Self-assembly material based on brominated dibenzocarbazole, preparation method of self-assembly material, hole transport material and photoelectric device

Abstract

The invention relates to the technical field of photoelectric materials, in particular to a self-assembly material based on brominated dibenzocarbazole, a preparation method of the self-assembly material, a hole transport material and a photoelectric device. The structural formula of the self-assembly material based on brominated dibenzocarbazole is shown in the formula 1, a dibenzocarbazole parent nucleus is an excellent hole transport material, bromine atoms are introduced into a framework of the dibenzocarbazole parent nucleus, the energy level of the material can be effectively adjusted, phosphoric acid is an anchoring group used for making contact with the surface of a metal oxide, R1 is used for connecting the parent nucleus and the anchoring group, and R2 is used for connecting the parent nucleus and the anchoring group. And excellent hole transport performance is shown. The compound in the formula 1 and the compound in the formula 2 are mixed to serve as the hole transport material, and the mixing strategy ensures that the material can obtain enhanced hole transport performance, improve interface contact and improve the work function of the conductive metal oxide under the condition of keeping good solubility. The hole transport material can improve the efficiency and stability of a device when being used in the device, and is suitable for manufacturing large-area devices.

Description

Technical Field

[0001] The present invention relates to the technical field of optoelectronic materials, and particularly to a self-assembled material based on dibenzocarbazole bromide, a preparation method thereof, a hole transport material, and an optoelectronic device. Background Art

[0002] Perovskite solar cells (PSCs) are a new type of photovoltaic device, which have the characteristics of low cost, low production energy consumption, and high photoelectric conversion efficiency. In addition, due to the adjustable bandgap of their light absorption layer, they are also widely used in the preparation of tandem solar cells, such as organic / perovskite tandem solar cells, copper indium gallium selenide (CIGS) / perovskite tandem solar cells, silicon / perovskite tandem solar cells, and perovskite / perovskite tandem solar cells, etc., and have good commercial development prospects.

[0003] In recent years, perovskite solar cells have developed rapidly, and the photoelectric conversion efficiency has been increased to 26.95%, showing broad application prospects. Among them, the hole transport material is very important for reducing the manufacturing cost, improving the efficiency and operating stability of the battery. Self-assembled hole transport materials have received extensive attention due to their convenient preparation, simple structure, high stability, and high hole transport performance. At present, this strategy has been successfully applied to single-junction perovskite solar cells and perovskite tandem cells. In perovskite solar cells, the self-assembled hole transport material plays the role of conducting holes, increasing the work function of the conductive metal oxide, and improving the quality of the lower interface of the perovskite layer, thereby affecting the efficiency and stability of the battery. However, the existing such materials have problems such as poor wettability, low stability, and weak hole transport ability, which hinder the further development of perovskite solar cells.

[0004] Therefore, the prior art still needs to be improved and developed. Summary of the Invention

[0005] In view of the above deficiencies of the prior art, the purpose of the present invention is to provide a self-assembled material based on dibenzocarbazole bromide, a preparation method thereof, a hole transport material, and an optoelectronic device, aiming to solve the problems of poor wettability, low stability, and weak hole transport ability of the existing hole transport materials.

[0006] The technical solution of the present invention is as follows:

[0007] In the first aspect of the present invention, a self-assembled material based on dibenzocarbazole bromide is provided, wherein the structural formula of the self-assembled material based on dibenzocarbazole bromide is shown in Formula 1:

[0008]

[0009] In Formula 1, R1 is selected from an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 ring carbon atoms, or a heteroarylene group having 5 to 12 ring atoms.

[0010] In a second aspect of the present invention, there is provided a method for preparing a self-assembled material based on dibenzocarbazole bromide as described in the present invention, which includes the steps of:

[0011] Step S1: Performing a carbon-nitrogen coupling reaction on the compound of Formula I and the compound of Formula II to obtain a compound of Formula III;

[0012] Step S2: Performing a carbon-phosphorus coupling reaction on the compound of Formula III and the compound of Formula IV to obtain a compound of Formula V;

[0013] Step S3: Performing a bromination reaction on the compound of Formula V and a brominating reagent to obtain a compound of Formula VI;

[0014] Step S4: Performing a hydrolysis reaction on the compound of Formula VI to obtain the self-assembled material based on dibenzocarbazole bromide shown in the structure of Formula 1;

[0015] Among them, the structural formula of the compound of Formula I is The structural formula of the compound of Formula II is The structural formula of the compound of Formula III is The structural formula of the compound of Formula IV is The structural formula of the compound of Formula V is The structural formula of the compound of Formula VI is

[0016] In the compounds of Formula I - Formula VI, X1 and X2 are halogens, and X1 and X2 are the same or different; R1 is selected from an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 ring carbon atoms, or a heteroarylene group having 5 to 12 ring atoms; R2 is selected from an alkyl group having 1 to 4 carbon atoms.

[0017] In a third aspect of the present invention, there is provided a hole transport material, which includes the self-assembled material based on dibenzocarbazole bromide and the self-assembled material based on dibenzocarbazole as described in the present invention. The structural formula of the self-assembled material based on dibenzocarbazole is as shown in Formula 2:

[0018]

[0019] In Formula 2, R3 is selected from an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 ring carbon atoms, or a heteroarylene group having 5 to 12 ring atoms.

[0020] In a fourth aspect of the present invention, an optoelectronic device is provided, including a hole transport layer, and the material of the hole transport layer includes the self-assembled material based on dibenzocarbazole bromide described in the present invention or the hole transport material described in the present invention.

[0021] Beneficial effects: The self-assembled material based on dibenzocarbazole bromide represented by the formula 1 structure provided by the present invention, wherein the dibenzocarbazole mother nucleus is an excellent hole transport material. Introducing bromine atoms into its skeleton can effectively adjust the energy level of the material. Phosphoric acid is used as an anchoring group for contacting the surface of metal oxides, and R1 is used to connect the mother nucleus and the anchoring group, showing excellent hole transport performance. Mixing the self-assembled material based on dibenzocarbazole bromide represented by the formula 1 structure and the self-assembled material based on dibenzocarbazole represented by the formula 2 structure as the hole transport material, the mixing strategy ensures that this type of material can obtain enhanced hole transport performance, improve interfacial contact, and increase the work function of the conductive metal oxide while maintaining good solubility. The hole transport material can improve the efficiency and stability of the device when used in the device and is suitable for large-area device manufacturing. Description of the Drawings

[0022] Figure 1 It is a schematic structural diagram of a single-junction perovskite solar cell.

[0023] Figure 2 It is a schematic structural diagram of a perovskite / silicon tandem solar cell.

[0024] Figure 3 It is a schematic structural diagram of a perovskite / silicon tandem solar cell.

[0025] Figure 4 It is a J-V curve diagram of the single-junction perovskite solar cells in Examples 3-5.

[0026] Figure 5 It is a J-V curve diagram of the perovskite / silicon tandem solar cells in Examples 6-8.

