Self-assembled hole transport material and use thereof

Abstract

The present invention relates to the field of photovoltaic materials. The present invention provides a self-assembled hole transport material and a use thereof. The self-assembled hole transport material is a new carbazole derivative. The new carbazole derivative has a phosphonic acid anchoring group and can realize the self-assembly of a monolayer. In addition, a hydrophilic group containing an aromatic ring is introduced on one side of two benzene rings in carbazole. The hydrophilic group comprises methoxyphenyl, methylthiophenyl, cyanophenyl, formamidophenyl, or carboxyphenyl, and the hydrophilic group can effectively improve the good wettability of a perovskite precursor solution on the self-assembled monolayer and can form good complexation with a perovskite component, thereby achieving the purpose of passivating a lower interface of perovskite. In addition, the aromatic ring added to the carbazole can modulate the energy levels of self-assembled small molecules and a perovskite layer, thereby better matching the perovskite, optimizing the charge transfer efficiency of a battery, and finally achieving the effect of improving the conversion efficiency and stability of a perovskite battery.

Description

Self-assembled hole transport material and use thereof TECHNICAL FIELD

[0001] The present application belongs to the field of photovoltaic materials, and relates to a self-assembled hole transport material and use thereof. BACKGROUND

[0002] Perovskite solar cells have attracted much attention due to their high efficiency, low cost and easy preparation. The hole transport layer (hole transport material) is a key component in perovskite solar cells, and its main function is to transport the generated holes from the perovskite layer to the electrode layer after the perovskite absorbs photons, thereby improving the photoelectric conversion efficiency of the cell.

[0003] At present, researchers have developed a variety of hole transport materials with excellent performance, which can be classified into multiple categories according to different classification standards: for example, according to chemical properties, existing hole transport materials include inorganic materials and organic materials; for example, according to the structural characteristics of perovskite, hole transport materials can be divided into normal structure (n-i-p) hole transport materials and inverted structure (p-i-n) hole transport materials; specifically, in the current perovskite device, commonly used hole transport materials include NiO x , CuI, spiro-OMeTAD, PTAA and self-assembled small molecule (SAM) materials, etc.

[0004] Compared with other hole transport materials, self-assembled small molecule (SAM) materials have developed rapidly due to their use in inverted structure cells, among which, the carbazole-based self-assembled small molecule hole transport material with phosphoric acid as an anchor group has improved the efficiency of p-i-n structure cells to more than 26%, and has very good application prospect. However, the surface of the existing SAM material (such as carbazole butyl phosphonic acid, 3,6-diphenyl carbazole butyl phosphonic acid, etc.) is a non-hydrophilic group, which leads to very poor wettability of the perovskite precursor solution on the surface of the small molecule layer, and when preparing a large-area perovskite thin film, the solution will be condensed, the precursor solution will be difficult to spread well on the surface of the small molecule layer, and then holes will appear in the perovskite thin film, which has a negative impact on the preparation of large-area perovskite thin film and components, and also cannot play the role of passivating the lower interface of perovskite, all of which lead to poor quality and poor stability of large-area perovskite film, and limit the further application of such materials and the further development of perovskite devices. SUMMARY

[0005] In view of the problems in the prior art, the purpose of the present application is to provide a self-assembled hole transport material and use thereof, by designing and synthesizing a new class of carbazole derivatives, to improve the hydrophilicity and optimize the passivation of the lower interface of perovskite, thereby further improving the conversion efficiency and stability of perovskite cells.

[0006] To achieve this purpose, the present application adopts the following technical solutions:

[0007] In a first aspect, the present application provides a self-assembled hole transport material, comprising a compound having a structure shown in Formula I:

[0008] wherein n is an integer between 2 and 6, for example 2, 3, 4, 5 or 6, R 11 and R 12 are each independently selected from any one of the following groups:

[0009] m1, m2, m3, m4 and m5 represent the number of corresponding groups, and each of m1, m2, m3, m4 and m5 is independently selected from an integer between 1 and 5, for example 1, 2, 3, 4 or 5; the dotted line represents the connection site of the group.

[0010] Since the lower end of the self-assembled hole transport material needs to be anchored with ITO, FTO or other metal oxides, and the upper end of the self-assembled material needs to be in contact with perovskite to form a hole transport layer film. However, the existing carbazole has insufficient wettability to the perovskite precursor solution, resulting in poor spreading of the perovskite precursor solution. Therefore, the present application designs and synthesizes a class of carbazole derivatives as self-assembled monolayer hole transport materials, which have phosphonic acid anchoring groups to realize self-assembly of monolayer; at the same time, a hydrophilic group containing aromatic ring is introduced on one side of the two benzene rings in carbazole, and the hydrophilic group containing aromatic ring includes any one of methoxyphenyl, methylthiophenyl, cyanophenyl, formamidophenyl or carboxyphenyl, which can effectively improve the good wettability of the perovskite precursor solution on the self-assembled monolayer, and at the same time, the hydrophilic group containing aromatic ring can form good complexation with perovskite components, such as lead, so as to achieve the purpose of passivating the lower interface of perovskite; at the same time, the increased aromatic ring in carbazole can adjust the energy level of the self-assembled small molecule and the perovskite layer, better match the perovskite, optimize the charge transport efficiency of the battery, and finally realize the effect of improving the conversion efficiency and stability of the perovskite battery.

[0011] The following is a preferred technical solution of the present application, but not as a limitation of the technical solutions provided by the present application. Through the following technical solutions, the technical purposes and beneficial effects of the present application can be better achieved and realized.

[0012] As a preferred technical solution of the present application, in Formula I, the R 11 and R 12 are each independently selected from any one of the following groups:

[0013] That is, in the present application, the R 11 and R 12Preferably, each is independently selected from any one of p-methoxyphenyl, p-methylthiophenyl, p-cyanophenyl, p-formamidophenyl, or p-carboxyphenyl.

[0014] As a preferred technical solution of the present invention, the R 11 and R 12 They are the same group.

[0015] In this invention, considering the ease of synthesis, synthesis yield, and cost, R is preferred. 11 and R 12 Using the same functional groups can reduce the types of raw materials used.

