Spirocyclic aromatic hydrocarbon phosphonic acid derivative containing cross structure, preparation method and application of spirocyclic aromatic hydrocarbon phosphonic acid derivative in photoelectric device

Abstract

The invention discloses a spirocyclic aromatic hydrocarbon phosphonic acid derivative containing a cross structure, a preparation method and application of the spirocyclic aromatic hydrocarbon phosphonic acid derivative in a photoelectric device. The spirocyclic aromatic hydrocarbon phosphonic acid derivative takes a unique cross pi conjugate plane aromatic ring element as a parent nucleus and alkyl phosphonic acid as an anchoring group; the method has the advantages of simple synthesis steps, mild synthesis conditions, high hole extraction speed, good physical and chemical stability and the like; therefore, the hole selective contact layer can be used as an efficient and stable hole selective contact layer to be applied to a single-junction perovskite solar cell, an organic solar cell, a laminated solar cell, a perovskite light-emitting diode, an organic light-emitting diode, a perovskite photoelectric detector and an organic photoelectric detector.

Description

Technical Field

[0001] The invention belongs to the technical field of optoelectronic materials and devices, and in particular relates to a spiroaromatic phosphonic acid derivative containing a cross structure, a preparation method and application thereof in optoelectronic devices. Background Art

[0002] Perovskite and organic materials have unique advantages such as low cost, strong radiation resistance, high photosensitivity, light weight, good flexibility and high photoelectric conversion efficiency. Solar cells, light-emitting diodes and photodetectors have a wide range of application scenarios. Taking perovskite solar cells as an example, perovskite solar cells contain traditional formal (nip) structures and trans (pin) PSCs structures. Due to the absence of harmful doping, the top electron transport layer and the bottom hole selection contact layer are more stable. The improved stability, good device scalability, and easy integration of series applications make pin solar cells attractive in practical applications. However, the photoelectric conversion efficiency (PCE) of single-junction pin solar cells has long lagged behind that of their nip structure counterparts. This performance gap is mainly caused by the larger open circuit voltage (V OC ) loss, while the open circuit voltage loss is caused by the non-radiative recombination process inside the perovskite absorber layer and at the interface with the charge transport layer. The emergence of the hole-selective contact layer paves the way for inverted PSCs, achieving revolutionary progress in single-junction inverted PSCs and tandem PSCs.

[0003] Hole-selective contacts (MSCs) have emerged as a key factor in achieving high power conversion efficiency (PCE) in perovskite solar cells. The organic molecules used to construct such contacts are usually composed of oxoacid groups connected by π-conjugated cores. When assembled at the interface between the perovskite absorber layer and the transparent conducting electrode, such molecular layers enable efficient selective carrier transport. The extended π-electron delocalization provided by the conjugated tail functional groups is crucial to ensure efficient carrier transport, and the extended conjugation ensures the orderly stacking of molecules through π-π interactions, which is widely believed to be beneficial for carrier transport in the field of organic electronics. However, this orderly arrangement of these molecules, or crystallized organic structure, makes them prone to phase transition or structural collapse when exposed to external stimuli such as thermal and mechanical stress. The transformed or deformed interface structure may lose the ability to ensure efficient carrier transport, leading to a decrease in PCE and ultimately limiting the long-term durability of perovskite solar cells (Jiang, Q.; Tirawat, R.; Kerner, R. A.; Gaulding, E. A.; Xian, Y.; Wang, X.; Newkirk, J. M.; Yan, Y.; Berry, J. J.; Zhu, K., Towards linking lab and field lifetimes of perovskite solar cells cells.Nature,2023,623,313-318.), and this problem exists in organic solar cells, tandem solar cells (including perovskite-crystalline silicon tandem cells, all-perovskite tandem cells, perovskite-Cu(InGa)Se2(CIGS) tandem cells and perovskite-organic (OPV) tandem cells), perovskite / organic light-emitting diodes and perovskite / organic photodetectors. At present, there is an urgent need to design and synthesize a new class of molecules to replace the traditional hole-selective contact layer, so as to take into account both structural durability and carrier selectivity and transport. Summary of the invention

[0004] In view of the shortcomings of the prior art, the present invention proposes a spiroaromatic hydrocarbon phosphonic acid derivative containing a cross structure, a preparation method and an application thereof in optoelectronic devices. The spiroaromatic hydrocarbon phosphonic acid derivative uses a unique cross-shaped π-conjugated planar aromatic ring motif as a parent core and an alkyl phosphonic acid as an anchoring group. The spiroaromatic hydrocarbon phosphonic acid derivative has the advantages of simple synthesis steps, mild synthesis conditions, fast hole extraction speed, good physical and chemical stability, etc., so that it can be used as an efficient and stable hole-selective contact layer in single-junction perovskite solar cells, organic solar cells, tandem solar cells (including perovskite-crystalline silicon tandem cells, all-perovskite tandem cells, perovskite-Cu(InGa)Se2 tandem cells and perovskite-organic tandem cells), perovskite light-emitting diodes, organic light-emitting diodes, perovskite photodetectors and organic photodetectors.

[0005] The design concept of the spiroaromatic hydrocarbon phosphonic acid derivatives of the present invention is that the polycyclic aromatic ring unit of the cross-π conjugated plane is the mother core, and the upper and lower rings of the spiroaromatic hydrocarbon can be modified with substituents with different inductive effects to adjust the charge density of the molecule, thereby adjusting the energy level of the hole transport material; different heteroatoms can also be introduced into the upper ring of the spiroaromatic hydrocarbon, which can adjust the energy level and the interaction with the upper perovskite; more importantly, the cross-π conjugated plane produces a highly disordered molecular layer structure. Compared with the crystalline ordered film formed by traditional planar conjugated molecules, this type of highly disordered molecular film has better stability under external stimulation conditions (thermal aging and mechanical aging, etc.), and uses alkyl phosphonic acid as the anchoring group.

