Anchoring self-assembly polymer semiconductor transmission layer material containing cross-linking unit and preparation and application of anchoring self-assembly polymer semiconductor transmission layer material

Abstract

The invention belongs to the field of organic photoelectricity, and discloses a preparation method and application of an anchoring self-assembly polymer semiconductor transmission layer material containing a crosslinking unit. The chemical structural formula of the anchoring self-assembly polymer semiconductor transmission layer material containing the cross-linking unit meets the general formula of the following formula 1 or formula 2, Ar1, Ar2 and Ar3 units are common aromatic ring units or heteroaromatic ring units, B2, B3 and common alkyl chain or alkoxy chain units, A2 is a common acid unit, linker is a cross-linkable group, the polymerization degree n is 5-300, x, y and z represent repetitive units, and n is a positive integer. 0 < x < 1, 0 < y < 1, 0 < z < 1, and x + y + z = 1. According to the invention, the cross-linking unit is introduced, so that the optimal form can be locked in a cross-linking network after being formed, and the optimal state can be kept in subsequent processing, device working and long-term use, so that the aging performance and environmental stability of the polymer photovoltaic device can be improved.

Description

Technical Field

[0001] This invention belongs to the field of organic optoelectronics, and specifically relates to a class of anchored self-assembled polymer semiconductor transport layer materials containing cross-linking units, their preparation and application. Background Technology

[0002] In recent years, with the rapid development of new-generation high-efficiency photovoltaic devices and other organic optoelectronic devices, higher requirements have been placed on the performance of interface transport layer materials. Especially in devices such as inverted perovskite solar cells, organic solar cells, organic light-emitting diodes (OLEDs), and quantum dot OLEDs, the hole or electron transport layer not only needs excellent charge transport capabilities but also requires multiple functions including interface energy level modulation, surface wettability regulation, and long-term environmental stability. While traditional polymer semiconductor transport layers can be formed over large areas through solution processing, their adhesion to inorganic electrodes or functional layers is weak, making them prone to interfacial peeling or migration during subsequent fabrication or operation, thus affecting the efficiency and stability of the device.

[0003] To improve interfacial stability, the strategy of introducing self-assembled single molecules (SAMs) into polymer transport layers has gained popularity in recent years. Anchoring groups in self-assembled molecules (such as phosphate groups, carboxylic acid groups, and silane groups) can form strong bonds with metal oxides or metal electrode surfaces, thereby significantly enhancing interfacial adhesion. However, pure SAM films have limited thickness and their continuity depends on surface conditions. In large-area devices, uneven coverage or localized defects are prone to occur, limiting their long-term stability performance.

[0004] Anchored self-assembled polymer semiconductor materials containing crosslinking units offer a novel approach to addressing the aforementioned challenges. These materials introduce controllable crosslinking units into the polymer backbone or side chains, triggering crosslinking reactions through heat treatment or light irradiation to form a stable three-dimensional network structure. This approach retains the strong interfacial bonding of the self-assembled anchoring groups while significantly improving the mechanical integrity and solvent resistance of the film, thus preventing interfacial damage during subsequent deposition of active layers or multilayer structures. Simultaneously, the semiconductor properties of the polymer backbone provide continuous π-conjugated channels for charge transport, and its HOMO / LUMO energy levels can be precisely controlled through molecular design to achieve energy level matching with adjacent layers, thereby improving the open-circuit voltage, fill factor, and overall efficiency of the device.

[0005] Therefore, developing a type of polymer semiconductor transport layer material that combines anchoring self-assembly capability and controllable cross-linking characteristics can not only significantly improve device interface stability and fabrication process compatibility, but also provide a new material basis for high-efficiency, long-life organic optoelectronic devices. Summary of the Invention

[0006] To overcome the shortcomings and deficiencies of the prior art, the primary objective of this invention is to provide a class of anchored self-assembled polymer semiconductor transport layer materials containing crosslinked units. The fused ring structure endows the polymers with good thermal stability, while also enabling better phase separation scale and energy level difference, thereby improving hole transport capability, increasing short-circuit current density and open-circuit voltage, and enhancing photoelectric performance.

[0007] Another object of the present invention is to provide a method for preparing the above-mentioned anchored self-assembled polymer semiconductor transport layer material containing crosslinking units.

[0008] Another objective of this invention is to provide the application of the above-mentioned anchored self-assembled polymer semiconductor transport layer material containing crosslinking units in the field of optoelectronic devices.

[0009] The objective of this invention is achieved through the following solution:

[0010] A class of anchored self-assembled polymer semiconductor transport layer materials containing cross-linked units have chemical structural formulas that satisfy the general formula shown in Formula 1 or Formula 2 below:

[0011]

[0012] In Formulas 1 and 2, Ar1, Ar2 and Ar3 units are common aromatic ring units or heteroaromatic ring units, B2 and B3 are common alkyl chain or alkoxy chain units, A2 is a common acid unit, linker is a crosslinkable group, the degree of polymerization n is 5-300, and x, y and z represent repeating units, 0 < x < 1, 0 < y < 1, 0 < z < 1, x + y + z = 1;

[0013] Furthermore, the Ar1, Ar2, and Ar3 units described above are preferably, relatively independently, at least one of the following chemical structures:

[0014]

[0015] In Formulas 1 and 2, the B2 and B3 units are preferably -R1-, which are relatively independent and are one of the following unsubstituted groups: alkyl with 1-20 carbon atoms, aryl with 4-20 carbon atoms, heteroaryl with 4-20 carbon atoms, aralkyl with 4-20 carbon atoms, heteroarylalkyl with 4-20 carbon atoms, aryloxy with 4-20 carbon atoms, heteroaryloxy with 4-20 carbon atoms, arylalkoxy with 4-20 carbon atoms, and heteroarylalkoxy with 4-20 carbon atoms.