[0016] As a preferred embodiment of the present invention, the self-assembled hole transport material comprises compounds having the following specific structures:

[0017] That is, when n=2, the obtained self-assembled hole transport material is a 2PACz type material, preferably any one of bis(4-methoxy)-3,6-diphenylcarbazole ethyl phosphoric acid (denoted as 2P-1), bis(4-methylthio)-3,6-diphenylcarbazole ethyl phosphoric acid (denoted as 2P-2), bis(4-cyano)-3,6-diphenylcarbazole ethyl phosphoric acid (denoted as 2P-3), bis(4-formamide)-3,6-diphenylcarbazole ethyl phosphoric acid (denoted as 2P-4), and bis(4-carboxyl)-3,6-diphenylcarbazole ethyl phosphoric acid (denoted as 2P-5);

[0018] That is, when n=3, the obtained self-assembled hole transport material is a 3PACz type material, preferably any one of bis(4-methoxy)-3,6-diphenylcarbazolepropyl phosphate (denoted as 3P-1), bis(4-methylthio)-3,6-diphenylcarbazolepropyl phosphate (denoted as 3P-2), bis(4-cyano)-3,6-diphenylcarbazolepropyl phosphate (denoted as 3P-3), bis(4-formamide)-3,6-diphenylcarbazolepropyl phosphate (denoted as 3P-4), and bis(4-carboxyl)-3,6-diphenylcarbazolepropyl phosphate (denoted as 3P-5);

[0019] That is, when n=4, the obtained self-assembled hole transport material is a 4PACz type material, preferably any one of bis(4-methoxy)-3,6-diphenylcarbazole butyl phosphate (denoted as 4P-1), bis(4-methylthio)-3,6-diphenylcarbazole butyl phosphate (denoted as 4P-2), bis(4-cyano)-3,6-diphenylcarbazole butyl phosphate (denoted as 4P-3), bis(4-formamide)-3,6-diphenylcarbazole butyl phosphate (denoted as 4P-4), and bis(4-carboxyl)-3,6-diphenylcarbazole butyl phosphate (denoted as 4P-5);

[0020] That is, when n = 5, the self-assembled hole transport material obtained is any one of 5PACz class materials, preferably bis(4-methoxy)-3,6-diphenylcarbazole pentyl phosphonic acid (denoted as 5P-1), bis(4-methylthio)-3,6-diphenylcarbazole pentyl phosphonic acid (denoted as 5P-2), bis(4-cyano)-3,6-diphenylcarbazole pentyl phosphonic acid (denoted as 5P-3), bis(4-formamido)-3,6-diphenylcarbazole pentyl phosphonic acid (denoted as 5P-4), and bis(4-carboxyl)-3,6-diphenylcarbazole pentyl phosphonic acid (denoted as 5P-5);

[0021] That is, when n = 6, the self-assembled hole transport material obtained is any one of 6PACz class materials, preferably bis(4-methoxy)-3,6-diphenylcarbazole hexyl phosphonic acid (denoted as 6P-1), bis(4-methylthio)-3,6-diphenylcarbazole hexyl phosphonic acid (denoted as 6P-2), bis(4-cyano)-3,6-diphenylcarbazole hexyl phosphonic acid (denoted as 6P-3), bis(4-formamido)-3,6-diphenylcarbazole hexyl phosphonic acid (denoted as 6P-4), and bis(4-carboxyl)-3,6-diphenylcarbazole hexyl phosphonic acid (denoted as 6P-5).

[0022] The present application does not specifically limit the preparation method of the self-assembled hole transport material, and exemplarily provides a preparation method of the self-assembled hole transport material of the first aspect, which comprises:

[0023] (1) mixing raw material compound VIII with raw material compound VII, and performing alkylation under the action of a strong base and a phase transfer catalyst to generate intermediate compound VI;

[0024] wherein n is an integer between 2 and 6, for example 2, 3, 4, 5 or 6; X 11 , X 12 and X2are each independently selected from any one of halogen;

[0025] (2) mixing intermediate compound VI with raw material compound V or raw material compound V', and performing substitution to generate intermediate compound IV;

[0026] wherein L is selected from any one of C2-C4 straight chain alkyl groups;

[0027] (3) mixing intermediate compound IV with raw material compound IIIa and raw material compound IIIb in a solvent, and performing coupling under the action of a basic substance and a coupling catalyst to generate intermediate compound II;

[0028] wherein R 11 and R12 the same or different, each independently selected from any one of the following groups:

[0029] m1, m2, m3, m4 and m5 represent the number of corresponding groups, and m1, m2, m3, m4 and m5 are each independently selected from an integer between 1 and 5, such as 1, 2, 3, 4 or 5; the dotted line represents the connecting site of the group;

[0030] (4) subjecting the intermediate compound II to a hydrolysis reaction to generate a self-assembled hole transport material having a structure shown in formula I;

[0031] The preparation method provided by the present application can synthesize five types of self-assembled hole transport materials in four steps. The method is simple and has high yield, and is suitable for mass production. Specifically, the preparation method can avoid using expensive raw materials. The third step is a coupling substitution reaction with bromine carbazole substituent group, and then connects the hydrophilic group containing aromatic ring. Considering that the carbazole containing methoxyphenyl, methylthio phenyl and other hydrophilic substituents containing aromatic ring cannot be directly purchased at a low price on the market, the present application also provides a method for introducing a hydrophilic functional group containing aromatic ring at the top of carbazole. If the carbazole containing methoxyphenyl, methylthio phenyl and other hydrophilic substituents containing aromatic ring is used in the first step of the present application, or the dibromocarbazole is subjected to a coupling substitution reaction in the first step, at least three or four completely different reaction nodes are required for the synthesis route of each final product, thereby increasing the cost and affecting the yield and production progress.

[0032] As a preferred technical solution of the present application, in step (1), the raw material compound VIII includes a compound having the following structure:

[0033] Optionally, it is at least one of 1,2-dibromoethane, 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane or 1,6-dibromohexane, which belongs to any one of the dibromoalkanes with bromine groups at both ends.

[0034] Optionally, the raw material compound VII is 3,6-dibromocarbazole (denoted as VIIa) or 3,6-dichlorocarbazole (denoted as VIIb).

[0035] Optionally, the strong base includes potassium hydroxide and / or sodium hydroxide.

[0036] Optionally, the strong base is an aqueous solution with a concentration of 20% to 60%, such as 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55% or 60%, etc.

[0037] Optionally, the phase transfer catalyst comprises tetrabutylammonium bromide and / or tetrabutylammonium iodide.

[0038] Optionally, the alkylation reaction is refluxed and stirred under a protective atmosphere.

[0039] Optionally, the alkylation reaction is at a temperature of 20-70℃, such as 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃ or 70℃, etc.

[0040] Optionally, the alkylation reaction is for a time of 8-16h, such as 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h or 16h, etc., to achieve a yield of the intermediate compound VI of ≥90%, such as 90%, 91%, 92%, 93%, 94% or 95%, etc.

[0041] Optionally, the intermediate compound VI is any one of 3,6-dibromocarbazyl ethyl bromide, 3,6-dibromocarbazyl propyl bromide, 3,6-dibromocarbazyl butyl bromide, 3,6-dibromocarbazyl pentyl bromide or 3,6-dibromocarbazyl hexyl bromide.

[0042] Optionally, in step (2), the raw material compound V is triethyl phosphite (denoted as Va), and the raw material compound V’ is diethyl phosphite (denoted as Va’).

