 is the same as that of compound 1-2, except that compound 1-2 is replaced by compound 4-4, and NIS is replaced by NBS; Synthesis of compound c-4: The synthesis method of compound c-4 is the same as that of compound c-1, except that compound 1-4 is replaced by compound 4-5;

[0175] In step (5), compound g-1 was changed to compound g-2 to obtain compound M4 (1138 mg, yield 76%), melting point 145°C to 145.8°C, mass spectrometry result m / z = 1499.79 [M+H] + .

[0176] After testing, the HOMO energy level of the M4 compound is -5.6ev and the LUMO energy level is -2.1ev.

[0177] Material Example 5

[0178] The synthesis steps of organic compound M5 in this example are as follows:

[0179]

[0180] The scheme of this material example is basically the same as that of material example 1, except that the compound prepared in this material example is M5, and correspondingly, in the synthesis steps:

[0181] In step (3), compound c-1 is changed to compound c-5, and the preparation steps of compound c-5 are:

[0182] Compound 5-1 (10 mmol, 2.06 g; CAS: 62083-20-9), NaOH (40 mmol, 16 g), and n-hexyl bromide (10 mmol, 1.65 g) were added to a 250 ml two-necked bottle, and 150 ml DMSO was added. The mixture was stirred and heated at 85°C for 24 h. DMSO was removed by vacuum distillation, and the remaining residue was subjected to column chromatography with petroleum ether as eluent to obtain a colorless liquid compound 5-2. Synthesis of compound 5-3: The synthesis of compound 5-3 was the same as that of compound 1-2, except that compound 1-1 was replaced by 5-2 and NIS was replaced by NBS. Synthesis of compound c-5: The synthesis method of compound c-5 was the same as that of compound c-1, except that compound 1-4 was replaced by compound 5-3.

[0183] In step (5), compound g-1 was replaced by compound g-2 to obtain compound M5 (1163 mg, yield 79%), melting point 125°C to 126.8°C, mass spectrometry result m / z = 1474.01 [M+H] + .

[0184] After testing, the HOMO energy level of the M5 compound is -5.5ev, and the LUMO energy level is -2.21ev.

[0185] Material Example 6

[0186] The structure of the organic compound M6 in this embodiment is as follows:

[0187]

[0188] The synthesis steps of organic compound M6 in this example are as follows:

[0189]

[0190] The scheme of this material example is basically the same as that of material example 5, except that the compound prepared in this material example is M6, and correspondingly, in the synthesis steps:

[0191] In step (5), compound g-2 was replaced by compound g-1 to obtain compound M6 (1053 mg, yield 70%), melting point 123°C to 124.8°C, mass spectrometry result m / z = 1506 [M+H] + .

[0192] After testing, the HOMO energy level of the M6 ​​compound is -5.23ev and the LUMO energy level is -2.25ev.

[0193] Material Example 7

[0194] The synthesis steps of organic compound M7 in this example are as follows:

[0195]

[0196] The scheme of this material example is basically the same as that of material example 1, except that the compound prepared in this material example is M7, and correspondingly, in the synthesis steps:

[0197] In step (3), compound c-1 is changed to compound c-6, and the preparation steps of compound c-6 are:

[0198] Synthesis of compound 6-2: The synthesis method of compound 6-2 is the same as that of compound 1-2, except that compound 1-1 is replaced by compound 6-1 and NIS is replaced by NBS; Synthesis of compound c-6: The synthesis of compound c-6 is the same as that of compound 1-5, except that compound 1-4 is replaced by compound 6-2.

[0199] In step (5), compound g-1 was replaced by compound g-2 to obtain compound M7 (1069 mg, yield 83%), melting point 135°C to 136.2°C, mass spectrometry result m / z = 1289.77 [M+H] + .

[0200] After testing, the HOMO energy level of the M7 compound is -5.43ev and the LUMO energy level is -2.21ev.

