Dihydroindofluorene conjugated organic small molecule hole transport materials, their preparation methods and applications

Abstract

This invention belongs to the field of organic small molecule hole transport materials technology, specifically dihydroindofluorene conjugated organic small molecule hole transport materials, their preparation methods, and applications. The hole transport materials use triphenylamine carbazole as the terminal group and long carbon chains and anisole as side chain end-groups, respectively abbreviated as ALK-DSF and MeOP-DSF. The introduction of functional materials with dihydroindofluorene as the core structure is beneficial for rationally optimizing the internal energy level arrangement of the battery, improving charge transport efficiency, avoiding excessive energy loss, and thus improving the battery's photoelectric conversion efficiency. Furthermore, the end-group modifications of this functional material, including nitrogen-containing carbazole and benzyloxy groups, can effectively passivate quantum dot interface defects and promote charge collection. Devices prepared using both materials as hole transport materials have achieved higher photoelectric conversion efficiency and open-circuit voltage than corresponding devices using the traditional hole transport material -1,2-ethylenedithiol, thus improving the device's photoelectric performance.

Description

Technical Field

[0001] This invention belongs to the field of organic small molecule hole transport materials technology, specifically relating to dihydroindofluorene conjugated organic small molecule hole transport materials, their preparation methods, and applications. Background Technology

[0002] The global energy crisis is becoming increasingly severe, and "innovation in high-efficiency solar energy utilization technology" has been listed as one of the 15 key innovation tasks. Photovoltaic technology can directly convert solar energy into electricity and utilize it, making it one of the most effective means of high-efficiency solar energy utilization. Quantum dot solar cells (QDSCs) have characteristics such as tunable bandgap and doping type, strong visible-infrared absorption, and multi-exciton effects. Single-junction QDSCs have a theoretical efficiency of up to 44%, making them one of the hot topics in third-generation photovoltaic technology with enormous development potential [Adv. Energy Mater. 2021, 11, 2003 457.]. Among them, lead sulfide quantum dot solar cells (PbS-QDSCs) exhibit outstanding stability and are the most promising candidate to break the Shockley-Quisser efficiency limit, with the highest certified efficiency reaching 13.3%, attracting significant attention [Nat. Commun. 2020, 11, 103; Adv. Mater. 2021, 33, 2008 115.].

[0003] Currently, high-performance PbS-QDSCs generally employ a device structure combining heterojunctions and quantum dot junctions. The introduction of electron transport layers (ETLs) and hole transport layers (HTLs) is essential for improving device performance [Nat. Energy 2019, 4, 969-976; ACS Energy Lett. 2020, 5, 2335-2342.]. In particular, since Chuang et al. first reported the use of 1,2-ethylenedithiol (EDT) as HTL passivation in 2014, PbS-QDSCs have achieved continuous improvements in surface modification and device engineering, with their photoelectric conversion efficiency increasing from 8.5% to the current 13.8% [Adv. Mater. 2020, 32, 2004657; Nat. Mater. 2014, 13, 796-801; Joule 2020, 4, 1542-1556.]. To date, EDT is the commonly used HTL material in PbS-QDSCs, and PbS-EDT has been widely proven to introduce additional defects and increase Vt. ocThe process of preparing PbS-QDSCs suffers from drawbacks such as high energy loss and complex fabrication processes, which hinder large-area fabrication [Adv. Mater. 2021, 33, 2008 115]. In attempts to replace EDT materials, some p-type organic polymers (PTB7-Th, PBDTTT-ET, TIPS-TPD, etc.) have been used as high-performance metamaterials (HTMs) in PbS-QDSCs, achieving photoelectric efficiencies exceeding 12%. This demonstrates that by rationally adjusting the molecular structure and heterojunction composition, it is possible to improve surface and interface defects and increase VT. oc In terms of device efficiency, it is highly feasible [Nat. Energy 2019, 4, 969-976; Adv. Energy Mater. 2020, 10, 1902933.]. However, compared to organic polymer materials, pure organic small molecule materials have advantages such as low raw material cost, easier modification and adjustment of structure and doping type, expansion of conjugated system to improve material thermal stability, and large electron barrier to reduce back current leakage, making them an ideal choice for HTM.

[0004] Therefore, the development of the interface has fewer defects and V oc Non-EDT hole transport materials (HTMs) with low loss and high hole mobility are of great significance for further improving the photoelectric conversion efficiency and stability of PbS-QDSCs. Summary of the Invention

[0005] To address the aforementioned problems, this paper proposes a dihydroindofluorene conjugated organic small molecule hole transport material, its preparation method, and its applications.

[0006] In a first aspect, the present invention provides a dihydroindofluorene conjugated organic small molecule hole transport material, wherein the hole transport material uses triphenylamine carbazole as the terminal group and long carbon chain and anisole as the side chain terminal modification groups, respectively. The chemical names are 5,14-dihexyl-8,8,17,17-tetra(4-hexylphenyl)-N2,N2,N11,N11-tetra(4-methoxyphenyl)-5,8,14,17-tetrahydro-s-indo[1,2-b:5,6-b']dicarbazole-2,11-diamine, abbreviated as ALK-DSF, and the chemical formula is shown in formula (1).

[0007] Or 5,14-bis(4-methoxyphenyl)-8,8,17,17-tetra(4-hexylphenyl)-N2,N2,N11,N11-tetra(4-methoxyphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole-2,11-diamine, abbreviated as MeOP-DSF, with the chemical formula shown in formula (2);

[0008]

[0009] Secondly, the present invention provides a method for preparing the dihydroindendrofluorene conjugated organic small molecule hole transport material, the synthetic route of which is shown below:

[0010]

[0011] Where R = C6H 13 or

[0012] Furthermore, when R = C6H 13 The specific preparation method is as follows:

[0013] Step 1: 1-Bromo-4-hexylbenzene, diethyl 2,5-bis(9-hexyl-9h-carbazole-2-yl)terephthalate and n-butyllithium were mixed in a molar ratio of 4:1:5 and added to a two-necked flask at -78°C. Tetrahydrofuran was added, and the mixture was reacted at -78°C for 12 hours. After the reaction was completed, the mixture was heated to room temperature and then subjected to hydrolysis. The mixture was then extracted with ethyl acetate in water, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation to obtain the crude product. The crude product was separated by silica gel mobile phase chromatography using a mixed solution of ethyl acetate, petroleum ether, and triethylamine as the eluent to obtain compound 2,5-bis(9-hexyl-9h-carbazole-2-yl)-1,4-phenyl-bis(bis(4-hexylphenyl)ol).