[0043] Optionally, the substitution reaction is refluxed and stirred under a protective atmosphere.

[0044] Optionally, the substitution reaction is for a time of 12-36h, such as 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 32h, 34h or 36h, etc., to achieve a yield of the intermediate compound IV of ≥95%, such as 95%, 96%, 97%, 98% or 99%, etc.

[0045] Optionally, the intermediate compound IV is any one of 3,6-dibromocarbazyl diethyl phosphonate, 3,6-dibromocarbazyl propyl diethyl phosphonate, 3,6-dibromocarbazyl butyl diethyl phosphonate, 3,6-dibromocarbazyl pentyl diethyl phosphonate or 3,6-dibromocarbazyl hexyl diethyl phosphonate.

[0046] As a preferred technical solution of the present application, in step (3), the raw material compound IIIa and the raw material compound IIIb are of the chemical formula R1B(OH)2 and R2B(OH)2, respectively, and are optionally any one independently selected from 4-methoxyphenylboronic acid, 4-methylthio-phenylboronic acid, 4-cyanophenylboronic acid, 4-formamidophenylboronic acid or 4-carboxyphenylboronic acid.

[0047] Optionally, the raw material compound IIIa is the same as the raw material compound IIIb.

[0048] In the present application, when the raw material compound IIIa is the same as the raw material compound IIIb, the raw material compound IIIa and the raw material compound IIIb are collectively referred to as a raw material compound III', which has a chemical formula of RB(OH)2 and a structural formula of:

[0049] R is selected from any one of the following groups:

[0050] m1, m2, m3, m4 and m5 represent the number of corresponding groups, and each of m1, m2, m3, m4 and m5 is independently selected from an integer between 1 and 5, such as 1, 2, 3, 4 or 5; the dotted line represents the connection site of the group.

[0051] Optionally, R is any one of a p-methoxyphenyl group, a p-methylthio phenyl group, a p-cyanophenyl group, a p-formamidophenyl group or a p-carboxyphenyl group, i.e., the raw material compound III' is any one of 4-methoxyphenyl boronic acid, 4-methylthiophenyl boronic acid, 4-cyanophenyl boronic acid, 4-formamidophenyl boronic acid or 4-carboxyphenyl boronic acid.

[0052] As a preferred technical solution of the present application, the preparation method of the self-assembled hole transport material comprises:

[0053] (1) mixing a raw material compound VIIIa with a raw material compound VIIa, and performing an alkylation reaction under the action of a strong base and a phase transfer catalyst to generate an intermediate compound VIa;

[0054] wherein n is an integer between 2 and 6, such as 2, 3, 4, 5 or 6;

[0055] (2) mixing the intermediate compound VIa with a raw material compound Va or a raw material compound V'a, and performing a substitution reaction to generate an intermediate compound IVa;

[0056] (3) mixing the intermediate compound IVa with a raw material compound III' in a solvent, and performing a coupling reaction under the action of a basic substance and a coupling catalyst to generate an intermediate compound II';

[0057] wherein R is any one of a p-methoxyphenyl group, a p-methylthio phenyl group, a p-cyanophenyl group, a p-formamidophenyl group or a p-carboxyphenyl group;

[0058] (4) performing a hydrolysis reaction on the intermediate compound II' to generate a self-assembled hole transport material having a structure shown in formula I';

[0059] As a preferred technical solution of the present application, in step (3), the solvent comprises N,N-dimethylacetamide and / or tetrahydrofuran.

[0060] Optionally, the basic substance comprises potassium carbonate and / or sodium carbonate.

[0061] Optionally, the coupling catalyst comprises tetrakis(triphenylphosphine)palladium and / or palladium acetate.

[0062] Optionally, the coupling reaction is refluxed and stirred under a protective atmosphere.

[0063] Optionally, the coupling reaction temperature is 70-180℃, such as 70℃, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃ or 180℃, and preferably 160-180℃.

[0064] Optionally, the coupling reaction time is 18-30h, such as 18h, 20h, 22h, 24h, 26h, 28h or 30h, and the yield of intermediate compound II (or intermediate compound II') is ≥80%, such as 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89% or 90%.

[0065] Optionally, the intermediate compound II (or intermediate compound II') is any one of bis(4-methoxy)-3,6-diphenylcarbazole ethyl phosphonic acid diethyl ester, bis(4-methylthio)-3,6-diphenylcarbazole ethyl phosphonic acid diethyl ester, bis(4-cyano)-3,6-diphenylcarbazole ethyl phosphonic acid diethyl ester, bis(4-carboxyl)-3,6-diphenylcarbazole ethyl phosphonic acid diethyl ester, bis(4-formamido)-3,6-diphenylcarbazole ethyl phosphonic acid diethyl ester; bis(4-methoxy)-3,6-diphenylcarbazole propyl phosphonic acid diethyl ester, bis(4-methylthio)-3,6-diphenylcarbazole propyl phosphonic acid diethyl ester, bis(4-cyano)-3,6-diphenylcarbazole propyl phosphonic acid diethyl ester, bis(4-carboxyl)-3,6-diphenylcarbazole propyl phosphonic acid diethyl ester, bis(4-formamido)-3,6-diphenylcarbazole propyl phosphonic acid diethyl ester; bis(4-methoxy)-3,6-diphenylcarbazole butyl phosphonic acid diethyl ester, bis(4-methylthio)-3,6-diphenylcarbazole butyl phosphonic acid diethyl ester, bis(4-cyano)-3,6-diphenylcarbazole butyl phosphonic acid diethyl ester, bis(4-carboxyl)-3,6-diphenylcarbazole butyl phosphonic acid diethyl ester, bis(4-formamido)-3,6-diphenylcarbazole butyl phosphonic acid diethyl ester; bis(4-methoxy)-3,6-diphenylcarbazole pentyl phosphonic acid diethyl ester, bis(4-methylthio)-3,6-diphenylcarbazole pentyl phosphonic acid diethyl ester, bis(4-cyano)-3,6-diphenylcarbazole pentyl phosphonic acid diethyl ester, bis(4-carboxyl)-3,6-diphenylcarbazole pentyl phosphonic acid diethyl ester, bis(4-formamido)-3,6-diphenylcarbazole pentyl phosphonic acid diethyl ester; bis(4-methoxy)-3,6-diphenylcarbazole hexyl phosphonic acid diethyl ester, bis(4-methylthio)-3,6-diphenylcarbazole hexyl phosphonic acid diethyl ester, bis(4-cyano)-3,6-diphenylcarbazole hexyl phosphonic acid diethyl ester, bis(4-carboxyl)-3,6-diphenylcarbazole hexyl phosphonic acid diethyl ester, or bis(4-formamido)-3,6-diphenylcarbazole hexyl phosphonic acid diethyl ester.

[0066] Optionally, in step (4), the hydrolysis reaction is carried out under a protective atmosphere with stirring at room temperature.