[0027] Figure 6 It is a J-V curve diagram of the perovskite / perovskite tandem solar cells in Examples 9-11. Detailed Embodiments

[0028] The present invention provides a self-assembled material based on dibenzocarbazole bromide, its preparation method, a hole transport material, and an optoelectronic device. To make the purpose, technical solution, and effects of the present invention clearer and more definite, the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0029] An embodiment of the present invention provides a self-assembled material based on dibenzocarbazole bromide, and the structural formula of the self-assembled material based on dibenzocarbazole bromide is shown in Formula 1:

[0030]

[0031] In Formula 1, R1 is selected from an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 ring carbon atoms, or a heteroarylene group having 5 to 12 ring atoms.

[0032] The self-assembled material based on dibenzocarbazole bromide represented by the structural formula of Formula 1 provided by the embodiment of the present invention, wherein the dibenzocarbazole mother nucleus is an excellent hole transport material. Introducing a bromine atom into its skeleton can effectively adjust the energy level of the material. Phosphoric acid is an anchoring group for contacting the surface of metal oxide, and R1 is used to connect the mother nucleus and the anchoring group, showing excellent hole transport performance. The self-assembled material based on dibenzocarbazole bromide is a new type of optoelectronic functional material with high stability and strong hole transport ability, which can further improve the optoelectronic efficiency and stability of the device.

[0033] In some embodiments, R1 is selected from any one of the following groups:

[0034]

[0035]

[0036] wherein represents the connection point.

[0037] In some embodiments, the self-assembled material based on dibenzocarbazole bromide is selected from any one of the following compounds:

[0038]

[0039] In some embodiments, the self-assembled material based on dibenzocarbazole bromide is used as a hole transport material.

[0040] An embodiment of the present invention provides a preparation method of the self-assembled material based on dibenzocarbazole bromide described in the foregoing embodiment, including the steps of:

[0041] Step S1: Perform a carbon-nitrogen coupling reaction on the compound of Formula I and the compound of Formula II to obtain the compound of Formula III;

[0042] Step S2: Perform a carbon-phosphorus coupling reaction on the compound of Formula III and the compound of Formula IV to obtain the compound of Formula V;

[0043] Step S3: Perform a bromination reaction on the compound of Formula V and a brominating reagent to obtain the compound of Formula VI;

[0044] Step S4: Hydrolyze the compound of Formula VI to obtain the self-assembled material based on dibenzocarbazole bromide shown in the structure of Formula 1;

[0045] Among them, the structural formula of the compound of Formula I is The structural formula of the compound of Formula II is The structural formula of the compound of Formula III is The structural formula of the compound of Formula IV is The structural formula of the compound of Formula V is The structural formula of the compound of Formula VI is

[0046] In the compounds of Formula I - Formula VI, X1 and X2 are halogens, and X1 and X2 are the same or different; R1 is selected from alkylene with 1 - 8 carbon atoms, arylene with 6 - 20 ring carbon atoms, or heteroarylene with 5 - 12 ring atoms; R2 is selected from alkyl with 1 - 4 carbon atoms.

[0047] The synthesis route of the preparation method of the self-assembled material based on dibenzocarbazole bromide provided by the present invention is as follows:

[0048]

[0049] In some embodiments, when R1 is selected from alkylene with 1 - 8 carbon atoms, Step S1 specifically includes: mixing the compound of Formula I, the compound of Formula II, a base, a catalyst, and a solvent, and carrying out a carbon-nitrogen coupling reaction to obtain the compound of Formula III.

[0050] In this embodiment, the molar ratio of the compound of Formula I to the compound of Formula II is 1:(2 - 40); the base can be selected from at least one of potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, sodium hydroxide, and potassium hydroxide; the catalyst can be selected from tetrabutylammonium bromide (TBAB); the temperature of the carbon-nitrogen coupling reaction is 20 - 100 °C, and the reaction time is 12 - 48 h; the solvent is an organic solvent or water.

[0051] In some embodiments, when R1 is selected from arylene with 6 - 20 ring carbon atoms or heteroarylene with 5 - 12 ring atoms, Step S1 specifically includes: mixing the compound of Formula I, the compound of Formula II, a base, a catalyst, a catalyst ligand, and a solvent, and carrying out a carbon-nitrogen coupling reaction to obtain the compound of Formula III.

[0052] In this embodiment, the molar ratio of the compound of formula I to the compound of formula II is 1:(1 to 4); the base can be selected from at least one of potassium carbonate, sodium carbonate, potassium phosphate, cesium carbonate, sodium hydroxide, potassium hydroxide, sodium tert-butoxide, and potassium tert-butoxide; the catalyst can be selected from at least one of copper powder, cuprous oxide, cuprous iodide, cuprous bromide, and cuprous chloride; the catalyst ligand can be selected from at least one of L-proline, 18-crown-6, 1,2-cyclohexanediamine, 1,10-phenanthroline, and oxalyl diamine ligands; the temperature of the carbon-nitrogen coupling reaction is 20 to 150 °C, and the reaction time is 12 to 48 h; the solvent is an organic solvent (preferably toluene).

[0053] In some embodiments, when R1 is selected from an alkylene group having 1 to 8 carbon atoms, step S2 specifically includes: mixing the compound of formula III with an excess of the compound of formula IV ( phosphate triester), and reacting at 100 to 160 °C for 12 to 48 h (carbon-phosphorus coupling reaction) to obtain the compound of formula V.

[0054] In some embodiments, when R1 is selected from an arylene group having 6 to 20 ring carbon atoms or a heteroarylene group having 5 to 12 ring atoms, step S2 specifically includes: mixing the compound of formula III, the compound of formula IV ( phosphate diester), a base, a catalyst, a catalyst ligand, an additive, and a solvent, and carrying out a carbon-phosphorus coupling reaction to obtain the compound of formula V.

[0055] In this embodiment, the molar ratio of the compound of formula III to the compound of formula IV is 1:(0.9 to 1.5); the base can be selected from at least one of triethylamine, tripropylamine, and N-methylbicyclohexylamine; the catalyst can be selected from at least one of palladium acetate, palladium on carbon, tetrakis(triphenylphosphine)palladium, and palladium chloride; the catalyst ligand can be selected from at least one of triphenylphosphine and 1,1′-bis(diphenylphosphino)ferrocene; the additive can be selected from at least one of potassium acetate and sodium acetate; the temperature of the carbon-phosphorus coupling reaction is 40 to 120 °C, and the reaction time is 12 to 48 h; the solvent is an organic solvent (preferably tetrahydrofuran).

[0056] In some embodiments, step S3 specifically includes: mixing the compound of formula V, a brominating reagent, and a solvent, and carrying out a bromination reaction to obtain the compound of formula VI.

[0057] In this embodiment, the molar ratio of the compound of formula V to the brominating reagent is 1:(0.9 to 1.1); the brominating reagent is preferably N-bromosuccinimide; the temperature of the bromination reaction is 0 to 30 °C, and the reaction time is 8 to 12 h; the solvent is an organic solvent (preferably N,N-dimethylformamide).