[0016] In Equations 1 and 2, the A2 unit is preferably one of the following structures:

[0017]

[0018] In Equations 1 and 2, the linker unit is preferably one of the following structures:

[0019]

[0020] In the structure of the linker unit described above, R is an alkyl group with 1-4 carbon atoms;

[0021] The chemical structure of the above-mentioned anchored self-assembled polymer semiconductor transport layer material containing cross-linking units is preferably one of the following structures:

[0022]

[0023] The degree of polymerization, n, ranges from 5 to 300.

[0024] A method for preparing the above-mentioned anchored self-assembled polymer semiconductor transport layer material containing cross-linked units specifically includes the following steps:

[0025] (1) Under a nitrogen atmosphere, compound I or compound I', compound II, and compound III undergo a Suzuki coupling reaction in the presence of a base and a catalyst to generate formula 1' or formula 2';

[0026] (2) Under a nitrogen atmosphere, dissolve formula 1' or formula 2' in a solvent, then add bromotrimethylsilane and methanol and stir to react, thus obtaining the anchored self-assembled polymer semiconductor transport layer material containing crosslinking units.

[0027] The specific reaction route is shown below:

[0028]

[0029] The reaction described in step (1) refers to a reaction at 100-150℃ for 24 hours;

[0030] In step (1), R2 in compounds I and I' has one of the following structures:

[0031]

[0032] The molar ratio of compound I or compound I', compound II and compound III mentioned in step (1) is y:z:x, where z = x + y, preferably 1:2:1;

[0033] The alkali mentioned in step (1) is at least one of cesium carbonate, potassium carbonate, sodium methoxide, and sodium tert-butoxide. The catalyst mentioned in step (1) is at least one of tetra(triphenylphosphine)palladium and di(triphenylphosphine)palladium dichloride.

[0034] The solvent mentioned in step (2) is 1,4-dioxane;

[0035] The molar ratio of formula 1' or formula 2', trimethylbromosilane and methanol in step (2) is 1:10:200-300;

[0036] The stirring reaction mentioned in step (2) refers to stirring the reaction at 25-30℃ for 12-24 hours.

[0037] The above-mentioned anchored self-assembled polymer semiconductor transport layer material containing crosslinking units is used in the fabrication of hole transport layers for optoelectronic devices. The optoelectronic devices are preferably at least one of quantum dot light-emitting diodes (QLEDs), perovskite solar cell devices, and organic solar cells. The anchoring groups can form strong chemical bonds or physical adsorption with the substrate, which greatly enhances the adhesion between the film and the substrate. The anchored self-assembly process typically achieves optimal molecular arrangement and stacking morphology during solution film formation or during specific post-film formation treatments (such as thermal annealing). Introducing crosslinking units can "lock" the optimal morphology within the crosslinking network after formation, maintaining this optimized state during subsequent processing, device operation, and long-term use.

[0038] A method for preparing a hole transport layer for an optoelectronic device includes the following steps: dissolving an anchored self-assembled polymer semiconductor transport layer material containing cross-linked units in a solvent to form a solution, adding a cross-linking agent, then spin-coating it onto an ITO substrate, and annealing it under ultraviolet light to obtain a hole transport layer; or dissolving an anchored self-assembled polymer semiconductor transport layer material containing cross-linked units in a solvent to form a solution, then spin-coating it onto an ITO substrate, and annealing it to obtain a hole transport layer.

[0039] The solvent is at least one of toluene, chlorobenzene, and tetrahydrofuran.

[0040] The crosslinking agent is at least one of pentaerythritol tetrakis(3-mercaptopropionic acid) (PETMP) and 2,2′-(ethylenedioxy)diethylthiol (DODT), and the amount of the crosslinking agent is 5% to 10% of the mass of the anchored self-assembled polymer semiconductor transport layer material containing crosslinking units.

[0041] The heating annealing mentioned above refers to annealing at 100℃~110℃ for 5~10 minutes.

[0042] The ultraviolet light irradiation mentioned refers to irradiation at a wavelength of 365nm.

[0043] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0044] (1) The core function of the cross-linking unit in this invention is to “solidify” or “lock” the material in the optimal state (including anchored self-assembly optimized interface morphology, favorable molecular arrangement and stacking, uniform doping distribution, etc.) by forming a covalent bond network.

[0045] (2) The anchoring unit of the present invention achieves strong interface bonding, optimized interface order and low defect interface through anchoring self-assembly.

[0046] (3) The anchored self-assembled polymer semiconductor transport layer material containing cross-linked units of the present invention is suitable for simple and low-cost solution processing. At the same time, the polymer fused ring unit has good stability, which can improve the aging performance and environmental stability of optoelectronic devices. Attached Figure Description

[0047] Figure 1 The voltage-current density curves are for organic solar cells with P1, P1(+5%PETMP), and P1(+10%PETMP) as hole transport layers.