[0067] Optionally, the hydrolysis reaction includes a hydrolysis aid, and the hydrolysis aid includes trimethylsilyl bromide.

[0068] Optionally, the hydrolysis reaction includes an auxiliary solvent, and the auxiliary solvent includes 1,4-dioxane and / or dichloromethane.

[0069] Optionally, the self-assembled hole transport material having the structure shown in Formula I (or Formula I') includes at least one of bis(4-methoxy)-3,6-diphenylcarbazole ethyl phosphate, bis(4-methylthio)-3,6-diphenylcarbazole ethyl phosphate, bis(4-cyano)-3,6-diphenylcarbazole ethyl phosphate, bis(4-carboxyl)-3,6-diphenylcarbazole ethyl phosphate, bis(4-formamido)-3,6-diphenylcarbazole ethyl phosphate, bis(4-methoxy)-3,6-diphenylcarbazole propyl phosphate, bis(4-methylthio)-3,6-diphenylcarbazole propyl phosphate, bis(4-cyano)-3,6-diphenylcarbazole propyl phosphate, bis(4-carboxyl)-3,6-diphenylcarbazole propyl phosphate, bis(4-formamido)-3,6-diphenylcarbazole propyl phosphate, bis(4-methoxy)-3,6-diphenylcarbazole butyl phosphate, bis(4-methylthio)-3,6-diphenylcarbazole butyl phosphate, bis(4-cyano)-3,6-diphenylcarbazole butyl phosphate, bis(4-carboxyl)-3,6-diphenylcarbazole butyl phosphate, bis(4-formamido)-3,6-diphenylcarbazole butyl phosphate, bis(4-methoxy)-3,6-diphenylcarbazole pentyl phosphate, bis(4-methylthio)-3,6-diphenylcarbazole pentyl phosphate, bis(4-cyano)-3,6-diphenylcarbazole pentyl phosphate, bis(4-carboxyl)-3,6-diphenylcarbazole pentyl phosphate, bis(4-formamido)-3,6-diphenylcarbazole pentyl phosphate, bis(4-methoxy)-3,6-diphenylcarbazole hexyl phosphate, bis(4-methylthio)-3,6-diphenylcarbazole hexyl phosphate, bis(4-cyano)-3,6-diphenylcarbazole hexyl phosphate, bis(4-carboxyl)-3,6-diphenylcarbazole hexyl phosphate, or bis(4-formamido)-3,6-diphenylcarbazole hexyl phosphate.

[0070] In a second aspect, the present application provides a hole transport layer containing the self-assembled hole transport material of the first aspect.

[0071] In a third aspect, the present application provides a method for preparing the hole transport layer of the second aspect, wherein the self-assembled hole transport material is formulated into a precursor solution, the precursor solution is used for film formation, and the hole transport layer is obtained after annealing.

[0072] As a preferred technical solution of the present application, the solvent in the precursor solution includes at least one of methanol, ethanol, isopropanol, N,N-dimethylformamide, dimethyl sulfoxide, or N-methyl pyrrolidone.

[0073] Optionally, the concentration of the self-assembled hole transport material in the precursor solution is 0.1-5 mg / mL, such as 0.1 mg / mL, 0.5 mg / mL, 0.8 mg / mL, 1 mg / mL, 1.5 mg / mL, 2 mg / mL, 2.5 mg / mL, 3 mg / mL, 3.5 mg / mL, 4 mg / mL, 4.5 mg / mL, or 5 mg / mL, etc.

[0074] Optionally, the method of film formation comprises coating, which comprises at least one of spin coating, spray coating, blade coating, or dip coating (dip coating).

[0075] Optionally, the annealing temperature is 100-120℃, such as 100℃, 105℃, 110℃, 115℃, or 120℃, etc.

[0076] Optionally, the thickness of the hole transport layer is 10-200 nm, such as 10 min, 30 min, 50 min, 80 min, 100 min, 120 min, 140 min, 160 min, 180 min, or 200 min, etc.

[0077] In a fourth aspect, the present application provides a battery component comprising the hole transport layer of the second aspect, or the hole transport layer obtained by the method of the third aspect.

[0078] The self-assembled hole transport material described in the present application has the functions of perovskite layer lower interface passivation and improving hydrophilicity, and can be used in, but not limited to, perovskite solar cells, and can also be used in the preparation of perovskite LED or perovskite sensor components, etc.

[0079] As a preferred technical solution of the present application, the battery component comprises a conductive substrate, the hole transport layer, a perovskite layer, an electron transport layer, and an electrode.

[0080] Optionally, the battery component further comprises a passivation layer.

[0081] Optionally, the conductive substrate comprises any one of FTO conductive glass, ITO conductive glass, FTO conductive plastic, or ITO conductive plastic; wherein the thickness of the FTO film layer is 500-600 nm, such as 500 nm, 510 nm, 520 nm, 530 nm, 540 nm, 550 nm, 560 nm, 570 nm, 580 nm, 590 nm, or 600 nm, etc., and the thickness of the ITO film layer is 300-400 nm, such as 300 nm, 310 nm, 320 nm, 330 nm, 340 nm, 350 nm, 360 nm, 370 nm, 380 nm, 390 nm, or 400 nm, etc.

[0082] Optionally, the thickness of the hole transport layer is 10-200 nm, such as 10 nm, 30 nm, 50 nm, 80 nm, 100 nm, 120 nm, 140 nm, 160 nm, 180 nm, or 200 nm, etc.

[0083] Optionally, the perovskite material of the perovskite layer comprises MA x FA 1-x CsPbI 3-a Br a , MA y FA 1-y CsPbI 3-b Cl b , MA z FA 1- z CsPbBr 3-c Cl c , MA + FA + .

[0084] Optionally, the thickness of the perovskite layer is 300-1000 nm, such as 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, 850 nm, 900 nm, 950 nm, or 1000 nm, etc.

[0085] Optionally, the electron transport layer comprises any one of SnO2, TiO2, ZnO, Al2O3, fullerene, and derivatives thereof.

[0086] Optionally, the thickness of the electron transport layer is 10-50 nm, such as 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, or 50 nm, etc.

[0087] Optionally, the electrode comprises any one of Ag, Al, Au, IWO, or ITO.

[0088] Optionally, the thickness of the electrode is 100-200 nm, such as 100 nm, 110 nm, 120 nm, 130 nm, 140 nm, 150 nm, 160 nm, 170 nm, 180 nm, 190 nm or 200 nm, etc.

[0089] It should be noted that the present application does not specifically limit the specific preparation method and process of other layer structures in the battery assembly except the hole transport layer formed by the self-assembled hole transport material, which should be reasonably adjusted and selected as needed. Exemplarily, the TCO film layer on the conductive substrate can be prepared by physical vapor deposition, evaporation or sputtering method; the perovskite layer, the electron transport layer or the passivation layer, etc. can be prepared by any one of spin coating, spraying or scraping coating method; the electrode can be prepared by vacuum evaporation or vacuum sputtering method.