[0201] Material Example 8

[0202] The structural formula of the organic compound M8 in this embodiment is as follows:

[0203]

[0204] The synthesis steps of organic compound M8 in this example are as follows:

[0205]

[0206] The scheme of this material example is basically the same as that of material example 7, except that the compound prepared in this material example is M8, and correspondingly, in the synthesis steps:

[0207] In step (5), compound g-1 was changed to compound g-2 to obtain compound M8 (976 mg, yield 74%), melting point 133°C to 134.8°C, mass spectrometry result m / z = 1321.76 [M+H] + .

[0208] After testing, the HOMO energy level of the M8 compound is -5.7ev and the LUMO energy level is -2.18ev.

[0209] Material Comparative Example 1

[0210] The material provided in Material Comparative Example 1 is TFB, and the corresponding solution is a TFB solution without adding an organic compound. Correspondingly:

[0211] This comparative example is as follows: TFB is dispersed in a mixed solution of xylene and cyclohexylbenzene to form a HT solution with a concentration of 30 mg / ml for later use.

[0212] Material Comparative Example 2

[0213] This material comparison example is basically the same as material comparison example 1, and the only difference is that in this material comparison example, TFB is replaced by PVK.

[0214] Material Comparative Example 3

[0215] This material comparison example is substantially the same as material comparison example 1, except that in this material comparison example, TFB is replaced with CBP-V.

[0216] Table 1

[0217]

[0218]

[0219] Device Example 1

[0220] (1) Indium zinc oxide (IZO) coated glass (specifications: thickness 75nm, sheet resistance 10Ω / m 2, the surface is 30mm×30mm in size) and then pre-treated as an anode: the cleaning machine is used for program cleaning in sequence, each cleaning step is carried out for 120s, and the stains and dust on the surface of the glass substrate are thoroughly cleaned, and then baked at 230℃ for 30min. Then it is placed in an electric hot air drying oven for 24h and dried. Then the dried glass substrate is exposed to UV and treated with O2 plasma for 15min to reduce the surface work enthalpy and set aside.

[0221] (2) In a nitrogen glove box, PEDOT:PPS was poured into an inkjet printer cartridge, 9 pL of ink was injected into each pixel, and VD was performed for 5 min (vacuum degree was 1×10 -4 mPa) to form a 30 nm thick hole injection layer, and annealed at 230 °C for 30 min.

[0222] (3) The HT solution prepared in Material Example 1 was poured into an inkjet printer cartridge, 12 picoliters of ink was injected into each pixel luminous point, and VD was performed for 5 min (the vacuum degree was 1×10 -4 mPa) to form a 25 nm thick hole transport layer, and annealing treatment was performed at 230°C for 30 min.

[0223] (4) The dissolved luminescent layer material (concentration 20 mg / ml) was prepared into ink and poured into the inkjet printer cartridge. 10 picoliters was injected into each pixel of the hole transport layer and VD was performed for 5 min (vacuum degree 1×10 -4 mPa) to form a light-emitting layer with a thickness of 35 nm, and annealing treatment was performed at 140°C for 20 min.

[0224] (5) ZnO and PVP were dissolved in ethanol to prepare EML ink with a ZnO concentration of 20 mg / ml, which was then poured into an inkjet printer cartridge. 6 picoliters of the ink was injected into the pixel point where the light-emitting layer was located and VD was performed for 5 min (the vacuum degree was 1×10 - 4 mPa), forming an electron transport layer with a thickness of 20 nm.

[0225] (6) Place the semi-finished product obtained in step (5) into a vacuum chamber, and place the semi-finished product into a vacuum chamber (vacuum degree is 5×10 - 7 Pa), vacuum evaporation is performed to evaporate 100nm thick Al onto the electron transport layer as the device cathode, and finally UV curing packaging is performed, and heating and baking are performed for 20min to prepare the light-emitting device.

[0226] Device Examples 2 to 8

[0227] The scheme of device embodiment n is basically the same as that of device embodiment 1, with the only difference being that in device embodiment n, in step (3), the HT solution prepared in material embodiment 1 is replaced by the HT solution prepared in material embodiment n, where n is any integer from 2 to 8.