[0048] Figure 2 The open-circuit voltage aging degradation test curves of organic solar cells with P1, P1(+5%PETMP) and P1(+10%PETMP) as hole transport layers are shown.

[0049] Figure 3 The voltage-current density curves are shown for perovskite solar cells with P3, P3 (annealed for 5 minutes), and P2 (annealed for 10 minutes) as hole transport layers.

[0050] Figure 4 The open-circuit voltage aging degradation test curves of perovskite solar cells with P3, P3 (annealed for 5 minutes), and P3 (annealed for 10 minutes) as hole transport layers are shown. Detailed Implementation

[0051] The present invention will be further described in detail below with reference to embodiments and accompanying drawings, but the embodiments of the present invention are not limited thereto. Unless otherwise specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments used, unless otherwise specified, are all commercially available conventional products.

[0052] Unless otherwise specified, all reagents used in the examples are commercially available.

[0053] Example 1

[0054] (1) Synthesis of compound 3 (i.e. compound M1)

[0055] Under nitrogen protection, compound 1 (1.0 g, 2.97 mmol), compound 2 (0.97 g, 5.94 mmol), and potassium carbonate (0.82 g, 5.94 mmol) were dissolved in 150 mL of DMA in a three-necked flask and reacted under reflux at 60 °C for 20 h. After cooling the reaction mixture, the resulting mixture was precipitated in 300 mL of deionized water, filtered, and then extracted three times with EtOAc and water to obtain an organic layer. The organic layer was dried, filtered, and the solvent was evaporated to give a white solid product (1 g, 80% yield). 1 H NMR (500MHz, Chloroform-d) δ6.88(s,2H),5.76(tt,1H),5.11(ddt,1H),4.97(ddt,1H),4.25(t,2H),2.04(tdt,2H),1.72(p,2H),1.51-1.33(m,2H).

[0056]

[0057] Example 2

[0058] (1) Synthesis of compound 6

[0059] Under nitrogen protection, compound 4 (1.0 g, 5.98 mmol) and compound 5 (2.24 g, 12.56 mmol) were dissolved in 100 mL of chloroform in a three-necked flask. The mixture was stirred for 30 minutes under nitrogen atmosphere, then heated to 50 °C and refluxed for 8 hours. The resulting mixture was precipitated in 300 mL of deionized water, extracted, and the lower organic extracts were combined. After drying, filtration, and rotary evaporation, the crude product was preliminarily purified by silica gel column chromatography and then recrystallized in a dichloromethane / methanol system to give a light brown solid product (1.4 g, yield 72%). 1 HNMR(500MHz,Chloroform-d)δ10.24(s,1H),7.99(d,2H),7.39(dd,1.5Hz,2H),7.29(d,2H).

[0060] (2) Synthesis of monomer M2 (i.e. compound 8) used for polymerization

[0061] Under nitrogen protection, compound 6 (1.0 g, 3.08 mmol) and compound 7 (1.12 g, 4.62 mmol) were dissolved in 100 mL of DMF in a three-necked flask and stirred at room temperature for 30 minutes. Potassium carbonate (1.28 g, 9.24 mmol) was then dissolved in 20 mL of DMF and added to the flask using a syringe. The mixture was refluxed at 70 °C for 12 hours. The precipitate was collected in water, extracted three times with ethyl acetate and water, dried over anhydrous sodium sulfate, and purified by recrystallization from a dichloromethane / methanol system to give a pale yellow solid product (1.15 g, 77% yield). 1 H NMR(500MHz,Chloroform-d)δ8.23(dd,2H),7.97-7.91(m,2H),7.55(dd,2H),7.40(ddd,2H),7.28(dt,2H),5.67(t,2H),4.35(q,2H),1.39(t,3H).

[0062]

[0063] Example 3

[0064] (1) Synthesis of compound 11

[0065] Under nitrogen protection, compound 9 (5.62 g, 50 mmol) was dissolved in 100 mL of ethanol and added to a mixture of powdered compound 10 (22.4 g, 100 mmol), sodium acetate (8.2 g, 100 mmol), and 200 mL of ethanol. The mixture was rapidly heated to 50 °C and stirred continuously for 2 hours. The mixture was then cooled to room temperature and stirred before being poured into ice water. The liquid was filtered off, and the solid was carefully washed with water to give a brown solid (20 g, 89% yield). 1 H NMR(500MHz,Chloroform-d)δ9.66(s,2H),7.60-7.54(m,4H),7.30-7.24(m,4H),2.62(s,8H).

[0066] (2) Synthesis of compound 12

[0067] Under nitrogen protection, compound 11 (10 g, 22 mmol) was added to a mixture of 130 mL acetic acid and 32 mL sulfuric acid and stirred at 0 °C for 5 min. The mixture was heated to 30 °C and stirred for 1 hour, then further heated to 60–70 °C and stirred for another hour. It was then cooled to room temperature and stirred before being poured into ice water. The green solid was filtered and washed with water and ethanol until neutral pH was reached, finally yielding a dry, pure green solid powder (8 g, yield 87%). 1H NMR(500MHz,Chloroform-d)δ10.37(s,2H),8.08(d,2H),7.50(s,2H),7.40(dd,1.5Hz,2H),7.28(d,2H).