[0014] Step 2: The compound obtained in Step 1 and Amberlyst 15 ion exchange resin were mixed in anisole at a molar ratio of 1:2 and added to a round-bottom flask. The flask was evacuated, purged with N2 three times, and then refluxed for 12 hours. After the reaction was completed, the mixture was extracted with DCM, the organic phase was dried with MgSO4, and the crude product was obtained by rotary evaporation. The crude product was separated by silica gel mobile phase column chromatography using a mixed solution of dichloromethane and petroleum ether as eluent to obtain compound 5,14-dihexyl-8,8,17,17-tetra(4-hexylphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole.

[0015] Step 3: The compound obtained in Step 2 and 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione were added to a two-necked flask at a molar ratio of 1:2. The flask was evacuated and purged with N2 three times. Tetrahydrofuran solvent was added, and the mixture was reacted at room temperature for 12 hours. After the reaction was completed, the organic layer was extracted with CH2Cl2, dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation to obtain the crude product. The crude product was purified by chromatography on a silica gel column using a mixture of CH2Cl2 and petroleum ether as the eluent to obtain compound 2,11-dibromo-5,14-dihexyl-8,8,17,17-tetra(4-hexylphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole.

[0016] Step 4: The compound obtained in Step 3, bis(4-methoxyphenyl)amine, sodium tert-butoxide, tri-tert-butylphosphine tetrafluoroborate, and palladium acetate were added to a two-necked round-bottom flask in a molar ratio of 1:2:3:0.2:0.3. The mixture was purged with N2 three times, and anisole solvent was added. The mixture was then bubbled with N2 to remove oxygen for 15 min, and refluxed for 12 h. After cooling to room temperature, the mixture was rinsed with water, and the organic layer was extracted with CH2Cl2. The residue was then dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The crude product was obtained by eluenting with a mixture of CH2Cl2 and petroleum ether and purified by chromatography on a silica gel column to obtain compound 5,14-dihexyl-8,8,17,17-tetra(4-hexylphenyl)-N2,N2,N11,N11-tetra(4-methoxyphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole-2,11-diamine, i.e., Alk-DSF.

[0017] Furthermore, when The specific preparation method is as follows:

[0018] Step (1): 1-Bromo-4-hexylbenzene, 2,5-bis(9-(4-methoxyphenyl)-9h-carbazole-2-yl)terephthalate and n-butyllithium were mixed in a molar ratio of 4:1:5 and added to a two-necked flask at -78°C. Tetrahydrofuran was added, and the mixture was reacted at -78°C for 12 hours. After the reaction was completed, the mixture was heated to room temperature and then hydrolyzed. The mixture was then extracted with ethyl acetate in water. The organic phases were combined and dried with anhydrous magnesium sulfate. The solvent was removed by rotary evaporation to obtain the crude product. The crude product was separated by silica gel mobile phase chromatography using a mixed solution of ethyl acetate, petroleum ether, and triethylamine as eluent to obtain compound 2,5-bis(9-(4-methoxyphenyl)-9h-carbazole-2-yl)-1,4-phenyl-bis(bis(4-hexylphenyl)ol).

[0019] Step (2): The compound obtained in step (1) and Amberlyst 15 ion exchange resin were mixed in anisole at a molar ratio of 1:2 and added to a round-bottom flask. The flask was evacuated, purged with N2 three times, and then refluxed for 12 hours. After the reaction was completed, the mixture was extracted with DCM, the organic phase was dried with MgSO4, and the crude product was obtained by rotary evaporation. The crude product was separated by silica gel mobile phase column chromatography using a mixed solution of dichloromethane and petroleum ether as the eluent to obtain compound 5,14-bis(4-methoxyphenyl)-8,8,17,17-tetra(4-hexylphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole.

[0020] Step (3): The compound obtained in step (2) and 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione were added to a two-necked flask at a molar ratio of 1:2. The flask was evacuated and purged with N2 three times. Tetrahydrofuran solvent was added, and the mixture was reacted at room temperature for 12 hours. After the reaction was completed, the organic layer was extracted with CH2Cl2, dried with anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation to obtain the crude product. The crude product was purified by chromatography on a silica gel column using a mixed solution of CH2Cl2 and petroleum ether as the eluent to obtain the compound 2,11-dibromo-5,14-di(4-methoxyphenyl)-8,8,17,17-tetra(4-hexylphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole.

[0021] Step (4): The compound obtained in step (3), bis(4-methoxyphenyl)amine, sodium tert-butoxide, tritert-butylphosphine tetrafluoroborate, and palladium acetate were added to a two-necked round-bottom flask in a molar ratio of 1:2:3:0.2:0.3. The mixture was purged with N2 three times, anisole solvent was added, and then N2 was bubbled to remove oxygen for 15 min. The mixture was then refluxed for 12 h. After cooling to room temperature, the mixture was rinsed with water, the organic layer was extracted with CH2Cl2, dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation to obtain the final product. The crude product was purified by chromatographic analysis on a silica gel column using a mixed solution of CH2Cl2 and petroleum ether as the eluent to obtain compound 5,14-bis(4-methoxyphenyl)-8,8,17,17-tetra(4-hexylphenyl)-N2,N2,N11,N11-tetra(4-methoxyphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole-2,11-diamine, i.e., MeOP-DSF.