[0058] In some embodiments, step S4 specifically includes: mixing the compound of Formula VI and a solvent, and then adding trimethylsilyl bromide to undergo a hydrolysis reaction to obtain the self-assembled material based on dibenzocarbazole bromide represented by the structure of Formula 1.

[0059] In this embodiment, the molar ratio of the compound of Formula VI to trimethylsilyl bromide is 1:(3 - 12); the hydrolysis reaction temperature is 0 - 30 °C, and the reaction time is 24 - 48 h; the solvent is an organic solvent (preferably dichloromethane).

[0060] An embodiment of the present invention provides a hole transport material, which includes the self-assembled material based on dibenzocarbazole bromide described in the foregoing embodiment and another self-assembled material based on dibenzocarbazole. The structural formula of the self-assembled material based on dibenzocarbazole is as shown in Formula 2:

[0061]

[0062] In Formula 2, R3 is selected from an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 ring carbon atoms, or a heteroarylene group having 5 to 12 ring atoms.

[0063] In this embodiment, the self-assembled material based on dibenzocarbazole bromide represented by the structure of Formula 1 and the self-assembled material based on dibenzocarbazole represented by the structure of Formula 2 are mixed as the hole transport material. The mixing strategy ensures that such materials can obtain enhanced hole transport performance, improved interfacial contact, and increased work function of the conductive metal oxide while maintaining good solubility. The hole transport material can improve the efficiency and stability of the device when used in the device and is suitable for large-area device manufacturing.

[0064] In some embodiments, R3 is selected from any one of the following groups:

[0065]

[0066] where represents the connection point.

[0067] In a preferred embodiment, R2 in the structure of Formula 1 is the same as R3 in the structure of Formula 2.

[0068] In some embodiments, the self-assembled material based on the dibenzocarbazole group is selected from any one of the following compounds:

[0069]

[0070] In some embodiments, the hole transport material includes a combination of combination

[0071] In some embodiments, the hole transport material is composed of the self-assembled material based on dibenzocarbazole bromide (structure of Formula 1) and the self-assembled material based on dibenzocarbazole (structure of Formula 2). Preferably, the molar ratio of the self-assembled material based on dibenzocarbazole bromide to the self-assembled material based on dibenzocarbazole is 1:1 to 1:20, and can be, for example, 1:20, 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, etc.

[0072] An embodiment of the present invention provides an optoelectronic device, including a hole transport layer, and the material of the hole transport layer includes the self-assembled material based on dibenzocarbazole bromide described in the foregoing embodiments or the hole transport material described in the foregoing embodiments.

[0073] In some embodiments, the optoelectronic device is a single-junction perovskite solar cell or a battery module, including a transparent electrode layer, a hole transport layer, a perovskite light-absorbing layer, an electron transport layer, a hole blocking layer, and an electrode layer in a layered structure, and the material of the hole transport layer is selected from the self-assembled material based on dibenzocarbazole bromide described in the foregoing embodiments or the hole transport material described in the foregoing embodiments.

[0074] Specifically, as Figure 1As shown, the single-junction perovskite solar cell includes a glass layer A1, a transparent electrode layer A2, a hole transport layer A3, a perovskite light-absorbing layer A4, an electron transport layer A5, a hole-blocking layer A6, and a metal electrode layer A7 that are stacked. Among them, the conductive layer of the transparent electrode layer is one or more of ITO, FTO, IZO, and AZO. The preparation method of the hole transport layer includes, but is not limited to, any suitable method in the prior art such as spin coating, blade coating, slot die coating, spraying, evaporation, magnetron sputtering, and electrochemical deposition. The hole transport layer can be composed of a single-layer structure or a two-layer structure. When composed of a single-layer structure, it is prepared from the compound of Formula 1 of the present invention or a mixed material of the compound of Formula 1 and the compound of Formula 2. When composed of a two-layer structure, the layer close to the transparent electrode layer A2 is prepared from at least one of nickel oxide or titanium oxide, and the layer far from the transparent electrode layer A2 is prepared from the compound of Formula 1 of the present invention or a mixed material of the compound of Formula 1 and the compound of Formula 2. The preparation method of the perovskite light-absorbing layer can be any one in the prior art, such as one or more of spin coating, blade coating, slot die coating, spraying, inkjet printing, and evaporation; the preparation method of the perovskite light-absorbing layer can also be a two-step method. The material of the perovskite light-absorbing layer can be ABX3 (perovskite structure), where A is any organic cation, such as formamidinium (FA), methylammonium (MA), cesium, etc.; B is any metal cation, such as lead, tin, etc.; X is any halogen anion, such as chlorine, bromine, iodine, etc.; the perovskite light-absorbing layer is prepared by dissolving ABX3 in solvents such as DMF, DMSO, and NMP. The preparation method of the electron transport layer includes, but is not limited to, spin coating, blade coating, slot die coating, spraying, evaporation, magnetron sputtering, and electrochemical deposition. The material of the electron transport layer can be selected from existing electron transport materials in the prior art, for example, it can be selected from at least one of C60 and [6,6]-phenyl-C61-butyric acid methyl ester. The preparation method of the hole-blocking layer includes, but is not limited to, spin coating, blade coating, slot die coating, spraying, evaporation, magnetron sputtering, and electrochemical deposition. The material of the hole-blocking layer can be selected from existing hole-blocking materials in the prior art, such as one of BCP or tin oxide. The metal electrode layer can be made of Ag, and can also be made of one or more of Au, Cu, Al, and carbon electrodes.

[0075] In some embodiments, the optoelectronic device is a perovskite-based tandem solar cell.

[0076] In some embodiments, the perovskite-based tandem solar cell is a perovskite / silicon tandem solar cell, which includes a guiding metal electrode layer with a layered structure, a light reflection reduction layer, a transparent electrode layer, a hole blocking layer, an electron transport layer, a perovskite light absorption layer, a hole transport layer, a transparent electrode layer, an N-type emitter layer, an electron contact passivation layer, a crystalline silicon light absorption layer, a hole contact passivation layer, and a hole selective contact layer. The material of the hole transport layer is selected from the self-assembled material based on dibenzocarbazole bromide described in the foregoing embodiments or the hole transport material described in the foregoing embodiments.