[0068] (3) Synthesis of compound 14

[0069] Under nitrogen protection, compound 12 (0.5 g, 1.95 mmol) dissolved in compound 13 (9.4 mL, 78.03 mmol), tetrabutylammonium bromide (0.25 g, 0.78 mmol), and 50% aqueous potassium hydroxide solution (2.2 mL, 19.5 mmol). The reaction mixture was heated to 60 °C and stirred overnight. After the reaction was complete, it was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The crude oil was dissolved in dichloromethane, and petroleum ether precipitated. The resulting solid particles were filtered off and washed repeatedly with petroleum ether to give a yellow solid (0.90 g, 88% yield). 1 H NMR(500MHz,Chloroform-d)δ8.10(t,1H),8.06(d,1H),7.48-7.40(m,4H),7.23(s,2H),4.22(t,4H),3.57(t,4H),1.97-1.81(m,8H).

[0070] (4) Synthesis of compound 16 (i.e., compound M3)

[0071] Under nitrogen protection, compound 14 (0.8 g, 1.52 mmol) was dissolved in compound 15 (5.2 ml, 30.4 mmol), and the reaction mixture was refluxed and heated for 16 hours. After cooling the mixture to room temperature, it was poured into 200 ml of petroleum ether and stirred at -70 °C for two hours until no more solid precipitate formed. The solid was then filtered off, washed, and dried to give a yellow solid (0.76 g, 78% yield). 1 H NMR(500MHz,Chloroform-d)δ8.04(dd,2H),7.52-7.44(m,4H),7.21(s,2H),4.20-4.12( m,8H),4.12-4.03(m,4H),1.91(dt,4H),1.83(p,4H),1.71-1.62(m,4H),1.38(td,12H).

[0072]

[0073] Example 4

[0074] (1) Synthesis of compound 18

[0075] Under nitrogen protection, compound 16 (6.63 g, 26.5 mmol) was dissolved in compound 17 (5 mL, 29.2 mmol). The mixture was rapidly heated to 85 °C and stirred overnight. The mixture was then cooled to room temperature, stirred, and poured into ice water. The liquid was filtered off, and the solid was washed carefully with water to give a white solid (12 g, yield 82%). 1 H NMR(500MHz,Chloroform-d)δ7.70-7.62(m,2H),7.33(ddq,2H),4.51(t,2H),4.11(p,4H),1.32(t,6H).

[0076] (2) Synthesis of compound M4

[0077] Under nitrogen protection, compound 6 (1.0 g, 3.08 mmol) and compound 18 (1.42 g, 4.62 mmol) were dissolved in 100 mL of DMF in a three-necked flask and stirred at room temperature for 30 minutes. Potassium carbonate (1.28 g, 9.24 mmol) was then dissolved in 20 mL of DMF and added to the flask using a syringe. The mixture was refluxed at 70 °C for 12 hours. The mixture was precipitated in water, extracted three times with ethyl acetate and water, dried over anhydrous sodium sulfate, and purified by recrystallization from a dichloromethane / methanol system to give a pale yellow solid product (1.5 g, 88% yield). 1 H NMR(500MHz,Chloroform-d)δ8.23(dd,2H),7.63-7.55(m,2H),7.51-7.45(m, 2H),7.45-7.39(m,4H),7.31(ddt,2H),5.67(t,2H),4.14(p,2H),1.31(t,6H).

[0078]

[0079] Example 5

[0080] (1) Synthesis of compound M5

[0081] Under nitrogen protection, compound 19 (0.63 g, 1.95 mmol) dissolved in compound 20 (0.575 g, 3.9 mmol), tetrabutylammonium bromide (0.130 g, 0.39 mmol), and 50% potassium hydroxide aqueous solution (1.1 mL, 9.75 mmol). The reaction mixture was heated to 60 °C and stirred overnight. After the reaction was complete, it was extracted with dichloromethane. The organic layer was dried on anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The crude oil was dissolved in dichloromethane, and petroleum ether precipitated. The resulting solid particles were filtered off and washed repeatedly with petroleum ether to give a yellow solid M5 (0.6 g, 79% yield). 1 H NMR(500MHz,Chloroform-d)δ7.86(d,2H),7.70(d,2H),7.46(dd,2H),4.18(t,2H),2.55(td,2H),2.06(t,1H),1.90(p,2H).

[0082]

[0083] Example 6: Preparation of polymer P1 containing crosslinking units

[0084] Monomer M1 (209 mg, 0.5 mmol), common Ar unit monomer N,N-bis(4-boronic acid pinene ester phenyl)-2,4,6-trimethylaniline (539.4 mg, 1 mmol), compound M4 (275.5 mg, 0.5 mmol), 1 ml tetraethylammonium hydroxide aqueous solution, and 5 ml chlorobenzene were added to a 15 ml polymerization tube and stirred at room temperature until dissolved. Then, tetra(triphenylphosphine)palladium (9 mg) catalyst was added. Under nitrogen protection, the reaction system was stirred at 120 °C for 24 hours. The reaction solution was added dropwise to methanol to precipitate a solid. After complete sedimentation, the precipitate was filtered and collected, and washed several times with methanol. The crude product was then placed in a Soxhlet extractor and washed successively with methanol, acetone, n-hexane, and chloroform, each solution for 8 hours. The obtained chloroform solution was evaporated and concentrated to 1 ml, added dropwise to n-hexane for precipitation, filtered, and dried to obtain a white solid polymer P1'.