[0090] Compared with the prior art, the present application has at least the following beneficial effects:

[0091] The carbazole derivative designed and synthesized in the present application is used as a self-assembled monolayer hole transport material, which has a phosphonic acid anchoring group to realize self-assembly of a monolayer. At the same time, a hydrophilic group containing an aromatic ring is introduced on one side of the two benzene rings in the carbazole, and the hydrophilic group containing an aromatic ring includes any one of a methoxyphenyl group, a methylthiophenyl group, a cyanophenyl group, a formamidophenyl group or a carboxyphenyl group. The hydrophilic group containing an aromatic ring can effectively improve the good wettability of the perovskite precursor solution on the self-assembled monolayer, and at the same time, the hydrophilic group containing an aromatic ring can form a good complexation with the perovskite components, thereby achieving the purpose of passivating the lower interface of the perovskite. At the same time, the aromatic ring added in the carbazole can mediate the energy level between the self-assembled small molecules and the perovskite layer, better match the perovskite, optimize the charge transport efficiency of the battery, and finally achieve the effect of improving the conversion efficiency and stability of the perovskite battery. BRIEF DESCRIPTION OF DRAWINGS

[0092] FIGS. 1-7 are respectively the nuclear magnetic resonance hydrogen spectrum test result graphs of the self-assembled hole transport materials obtained in Examples 1-7;

[0093] FIGS. 8-16 are respectively the contact angle test result graphs of the perovskite solution on the hole transport layers prepared by the hole transport materials obtained in Examples 1-7 and Comparative Examples 1-2. DETAILED DESCRIPTION

[0094] The technical solutions of the present application are further illustrated by the specific embodiments below.

[0095] Those skilled in the art should understand that the embodiments are only to help understand the present application and should not be regarded as specific limitations of the present application.

[0096] Example 1

[0097] The embodiment provides a self-assembled hole transport material, which is bis(4-methoxy)-3,6-diphenyl carbazole butyl phosphonic acid (denoted as 4P-1), and the structure of the compound is as follows:

[0098] Figure 1 is a graph of the test results of the nuclear magnetic resonance hydrogen spectrum of bis(4-methoxy)-3,6-diphenyl carbazole butyl phosphonic acid obtained in Example 1, and it can be seen from the graph that the structure of the obtained compound is correct.

[0099] The preparation method of the self-assembled hole transport material comprises the following steps:

[0100] (1) mixing a raw material compound 1,4-dibromobutane and 3,6-dibromocarbazole, under the action of a strong base potassium hydroxide aqueous solution with a concentration of 50% and a phase transfer catalyst tetrabutylammonium bromide, refluxing and stirring under a nitrogen atmosphere and at 35°C to perform an alkylation reaction for 12 hours to generate an intermediate compound 3,6-dibromocarbazole butyl bromide with a yield of ≥90%;

[0101] (2) mixing the intermediate compound 3,6-dibromocarbazole butyl bromide and triethyl phosphite, refluxing and stirring under a nitrogen atmosphere to perform a substitution reaction for 24 hours to generate an intermediate compound 3,6-dibromocarbazole butyl phosphonic acid diethyl ester with a yield of ≥95%;

[0102] (3) mixing the intermediate compound 3,6-dibromocarbazole butyl phosphonic acid diethyl ester and a raw material compound 4-methoxyphenylboronic acid in a solvent N,N-dimethylacetamide, under the action of an alkaline substance potassium carbonate and a coupling catalyst tetrakis(triphenylphosphine)palladium, performing a coupling reaction under a nitrogen atmosphere and at 170°C for 24 hours to generate an intermediate compound bis(4-methoxy)-3,6-diphenyl carbazole butyl phosphonic acid diethyl ester with a yield of ≥80%;

[0103] (4) mixing the intermediate compound bis(4-methoxy)-3,6-diphenyl carbazole butyl phosphonic acid diethyl ester and 1,4-dioxane, stirring under the action of trimethylsilyl bromide at room temperature under a nitrogen atmosphere for 12 hours, removing the 1,4-dioxane by rotary evaporation under reduced pressure, then adding methanol and stirring for 5 hours, finally adding pure water dropwise to precipitate the product, and performing a hydrolysis reaction to generate the bis(4-methoxy)-3,6-diphenyl carbazole butyl phosphonic acid.

[0104] Example 2

[0105] The embodiment provides a self-assembled hole transport material, which is bis(4-methylthio)-3,6-diphenyl carbazole butyl phosphonic acid (denoted as 4P-2), and the structure of the compound is as follows:

[0106] Figure 2 is a graph of the results of the nuclear magnetic resonance hydrogen spectrum test of the obtained bis(4-methylthio)-3,6-diphenylcarbazole butyl phosphonic acid of Example 2, from which it can be seen that the structure of the obtained compound is correct.

[0107] The preparation method of the self-assembled hole transport material comprises:

[0108] (1) mixing raw material compound 1,4-dibromobutane and 3,6-dibromocarbazole, under the action of potassium hydroxide with a concentration of 50% and phase transfer catalyst tetrabutylammonium bromide, refluxing and stirring under a nitrogen atmosphere and at 35°C to perform an alkylation reaction for 12 hours to generate intermediate compound 3,6-dibromocarbazole butyl bromide with a yield of ≥90%;

[0109] (2) mixing intermediate compound 3,6-dibromocarbazole butyl bromide and triethyl phosphite, refluxing and stirring under a nitrogen atmosphere to perform a substitution reaction for 24 hours to generate intermediate compound 3,6-dibromocarbazole butyl phosphonic acid diethyl ester with a yield of ≥95%;

[0110] (3) mixing intermediate compound 3,6-dibromocarbazole butyl phosphonic acid diethyl ester and raw material compound 4-methylthiophenylboronic acid in solvent N,N-dimethylacetamide, under the action of basic substance potassium carbonate and coupling catalyst tetrakis(triphenylphosphine)palladium, performing a coupling reaction under a nitrogen atmosphere and at 170°C for 24 hours to generate intermediate compound bis(4-methylthio)-3,6-diphenylcarbazole butyl phosphonic acid diethyl ester with a yield of ≥80%;

[0111] (4) mixing intermediate compound bis(4-methylthio)-3,6-diphenylcarbazole butyl phosphonic acid diethyl ester and 1,4-dioxane, under the action of trimethylsilyl bromide, stirring at room temperature under a nitrogen atmosphere for 12 hours, removing 1,4-dioxane by rotary evaporation under reduced pressure; then adding methanol and stirring for 5 hours, finally adding pure water dropwise to precipitate the product, completing the hydrolysis reaction to generate bis(4-methylthio)-3,6-diphenylcarbazole butyl phosphonic acid.