[0077] Specifically, as Figure 2As shown in the figure, the perovskite / silicon tandem solar cell includes a guiding metal electrode layer B1, a light-reducing reflection layer B2, a transparent electrode layer B3, a hole-blocking layer B4, an electron transport layer B5, a perovskite light-absorbing layer B6, a hole transport layer B7, a transparent electrode layer B8, an N-type emitter layer B9, an electron contact passivation layer B10, a crystalline silicon light-absorbing layer B11, a hole contact passivation layer B12, and a hole-selective contact layer B13 which are stacked. Among them, the metal electrode layer can be made of Ag, or can be made of one or more of Au, Cu, Al, and carbon electrodes. The light-reducing reflection layer can be made of MgF2. The transparent electrode layer can be made of one of ITO, IZO, and AZO, or can be made of one or more of Au, Cu, Al, and carbon electrodes. The preparation method of the hole-blocking layer includes but is not limited to spin coating, blade coating, slot deposition, spraying, evaporation, magnetron sputtering, and electrochemical deposition. The material of the hole-blocking layer can be selected from the existing hole-blocking materials in the prior art, such as one of BCP or tin oxide. The preparation method of the electron transport layer includes but is not limited to spin coating, blade coating, slot deposition, spraying, evaporation, magnetron sputtering, and electrochemical deposition. The material of the electron transport layer can be selected from the existing electron transport materials in the prior art, such as at least one selected from C60 and [6,6]-phenyl-C61-butyric acid methyl ester. The preparation method of the perovskite light-absorbing layer can be any one in the prior art, such as one or more of spin coating, blade coating, slot deposition, spraying, inkjet printing, and evaporation; the preparation method of the perovskite light-absorbing layer can also be a two-step method. The material of the perovskite light-absorbing layer can be ABX3 (perovskite structure), where A is any organic cation, such as formamidine (FA), methylamine (MA), cesium, etc.; B is any metal cation, such as lead, tin, etc.; X is any halogen anion, such as chlorine, bromine, iodine, etc.; the perovskite light-absorbing layer is prepared by dissolving ABX3 in solvents such as DMF, DMSO, and NMP. The preparation method of the hole transport layer includes but is not limited to any suitable method in the prior art such as spin coating, blade coating, slot deposition, spraying, evaporation, magnetron sputtering, and electrochemical deposition. The hole transport layer can be composed of a single-layer structure or a two-layer structure. When composed of a single-layer structure, it is prepared from the compound of Formula 1 of the present invention or a mixed material of the compound of Formula 1 and the compound of Formula 2. When composed of a two-layer structure, the layer close to the transparent electrode layer A2 is prepared from at least one of nickel oxide or titanium oxide, and the layer far from the transparent electrode layer A2 is prepared from the compound of Formula 1 of the present invention or a mixed material of the compound of Formula 1 and the compound of Formula 2. The transparent electrode layer can be one of IZO, ITO, and AZO, and the remaining N-type emitter layer, electron contact passivation layer, crystalline silicon light-absorbing layer, hole contact passivation layer, and hole-selective contact layer can all be provided by directly purchased silicon substrates.

[0078] In some embodiments, the perovskite-based tandem solar cell is a perovskite / perovskite tandem solar cell, which includes a guiding metal electrode layer, a hole blocking layer, an electron transport layer, a perovskite light-absorbing layer, a hole transport layer, a carrier recombination layer, a hole blocking layer, an electron transport layer, a perovskite light-absorbing layer, a hole transport layer, a transparent electrode layer, and a glass layer. The material of at least one of the hole transport layers is selected from the self-assembled material based on dibenzocarbazole bromide described in the foregoing embodiments or the hole transport material described in the foregoing embodiments.

[0079] Specifically, as Figure 3 shown, the perovskite / perovskite tandem solar cell includes a guiding metal electrode layer C1, a hole blocking layer C2, an electron transport layer C3, a perovskite light-absorbing layer C4, a hole transport layer C5, a carrier recombination layer C6, a hole blocking layer C7, an electron transport layer C8, a perovskite light-absorbing layer C9, a hole transport layer C10, a transparent electrode layer C11, and a glass layer C12 which are stacked. Among them, the guiding metal electrode layer, the hole blocking layer, the electron transport layer, the perovskite light-absorbing layer, the hole transport layer, the hole blocking layer, the electron transport layer, and the transparent electrode layer are the same as those defined in the foregoing perovskite / silicon tandem solar cell. The carrier recombination layer can be made of one of ITO, IZO, AZO, or can also be made of one or more of Au, Cu, Al, and carbon electrodes.

[0080] In some embodiments, the optoelectronic device is a light-emitting diode, which includes a first electrode, a second electrode, and one or more organic functional layers located between the first electrode and the second electrode. The material of at least one of the organic functional layers is selected from the self-assembled material based on dibenzocarbazole bromide described in the foregoing embodiments or the hole transport material described in the foregoing embodiments.

[0081] In some embodiments, the optoelectronic device is an organic solar cell, which includes a conductive glass layer, a hole transport layer, a bulk heterojunction (BHJ) active layer, an electron transport layer, and an electrode. The material of the hole transport layer is selected from the self-assembled material based on dibenzocarbazole bromide described in the foregoing embodiments or the hole transport material described in the foregoing embodiments.

[0082] The present invention will be further described below through specific examples.

[0083] Example 1

[0084] This example provides a preparation method of compound Bz-4PABrCz. The synthesis route of compound Bz-4PABrCz is as follows:

[0085]

[0086] Specifically, it includes the following steps:

[0087] (1) Synthesis of Intermediate A

[0088] Dibenzocarbazole (2.67 g, 10 mmol), tetrabutylammonium bromide (TBAB, 0.48 g, 1.5 mmol), 1,4-dibromobutane (43.18 g, 200 mmol), and an aqueous solution of 50% potassium hydroxide (2.8 g, 50 mmol) were added to a dried 250 mL two-necked flask. The mixture was stirred at 60 °C for 12 h under an argon atmosphere. After the reaction mixture was cooled to room temperature, it was filtered through diatomaceous earth. The obtained filtrate was concentrated using a rotary evaporator to obtain a crude product, which was further purified by column chromatography using silica gel as the stationary phase and dichloromethane and petroleum ether as the eluents to obtain a white solid product (3.02 g, 75%), which was Intermediate A.

[0089] The 1H NMR data of Intermediate A are as follows: 1 H NMR (400 MHz, CDCl3) δ 9.21 (d, J = 8.5 Hz, 2H), 8.05 (dd, J = 8.1, 1.4 Hz, 2H), 7.93 (d, J = 8.8 Hz, 2H), 7.76 - 7.64 (m, 4H), 7.52 (ddd, J = 7.9, 6.9, 1.0 Hz, 2H), 4.62 (t, J = 7.1 Hz, 2H), 3.38 (t, J = 6.5 Hz, 2H), 2.15 (dq, J = 11.7, 7.2 Hz, 2H), 1.99 - 1.87 (m, 2H).

[0090] (2) Synthesis of Intermediate B

[0091] Intermediate A (1.2 g, 3 mmol) was added to a dried 100 mL two-necked flask, and then 15 mL of triethyl phosphite was added. The reaction mixture was stirred at 140 °C for 12 h. After cooling to room temperature, the solvent was removed using a rotary evaporator. The obtained crude product was purified by silica gel column chromatography to obtain a pale yellow oily product (1.31 g, 95%), which was Intermediate B.