[0085] The solid polymer P1' (0.4 g, 0.41 mmol) was then dissolved in 20 mL of anhydrous 1,4-dioxane. Trimethylbromosilane (0.54 mL, 4.1 mmol) was added to the solution. The reaction was stirred for 24 hours at room temperature under a nitrogen atmosphere. Then, 4 mL of methanol was added and stirred for 3 hours. Finally, 30 mL of distilled water was added dropwise until the solution became opaque. The product was filtered and washed with water to obtain a white solid (0.38 g, yield 84%, high-temperature GPC: Mw = 24 kDa). 1H NMR(500MHz,Chloroform-d)δ10.93(s,2H),7.84-7.78(m,2H),7.76(d,1H),7.71-7.65(m,2H),7.5 9-7.53(m,5H),7.49(t,2H),7.33(dt,2H),7.30-7.24(m,2H),7.23-7.17(m,4H),7.17-7.13(m,2H) ,7.07-7.02(m,3H),6.97-6.92(m,2H),6.87(d,4H),6.75(s,1H),5.82-5.70(m,3H),5.12(ddt,1H) ,4.97(ddt,1H),4.25(t,2H),2.27(s,6H),2.21(d,12H),2.04(tdt,2H),1.70(p,2H),1.41(p,2H).

[0086]

[0087] Example 7: Preparation of polymer P2 containing crosslinking units

[0088] Monomer M2 (243.5 mg, 0.50 mmol), common Ar unit monomer N,N-bis(4-boronic acid pinene ester phenyl)-2,4,6-trimethylaniline (539.4 mg, 1 mmol), compound M5 (195.5 mg, 0.50 mmol), 1 ml tetraethylammonium hydroxide aqueous solution, and 5 ml chlorobenzene were added to a 15 ml polymerization tube and stirred at room temperature until dissolved. Then, tetra(triphenylphosphine)palladium (9 mg) catalyst was added. Under nitrogen protection, the reaction system was stirred at 120 °C for 24 hours. The reaction solution was added dropwise to methanol to precipitate a solid. After complete sedimentation, the precipitate was filtered and collected, and washed several times with methanol. The crude product was then placed in a Soxhlet extractor and washed successively with methanol, acetone, n-hexane, and chloroform, each solution for 8 hours. The obtained chloroform solution was evaporated and concentrated to 1 ml, added dropwise to n-hexane for precipitation, filtered, and dried to obtain a white solid polymer P2'.

[0089] The solid polymer P2' (0.37 g, 0.42 mmol) was then dissolved in 20 mL of anhydrous 1,4-dioxane. Trimethylbromosilane (0.55 mL, 4.2 mmol) was added to the solution. The reaction was stirred for 24 hours at room temperature under a nitrogen atmosphere. Then, 4 mL of methanol was added and stirred for 3 hours. Finally, 30 mL of distilled water was added dropwise until the solution became opaque. The product was filtered and washed with water to obtain a white solid (0.3 g, 70% yield, high-temperature GPC: Mw = 22 kDa). 1H NMR(500MHz,Chloroform-d)δ11.78(s,1H),7.93-7.87(m,2H),7.85(dd,1H),7.82(d ,1H),7.80-7.73(m,3H),7.66(dd,1H),7.59-7.53(m,6H),7.53-7.46(m,5H),7.30(dd d,3H),7.23-7.16(m,6H),7.07-7.01(m,2H),6.97-6.92(m,2H),6.87(d,4H),5.72(t, 2H),4.21(t,2H),2.55(td,2H),2.27(s,6H),2.21(d,12H),2.06(t,1H),1.87(p,2H).

[0090]

[0091] Example 8: Preparation of polymer P3 containing crosslinking units

[0092] Monomer M3 (399.2 mg, 0.50 mmol), common Ar unit monomer N,N-bis(4-boronic acid pinene ester phenyl)-2,4,6-trimethylaniline (539.4 mg, 1 mmol), compound M5 (195.5 mg, 0.50 mmol), 1 ml tetraethylammonium hydroxide aqueous solution, and 5 ml chlorobenzene were added to a 15 ml polymerization tube and stirred at room temperature until dissolved. Then, tetra(triphenylphosphine)palladium (9 mg) catalyst was added. Under nitrogen protection, the reaction system was stirred at 120 °C for 24 hours. The reaction solution was added dropwise to methanol to precipitate a solid. After complete sedimentation, the precipitate was filtered and collected, and washed several times with methanol. The crude product was then placed in a Soxhlet extractor and washed successively with methanol, acetone, n-hexane, and chloroform, each solution for 8 hours. The obtained chloroform solution was evaporated and concentrated to 1 ml, added dropwise to n-hexane for precipitation, filtered, and dried to obtain a white solid polymer P3'.

[0093] The solid polymer P3' (0.5 g, 0.44 mmol) was then dissolved in 20 mL of anhydrous 1,4-dioxane. Trimethylbromosilane (0.58 mL, 4.4 mmol) was added to the solution. The reaction was stirred for 24 hours at room temperature under a nitrogen atmosphere. Then, 4 mL of methanol was added and stirred for 3 hours. Finally, 30 mL of distilled water was added dropwise until the solution became opaque. The product was filtered and washed with water to obtain a white solid (0.5 g, yield 88%, high-temperature GPC: Mw = 32 kDa). 1H NMR(500MHz,Chloroform-d)δ8.84(s,4H),7.99(d,1H),7.88(d,1H),7.73(t,2H) ,7.68(dd,1H),7.66-7.62(m,2H),7.61-7.49(m,9H),7.34-7.28(m,1H),7.22-7.1 2(m,9H),7.07-7.02(m,2H),6.97-6.92(m,2H),6.87(d,4H),4.21(dt,6H),2.55( td,2H),2.27(s,6H),2.21(d,12H),2.06(t,1H),1.93-1.78(m,10H),1.66(q,4H).