[0112] Example 3

[0113] This example provides a self-assembled hole transport material, which is bis(4-cyano)-3,6-diphenylcarbazole butyl phosphonic acid (denoted as 4P-3), and the structure of the compound is as follows:

[0114] Figure 3 is a graph of the results of the nuclear magnetic resonance hydrogen spectrum test of the obtained bis(4-cyano)-3,6-diphenylcarbazole butyl phosphonic acid of Example 3, from which it can be seen that the structure of the obtained compound is correct.

[0115] The preparation method of the self-assembled hole transport material comprises:

[0116] (1) mixing raw material compound 1,4-dibromobutane with 3,6-dibromocarbazole, under the action of potassium hydroxide with a concentration of 50% and phase transfer catalyst tetrabutylammonium bromide, refluxing and stirring under nitrogen atmosphere at 35°C for 12 hours to perform alkylation reaction, to generate intermediate compound 3,6-dibromocarbazole butyl bromide with a yield of ≥90%;

[0117] (2) mixing intermediate compound 3,6-dibromocarbazole butyl bromide with triethyl phosphite, refluxing and stirring under nitrogen atmosphere for 24 hours to perform substitution reaction, to generate intermediate compound 3,6-dibromocarbazole butyl diethyl phosphonate with a yield of ≥95%;

[0118] (3) mixing intermediate compound 3,6-dibromocarbazole butyl diethyl phosphonate with raw material compound 4-cyanophenylboronic acid in solvent N,N-dimethylacetamide, under the action of basic substance potassium carbonate and coupling catalyst tetrakis(triphenylphosphine)palladium, coupling reaction under nitrogen atmosphere at 170°C for 24 hours, to generate intermediate compound bis(4-cyano)-3,6-diphenylcarbazole butyl diethyl phosphonate with a yield of ≥80%;

[0119] (4) mixing intermediate compound bis(4-cyano)-3,6-diphenylcarbazole butyl diethyl phosphonate with 1,4-dioxane, under the action of trimethylsilyl bromide, stirring at room temperature under nitrogen atmosphere for 12 hours, removing 1,4-dioxane by rotary evaporation under reduced pressure; then adding methanol and stirring for 5 hours, finally adding pure water dropwise to precipitate the product, to complete the hydrolysis reaction, to generate bis(4-cyano)-3,6-diphenylcarbazole butyl phosphonic acid.

[0120] Example 4

[0121] The present example provides a kind of self-assembled hole transport material, the self-assembled hole transport material is bis(4-formylamino)-3,6-diphenylcarbazole butyl phosphonic acid (denoted as 4P-4), the structure of this compound is:

[0122] Fig. 4 is the test result diagram of the nuclear magnetic resonance hydrogen spectrum of bis(4-formylamino)-3,6-diphenylcarbazole butyl phosphonic acid obtained in Example 4, it can be seen from the diagram that the structure of the obtained compound is correct.

[0123] The preparation method of the self-assembled hole transport material comprises:

[0124] (1) mixing raw material compound 1,4-dibromobutane with 3,6-dibromocarbazole, under the action of potassium hydroxide with a concentration of 50% and phase transfer catalyst tetrabutylammonium bromide, refluxing and stirring under nitrogen atmosphere at 35°C for 12 hours to perform alkylation reaction, to generate intermediate compound 3,6-dibromocarbazole butyl bromide with a yield of ≥90%;

[0125] (2) mixing the intermediate compound 3,6-dibromo-carbazole-butyl bromide with triethyl phosphite, refluxing and stirring under nitrogen atmosphere to perform substitution reaction for 24 h to generate the intermediate compound 3,6-dibromo-carbazole-butyl diethyl phosphonate with a yield of ≥95%;

[0126] (3) mixing the intermediate compound 3,6-dibromo-carbazole-butyl diethyl phosphonate with the raw material compound 4-formylamino-phenylboronic acid in a solvent N,N-dimethylacetamide, coupling reaction under the action of the basic substance potassium carbonate and the coupling catalyst tetrakis(triphenylphosphine)palladium under nitrogen atmosphere and at 170°C for 24 h to generate the intermediate compound bis(4-formylamino)-3,6-diphenyl-carbazole-butyl diethyl phosphonate with a yield of ≥80%;

[0127] (4) mixing the intermediate compound bis(4-formylamino)-3,6-diphenyl-carbazole-butyl diethyl phosphonate with 1,4-dioxane, stirring under the action of trimethylsilyl bromide at room temperature under nitrogen atmosphere for 12 h, removing 1,4-dioxane by rotary evaporation under reduced pressure; then adding methanol and stirring for 5 h, finally adding pure water dropwise to precipitate, completing the hydrolysis reaction of the product to generate the bis(4-formylamino)-3,6-diphenyl-carbazole-butyl phosphonic acid.

[0128] Example 5

[0129] The present example provides a kind of self-assembled hole transport material, and the self-assembled hole transport material is bis(4-carboxyl)-3,6-diphenyl-carbazole-butyl phosphonic acid (denoted as 4P-5), the structure of this compound is:

[0130] Fig. 5 is the test result diagram of the nuclear magnetic resonance hydrogen spectrum of bis(4-carboxyl)-3,6-diphenyl-carbazole-butyl phosphonic acid obtained in Example 5, and it can be seen from the diagram that the structure of the obtained compound is correct.

[0131] The preparation method of the self-assembled hole transport material comprises:

[0132] (1) mixing the raw material compound 1,4-dibromo-butane with 3,6-dibromo-carbazole under the action of strong base potassium hydroxide with a concentration of 50% and phase transfer catalyst tetrabutylammonium bromide, refluxing and stirring under nitrogen atmosphere and at 35°C to perform alkylation reaction for 12 h to generate the intermediate compound 3,6-dibromo-carbazole-butyl bromide with a yield of ≥90%;

[0133] (2) mixing the intermediate compound 3,6-dibromo-carbazole-butyl bromide with triethyl phosphite, refluxing and stirring under nitrogen atmosphere to perform substitution reaction for 24 h to generate the intermediate compound 3,6-dibromo-carbazole-butyl diethyl phosphonate with a yield of ≥95%;

[0134] (3) mixing the intermediate compound 3,6-dibromo-carbazole butyl phosphonic acid diethyl ester with the raw material compound 4-carboxy-phenyl boronic acid in a solvent N,N-dimethylacetamide, under the action of a basic substance potassium carbonate and a coupling catalyst tetrakis(triphenylphosphine)palladium, under a nitrogen atmosphere and at 170°C, coupling reaction for 24h to generate the intermediate compound bis(4-carboxy)-3,6-diphenyl-carbazole butyl phosphonic acid diethyl ester, yield≥80%;

[0135] (4) mixing the intermediate compound bis(4-carboxy)-3,6-diphenyl-carbazole butyl phosphonic acid diethyl ester with 1,4-dioxane, under the action of trimethylsilyl bromide, stirring reaction at room temperature under a nitrogen atmosphere for 12h, removing 1,4-dioxane by rotary evaporation under reduced pressure; then adding methanol and stirring reaction for 5h, finally adding pure water to precipitate the product to complete the hydrolysis reaction to generate the bis(4-carboxy)-3,6-diphenyl-carbazole butyl phosphonic acid.