[0022] Furthermore, in steps 1 and (1), the volume ratio of ethyl acetate, petroleum ether, and triethylamine in the mixed solution is 1:5:0.01.

[0023] Furthermore, in steps 2 and (2), the volume ratio of dichloromethane to petroleum ether in the mixed solution is 1:4.

[0024] Furthermore, in steps 3 and (3), the volume ratio of CH2Cl2 to petroleum ether in the CH2Cl2 and petroleum ether mixed solution is 1:8.

[0025] Furthermore, in step 4 or step (4), the volume ratio of CH2Cl2 to petroleum ether in the CH2Cl2 and petroleum ether mixed solution is 3:2.

[0026] Thirdly, the present invention provides the application of the dihydroindofluorene conjugated organic small molecule hole transport material in quantum dot solar cells.

[0027] The specific application is as follows:

[0028] Step S1: Prepare PbS-I quantum dot solids;

[0029] Step S2: Pre-treat the transparent conductive substrate ITO;

[0030] Step S3: In a fume hood, spin-coat the ZnO nano solution onto the pretreated transparent conductive substrate ITO at 5000 rpm for 20 seconds, and spin-coat two layers.

[0031] Step S4: After waiting for more than two hours following step S3, prepare the PbS-I quantum dot solid in step 1 using a mixed solution of N,N-dimethylformamide, acetonitrile, and dimethyl sulfoxide to obtain a concentration of 600 mg / mL. -1 The solution was immediately centrifuged at 12000 rpm for 1 min, then spin-coated at 2000 rpm onto the ZnO layer from step 3 for 40 s, and then annealed at 70 °C for 15 min in a glove box.

[0032] Step S5: Prepare a 0.04% 1,2-ethylenedithiol solution using a mixed solution of diethyl acetate and acetonitrile in a volume ratio of 1:2. Then, apply 20 mg / mL of 850 nm solution. -1 Lead sulfide quantum dots were spin-coated onto the functional layer of step 4 at 3000 rpm for 10 s, then treated with 0.04% 1,2-ethanedithiol solution and left to stand for 30 s. After that, they were spin-coated at 3000 rpm for 10 s. The film was then cleaned three times with a washing solution of ethyl acetate:acetonitrile = 1:2 by spin-coating at 3000 rpm for 10 s.

[0033] Step S6: After placing the product from step S4 in a drying oven for 12 hours, transfer it to a glove box and dissolve Alk-DSF or MeOP-DSF in chlorobenzene to prepare a solution of 3 mg / mL. -1The solution was spin-coated onto the cavity layer in step 5 at 3000 rpm for 30 seconds, and then annealed at 80°C for 10 minutes in a glove box.

[0034] Step S7, first using vacuum evaporation method... 9nm MoO3 was deposited at a rate of [speed not specified], and then [further details not specified]. At a speed of 80 nm, Ag is deposited onto the top layer of the device as an electrode.

[0035] This invention offers the following advantages: It designs two organic small-molecule functional materials with dihydroindenone as the core, their synthesis methods, and their applications in quantum dot solar cells. On one hand, the introduction of functional materials with dihydroindenone as the core structure helps to rationally optimize the internal energy level arrangement of the cell, improve charge transport efficiency, avoid excessive energy loss, and thus improve the photoelectric conversion efficiency. On the other hand, the end-group modifications of these functional materials, such as nitrogen-containing carbazole and benzyloxy groups, can effectively passivate defects at the quantum dot interface and promote charge collection. Furthermore, the long carbon chains modified on the periphery of these functional materials have strong hydrophobicity, effectively preventing the penetration of harmful dopants and water vapor from the hole transport layer into the quantum dot layer, inhibiting quantum dot degradation, and improving the stability of the cell. Ultimately, devices prepared from both materials achieved higher photoelectric conversion efficiencies and open-circuit voltages than the control group, effectively reducing device surface defects and improving the device's photoelectric performance. Attached Figure Description

[0036] Figure 1 This is a structural diagram of a lead sulfide quantum dot solar cell based on dihydroindofluorene conjugated organic small molecule hole transport material, as per the present invention.

[0037] Figure 2 This is the energy level arrangement diagram of lead sulfide quantum dot solar cells based on a hybrid hole transport layer of 1,2-ethanedithiol and dihydroindofluorene conjugated organic small molecule Alk-DSF or MeOP-DSF hole transport materials according to the present invention.

[0038] Figure 3 JV curves of lead sulfide quantum dot solar cells prepared in the examples and comparative examples;

[0039] Figure 4 IPCE curves of lead sulfide quantum dot solar cells prepared in the examples and comparative examples; Detailed Implementation

[0040] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings.

[0041] The hole transport material is a dihydroindofluorene conjugated organic small molecule hole transport material with triphenylamine carbazole as the terminal group and long carbon chain and anisole as the side chain terminal group, respectively. The chemical names are 5,14-dihexyl-8,8,17,17-tetra(4-hexylphenyl)-N2,N2,N11,N11-tetra(4-methoxyphenyl)-5,8,14,17-tetrahydro-s-indo[1,2-b:5,6-b']dicarbazole-2,11-diamine, abbreviated as ALK-DSF, and the chemical formula is shown in formula (1).