[0094]

[0095] Example 9: Fabrication of an organic solar cell device based on an anchored self-assembly polymer semiconductor transport layer material containing cross-linked units

[0096] Using the anchored self-assembled polymer semiconductor transport layer material P1 containing cross-linked units from Example 6 above as the hole transport layer material, and the common donor-acceptor material PM6:PFA = 1:1.2 as the active layer, a polymer photovoltaic device is fabricated. The device structure is: ITO / P1 / active layer / PFN-Br (methanol 0.5 mg / mL) -1 The structure of PFA is shown in Formula IV:

[0097]

[0098] The specific steps for fabricating this polymer photovoltaic device are as follows:

[0099] (1) Cleaning of conductive glass ITO substrate: The ITO glass substrate is placed in acetone, isopropanol, detergent, deionized water and isopropanol in sequence for ultrasonic cleaning to remove any residues (such as photoresist) that may remain on the surface of the ITO glass substrate and to improve the interface contact. After cleaning, it is placed in a vacuum oven to dry.

[0100] (2) Place the ITO in an oxygen plasma etching instrument and bombard it with oxygen plasma for twenty minutes to thoroughly remove any organic matter that may remain on the surface of the ITO glass substrate.

[0101] (3) Dissolve P1 in toluene to a concentration of 1 mg / mL, without adding, with 5% or 10% of pentaerythritol tetrakis(3-mercaptopropionic acid) crosslinking agent, where 5% and 10% refer to the mass ratio of PETMP to P1. Spin-coat a hole transport interface about 30 nm thick, and then heat-anneal at 100 °C for 10 minutes under 365 nm ultraviolet light to firmly anchor it on the ITO electrode and form a crosslinked structure.

[0102] (4) In a glove box under a nitrogen atmosphere, the polymer active layer material PM6:PFA was blended at a mass ratio of 1:1.2 and dissolved in methyltetrahydrofuran to prepare a solution with a concentration of 20 mg / mL. After spin-coating an active layer with a thickness of 130 nm onto the P1 transport layer, the active layer was heated and annealed at 100 °C for 15 minutes on a heating stage to remove residual solvent and improve the morphology of the active layer film.

[0103] (5) In a glove box under a nitrogen atmosphere, spin-coat a layer of electron transport material with a thickness of 20 nm onto the active layer material. The material used is 0.5 mg / mL poly[(9,9-di(3'-(N,N-dimethylamino)propyl)fluorenyl-2,7-diyl)-ALT-[(9,9-di-n-octylfluorenyl-2,7-diyl)bromo(PFN-Br);

[0104] (6) Finally, the prepared device is placed in the vapor deposition chamber and an Ag electrode with a thickness of 100 nm is vapor deposited in a vacuum environment.

[0105] (7) The photoelectric conversion efficiency and current-voltage characteristic curves of polymer solar cell devices were tested under an AM 1.5G simulated sunlight lamp.

[0106] The photoelectric performance of the prepared organic solar cell devices was tested, and the test results are shown in Table 1.

[0107] Table 1 Device parameters of organic solar cells

[0108]

[0109] The data in Table 1 show that the organic solar cell device using P1 (+5% PETMP) as the transport layer material has good photoelectric performance. The short-circuit current density of the device is 26.40 mA / cm², the open-circuit voltage is 0.89 V, the fill factor is 72.09%, and the final device efficiency is 16.93%.

[0110] The anchored transport layer polymer material prepared with almost no crosslinking agent P1 exhibits a short-circuit current density of 24.59 mA / cm², an open-circuit voltage of 0.869 V, a fill factor of 60.98%, and a final device efficiency of 13.03%. Using P1 (+10% PETMP) as the transport layer, the device exhibits a short-circuit current density of 25.90 mA / cm², an open-circuit voltage of 0.888 V, a fill factor of 72.29%, and a final device efficiency of 16.62%.

[0111] Figure 1 The voltage-current density curves are for organic solar cells with P1, P1(+5%PETMP), and P1(+10%PETMP) as hole transport layers.

[0112] Figure 2 The open-circuit voltage aging degradation test curves of organic solar cells with P1, P1(+5%PETMP) and P1(+10%PETMP) as hole transport layers are shown.

[0113] Example 10: Fabrication of a perovskite photovoltaic device based on a cross-linked unit-anchored self-assembled polymer semiconductor transport layer material

[0114] Using the anchored self-assembly polymer semiconductor transport layer material P3 containing cross-linked units in Example 8 above as the hole transport layer material, with a 1.55 eV perovskite:Cs 0.05 (FA 0.95 MA 0.05 ) 0.95 Pb(I 0.95 Br 0.95 ITO / P3 / Cs is used as the active layer to fabricate perovskite photovoltaic devices, and the device structure is: ITO / P3 / Cs 0.05 (FA 0.95 MA 0.05 ) 0.95 Pb(I 0.95 Br 0.95 )3 / C 60 / BCP / Ag.