[0228] Device Comparison Example

[0229] The device comparison example m is basically the same as the device embodiment 1, except that in the device comparison example m, in step (3), the HT solution prepared in material embodiment 1 is replaced by the HT solution prepared in material comparison example m, where m is any integer from 1 to 3.

[0230] Experimental example

[0231] (i) The corresponding single-carrier devices were prepared using the HT solutions provided in the material examples and comparative examples, and then their hole mobility was tested. The results are shown in Table 2.

[0232] Preparation method of single-carrier device: pretreatment of zinc oxide (IZO) coated glass (specification: thickness 75nm, surface 30×30mm): use a cleaning machine to perform program cleaning in sequence, each step is 120s, a total of six steps, and then place the cleaned substrate on a 230℃ hot stage for baking for 30min, and then put the dried substrate into UV exposure and O2 plasma treatment for 15min; use the pretreated glass substrate as the device anode; then spin-coat PEDOT:PSS on the pretreated substrate at 2000rmp / 60s in air to form a HI layer (100nm); then bake on a 230℃ hot stage for 30min, and then transfer it to a nitrogen glove box, spin-coat HT material on the surface of the HI layer at 1500rmp / 30s to form a 25nm thick HT layer; finally, evaporate the cathode layer MoO3 (5nm) / Ag (80nm) on the HT surface. The HT material is the HT material solution prepared from Material Examples 1 to 8 and Material Comparative Examples 1 to 3.

[0233] Table 2

[0234] <![CDATA[Hole mobility (cm 2 v -1 s -1 )]]> Material Example 1 <![CDATA[3.1×10 -2 ]]> Material Example 2 <![CDATA[2×10 -2 ]]> Material Example 3 <![CDATA[1×10 -2 ]]> Material Example 4 <![CDATA[4×10 -2 ]]> Material Example 5 <![CDATA[3.5×10 -2 ]]> Material Example 6 <![CDATA[2.5×10 -2 ]]> Material Example 7 <![CDATA[4×10 -2 ]]> Material Example 8 <![CDATA[6×10 -2 ]]> Material Comparative Example 1 <![CDATA[3.1×10 -3 ]]> Material Comparative Example 2 <![CDATA[2.5×10 -6 ]]> Material Comparative Example 3 <![CDATA[3.1×10 -5 ]]>

[0235] Refer to Table 2, we can see that:

[0236] Compared with Comparative Examples 1 to 3, each material embodiment has a higher hole mobility, which indicates that the addition of the organic compound proposed in the present application into the hole transport material helps to increase its hole transport channel and improve the hole transport efficiency.

[0237] (ii) The devices prepared in the above device embodiments and device comparative examples were tested, and the test items included the start-up voltage V on , luminescence peak λmax , maximum brightness L max , external quantum efficiency EQE and lifetime LT 90 The results are recorded in Table 3. The test method is as follows:

[0238] (1) External quantum efficiency EQE test

[0239] External quantum efficiency EQE represents the ratio of the number of electron-hole pairs injected into quantum dots to the number of emitted photons. The unit is %, which is an important parameter to measure the quality of electroluminescent devices. It can be obtained by measuring with EQE optical testing instruments. The specific calculation formula is as follows:

[0240] Among them, η e is the light output coupling efficiency, η γ is the ratio of the number of recombined carriers to the number of injected carriers, x is the ratio of the number of excitons that generate photons to the total number of excitons, K R is the radiation process rate, K NR is the rate of the non-radiative process.

[0241] Test conditions: carried out at room temperature, air humidity is 30-60%.

[0242] (2) Life test refers to the time taken for the device brightness to decay to a certain percentage of the maximum brightness under 2mA constant current drive. The time taken for the brightness to decay to 95% of the maximum brightness is defined as T95, and this life is the measured life. In order to shorten the life test cycle, the device life test is usually carried out at high brightness by accelerating device aging, and the life at low brightness is obtained by fitting the decay fitting formula. For example, the life at 1000nits is recorded as T95 1000nits, and the calculation formula is:

[0243]

[0244] Among them, T95 L The lifespan under low brightness, generally 1000nits, T95 H is the lifespan under high brightness, that is, the measured lifespan, L H is the maximum brightness that the device is accelerated to, L L Generally it is 1000nits, A is the acceleration factor, which is 1.7.