[0042] And 5,14-bis(4-methoxyphenyl)-8,8,17,17-tetra(4-hexylphenyl)-N2,N2,N11,N11-tetra(4-methoxyphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole-2,11-diamine, abbreviated as MeOP-DSF, with the chemical formula shown in formula (2);

[0043]

[0044] The synthesis route is shown below:

[0045]

[0046] Example 1: Preparation of ALK-DSF and Fabrication of Lead Sulfide Quantum Dot Solar Cells

[0047] 1.1 Preparation of ALK-DSF

[0048] Synthesis of Compound 3

[0049] Compound 1, compound 2 (2,5-di(9-hexyl-9h-carbazole-2-yl)terephthalate) and n-butyllithium were mixed at a molar ratio of 4:1:5 and added to 250 mL of a two-necked flask at -78 °C. 100 mL of tetrahydrofuran was added, and the mixture was reacted at -78 °C for 12 hours. After the reaction was complete, the mixture was heated to room temperature and then subjected to hydrolysis. The mixture was then poured into water, transferred to a 500 mL pear-shaped separatory funnel, and extracted with ethyl acetate. The organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation to obtain the crude product. The crude product was separated by silica gel mobile phase column chromatography using ethyl acetate / petroleum ether / triethylamine (1:5:0.01, v / v / v) to obtain colorless compound 3 (2,5-di(9-hexyl-9h-carbazole-2-yl)-1,4-phenyl-di(di(4-hexylphenyl)ol)).

[0050] Synthesis of Compound 4

[0051] Compound 3 (2,5-di(9-hexyl-9h-carbazole-2-yl)-1,4-phenyl-di(di(4-hexylphenyl)ol)) and Amberlyst 15 ion exchange resin were mixed in 50 mL of anisole at a molar ratio of 1:2 and added to a 100 mL round-bottom flask. The mixture was evacuated, purged with N2 three times, and then refluxed for 12 h. After the reaction was completed, the mixture was extracted with DCM, the organic phase was dried with MgSO4, and the crude product was obtained by rotary evaporation. The crude product was separated by silica gel mobile phase column chromatography with dichloromethane / petroleum ether (1:4, v / v) to obtain white compound 4 (5,14-dihexyl-8,8,17,17-tetra(4-hexylphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole).

[0052] Synthesis of Compound 5

[0053] Compound 4 (5,14-dihexyl-8,8,17,17-tetra(4-hexylphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole) and 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione were added to a 100 mL two-necked flask at a molar ratio of 1:2. The flask was evacuated and purged with N2 three times. 50 mL of tetrahydrofuran solvent was added, and the reaction was allowed to proceed at room temperature for 12 h. After cooling to room temperature, the mixture was washed with water, and then the reaction mixture was... The liquid was transferred into a pear-shaped separatory funnel, and the organic layer was extracted with CH2Cl2. The mixture was then dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation to obtain the crude product. The crude product was purified by chromatography on a silica gel column using CH2Cl2 / petroleum ether (1:8, v / v) as the eluent to obtain a light-colored solid compound 5 (2,11-dibromo-5,14-dihexyl-8,8,17,17-tetra(4-hexylphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole).

[0054] Synthesis of Compound 6

[0055] Compound 5 (2,11-dibromo-5,14-dihexyl-8,8,17,17-tetra(4-hexylphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole), bis(4-methoxyphenyl)amine, sodium tert-butoxide, tri-tert-butylphosphine tetrafluoroborate, and palladium acetate were added to a 50 mL two-necked round-bottom flask in a molar ratio of 1:2:3:0.2:0.3. The mixture was purged three times with N2, and 36 mL of anisole solvent was added. The mixture was then bubbled with N2 to remove oxygen for 15 min, and refluxed for 12 h. After cooling to room temperature, the mixture was rinsed with water, and then the reaction solution was transferred to a container... The organic layer was extracted with CH2Cl2 into a pear-shaped separatory funnel, dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation to obtain the crude product. The crude product was purified by chromatographic purification on a silica gel column using CH2Cl2 / petroleum ether (3:2, v / v) as the eluent to obtain a light-colored solid compound 6 (5,14-dihexyl-8,8,17,17-tetra(4-hexylphenyl)-N2,N2,N11,N11-tetra(4-methoxyphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole-2,11-diamine), i.e., Alk-DSF.

[0056] 1 H NMR (500MHz, C6D6) δ8.41 (s, 2H), 8.21 (s, 2H), 8.01 (d, J = 2.1Hz, 2H), 7.71 (s, 2H),7.55(d,J=8.3Hz,8H),7.36(dd,J=8.7,2.1Hz,2H),7.14–7.10(m,10H),6. 93(d,J=8.3Hz,8H),6.72–6.69(m,8H),3.82(t,J=7.1Hz,4H),3.30(s,12H),2 .44–2.38(m,8H),1.53–1.44(m,12H),1.22–1.07(m,36H),0.86–0.81(m,18H).

[0057] 1.2 Fabrication of Lead Sulfide Quantum Dot Solar Cells

[0058] Step 1: Prepare PbS-I quantum dot solids;

[0059] 8 mmol PbI₂ (3.688 mg) and 2 mmol (0.4526 mg) DPhTA were mixed and added to a nitrogen-filled glove box at room temperature and dissolved in 9 mL DMF with stirring. After the solid was completely dissolved in DMF (N,N-dimethylamide), 1 mL BTA (n-butylamine) was added. The solution immediately turned black. After reacting for 5 min, 50 mL toluene was added as an antisolvent, and the mixture was shaken and centrifuged at 8000 rpm for 5 min. The waste liquid was then poured out in the glove box, and the mixture was then placed in a vacuum chamber for 12 min. PbS-I quantum dot solids were finally obtained.

[0060] Step 2, pre-treat the transparent conductive substrate ITO;

[0061] The transparent conductive substrate ITO was ultrasonically cleaned sequentially with deionized water, acetone, and isopropanol for 30 minutes. The dried ITO substrate was then set aside for use. The transparent conductive substrate ITO was treated with oxygen plasma for 10 minutes to remove any remaining organic residues.

[0062] Step 3: In a fume hood, spin-coat the ZnO nano solution onto the pretreated transparent conductive substrate ITO at 5000 rpm for 20 seconds, and spin-coat two layers.