[0115] The specific steps for fabricating this polymer photovoltaic device are as follows:

[0116] (1) The ITO substrate was cleaned in the following order: once with detergent, three times with deionized water, and twice with isopropanol. Then it was dried in an oven at 80°C. After drying, the ITO substrate was subjected to a plasma treatment for 20 minutes and then quickly transferred to a nitrogen glove box.

[0117] (2) Preparation of hole transport layer: P3 is dissolved in toluene at a concentration of 1 mg / mL and spin-coated at 3000 rpm for 30 seconds. It can be used directly in the next step, or annealed on a hot plate at 100°C for 5 or 10 minutes before use in the next step.

[0118] (3) Dissolve 19.49 mg cesium iodide, 232.8 mg formamidin hydroiodate, 721.72 mg lead iodide, 7.98 mg methylammonium bromide, and 28.47 mg lead bromide in 800 μL DMF and 200 μL DMSO. Then add 3 mol% (percentage of total molar amount) lead iodide and 10 mol% (percentage of total molar amount) methylammonium chloride. Stir for 8 hours and use this solution to prepare the perovskite active layer. Spin coat at 5000 rpm for 30 seconds, add the antisolvent chlorobenzene dropwise in the last 12 seconds, and then anneal on a hot plate at 110 °C for 30 minutes to prepare the perovskite layer.

[0119] (4) After the device has cooled to room temperature, a 0.3 mg / ml isopropanol solution of piperazine monohydroiodate is spin-coated onto the perovskite layer at 5000 rpm for 30 seconds as a passivation layer, followed by annealing at 100°C for 5 minutes. After cooling, the device is transferred to a vacuum of less than 3 × 10 mbar. -7 In the vacuum evaporation system, 20nm C60, 7nm BCP and 100nm silver electrodes are deposited sequentially.

[0120] (5) Finally, the prepared device was placed in the evaporation chamber, and a 100 nm thick Ag electrode was deposited under vacuum. The effective area of ​​the device, calibrated using a blackened mask, was 0.04 cm². 2 .

[0121] (6) The photoelectric conversion efficiency and current-voltage characteristic curves of the solar cell device were tested under an AM 1.5G simulated sunlight lamp.

[0122] The photoelectric performance of the prepared perovskite solar cell devices was tested, and the test results are shown in Table 2.

[0123] Table 2 Device parameters of perovskite solar cells

[0124]

[0125]

[0126] The data in Table 2 show that the short-circuit current density of the perovskite solar cell device using P3 (unannealed) as the transport layer material is 23.76 mA / cm², the open-circuit voltage is 1.141 V, the fill factor is 64.35%, and the final device efficiency is 17.44%.

[0127] The cross-linked, anchored hole transport layer polymer material prepared with P3 (annealed for 5 minutes) significantly improved the performance of perovskite devices, with a short-circuit current density of 25.63 mA / cm², an open-circuit voltage of 1.200 V, a fill factor of 7.64%, and a final device efficiency of 24.19%. Using P3 (annealed for 10 minutes) as the transport layer, the device exhibited a short-circuit current density of 25.02 mA / cm², an open-circuit voltage of 1.168 V, a fill factor of 76.38%, and a final device efficiency of 22.32%.

[0128] Figure 3 The voltage-current density curves are shown for perovskite solar cells with P3, P3 (annealed for 5 minutes), and P3 (annealed for 10 minutes) as hole transport layers.

[0129] Figure 4 The open-circuit voltage aging degradation test curves of perovskite solar cells with P3, P3 (annealed for 5 minutes), and P3 (annealed for 10 minutes) as hole transport layers are shown.

[0130] Example 11: Fabrication of a quantum dot light-emitting diode (QLED) based on a cross-linked unit-anchored self-assembled polymer semiconductor transport layer material.

[0131] The ITO substrate was ultrasonically cleaned and dried sequentially using tetrahydrofuran, deionized water, and isopropanol. The ITO was then subjected to plasma treatment. P1, P2, and P3 were dissolved in toluene at a concentration of 1 mg / mL, and 5 wt% of pentaerythritol tetrakis(3-mercaptopropionic acid) crosslinking agent (PETMP) was added to each. A hole transport layer 1 approximately 30 nm thick was spin-coated onto this layer, followed by thermal annealing at 100 °C for 10 minutes under 365 nm UV irradiation. Subsequently, a hole transport polymer TFB (CAS: 220797-16-0) was spin-coated onto hole transport layer 1 to prepare hole transport layer 2, and baked at 100 °C for 10 minutes (~30 nm). Then, a 15 nm green quantum dot layer (CdSeS / ZnSe / ZnS) and a 40 nm ZnO nanoparticle layer (ethanol solution) were sequentially prepared and baked at 90 °C for 10 minutes. Finally, the device was transferred to a vacuum of 1 × 10⁻⁶. -4 An aluminum electrode (120 nm) was deposited in a vacuum chamber at Pa, and encapsulated using epoxy resin and a cover glass. Simultaneously, a QLED device based on PEDOT:PSS as the hole transport layer 1 was fabricated as a control; all other aspects were the same as in Example 11. Device results are shown in Table 3.

[0132] Table 3. QLED Device Performance

[0133] Hole transport layer 1 External quantum efficiency (%) Emission peak (nm) LT95@1000nit(h) PEODT:PSS 15.4 533 220 Polymer P1 16.2 533 308 Polymer P2 15.9 533 286 Polymer P3 16.5 533 382

[0134] As shown in Table 3, in terms of efficiency, the QLED device based on P1–P3 as hole transport layer 1 is slightly better than the device based on PEDOT:PSS. In terms of lifetime, the QLED device based on P1–P3 as hole transport layer 1 shows a significant improvement in LT95 lifetime. This indicates that these polymers can be used to fabricate high-performance quantum dot light-emitting diodes.