[0136] Example 6

[0137] The present embodiment provides a kind of self-assembled hole transport material, the self-assembled hole transport material is bis(4-methylthio)-3,6-diphenyl-carbazole ethyl phosphonic acid (marked as 2P-2), the structure of this compound is:

[0138] Fig. 6 is the nuclear magnetic resonance hydrogen spectrum test result diagram of bis(4-methylthio)-3,6-diphenyl-carbazole ethyl phosphonic acid obtained in example 6, it can be seen from the figure that the structure of the obtained compound is correct.

[0139] The preparation method of the self-assembled hole transport material comprises:

[0140] (1) mixing the raw material compound 1,2-dibromoethane with 3,6-dibromo-carbazole, under the action of strong base potassium hydroxide with a concentration of 50% and phase transfer catalyst tetrabutylammonium bromide, refluxing and stirring under a nitrogen atmosphere and at 25°C to perform alkylation reaction for 12h to generate the intermediate compound 3,6-dibromo-carbazole ethyl bromide, yield≥90%;

[0141] (2) mixing the intermediate compound 3,6-dibromo-carbazole ethyl bromide with triethyl phosphite, refluxing and stirring under a nitrogen atmosphere to perform substitution reaction for 24h to generate the intermediate compound 3,6-dibromo-carbazole ethyl phosphonic acid diethyl ester, yield≥95%;

[0142] (3) mixing the intermediate compound 3,6-dibromo-carbazole ethyl phosphonic acid diethyl ester with the raw material compound 4-methylthio-phenyl boronic acid in a solvent N,N-dimethylacetamide, under the action of a basic substance potassium carbonate and a coupling catalyst tetrakis(triphenylphosphine)palladium, under a nitrogen atmosphere and at 170°C, coupling reaction for 24h to generate the intermediate compound bis(4-methylthio)-3,6-diphenyl-carbazole ethyl phosphonic acid diethyl ester, yield≥80%;

[0143] (4) mixing the intermediate compound bis(4-methylthio)-3,6-diphenyl-carbazole ethyl phosphonic acid diethyl ester with 1,4-dioxane, under the action of trimethylsilyl bromide, stirring reaction at room temperature under a nitrogen atmosphere for 12h, removing 1,4-dioxane by rotary evaporation under reduced pressure; then adding methanol and stirring reaction for 5h, finally adding pure water to precipitate the product to complete the hydrolysis reaction to generate the bis(4-methylthio)-3,6-diphenyl-carbazole ethyl phosphonic acid.

[0144] Example 7

[0145] The embodiment provides a kind of self-assembled hole transport material, and the self-assembled hole transport material is bis(3-methylthio)-3,6-diphenyl-carbazole butyl phosphonic acid (marked as 4P-6), and the structure of the compound is:

[0146] Fig. 7 is the nuclear magnetic resonance hydrogen spectrum test result diagram of bis(3-methylthio)-3,6-diphenyl-carbazole butyl phosphonic acid obtained in example 7, and it can be seen from the figure that the structure of the obtained compound is correct.

[0147] The preparation method of the self-assembled hole transport material includes:

[0148] (1) mixing the raw material compound 1,4-dibromo-butane with 3,6-dibromo-carbazole, under the action of strong base potassium hydroxide with concentration of 50% and phase transfer catalyst tetrabutylammonium bromide, refluxing and stirring under a nitrogen atmosphere and at 25°C to perform alkylation reaction for 12h to generate the intermediate compound 3,6-dibromo-carbazole butyl bromide, yield≥90%;

[0149] (2) mixing the intermediate compound 3,6-dibromo-carbazole butyl bromide with triethyl phosphite, refluxing and stirring under a nitrogen atmosphere to perform substitution reaction for 24h to generate the intermediate compound 3,6-dibromo-carbazole ethyl phosphonic acid dibutyl ester, yield≥95%;

[0150] (3) the intermediate compound 3,6-dibromo-carbazole-butyl phosphonic acid diethyl ester is mixed with the raw material compound 3-methylthio-phenyl boronic acid in a solvent N,N-dimethylacetamide, and a coupling reaction is carried out under the action of a basic substance potassium carbonate and a coupling catalyst tetrakis(triphenylphosphine)palladium under a nitrogen atmosphere and at 170°C for 24 h, to generate the intermediate compound bis(3-methylthio)-3,6-diphenyl-carbazole-butyl phosphonic acid diethyl ester, with a yield of ≥80%;

[0151] (4) the intermediate compound bis(3-methylthio)-3,6-diphenyl-carbazole-butyl phosphonic acid diethyl ester is mixed with 1,4-dioxane, and stirred at room temperature under the action of trimethylsilyl bromide under a nitrogen atmosphere for 12 h, 1,4-dioxane is removed by rotary evaporation under reduced pressure; then methanol is added and stirred for 5 h, and finally pure water is added dropwise to precipitate the product, to complete the hydrolysis reaction, to generate the bis(3-methylthio)-3,6-diphenyl-carbazole-butyl phosphonic acid.

[0152] Comparative Example 1

[0153] This comparative example uses carbazole-butyl phosphonic acid (CAS: 20999-36-4) as a hole transport material, and the structure is as follows:

[0154] Comparative Example 2

[0155] This comparative example uses 3,6-diphenyl-carbazole-butyl phosphonic acid (CAS: 2814500-04-2) as a hole transport material, and the structure is as follows:

[0156] Application Example 1: this application example provides a hole transport layer, which is respectively composed of the hole transport materials obtained in Examples 1-7 and Comparative Examples 1-2, and the preparation method of the hole transport layer comprises:

[0157] The hole transport materials obtained in the examples and comparative examples are respectively prepared into precursor solutions with a concentration of 1 mg / mL in solvents N,N-dimethylformamide and dimethyl sulfoxide, the precursor solutions are used to perform spin coating at 3000 rpm for 30 s to form films, and then the films are annealed at 100°C for 10 min, to obtain hole transport layers with a thickness of 2-5 nm.