[0063] Step 4: After waiting for more than two hours following Step 3, prepare the PbS-I quantum dot solid in Step 1 using a mixed solution of N,N-dimethylformamide (DMF), acetonitrile (ACN), and dimethyl sulfoxide (DMSO) (volume ratio 10:10:1) to prepare a solution with a concentration of 600 mg / mL. -1 The solution was immediately centrifuged at 12,000 rpm for 1 min. Then it was spin-coated onto the ZnO layer from step 3 at 2,000 rpm for 40 s, followed by annealing at 70 °C for 15 min in a glove box.

[0064] Step 5: Prepare a 0.04% 1,2-ethylenedithiol solution (the solvent is a mixed solvent of ethyl acetate and acetonitrile = 1:2), then apply 20 mg / mL of the solution at 850 nm. -1 Lead sulfide quantum dots (preparation steps are the same as in step S1, but the obtained size and concentration are different) were spin-coated onto the functional layer of step 4 at 3000 rpm for 10 s. Then, the film was treated with 0.04% 1,2-ethylenedithiol solution and allowed to stand for 30 s. After that, it was spin-coated at 3000 rpm for 10 s. Then, the film was cleaned three times with a washing solution of ethyl acetate:acetonitrile = 1:2 (v / v) by spin-coating at 3000 rpm for 10 s.

[0065] Step 6: After placing the product from Step 4 in a drying oven for 12 hours, transfer it to a glove box and dissolve Alk-DSF in chlorobenzene (CB) to prepare a solution of 3 mg / mL. -1The solution was spin-coated onto the cavity layer from step 5 at 3000 rpm for 30 seconds. It was then annealed at 80°C for 10 minutes in a glove box.

[0066] Step 7, first use vacuum evaporation method to... 9nm MoO3 was deposited at a rate of [speed not specified], and then [further details not specified]. At a speed of 80 nm, Ag is deposited onto the top layer of the device as an electrode.

[0067] Example 2: Preparation of MeOP-DSF and Fabrication of Lead Sulfide Quantum Dot Solar Cells

[0068] 2.1 Preparation of MeOP-DSF

[0069] Synthesis of Compound 3

[0070] Compound 1, compound 2 (2,5-bis(9-(4-methoxyphenyl)-9h-carbazole-2-yl)diethyl terephthalate) and n-butyllithium were mixed in a molar ratio of 4:1:5 at -78°C and added to a 250 mL two-necked flask. 100 mL of tetrahydrofuran was added, and the mixture was reacted at -78°C for 12 hours. After the reaction was completed, the mixture was heated to room temperature and then subjected to hydrolysis. The mixture was then poured into water and transferred to a 500 mL pear-shaped separatory funnel for extraction with ethyl acetate. The organic phases were combined and dried over anhydrous magnesium sulfate. The solvent was removed by rotary evaporation to obtain the crude product. The crude product was separated by silica gel mobile phase column chromatography with ethyl acetate / petroleum ether / triethylamine (1:5:0.01, v / v / v) to obtain colorless compound 3 (2,5-bis(9-(4-methoxyphenyl)-9h-carbazole-2-yl)-1,4-phenyl-bis(bis(4-hexylphenyl)ol)).

[0071] Synthesis of Compound 4

[0072] Compound 3 (2,5-bis(9-(4-methoxyphenyl)-9h-carbazole-2-yl)-1,4-phenyl-bis(bis(4-hexylphenyl)ol)) and Amberlyst 15 ion exchange resin were mixed in 50 mL of anisole at a molar ratio of 1:2 and added to a 100 mL round-bottom flask. The mixture was evacuated, purged with N2 three times, and then refluxed for 12 h. After the reaction, the mixture was extracted with DCM, the organic phase was dried with MgSO4, and the crude product was obtained by rotary evaporation. The crude product was separated by silica gel mobile phase column chromatography with dichloromethane / petroleum ether (1:4, v / v) to obtain white compound 4 (5,14-bis(4-methoxyphenyl)-8,8,17,17-tetra(4-hexylphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole).

[0073] Synthesis of Compound 5

[0074] Compound 4 (5,14-di(4-methoxyphenyl)-8,8,17,17-tetra(4-hexylphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole) and 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione were added to a 100 mL two-necked flask at a molar ratio of 1:2. The flask was evacuated and purged with N2 three times. 50 mL of tetrahydrofuran solvent was added, and the reaction was carried out at room temperature for 12 h. After cooling to room temperature, the mixture was washed with water. The reaction solution was transferred into a pear-shaped separatory funnel, and the organic layer was extracted with CH2Cl2. The mixture was then dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation to obtain the crude product. The crude product was purified by chromatography on a silica gel column using CH2Cl2 / petroleum ether (1:8, v / v) as the eluent to obtain compound 5 (2,11-dibromo5,14-bis(4-methoxyphenyl)-8,8,17,17-tetra(4-hexylphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole).

[0075] Synthesis of Compound 6

[0076] Compound 5 (2,11-dibromo-5,14-bis(4-methoxyphenyl)-8,8,17,17-tetra(4-hexylphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole), bis(4-methoxyphenyl)amine, sodium tert-butoxide, tri-tert-butylphosphine tetrafluoroborate, and palladium acetate were added to a 50 mL two-necked round-bottom flask in a molar ratio of 1:2:3:0.2:0.3. The mixture was purged three times with N2, and 36 mL of anisole solvent was added. The mixture was then bubbled with N2 to remove oxygen for 15 min, and refluxed for 12 h. After cooling to room temperature, the mixture was rinsed with water, and then the reaction solution was transferred to… The organic layer was extracted with CH2Cl2 in a pear-shaped separatory funnel, dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation to obtain the crude product. The crude product was purified by chromatographic purification on a silica gel column using CH2Cl2 / petroleum ether (3:2, v / v) as the eluent to obtain a light-colored solid compound 6 (5,14-bis(4-methoxyphenyl)-8,8,17,17-tetra(4-hexylphenyl)-N2,N2,N11,N11-tetra(4-methoxyphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole-2,11-diamine), i.e., MeOP-DSF.