[0135] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A type of anchored self-assembled polymer semiconductor transport layer material containing cross-linked units, characterized in that... The chemical structural formula satisfies the general formula shown in Formula 1 or Formula 2: In Formulas 1 and 2, Ar1, Ar2 and Ar3 are aromatic ring units or heteroaromatic ring units, B2 and B3 are alkyl chain or alkoxy chain units, A2 is an acid unit, linker is a crosslinkable group, the degree of polymerization n is 5-300, and x, y and z represent repeating units, 0 < x < 1, 0 < y < 1, 0 < z < 1, x + y + z = 1.

2. The anchored self-assembled polymer semiconductor transport layer material containing cross-linked units according to claim 1, characterized in that: The Ar1, Ar2, and Ar3 units described above are all relatively independent of at least one of the following chemical structures: In Formulas 1 and 2, both B2 and B3 units are relatively independent of -R1-, where -R1- is relatively independent of one of the following groups: alkyl with 1-20 carbon atoms, aryl with 4-20 carbon atoms, heteroaryl with 4-20 carbon atoms, aralkyl with 4-20 carbon atoms, heteroarylalkyl with 4-20 carbon atoms, aryloxy with 4-20 carbon atoms, heteroaryloxy with 4-20 carbon atoms, arylalkoxy with 4-20 carbon atoms, and heteroarylalkoxy with 4-20 carbon atoms; In Equations 1 and 2, element A2 has one of the following structures: The linker unit in Equations 1 and 2 can be one of the following structures: In the structure of the linker unit described above, R is an alkyl group with 1-4 carbon atoms.

3. The anchored self-assembled polymer semiconductor transport layer material containing cross-linked units according to claim 1, characterized in that... Its chemical structural formula is one of the following: The degree of polymerization, n, ranges from 5 to 300.

4. A method for preparing an anchored self-assembled polymer semiconductor transport layer material containing cross-linked units according to any one of claims 1-3, characterized in that... Specifically, the following steps are included: (1) Under nitrogen or an inert atmosphere, compound I or compound I', compound II, and compound III undergo a Suzuki coupling reaction in the presence of a base and a catalyst to generate formula 1' or formula 2'; (2) Under nitrogen or inert atmosphere, dissolve formula 1' or formula 2' in solvent, then add bromotrimethylsilane and methanol and stir to react, thus obtaining anchored self-assembled polymer semiconductor transport layer material containing crosslinking units; The specific reaction route is shown below: In step (1), R2 in compounds I and I' has one of the following structures:

5. The method for preparing the anchored self-assembled polymer semiconductor transport layer material containing cross-linked units according to claim 4, characterized in that: The reaction described in step (1) refers to a reaction at 100-150℃ for 24 hours; The molar ratio of compound I or compound I', compound II and compound III mentioned in step (1) is y:z:x, where z = x + y, preferably 1:2:1; The alkali mentioned in step (1) is at least one of cesium carbonate, potassium carbonate, sodium methoxide, and sodium tert-butoxide, and the catalyst mentioned in step (1) is at least one of tetra(triphenylphosphine)palladium and di(triphenylphosphine)palladium dichloride.

6. The method for preparing the anchored self-assembled polymer semiconductor transport layer material containing cross-linked units according to claim 4, characterized in that: The solvent mentioned in step (2) is 1,4-dioxane; In step (2), the molar ratio of formula 1' or formula 2' to bromotrimethylsilane and methanol is 1:10:200-300; The stirring reaction mentioned in step (2) refers to stirring the reaction at 25-30℃ for 12-24 hours.

7. The application of the anchored self-assembled polymer semiconductor transport layer material containing cross-linked units according to any one of claims 1-3 in the fabrication of transport layers for optoelectronic devices.

8. A method for fabricating a hole transport layer in an optoelectronic device, characterized in that... The method includes the following steps: dissolving the anchored self-assembled polymer semiconductor transport layer material containing crosslinking units as described in any one of claims 1-3 in a solvent to form a solution, adding a crosslinking agent, then spin-coating it onto an ITO substrate, and annealing it under ultraviolet light to obtain a hole transport layer; or dissolving the anchored self-assembled polymer semiconductor transport layer material containing crosslinking units as described in any one of claims 1-3 in a solvent to form a solution, then spin-coating it onto an ITO substrate, and annealing it to obtain a hole transport layer.

9. The method for fabricating the transmission layer of the optoelectronic device according to claim 8, characterized in that: The solvent is at least one of toluene, chlorobenzene, and tetrahydrofuran; The crosslinking agent is at least one of pentaerythritol tetrakis(3-mercaptopropionic acid) and 2,2′-(ethylenedioxy)diethylthiol, and the amount of the crosslinking agent is 5% to 10% of the mass of the anchored self-assembled polymer semiconductor transport layer material containing crosslinking units.

10. The method for fabricating the transmission layer of the optoelectronic device according to claim 8, characterized in that: The heating annealing mentioned above refers to annealing at 100℃~110℃ for 5~10 minutes; The ultraviolet light irradiation mentioned refers to irradiation at a wavelength of 365nm.

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