[0158] Fig. 8 to Fig. 16 are respectively the contact angle test results of the hole transport layer prepared from the hole transport material of Example 1-7 and Comparative Example 1-2 to the perovskite solution, from which it can be seen that the contact angle from large to small is in turn: the hole transport layer prepared from 3,6-diphenylcarbazole butyl phosphate (CA = 17.08) of Comparative Example 2, the hole transport layer prepared from carbazole butyl phosphate (CA = 16.53) of Comparative Example 1, the hole transport layer prepared from bis(4-cyano)-3,6-diphenylcarbazole butyl phosphate (CA = 15.18) of Example 3, the hole transport layer prepared from bis(4-methoxy)-3,6-diphenylcarbazole butyl phosphate (CA = 14.70) of Example 1, the hole transport layer prepared from bis(3-methylthio)-3,6-diphenylcarbazole butyl phosphate (12.24) of Example 7, the hole transport layer prepared from bis(4-formylamino)-3,6-diphenylcarbazole butyl phosphate (CA = 12.16) of Example 4, the hole transport layer prepared from bis(4-methylthio)-3,6-diphenylcarbazole ethyl phosphate (11.8) of Example 6, the hole transport layer prepared from bis(4-methylthio)-3,6-diphenylcarbazole butyl phosphate (CA = 11.14) of Example 2, and the hole transport layer prepared from bis(4-carboxyl)-3,6-diphenylcarbazole butyl phosphate (CA = 10.42) of Example 5, the smaller the contact angle, the higher the wettability.

[0159] In this application example, a perovskite solar cell is provided, which comprises a conductive substrate, a hole transport layer, a perovskite layer, an electron transport layer and an electrode which are sequentially stacked; wherein the conductive substrate is FTO conductive glass, the thickness of the FTO film layer is 550 nm; the hole transport layer is the hole transport layer prepared in Application Example 1; the perovskite material of the perovskite layer is MA x FA 1-x CsPbI 3-a Br a , the structural formula of MA is CH3NH3 + , the structural formula of FA is CH(NH2)2 + ; the thickness of the perovskite layer is 460 nm; the electron transport layer is PCBM, and the thickness is 20 nm; the electrode is Ag, and the thickness is 120 nm.

[0160] The obtained perovskite solar cell is tested, and the results are shown in Table 1.

[0161] Table 1

[0162] Note: In Table 1, Voc represents open circuit voltage, Jsc represents short circuit current, FF represents fill factor (Fill Factor), and η represents conversion efficiency (Efficiency).

[0163] As can be seen from Table 1, the perovskite solar cell efficiency of the hole transport material having the methoxyphenyl, methylthiophenyl, cyanophenyl, carboxyphenyl, formamidophenyl is obviously superior to that of the common small molecule hole transport material, mainly reflected in the improved voltage and fill factor. The improved voltage indicates that the hole transport material has better energy level matching with the perovskite, and the improved fill factor indicates that the perovskite has better force with the hole transport material. The introduction of the above functional groups can improve the wettability to the perovskite, and complex with the perovskite components to passivate the lower interface of the perovskite layer, thereby improving the device efficiency.

[0164] The above describes the preferred embodiments of the present application in detail, but the present application is not limited to the specific details in the above embodiments, and various simple modifications can be made to the technical solutions of the present application within the technical concept of the present application, and these simple modifications all belong to the protection scope of the present application.

[0165] In addition, it should be noted that each specific technical feature described in the above specific embodiments can be combined in any appropriate manner without contradiction, and in order to avoid unnecessary repetition, the present application will not further describe various possible combinations.

[0166] In addition, various different embodiments of the present application can also be combined in any manner, as long as it does not deviate from the idea of the present application, and it should also be considered as disclosed by the present application.

Claims

1. A self-assembling hole transporting material, characterized in that, The self-assembled hole transport material comprises a compound having a structure represented by Formula I: wherein n is an integer between 2 and 6, R 11 and R 12 are each independently selected from any one of the following groups: m1, m2, m3, m4 and m5 are each independently selected from an integer between 1 and 5; the dotted line represents the connecting site of the group.

2. The self-assembled hole transport material of claim 1, wherein said R 11 and R 12 each independently is selected from any one of the following groups:

3. The self-assembled hole transport material of claim 1, wherein The R 11 and R 12 are the same group.

4. The self-assembled hole transport material of claim 1, wherein The self-assembled hole transport material includes a compound having the following structure:

5. A hole transport layer, characterized by, The self-assembled hole transport material according to any one of claims 1-4.

6. The hole transport layer according to claim 5, wherein The thickness of the hole transport layer is 10-200 nm.

7. A method of producing the hole transport layer according to claim 5 or 6, characterized by, The self-assembled hole transport material is formulated into a precursor solution, the precursor solution is used to form a film, and the hole transport layer is obtained after annealing.

8. The method of claim 7, wherein the hole transport layer is prepared by a method comprising: The solvent in the precursor solution comprises at least one of methanol, ethanol, isopropanol, N,N-dimethylformamide, dimethyl sulfoxide or N-methyl pyrrolidone.

9. The method of claim 8, wherein the hole transport layer is prepared by a method comprising: The concentration of the self-assembled hole transport material in the precursor solution is 0.1-5 mg / mL.

10. The method of claim 7, wherein the hole transport layer is prepared by a process comprising: The method for film formation comprises at least one of spin coating, spray coating, blade coating or dip coating.

11. The method of claim 7, wherein the hole transport layer is prepared by a method comprising: The annealing temperature is 100-120°C.

12. A battery assembly characterized by, The hole transport layer according to claim 5 or 6, or the hole transport layer obtained by the method according to any one of claims 7-11.

13. The battery assembly of claim 12, wherein, The battery component comprises a conductive substrate, the hole transport layer, a perovskite layer, an electron transport layer and an electrode.

14. The battery assembly of claim 13, wherein, The conductive substrate comprises any one of FTO conductive glass, ITO conductive glass, FTO conductive plastic or ITO conductive plastic; wherein the thickness of the FTO film layer is 500-600 nm, and the thickness of the ITO film layer is 300-400 nm.

15. The battery assembly of claim 13, wherein, The perovskite material of the perovskite layer comprises any one of MA x FA 1- x CsPbI 3-a Br a , MA y FA 1-y CsPbI 3-b Cl b , MA z FA 1-z CsPbBr 3-c Cl c , wherein x, y and z are each independently selected from 0-1, a, b and c are each independently selected from 0-3, the structural formula of MA is CH3NH3 + , and the structural formula of FA is CH(NH2)2 + .

16. The battery assembly of claim 15, wherein, The thickness of the perovskite layer is 300-1000 nm.

17. The battery assembly of claim 13, wherein, The electron transport layer comprises any one of SnO2, TiO2, ZnO, Al2O3, fullerene and derivatives thereof.

18. The battery assembly of claim 17, wherein, The thickness of the electron transport layer is 10-50 nm.

19. The battery assembly of claim 13, wherein, The electrode comprises any one of Ag, Al, Au, IWO or ITO.

20. The battery assembly of claim 19, wherein, The thickness of the electrode is 100-200 nm.

Images