[0245] Table 3

[0246] Part Number <![CDATA[V on (V)]]> <![CDATA[λ max (nm)]]> <![CDATA[L max (cd / m 2 )]]> EQE(%) <![CDATA[LT 90 (h)]]> Device Example 1 3.1 460 48000 20 45 Device Example 2 3.0 461 50000 22 38 Device Example 3 2.9 459 49000 24 50 Device Example 4 3.3 463 51000 23 55 Device Example 5 3.4 464 50000 29 41 Device Example 6 2.9 457 48500 30 39 Device Example 7 3.3 460 52000 31 42 Device Example 8 3.1 461 49000 27 42 Device Comparison Example 1 5.8 445 4500 15.6 10 Device Comparison Example 2 4.1 454 4140 10 11 Device Comparison Example 3 5.5 478 4000 9 8

[0247] Refer to Table 3, we can see that:

[0248] Compared with Comparative Examples 1 to 3, each device embodiment has higher LT90, EQE and Lmax , and lower V on , indicating that the addition of the organic compound proposed in this application into the hole transport layer helps to improve the hole transport efficiency, reduce the hole injection barrier between the hole transport layer and the hole injection layer, block electrons from the light-emitting layer, improve the interface effect between the hole transport layer and the light-emitting layer, and improve the carrier balance of the device, thereby effectively improving the luminous efficiency and service life of the device.

[0249] The organic compounds and preparation methods thereof, composite materials, optoelectronic devices and display devices provided in the embodiments of the present application are introduced in detail above. Specific examples are used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the methods and core ideas of the present application. At the same time, for technicians in this field, according to the ideas of the present application, there will be changes in the specific implementation methods and application scopes. In summary, the content of this specification should not be understood as a limitation on the present application.

Claims

1. An organic compound, characterized in that The organic compound has a structure shown in formula (1): Wherein, D1 and D2 are each independently selected from an aromatic group having 5 to 60 ring carbon atoms, which is substituted or unsubstituted by a first substituent, and the first substituent includes a combination of one or more of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a halogen group, and a cyano group; R1 and R2 are each independently selected from R3 is selected from any one of a C1-C30 alkyl group substituted or unsubstituted by a second substituent, and an aryl group having 6 to 30 ring carbon atoms substituted or unsubstituted by a third substituent, wherein the second substituent and the third substituent are each independently selected from a combination of one or more of a C1-C20 alkoxy group, a halogen group, and a cyano group; R4 to R7 are each independently selected from C1-C20 alkyl groups.

2. The organic compound according to claim 1, characterized in that D1 and D2 are each independently selected from an aryl group having 6 to 14 ring carbon atoms, which is substituted or unsubstituted by a first substituent; and / or, The first substituent includes a combination of one or more of a C1-C10 alkyl group, a C1-C10 alkoxy group, a halogen group, and a cyano group; and / or, D1 and D2 are the same.

3. The organic compound according to claim 2, characterized in that D1 and D2 are each independently selected from one of the structures of Formula 1-1 to Formula 1-32:

4. The organic compound according to claim 1, characterized in that R3 is selected from C1-C30 alkyl group which is substituted or unsubstituted by a second substituent; and / or, The second substituent is selected from a combination of one or more of C1-C10 alkoxy and cyano; and / or, R1 and R2 are the same; and / or, R4 to R7 are each independently selected from C1-C6 alkyl.