[0092] The 1H NMR data of Intermediate B are as follows: 11H NMR (400 MHz, CDCl3) δ 9.20 (d, J = 8.5 Hz, 2H), 8.04 (dd, J = 8.1, 1.4 Hz, 2H), 7.91 (d, J = 8.8 Hz, 2H), 7.74 - 7.63 (m, 4H), 7.51 (ddd, J = 8.0, 6.9, 1.0 Hz, 2H), 4.56 (t, J = 7.1 Hz, 2H), 3.98 (dqd, J = 7.9, 7.1, 1.0 Hz, 4H), 2.06 (td, J = 8.9, 8.2, 4.1 Hz, 2H), 1.74 - 1.66 (m, 4H), 1.20 (t, J = 7.1 Hz, 6H).

[0093] (3) Synthesis of Intermediate C

[0094] Add Intermediate B (0.92 g, 2 mmol) to a dried 100 mL two-necked flask, add 15 mL of N,N-dimethylformamide, cool the reaction mixture to 0 °C, and then dropwise add a mixed solution of N-bromosuccinimide (NBS, 0.36 mg, 2 mmol) and N,N-dimethylformamide (5 mL) thereto at a rate of one drop every 2 seconds under stirring. After the addition is complete, raise the reaction mixture to room temperature and continue stirring for 8 h. After the reaction is completed, extract with a system of ethyl acetate and saturated brine, combine the organic phases and dry over anhydrous sodium sulfate. After distilling off the solvent from the dried solution, a crude product is obtained, and then further purified by column chromatography using silica gel as the stationary phase and dichloromethane and methanol as the eluents to obtain a white solid product (0.66 g, 61%), which is Intermediate C.

[0095] The 1H NMR data of Intermediate C are as follows: 1 1H NMR (400 MHz, CDCl3) δ 9.19 (d, J = 8.4 Hz, 1H), 9.12 (d, J = 8.5 Hz, 1H), 8.47 (d, J = 8.3 Hz, 1H), 8.07 - 8.00 (m, 2H), 7.93 (d, J = 8.8 Hz, 1H), 7.69 (qd, J = 8.6, 6.6 Hz, 3H), 7.64 - 7.58 (m, 1H), 7.52 (t, J = 7.4 Hz, 1H), 4.53 (t, J = 7.2 Hz, 2H), 4.07 - 3.94 (m, 4H), 2.05 (q, J = 8.1, 7.7 Hz, 2H), 1.74 (tt, J = 12.9, 6.7 Hz, 4H), 1.22 (t, J = 7.3 Hz, 6H).

[0096] (4) Synthesis of Compound Bz-4PABrCz

[0097] Under an argon atmosphere, intermediate C (0.54 g, 1 mmol) and 15 mL of dichloromethane were added to a 50 mL two-necked flask. While stirring, trimethylsilyl bromide (0.612 g, 4 mmol) was added dropwise, and the reaction mixture was continuously stirred for 24 h. The reaction mixture was transferred to a 100 mL round-bottom flask, and the solvent was removed using a rotary evaporator. Then, 20 mL of methanol was added and the mixture was stirred for 4 h. After the reaction was completed, the solvent was removed again using a rotary evaporator to obtain the crude product, which was recrystallized using a methanol / dichloromethane / ether system to obtain a white solid product (0.47 g, 97%), which was compound Bz-4PABrCz.

[0098] The 1H NMR data of compound Bz-4PABrCz are as follows: 1 H NMR (400 MHz, DMSO-d6) δ 9.10 (d, J = 8.4 Hz, 1H), 9.00 (d, J = 8.5 Hz, 1H), 8.55 (s, 1H), 8.39 (d, J = 8.4 Hz, 1H), 8.14 (d, J = 8.0 Hz, 1H), 8.04 (s, 2H), 7.80 (t, J = 7.7 Hz, 1H), 7.69 (dt, J = 14.9, 7.6 Hz, 2H), 7.54 (t, J = 7.5 Hz, 1H), 4.72 (t, J = 7.2 Hz, 2H), 1.90 (h, J = 5.7, 4.4 Hz, 2H), 1.67 - 1.48 (m, J = 5.8, 5.1 Hz, 4H).

[0099] Example 2

[0100] This example provides a preparation method of compound Bz-PhpPABrCz. The synthetic route of compound Bz-PhpPABrCz is as follows:

[0101]

[0102] Specifically, it includes the following steps:

[0103] (1) Synthesis of intermediate D

[0104] Dibenzocarbazole (2.67 g, 10 mmol), 1-bromo-4-iodobenzene (5.66 g, 20 mmol), cuprous iodide (0.190 g, 1 mmol), 1,10-phenanthroline (0.364 g, 2 mmol) and potassium phosphate (6.37 g, 30 mmol) were added to a dried 250 mL double-necked flask, and 50 mL of toluene was added under argon atmosphere and heated to reflux for 24 h. After the reaction mixture was cooled to room temperature, the system was extracted with dichloromethane and saturated saline solution, the organic phases were combined and dried with anhydrous sodium sulfate, and the dried solution was distilled to remove the solvent to obtain a crude product, which was further purified by column chromatography using silica gel as the stationary phase and dichloromethane and petroleum ether as the eluent to obtain a white solid product (3.99 g, 95%), which was intermediate D.

[0105] The H NMR spectrum data of intermediate D is: 1 H NMR (400MHz, CDCl3) δ9.27(d,J=8.5Hz,2H),8.05(dd,J=8.1,1.4Hz,2H),7.84(d,J=8.9Hz,2H),7.81-7.76(m,2H ), 7.73 (ddd, J=8.4, 6.9, 1.4Hz, 2H), 7.56 (ddd, J=7.9, 6.8, 1.0Hz, 2H), 7.52 (d, J=8.8Hz, 2H), 7.47-7.40 (m, 2H).

[0106] (2) Synthesis of intermediate E

[0107] Palladium acetate (16.8 mg, 0.075 mmol), 1,1'-bis(diphenylphosphino)ferrocene (dppf, 83.2 mg, 0.15 mmol), potassium acetate (29.4 mg, 0.3 mmol) and intermediate D (1.27 g, 3 mmol) were added to a dried 100 mL two-necked flask, followed by triethylamine (364 mg, 3.6 mmol) and 30 mL of tetrahydrofuran treated with argon bubbling, and the reaction mixture was stirred at a boiling state for 15 min. Diethyl phosphite (414 mg, 3 mmol) was then added and continued to be stirred at a boiling state for 12 h. After cooling to room temperature, the reaction mixture was filtered through diatomaceous earth and rinsed with tetrahydrofuran. The obtained filtrate was used to remove the solvent using a rotary evaporator, and the obtained crude product was purified by silica gel column chromatography to obtain a white solid product (1.34 g, 93%), which was intermediate E.

[0108] The H NMR spectrum data of intermediate E is: 11H NMR (400 MHz, CDCl3) δ 9.24 (d, J = 8.5 Hz, 2H), 8.18 - 8.07 (m, 2H), 8.05 (dd, J = 8.2, 1.4 Hz, 2H), 7.86 (d, J = 8.9 Hz, 2H), 7.75 - 7.68 (m, 4H), 7.61 - 7.52 (m, 4H), 4.37 - 4.18 (m, 4H), 1.44 (t, J = 7.1 Hz, 6H).