[0077] 1H NMR(500MHz,C6D6)δ8.19(d,J=10.7Hz,4H),8.00(d,J=2.0Hz,2H),7.79(s,2H ),7.42(d,J=8.3Hz,8H),7.26(dd,J=8.7,2.1Hz,2H),7.14(s,2H),7.13–7.09 (m,12H),6.86(d,J=8.3Hz,8H),6.74–6.68(m,12H),3.29(s,12H),3.26(s,6H ),2.43–2.36(m,8H),1.45(m,8H),1.23–1.13(m,24H),0.83(t,J=7.0Hz,12H).

[0078] 2.2 Fabrication of Lead Sulfide Quantum Dot Solar Cells

[0079] Step 1: Prepare PbS-I quantum dot solids;

[0080] 8 mmol PbI₂ (3.688 mg) and 2 mmol (0.4526 mg) DPhTA were mixed and added to a nitrogen-filled glove box at room temperature and dissolved in 9 mL DMF with stirring. After the solid was completely dissolved in DMF (N,N-dimethylamide), 1 mL BTA (n-butylamine) was added. The solution immediately turned black. After reacting for 5 min, 50 mL toluene was added as an antisolvent, and the mixture was shaken and centrifuged at 8000 rpm for 5 min. The waste liquid was then poured out in the glove box, and the mixture was then placed in a vacuum chamber for 12 min. PbS-I quantum dot solids were finally obtained.

[0081] Step 2, pre-treat the transparent conductive substrate ITO;

[0082] The transparent conductive substrate ITO was ultrasonically cleaned sequentially with deionized water, acetone, and isopropanol for 30 minutes. The dried ITO substrate was then set aside for use. The transparent conductive substrate ITO was treated with oxygen plasma for 10 minutes to remove any remaining organic residues.

[0083] Step 3: In a fume hood, spin-coat the ZnO nano solution onto the pretreated transparent conductive substrate ITO at 5000 rpm for 20 seconds, and spin-coat two layers.

[0084] Step 4: After waiting for more than two hours following Step 3, prepare the PbS-I quantum dot solid in Step 1 using a mixed solution of N,N-dimethylformamide (DMF), acetonitrile (ACN), and dimethyl sulfoxide (DMSO) (volume ratio 10:10:1) to prepare a solution with a concentration of 600 mg / mL. -1The solution was immediately centrifuged at 12,000 rpm for 1 min. Then it was spin-coated onto the ZnO layer from step 3 at 2,000 rpm for 40 s, followed by annealing at 70 °C for 15 min in a glove box.

[0085] Step 5: Prepare a 0.04% 1,2-ethylenedithiol solution (the solvent is a mixed solvent of ethyl acetate and acetonitrile = 1:2), then apply 20 mg / mL of the solution at 850 nm. -1 Lead sulfide quantum dots (preparation steps are the same as in step S1, but the obtained size and concentration are different) were spin-coated onto the functional layer of step 4 at 3000 rpm for 10 s. Then, the film was treated with 0.04% 1,2-ethylenedithiol solution and allowed to stand for 30 s. After that, it was spin-coated at 3000 rpm for 10 s. Then, the film was cleaned three times with a washing solution of ethyl acetate:acetonitrile = 1:2 (v / v) by spin-coating at 3000 rpm for 10 s.

[0086] Step 6: After placing the product from Step 4 in a drying oven for 12 hours, transfer it to a glove box and dissolve the MeOP-DSF in chlorobenzene (CB) to prepare a solution of 3 mg / mL. -1 The solution was spin-coated onto the cavity layer from step 5 at 3000 rpm for 30 seconds. It was then annealed at 80°C for 10 minutes in a glove box.

[0087] Step 7, first use vacuum evaporation method to... 9nm MoO3 was deposited at a rate of [speed not specified], and then [further details not specified]. At a speed of 80 nm, Ag is deposited onto the top layer of the device as an electrode.

[0088] Comparative Example 1

[0089] The comparative preparation of lead sulfide quantum dot solar cells follows essentially the same steps as the examples, except for the spin-coating preparation of the 1,2-ethylenedithiol hole layer in step 5, and the absence of step 6. The specific steps are as follows: First, a 0.02% (v / v) 1,2-ethylenedithiol solution with a volume ratio of ethyl acetate:acetonitrile = 1:2 is prepared. Then, 20 mg / mL of 850 nm... -1 Lead sulfide quantum dots were spin-coated onto the ZnO layer in step 4 at 3000 rpm for 10 s, then treated with 0.02% 1,2-ethylenedithiol solution and allowed to stand for 30 s. Afterward, the coating was spin-coated at 3000 rpm for 10 s, followed by three washes with a washing solution of ethyl acetate:acetonitrile (volume ratio 1:2) at 3000 rpm for 10 s each time. Steps 1-4 and 7 were the same as in the example.

[0090] like Figure 1 As shown, the lead sulfide quantum dot solar cell structure is ITO / ZnO / PbS-I / PbS-EDT / Alk-DSFor MeOP-DSF / MoO3 / Ag, corresponding to Example 1 and Example 2, respectively.

[0091] Figure 2 This is a diagram showing the energy level arrangement of a lead sulfide quantum dot solar cell based on a hybrid hole transport layer of 1,2-ethanedithiol and dihydroindendrofluorene conjugated organic small molecule Alk-DSF or MeOP-DSF hole transport materials, as described in this invention. As shown in the diagram, the introduction of the organic small molecule functional material Alk-DSF or MeOP-DSF forms a quantum dot / organic material heterojunction in the hybrid hole transport material, enhancing the internal electric field and interface charge extraction of the device.

[0092] Figure 3 The figure shows the JV curves of the lead sulfide quantum dot solar cells prepared in the comparative and exemplary embodiments of this invention. As can be seen from the figure, the perovskite solar cells based on EDT / Alk-DSF and MeOP-DSF hole transport materials prepared in the exemplary embodiments achieved PCEs of 9.3% and 11.1%, respectively. Clearly, the presence of benzyl groups in MeOP-DSF corrects the HOMO, reduces energy level loss, and forms a hybrid hole transport material more conducive to charge transport, resulting in a quantum dot / organic material heterojunction and higher efficiency. In contrast, the comparative embodiment using EDT as the hole transport layer only achieved a PCE of 7.4%.