5. The organic compound according to claim 4, characterized in that R1 and R2 are each independently selected from one of the structures of Formula 2-1 to Formula 2-4:

6. The organic compound according to any one of claims 1 to 5, characterized in that The HOMO energy level of the organic compound is -5.3ev to -5.7ev; and / or, The LUMO energy level of the organic compound is -2.0 eV to -2.3 eV; and / or, The organic compound includes one or more compounds of the structures shown in Formula M1 to Formula M8:

7. A method for preparing an organic compound, characterized in that: The following steps are involved: Mixing compound a with a halogenating agent to carry out a halogenation reaction to obtain compound b; The compound b is mixed with the compound c, and subjected to a metal coupling reaction to obtain a compound d; The compound d is mixed with the compound e, and a cyclization reaction is performed to obtain a compound f; The compound f is mixed with the compound g to carry out an esterification reaction to obtain an organic compound; Wherein, the organic compound has a structure shown in formula (1): wherein X is selected from Cl, Br or I; D is selected from D1 or D2, and R is selected from R1 or R2; D1 and D2 are each independently selected from an aromatic group having 5 to 60 ring carbon atoms, which is substituted or unsubstituted by a first substituent, wherein the first substituent includes a combination of one or more of a C1 to C20 alkyl group, a C1 to C20 alkoxy group, a halogen group, and a cyano group; R1 and R2 are each independently selected from R3 is selected from any one of a C1-C30 alkyl group substituted or unsubstituted by a second substituent, and an aryl group having 6 to 30 ring carbon atoms substituted or unsubstituted by a third substituent, wherein the second substituent and the third substituent are each independently selected from a combination of one or more of a C1-C20 alkoxy group, a halogen group, and a cyano group; R4 to R7 are each independently selected from C1-C20 alkyl groups.

8. The preparation method according to claim 7, characterized in that: The molar ratio of the compound a to the halogenating agent is 1:(2.5-3.5); and / or, The temperature of the halogenation reaction is 10°C to 25°C; and / or, The halogenation reaction time is 0.5 to 1.5 hours; and / or, The step of mixing the compound b with the compound c and performing a metal coupling reaction to obtain the compound d comprises: mixing the compound b, the compound c, a base and a palladium catalyst in an inert atmosphere and performing a metal coupling reaction to obtain the compound d; and / or, The step of mixing the compound d with the compound e and performing a cyclization reaction to obtain the compound f comprises: mixing the compound d, the compound e and a Lewis acid catalyst and performing a cyclization reaction to obtain the compound f; and / or, The step of mixing the compound f with the compound g and performing an esterification reaction to obtain an organic compound comprises: in an inert atmosphere, mixing the compound f, the compound g, N,N'-dicyclohexylcarbodiimide and 4-dimethylaminopyridine and performing an esterification reaction to obtain an organic compound.

9. The preparation method according to claim 8, characterized in that: The Lewis acid catalyst includes one or more of ferric chloride and aluminum chloride; and / or, The alkali comprises one or more of alkali metal phosphates, alkali metal carbonates, and alkali metal bicarbonates; the alkali metal phosphate comprises one or more of potassium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium phosphate, sodium dihydrogen phosphate, and disodium hydrogen phosphate; the alkali metal carbonate comprises one or more of sodium carbonate and potassium carbonate; the alkali metal bicarbonate comprises one or more of sodium bicarbonate and potassium bicarbonate; and / or, The molar ratio of the compound b to the compound c is 1:(2-5); and / or, The molar ratio of the compound b to the palladium catalyst is 1:(0.05-0.1); and / or, The molar ratio of the compound b to the base is 1:(5-10); and / or, The temperature of the metal coupling reaction is 75°C to 90°C; and / or, The metal coupling reaction time is 12 to 24 hours; and / or, The molar ratio of the compound d to the compound e is 1:(1.5-3); and / or, The molar ratio of the compound d to the Lewis acid catalyst is 1:(3-6); and / or, The temperature of the cyclization reaction is 25°C to 40°C; and / or, The cyclization reaction time is 1 to 3 hours; and / or, The molar ratio of the compound f to the compound g is 1:(2-4); and / or, The molar ratio of the compound f to N,N'-dicyclohexylcarbodiimide is 1:(3-5); and / or, The molar ratio of the compound f to 4-dimethylaminopyridine is 1:(1.5-2.5); and / or, The temperature of the esterification reaction is 25°C to 50°C; and / or, The esterification reaction time is 12 to 24 hours.