[0109] (3) Synthesis of Intermediate F

[0110] Add intermediate E (0.96 g, 2 mmol) to a dried 100 mL two-necked flask, add 15 mL of N,N-dimethylformamide, cool the reaction mixture to 0 °C, and then dropwise add a mixed solution of N-bromosuccinimide (0.36 mg, 2 mmol) and N,N-dimethylformamide (5 mL) to it at a rate of one drop every 2 seconds under stirring. After the addition is complete, allow the reaction mixture to warm to room temperature and continue stirring for 8 h. After the reaction is completed, extract with an ethyl acetate and saturated brine system, combine the organic phases and dry over anhydrous sodium sulfate. After distilling off the solvent from the dried solution, a crude product is obtained, which is further purified by column chromatography using silica gel as the stationary phase and dichloromethane and methanol as the eluents to obtain a white solid product (0.76 g, 68%), which is intermediate F.

[0111] The 1H NMR data of intermediate F are as follows: 1 1H NMR (400 MHz, CDCl3) δ 9.20 (dd, J = 31.8, 8.4 Hz, 2H), 8.48 (dd, J = 8.5, 1.3 Hz, 1H), 8.19 - 8.10 (m, 2H), 8.05 (dd, J = 8.2, 1.4 Hz, 1H), 7.94 - 7.86 (m, 2H), 7.79 - 7.62 (m, 5H), 7.59 - 7.52 (m, 2H), 4.36 - 4.17 (m, 4H), 1.44 (t, J = 7.1 Hz, 6H).

[0112] (4) Synthesis of Compound Bz-PhpPABrCz

[0113] Under an argon atmosphere, intermediate F (0.56 g, 1 mmol) and 15 mL of dichloromethane were added to a 50 mL two-necked flask, and the reaction mixture was continuously stirred for 24 h. The reaction mixture was transferred to a 100 mL round-bottom flask, and the solvent was removed using a rotary evaporator. Then, 20 mL of methanol was added and stirred for 4 h. After the reaction was completed, the solvent was removed again using a rotary evaporator to obtain the crude product, which was recrystallized using a methanol / dichloromethane / ether system to obtain a white solid product (0.48 g, 96%), which is compound Bz-PhpPABrCz.

[0114] The 1H NMR data of compound Bz-PhpPABrCz are as follows: 1 H NMR (400 MHz, DMSO-d6) δ 9.16 (d, J = 8.4 Hz, 1H), 9.05 (d, J = 8.4 Hz, 1H), 8.39 (d, J = 8.3 Hz, 1H), 8.15 (d, J = 8.0 Hz, 1H), 8.10 - 7.99 (m, 3H), 7.90 - 7.69 (m, 6H), 7.59 (t, J = 8.5 Hz, 2H).

[0115] Example 3

[0116] This example provides a single-junction perovskite solar cell and its preparation method, which are as follows:

[0117] (1) Cleaning the transparent electrode layer: The etched ITO electrode layer was ultrasonically treated in a cleaning agent, deionized water, absolute ethanol, acetone, and isopropanol for 15 min, taken out, dried with clean air, placed in an oven, dried at 120 °C for 8 h, and then treated with ultraviolet / ozone for 30 min.

[0118] (2) Preparation of the hole transport layer: The hole transport layer was prepared by spin coating. Compound Bz-PhpPABrCz and compound Bz-PhpPACz with a molar ratio of 1:8 were used as the hole transport materials and dissolved in a solvent (methanol, ethanol, propanol, DMF, DMSO, ethylene glycol monomethyl ether, water, tetrahydrofuran) to prepare a solution. The solution was spin coated on the transparent electrode layer at a speed of 4000 rpm for 40 s, and the obtained film was annealed in nitrogen at 100 °C for 10 min to form the hole transport layer.

[0119] (3) Preparation of the perovskite light-absorbing layer: The perovskite light-absorbing layer was prepared by spin coating. The perovskite material CS 0.05 FA 0.8 MA 0.15 Pb(I 0.755 Br 0.255) 3 was dissolved in DMF to form a solution, and this solution was deposited on the hole transport layer by spin coating at a rotation speed of 6000 rpm for 40 s. When 5 s remained in the rotation time, chlorobenzene was dropped in the middle of the substrate, and the film was annealed at 100 °C for 0.5 h to form a perovskite light-absorbing layer.

[0120] (4) Preparation of the electron transport layer: The electron transport layer was prepared by evaporation. Under a vacuum of 1×10 -6 Pa, C60 was deposited on the surface of the perovskite light-absorbing layer to form an electron transport layer with a thickness of 20 nm.

[0121] (5) Preparation of the metal electrode layer: Under a vacuum of 1×10 -6 Pa, an Ag electrode layer with a thickness of 100 nm was formed on the electron transport layer.

[0122] Example 4

[0123] This example provides a single-junction perovskite solar cell. The preparation method is the same as that in Example 3, except that when preparing the hole transport layer, only the hole transport material compound Bz-PhpPABrCz was used.

[0124] Example 5

[0125] This example provides a single-junction perovskite solar cell. The preparation method is the same as that in Example 3, except that when preparing the hole transport layer, only the hole transport material compound Bz-PhpPACz was used.

[0126] Performance test of the single-junction perovskite solar cell:

[0127] The single-junction perovskite solar cells in Examples 3 - 5 were subjected to performance tests, and the effective area was 0.1 cm 2 . Test conditions: Spectral distribution AM1.5G, light intensity 100 mW / cm 2 , AAA solar simulator (Beijing Zhuoli Hanguang Co., Ltd.), and the J-V curve was measured using a Keithly 2400 digital source meter.

[0128] Figure 4 Figure is the J-V curve diagram of the single-junction perovskite solar cells in Examples 3 - 5, and the specific test results are shown in Table 1.

[0129] Table 1

[0130]

[0131] According to the data in Table 1, compared with the single-junction perovskite solar cells prepared using a single-component self-assembled hole transport material in Examples 4 and 5, the photoelectric conversion efficiency of the hybrid self-assembled hole transport material described in Example 3 is significantly improved, indicating that mixing the self-assembled material based on dibenzocarbazole bromide represented by Structure 1 and the self-assembled material based on dibenzocarbazole represented by Structure 2 as the hole transport material can improve the efficiency and stability of the device.

[0132] Example 6

[0133] This example provides a perovskite / silicon tandem solar cell and its preparation method, as follows:

[0134] (1) Fabricate a transparent electrode layer on a silicon substrate: Provide a silicon substrate (including an N-type emitter layer, an electron contact passivation layer, a crystalline silicon light-absorbing layer, a hole contact passivation layer, and a hole-selective contact layer). Using magnetron sputtering, under the deposition temperature of 50 °C and the chamber pressure of 0.3 Pa, the sputtering power is regulated in stages. In the initial stage, it is deposited at a power of 40 W, and the deposition rate is ~0.09 nm / s; subsequently, it is increased to 200 W, and the deposition rate increases to ~0.4 nm / s. Finally, an ITO transparent conductive thin film with a thickness of 100 nm is obtained on the silicon substrate.