[0093] Figure 4 The figures show the IPCE curves of the lead sulfide quantum dot solar cells prepared in the examples and comparative examples. As can be seen from the figures, the monochromatic light response values ​​of the lead sulfide quantum dot perovskite solar cells based on EDT / Alk-DSF and MeOP-DSF hole transport materials prepared in the examples are both higher than those of the comparative examples, achieving 26.2 mA / cm² after integration. -2 and 28.4mAcm -2 The photocurrent density was significantly higher than that of the EDT-based cell, which, when used as the hole transport layer, only achieved 24.1 mA / cm². -2 Photocurrent density, and Figure 3 The photocurrent obtained from the JV curve test is consistent with that of the photocurrent, which further verifies that the presence of benzyl groups in MeOP-DSF corrects the HOMO and reduces energy level loss, forming a hybrid hole transport material that is more conducive to charge transport. This results in the formation of a quantum dot / organic material heterojunction and higher efficiency.

[0094] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any modifications or substitutions that can be conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A dihydroindofluorene conjugated organic small molecule hole transport material, characterized in that, The hole transport material uses triphenylamine carbazole as the terminal group and long carbon chain and anisole as the side chain terminal modification groups, respectively. The chemical names are 5,14-dihexyl-8,8,17,17-tetra(4-hexylphenyl)-N2,N2,N11,N11-tetra(4-methoxyphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole-2,11-diamine, abbreviated as ALK-DSF, and the chemical formula is shown in formula (1). Or 5,14-bis(4-methoxyphenyl)-8,8,17,17-tetra(4-hexylphenyl)-N2,N2,N11,N11-tetra(4-methoxyphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole-2,11-diamine, abbreviated as MeOP-DSF, with the chemical formula shown in formula (2); 2. The preparation method of the dihydroindendrofluorene conjugated organic small molecule hole transport material according to claim 1, characterized in that, The synthesis route is shown below: Where R = C6H 13 or 3. The method for preparing the dihydroindendrofluorene conjugated organic small molecule hole transport material according to claim 2, characterized in that, When R = C6H 13 The specific preparation method is as follows: Step 1: 1-Bromo-4-hexylbenzene, diethyl 2,5-bis(9-hexyl-9h-carbazole-2-yl)terephthalate and n-butyllithium were mixed in a molar ratio of 4:1:5 and added to a two-necked flask at -78°C. Tetrahydrofuran was added, and the mixture was reacted at -78°C for 12 hours. After the reaction was completed, the mixture was heated to room temperature and then subjected to hydrolysis. The mixture was then extracted with ethyl acetate in water, the organic phases were combined, dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation to obtain the crude product. The crude product was separated by silica gel mobile phase chromatography using a mixed solution of ethyl acetate, petroleum ether, and triethylamine as the eluent to obtain compound 2,5-bis(9-hexyl-9h-carbazole-2-yl)-1,4-phenyl-bis(bis(4-hexylphenyl)ol). Step 2: The compound obtained in Step 1 and Amberlyst 15 ion exchange resin were mixed in anisole at a molar ratio of 1:2 and added to a round-bottom flask. The flask was evacuated, purged with N2 three times, and then refluxed for 12 hours. After the reaction was completed, the mixture was extracted with DCM, the organic phase was dried with MgSO4, and the crude product was obtained by rotary evaporation. The crude product was separated by silica gel mobile phase column chromatography using a mixed solution of dichloromethane and petroleum ether as eluent to obtain compound 5,14-dihexyl-8,8,17,17-tetra(4-hexylphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole. Step 3: The compound obtained in Step 2 and 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione were added to a two-necked flask at a molar ratio of 1:

2. The flask was evacuated and purged with N2 three times. Tetrahydrofuran solvent was added, and the mixture was reacted at room temperature for 12 hours. After the reaction was completed, the organic layer was extracted with CH2Cl2, dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation to obtain the crude product. The crude product was purified by chromatography on a silica gel column using a mixture of CH2Cl2 and petroleum ether as the eluent to obtain compound 2,11-dibromo-5,14-dihexyl-8,8,17,17-tetra(4-hexylphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole. Step 4: The compound obtained in Step 3, bis(4-methoxyphenyl)amine, sodium tert-butoxide, tri-tert-butylphosphine tetrafluoroborate, and palladium acetate were added to a two-necked round-bottom flask in a molar ratio of 1:2:3:0.2:0.

3. The mixture was purged with N2 three times, and anisole solvent was added. The mixture was then bubbled with N2 to remove oxygen for 15 min, and refluxed for 12 h. After cooling to room temperature, the mixture was rinsed with water, and the organic layer was extracted with CH2Cl2. The residue was then dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The crude product was obtained by eluenting with a mixture of CH2Cl2 and petroleum ether and purified by chromatography on a silica gel column to obtain compound 5,14-dihexyl-8,8,17,17-tetra(4-hexylphenyl)-N2,N2,N11,N11-tetra(4-methoxyphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole-2,11-diamine, i.e., Alk-DSF.