10. A composite material, characterized in that: It comprises a P-type semiconductor material and an additive, wherein the additive comprises the organic compound according to any one of claims 1 to 6, or comprises the organic compound prepared by the preparation method according to any one of claims 7 to 9.

11. The composite material according to claim 10, characterized in that In the composite material, the mass percentage of the additive is 5% to 30%; and / or, The HOMO energy level of the P-type semiconductor material is -5.3 eV to -5.9 eV.

12. The composite material according to claim 11, characterized in that The P-type semiconductor material includes at least one of PVK, CBP, TCTA, TFB, TPD, NPB, and CBP-V.

13. A photoelectric device, characterized in that: The invention comprises an anode, a hole functional layer and a cathode, wherein the material of the hole functional layer comprises the composite material according to any one of claims 10 to 12.

14. The optoelectronic device according to claim 13, characterized in that: The anode and the cathode are independently selected from a doped metal oxide particle electrode, a composite electrode of metal and metal oxide, a graphene electrode, a carbon nanotube electrode, a metal electrode or an alloy electrode; the material of the doped metal oxide particle electrode is selected from 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 of metal and metal oxide is selected from 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, ZnS / Al / ZnS; the material of the metal electrode is selected from one or more of Ag, Al, Cu, Mo, Au, Pt, Si, Ca, Mg and Ba; and / or, The photoelectric device also includes a light-emitting layer, which is arranged between the cathode and the hole functional layer; the material of the light-emitting layer includes one or more organic light-emitting materials and quantum dot light-emitting materials, and the organic light-emitting material is selected from 4,4'-bis(N-carbazole)-1,1'-biphenyl:tris[2-(p-tolyl)pyridine iridium(III), 4,4',4"-tri(carbazole-9-yl)triphenylamine:tris[2-(p-tolyl)pyridine iridium, poly[(9,9-dioctylfluorene-2,7-diyl)-alternate-(2,1,3-benzothiadiazole-4,7-diyl)], diaryl anthracene derivatives, diphenylethylene One or more of 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 covalent bonding of BN, hybrid localized charge transfer excited state materials, and exciplex luminescent materials, the quantum dot luminescent material includes at least one of single structure quantum dots, core-shell structure quantum dots and perovskite semiconductor materials; the material of the single structure quantum dots, the core material of the core-shell structure quantum dots and the shell material of the core-shell structure quantum dots are selected from II-VI compounds, I At least one of a V-VI group compound, a III-V group compound and a I-III-VI group compound; the II-VI group compound is selected from CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnT e, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe and HgZnSTe; the IV-VI group compound is selected from at least one of SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe and SnPbSTe;The III-V compound is selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, and AlN P, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInN P, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs and InAlPSb; the I-III-VI group compound is selected from at least one of CuInS2, CuInSe2 and AgInS2; the perovskite semiconductor material is selected from doped or undoped inorganic perovskite semiconductors, or organic-inorganic hybrid perovskite semiconductors; the inorganic perovskite semiconductor has a general structural formula of AMX3, wherein A is Cs; + ion, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2+ 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - At least one of the following; the general structural formula of the organic-inorganic hybrid perovskite semiconductor is BMX3, wherein B is an organic amine cation selected from CH3(CH2) n-2 NH3 + or [NH3(CH2) n NH3] 2+ , where n≥2, M is a divalent metal cation selected from Pb 2+ Sn 2+ , Cu 2+ 、Ni 2 + 、Cd 2+ Cr 2+ , Mn 2+ 、Co 2+ , Fe 2+ ,Ge 2+ , Yb 2+ 、Eu 2+ At least one of, X is a halogen anion selected from Cl - Br - ,I - At least one of .

15. A display device, characterized in that: Comprising the optoelectronic device according to claim 13 or 14.

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