[0135] (2) Prepare the hole transport layer: The hole transport layer is prepared by spin coating. The compounds Bz-PhpPABrCz and Bz-PhpPACz with a molar ratio of 1:8 are used as the hole transport material and dissolved in a solvent (methanol, ethanol, propanol, DMF, DMSO, ethylene glycol monomethyl ether, water, tetrahydrofuran) to prepare a solution. This solution is spin-coated on the transparent electrode layer at a rotation speed of 4000 rpm for 40 s, and then the obtained film is annealed in nitrogen at 100 °C for 10 min to form the hole transport layer.

[0136] (3) Prepare the perovskite light-absorbing layer: The perovskite light-absorbing layer is prepared by spin coating. The perovskite material CS 0.05 FA 0.8 MA 0.15 Pb(I 0.755 Br 0.255 )3 is dissolved in DMF to make a solution. This solution is deposited on the hole transport layer by spin coating at a rotation speed of 6000 rpm for 40 s. When the remaining rotation time is 5 s, chlorobenzene is dropped in the middle of the substrate, and the film is annealed at 100 °C for 0.5 h to form the perovskite light-absorbing layer.

[0137] (4) Prepare the electron transport layer: The electron transport layer is prepared by evaporation. Under a vacuum of 1×10 -6 Pa, C60 is deposited on the surface of the perovskite light-absorbing layer to form an electron transport layer with a thickness of 20 nm.

[0138] (5) Preparation of hole blocking layer: SnO is deposited on the electron transport layer by ALD X layer with a thickness of 20 nm to form a hole blocking layer on the electron transport layer.

[0139] (6) Preparation of transparent electrode layer: By magnetron sputtering method, under the deposition temperature of 50 °C and the chamber pressure of 0.3 Pa, the sputtering power is regulated in stages. In the initial stage, it is deposited at a power of 40 W with a deposition rate of ~0.09 nm / s; then it is increased to 200 W and the deposition rate increases to ~0.4 nm / s. Finally, an ITO transparent conductive thin film with a thickness of 30 nm is obtained on the SnOX layer to form a transparent electrode layer on the hole blocking layer.

[0140] (7) Preparation of metal electrode layer: At a vacuum degree of 1×10 -6 Pa, Ag is deposited on the surface of the transparent electrode layer to form an Ag metal electrode layer with a thickness of 100 nm.

[0141] (8) Preparation of light reduction reflection layer: At a vacuum degree of 1×10 -6 Pa, MgF2 is deposited on the surface of the whole device to form a MgF2 layer light reduction reflection layer with a thickness of 200 nm.

[0142] Example 7

[0143] This example provides a perovskite / silicon tandem solar cell, and the preparation method is the same as that of Example 6, except that when preparing the hole transport layer, only the hole transport material compound Bz-PhpPABrCz is used.

[0144] Example 8

[0145] This example provides a single-junction perovskite solar cell, and the preparation method is the same as that of Example 6, except that when preparing the hole transport layer, only the hole transport material compound Bz-PhpPACz is used.

[0146] Performance test of perovskite / silicon tandem solar cell:

[0147] For the perovskite / silicon tandem solar cells in Examples 6 - 8, the effective area is 0.1 cm 2 . Test conditions: Spectral distribution AM1.5G, light intensity 100 mW / cm 2 , AAA solar simulator (Beijing Zhuoli Hanguang Co., Ltd.), and the J-V curve is measured with a Keithly2400 digital source meter.

[0148] Figure 5It is the J-V curve diagram of the perovskite / silicon tandem solar cell in Examples 6 to 8, and the specific test results are shown in Table 2.

[0149] Table 2

[0150]

[0151] According to the data in Table 2, it can be seen that compared with the perovskite / silicon tandem solar cells prepared using single-component self-assembled hole transport materials in Examples 7 and 8, the photoelectric conversion efficiency of the perovskite / silicon tandem solar cell using the mixed self-assembled hole transport material described in Example 6 is significantly improved, indicating that mixing the self-assembled material based on dibenzocarbazole bromide represented by Structure 1 and the self-assembled material based on dibenzocarbazole represented by Structure 2 as the hole transport material can improve the efficiency and stability of the device.

[0152] Example 9

[0153] This example provides a perovskite / perovskite tandem solar cell and its preparation method, which are as follows:

[0154] (1) Clean the transparent electrode layer: The etched ITO electrode layer is ultrasonically treated in a cleaning agent, deionized water, absolute ethanol, acetone, and isopropanol for 15 minutes in sequence, taken out, dried with clean air, placed in an oven, dried at 120 °C for 8 hours, and then treated with ultraviolet / ozone for 30 minutes.

[0155] (2) Prepare the hole transport layer: The hole transport layer is prepared by spin coating. The compounds Bz-PhpPABrCz and Bz-PhpPACz with a molar ratio of 1:8 are used as the hole transport material and dissolved in a solvent (methanol, ethanol, propanol, DMF, DMSO, ethylene glycol monomethyl ether, water, tetrahydrofuran) to prepare a solution. The solution is spin-coated on the transparent electrode layer at a rotation speed of 4000 rpm for 40 seconds, and the obtained film is annealed in nitrogen at 100 °C for 10 minutes to form the hole transport layer.

[0156] (3) Prepare the perovskite light-absorbing layer: The perovskite light-absorbing layer is prepared by spin coating. The perovskite material CS 0.05 FA 0.8 MA 0.15 Pb(I 0.755 Br 0.255 )3 is dissolved in DMF to prepare a solution. The solution is deposited on the hole transport layer by spin coating at a rotation speed of 6000 rpm for 40 seconds. When the remaining rotation time is 5 seconds, chlorobenzene is dropped in the middle of the substrate, and the film is annealed at 100 °C for 0.5 hour to form the perovskite light-absorbing layer.

[0157] (4) Prepare the electron transport layer: The electron transport layer is prepared by evaporation coating. At 1×10-6 Under a Pa vacuum, deposit C60 on the surface of the perovskite light-absorbing layer to form an electron transport layer with a thickness of 20 nm.

[0158] (5) Prepare a hole blocking layer: Deposit SnO on the electron transport layer by ALD X layer with a thickness of 20 nm to form a hole blocking layer on the electron transport layer.

[0159] (6) Prepare a carrier recombination layer: Prepare a carrier recombination layer by evaporation. Under a 1×10 -6 Pa vacuum, deposit Au on the surface of the hole blocking layer to form a carrier recombination layer with a thickness of 1 nm.

[0160] (7) Prepare a hole transport layer: Use the same method as in (2) above to form a hole transport layer on the carrier recombination layer.