4. The method for preparing the dihydroindendrofluorene conjugated organic small molecule hole transport material according to claim 2, characterized in that, when The specific preparation method is as follows: Step (1): 1-Bromo-4-hexylbenzene, 2,5-bis(9-(4-methoxyphenyl)-9h-carbazole-2-yl)terephthalate and n-butyllithium were mixed in a molar ratio of 4:1:5 and added to a two-necked flask at -78°C. Tetrahydrofuran was added, and the mixture was reacted at -78°C for 12 hours. After the reaction was completed, the mixture was heated to room temperature and then hydrolyzed. The mixture was then extracted with ethyl acetate in water. The organic phases were combined and dried with anhydrous magnesium sulfate. The solvent was removed by rotary evaporation to obtain the crude product. The crude product was separated by silica gel mobile phase chromatography using a mixed solution of ethyl acetate, petroleum ether, and triethylamine as eluent to obtain compound 2,5-bis(9-(4-methoxyphenyl)-9h-carbazole-2-yl)-1,4-phenyl-bis(bis(4-hexylphenyl)ol). Step (2): The compound obtained in step (1) and Amberlyst 15 ion exchange resin were mixed in anisole at a molar ratio of 1:2 and added to a round-bottom flask. The flask was evacuated, purged with N2 three times, and then refluxed for 12 hours. After the reaction was completed, the mixture was extracted with DCM, the organic phase was dried with MgSO4, and the crude product was obtained by rotary evaporation. The crude product was separated by silica gel mobile phase column chromatography using a mixed solution of dichloromethane and petroleum ether as the eluent to obtain compound 5,14-bis(4-methoxyphenyl)-8,8,17,17-tetra(4-hexylphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole. Step (3): The compound obtained in step (2) and 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione were added to a two-necked flask at a molar ratio of 1:

2. The flask was evacuated and purged with N2 three times. Tetrahydrofuran solvent was added, and the mixture was reacted at room temperature for 12 hours. After the reaction was completed, the organic layer was extracted with CH2Cl2, dried with anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation to obtain the crude product. The crude product was purified by chromatography on a silica gel column using a mixed solution of CH2Cl2 and petroleum ether as the eluent to obtain the compound 2,11-dibromo-5,14-di(4-methoxyphenyl)-8,8,17,17-tetra(4-hexylphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole. Step (4): The compound obtained in step (3), bis(4-methoxyphenyl)amine, sodium tert-butoxide, tritert-butylphosphine tetrafluoroborate, and palladium acetate were added to a two-necked round-bottom flask in a molar ratio of 1:2:3:0.2:0.

3. The mixture was purged with N2 three times, anisole solvent was added, and then N2 was bubbled to remove oxygen for 15 min. The mixture was then refluxed for 12 h. After cooling to room temperature, the mixture was rinsed with water, the organic layer was extracted with CH2Cl2, dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation to obtain the final product. The crude product was purified by chromatographic analysis on a silica gel column using a mixed solution of CH2Cl2 and petroleum ether as the eluent to obtain compound 5,14-bis(4-methoxyphenyl)-8,8,17,17-tetra(4-hexylphenyl)-N2,N2,N11,N11-tetra(4-methoxyphenyl)-5,8,14,17-tetrahydro-s-indeno[1,2-b:5,6-b']dicarbazole-2,11-diamine, i.e., MeOP-DSF.

5. The method for preparing the dihydroindendrofluorene conjugated organic small molecule hole transport material according to claim 3 or 4, characterized in that, In steps 1 and (1), the volume ratio of ethyl acetate, petroleum ether, and triethylamine in the mixed solution is 1:5:0.

01.

6. The method for preparing the dihydroindendrofluorene conjugated organic small molecule hole transport material according to claim 3 or 4, characterized in that, In steps 2 and (2), the volume ratio of dichloromethane to petroleum ether in the mixed solution is 1:

4.

7. The method for preparing the dihydroindendrofluorene conjugated organic small molecule hole transport material according to claim 3 or 4, characterized in that, In steps 3 and (3), the volume ratio of CH2Cl2 to petroleum ether in the mixed solution is 1:

8.

8. The method for preparing the dihydroindendrofluorene conjugated organic small molecule hole transport material according to claim 3 or 4, characterized in that, In step 4 or step (4), the volume ratio of CH2Cl2 to petroleum ether in the mixed solution is 3:

2.

9. The application of the dihydroindofluorene conjugated organic small molecule hole transport material according to claim 1 in quantum dot solar cells.

10. The application according to claim 9, characterized in that, The specific application is as follows: Step S1: Prepare PbS-I quantum dot solids; Step S2: Pre-treat the transparent conductive substrate ITO; Step S3: In a fume hood, spin-coat the ZnO nano solution onto the pretreated transparent conductive substrate ITO at 5000 rpm for 20 seconds, and spin-coat two layers. Step S4: After waiting for more than two hours following step S3, prepare the PbS-I quantum dot solid in step 1 using a mixed solution of N,N-dimethylformamide, acetonitrile, and dimethyl sulfoxide to obtain a concentration of 600 mg / mL. -1 The solution was immediately centrifuged at 12000 rpm for 1 min, then spin-coated at 2000 rpm onto the ZnO layer from step 3 for 40 s, and then annealed at 70 °C for 15 min in a glove box. Step S5: Prepare a 0.04% 1,2-ethylenedithiol solution using a mixed solution of diethyl acetate and acetonitrile in a volume ratio of 1:

2. Then, apply 20 mg / mL of 850 nm solution. -1 Lead sulfide quantum dots were spin-coated onto the functional layer of step 4 at 3000 rpm for 10 s, then treated with 0.04% 1,2-ethanedithiol solution and left to stand for 30 s. After that, they were spin-coated at 3000 rpm for 10 s. The film was then cleaned three times with a washing solution of ethyl acetate:acetonitrile = 1:2 by spin-coating at 3000 rpm for 10 s. Step S6: After placing the product from step S4 in a drying oven for 12 hours, transfer it to a glove box and dissolve Alk-DSF or MeOP-DSF in chlorobenzene to prepare a solution of 3 mg / mL. -1 The solution was spin-coated onto the cavity layer in step 5 at 3000 rpm for 30 seconds, and then annealed at 80°C for 10 minutes in a glove box. Step S7, first using vacuum evaporation method... 9nm MoO3 was deposited at a rate of [speed not specified], and then [further details not specified]. At a speed of 80 nm, Ag is deposited onto the top layer of the device as an electrode.

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