[0161] (8) Prepare a perovskite light-absorbing layer: Prepare a perovskite light-absorbing layer by spin coating. Dissolve the perovskite material FA 0.7 MA 0.3 Pb 0.5 Sn 0.5 I3 in DMF to make a solution. Deposit this solution on the hole transport layer by spin coating at a rotation speed of 6000 rpm for 40 s. When there are 5 s left in the rotation time, drop chlorobenzene in the middle of the substrate and anneal the film at 100 °C for 0.5 h to form a perovskite light-absorbing layer.

[0162] (9) Prepare an electron transport layer: Use the same method as in (4) above to form an electron transport layer on the perovskite light-absorbing layer.

[0163] (10) Prepare a hole blocking layer: Use the same method as in (5) above to form a hole blocking layer on the electron transport layer.

[0164] (11) Prepare a metal electrode layer: Under a 1×10 -6 Pa vacuum, deposit Ag on the surface of the hole blocking layer to form an Ag metal electrode layer with a thickness of 100 nm.

[0165] Example 10

[0166] This example provides a perovskite / perovskite tandem solar cell. The preparation method is the same as that in Example 9, except that when preparing the hole transport layer, only the hole transport material compound Bz-PhpPABrCz is used.

[0167] Example 11

[0168] This embodiment provides a perovskite / perovskite tandem solar cell. The preparation method is the same as that of Example 9, except that when preparing the hole transport layer, only the compound Bz-PhpPACz is used as the hole transport material.

[0169] Performance test of the perovskite / perovskite tandem solar cell:

[0170] Perform performance tests on the perovskite / perovskite tandem solar cells in Examples 9 - 11. The effective area is 0.1 cm 2 . Test conditions: Spectral distribution AM1.5G, light intensity 100 mW / cm 2 , AAA solar simulator (Beijing Zhuoli Hanguang Co., Ltd.), and the J-V curve is measured using a Keithly 2400 digital source meter.

[0171] Figure 6 Figure 14 is the J-V curve diagram of the perovskite / perovskite tandem solar cells in Examples 9 - 11. The specific test results are shown in Table 3.

[0172] Table 3

[0173]

[0174] According to the data in Table 3, compared with the perovskite / perovskite tandem solar cells prepared using single-component self-assembled hole transport materials in Examples 10 and 11, the photoelectric conversion efficiency of the perovskite / perovskite tandem solar cell using the hybrid self-assembled hole transport material described in Example 9 is significantly improved, indicating that mixing the self-assembled material based on dibenzocarbazole bromide represented by Formula 1 and the self-assembled material based on dibenzocarbazole represented by Formula 2 as the hole transport material can improve the efficiency and stability of the device.

[0175] In summary, the self-assembled material based on dibenzocarbazole bromide represented by Formula 1 provided by the present invention, where the dibenzocarbazole mother nucleus is an excellent hole transport material. Introducing a bromine atom into its skeleton can effectively adjust the energy level of the material, phosphoric acid is an anchoring group for contacting the surface of the metal oxide, and R1 is used to connect the mother nucleus and the anchoring group, showing excellent hole transport performance. Mixing the self-assembled material based on dibenzocarbazole bromide represented by Formula 1 and the self-assembled material based on dibenzocarbazole represented by Formula 2 as the hole transport material, the mixing strategy ensures that under the condition of maintaining good solubility, this kind of material can obtain enhanced hole transport performance, improved interfacial contact, and increased work function of the conductive metal oxide. The hole transport material can improve the efficiency and stability of the device when used in the device.

[0176] It should be understood that the application of the present invention is not limited to the above examples. For those of ordinary skill in the art, improvements or changes can be made according to the above description, and all such improvements and changes should fall within the protection scope of the appended claims of the present invention.

Claims

1. A self-assembled material based on dibenzocarbazole bromide, characterized in that, The structural formula of the self-assembled material based on dibenzocarbazole bromide is shown in Formula 1: In Formula 1, R1 is selected from an alkylene group with 1 to 8 carbon atoms, an arylene group with 6 to 20 ring carbon atoms, or a heteroarylene group with 5 to 12 ring atoms.

2. The self-assembled material based on dibenzocarbazole bromide according to claim 1, wherein The R1 is selected from any one of the following groups: wherein represents the connection point position.

3. The self-assembled material based on dibenzocarbazole bromide according to claim 1, wherein The self-assembled material based on dibenzocarbazole bromide is selected from any one of the following compounds:

4. A preparation method of a self-assembled material based on dibenzocarbazole bromide as described in claim 1, characterized in that, Comprising the steps: Step S1: Perform a carbon-nitrogen coupling reaction on the compound of Formula I and the compound of Formula II to obtain the compound of Formula III; Step S2: Perform a carbon-phosphorus coupling reaction on the compound of Formula III and the compound of Formula IV to obtain the compound of Formula V; Step S3: Perform a bromination reaction on the compound of Formula V and a brominating reagent to obtain the compound of Formula VI; Step S4: Perform a hydrolysis reaction on the compound of Formula VI to obtain the self-assembled material based on dibenzocarbazole bromide shown in the structure of Formula 1; Among them, the structural formula of the compound of formula I is The compound of formula II The structural formula is The structural formula of the compound of Formula III is The structural formula of the compound of Formula IV is or The structural formula of the compound of Formula V is The structural formula of the compound of Formula VI is In the compounds of Formula I - Formula VI, X1 and X2 are halogens, and X1 and X2 are the same or different; R1 is selected from an alkylene group with 1 to 8 carbon atoms, an arylene group with 6 to 20 ring carbon atoms, or a heteroarylene group with 5 to 12 ring atoms; R2 is selected from an alkyl group with 1 to 4 carbon atoms.

5. A hole transporting material, characterized in that, Comprising the self-assembled material based on dibenzocarbazole bromide according to any one of claims 1 - 3 and the self-assembled material based on dibenzocarbazole. The structural formula of the self-assembled material based on dibenzocarbazole is shown in Formula 2: In Formula 2, R3 is selected from an alkylene group with 1 to 8 carbon atoms, an arylene group with 6 to 20 ring carbon atoms, or a heteroarylene group with 5 to 12 ring atoms.

6. The hole transporting material according to claim 5, wherein The R3 is selected from any one of the following groups: wherein represents the connection point position.

7. The hole transporting material according to claim 5, wherein The self-assembled material based on dibenzocarbazole is selected from any one of the following compounds:

8. The hole transport material according to claim 5, wherein The hole transport material is composed of the self-assembled material based on dibenzocarbazole bromide and the self-assembled material based on dibenzocarbazole. The molar ratio of the self-assembled material based on dibenzocarbazole bromide to the self-assembled material based on dibenzocarbazole is 1:1 - 1:

20.

9. An optoelectronic device includes a hole transport layer, characterized in that, The material of the hole transport layer comprises the self-assembled material based on dibenzocarbazole bromide according to any one of claims 1 - 3 or the hole transport material according to any one of claims 5 - 8.

10. The optoelectronic device according to claim 9, wherein The optoelectronic device is a single-junction perovskite solar cell or a battery module, a perovskite-based tandem solar cell, a light-emitting diode, or an organic solar cell.

Images