[0006] The purpose of the present invention is achieved through the following technical solutions:

[0007] A spiroaromatic phosphonic acid derivative containing a cross structure, the structure of which is as follows:

[0008]

[0009]

[0010] In formula (I-1) and formula (I-2), n is an integer of 1 to 6, and R is selected from any one of a halogen atom, an alkyl group, an alkoxy group, an alkoxy group substituted with a substituent, an aryl group, and an aryl group substituted with a substituent;

[0011] In formula (I-2), X is selected from any one of an oxygen atom, a sulfur atom, a selenium atom, a carbonyl group, a sulfinyl group, a sulfyl group, and a thiocarbonyl group.

[0012] Preferably, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom;

[0013] The alkyl group is a C1-C20 alkyl group;

[0014] The alkoxy group is a C1-C20 alkoxy group;

[0015] The substituents in the substituted aryl and the substituted alkoxy are selected from any one of methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, methoxy, ethoxy, propoxy, methylthio, ethylthio, propylthio, hydroxyl, carboxyl and thiol.

[0016] Preferably, the spiroaromatic phosphonic acid derivative containing a cross structure is Me-SAF, SAF, Br-SAF, Br-U-SAF, SAX, SAT, SAA, and the structural formulas are shown below:

[0017]

[0018] A method for preparing a spiroaromatic phosphonic acid derivative containing a cross structure, the method comprising the following steps:

[0019] Step 1: Under an inert gas atmosphere, compound 1 and dibromide are mixed at a molar ratio of 1:20, and tetrabutylammonium bromide and potassium hydroxide aqueous solution are added to allow the compound 1 to react with the dibromide to obtain compound 2;

[0020] Step 2: Under an inert gas atmosphere, the compound 2 is reacted with triethyl phosphite at a molar ratio of 1:20 to obtain compound 3;

[0021] Step 3: Under an inert gas atmosphere, the compound 3 is dissolved in 1,4-dioxane, and trimethylsilyl bromide is added, and the mixture is stirred until the spiroaromatic hydrocarbon phosphonate derivative is completely reacted; then, the 1,4-dioxane is evaporated under reduced pressure, and the residue is dissolved in methanol, and distilled water is added until the solution becomes white and opaque, and stirring is continued until the impurities are dissolved in the methanol; finally, the product is filtered out, washed with water, and vacuum dried to obtain a spiroaromatic hydrocarbon phosphonic acid derivative containing a cross structure;

[0022] The compound 1 is a spiroaromatic hydrocarbon raw material, and its structural formula is:

[0023]

[0024]

[0025] In formula (a) and formula (b), R is selected from any one of a halogen atom, an alkyl group, an alkoxy group, an alkoxy group substituted with a substituent, an aryl group, and an aryl group substituted with a substituent;

[0026] In formula (b), X is selected from any one of an oxygen atom, a sulfur atom, a selenium atom, a carbonyl group, a sulfinyl group, a sulfyl group, and a thiocarbonyl group;

[0027] The dibromide structural formula is Wherein, n is an integer from 1 to 6;

[0028] The structural formula of the compound 2 is

[0029] The structural formula of the compound three is

[0030] Preferably, the potassium hydroxide aqueous solution is a potassium hydroxide aqueous solution with a mass ratio of 50%, the reaction temperature of the compound 1 and the dibromide is 120° C., and the reaction time is 24 hours.

[0031] Preferably, the reaction temperature of the compound 2 and triethyl phosphite is 165° C., and the reaction time is 24 h.

[0032] Application of a spiroaromatic phosphonic acid derivative containing a cross structure in optoelectronic devices.

[0033] Further, the optoelectronic device is a single-junction perovskite solar cell, an organic solar cell, a tandem solar cell, a perovskite light-emitting diode, an organic light-emitting diode, a perovskite photodetector or an organic photodetector;

[0034] The stacked solar cell is a perovskite-crystalline silicon stacked cell, a full perovskite stacked cell, a perovskite-Cu(InGa)Se2 stacked cell or a perovskite-organic stacked cell.

[0035] Furthermore, the single-junction perovskite solar cell, organic solar cell, and stacked solar cell all include a conductive substrate, a hole selective contact layer, a perovskite light absorption layer, an electron transport layer, a modification layer, and a top electrode, wherein the hole selective contact layer is made of a spiroaromatic phosphonic acid derivative containing a cross-structure; the light absorption layer is prepared using any one of tin-based perovskite, lead-based perovskite, tin-lead perovskite, and organic materials by spin coating, blade coating, slit coating, screen printing, spraying, ink printing, roll-to-roll processing, or evaporation.

[0036] Furthermore, both the perovskite light-emitting diode and the organic light-emitting diode include a conductive substrate, a hole selective contact layer, a light-emitting layer, an electron transport layer, a modification layer and a top electrode, wherein the hole selective contact layer is made of a spiroaromatic phosphonic acid derivative containing a cross-structure; the light-emitting layer is prepared using any one of tin-based perovskite, lead-based perovskite, tin-lead perovskite and organic materials by spin coating, blade coating, slit coating, screen printing, spraying, ink printing, roll-to-roll process or evaporation.

[0037] Furthermore, the conductive substrates of the solar cell and the light-emitting diode are selected from any one of ITO, FTO, AZO, IZO, Si and CIGS; the electron transport layers of the solar cell and the light-emitting diode are made of C 60 , C 70 、PC 61 BM, PC 71 Any one of BM, TiO2, ZnO or SnO2 is prepared by methods such as spin coating, scraper coating, evaporation, atomic deposition or magnetron sputtering; the top electrodes of the solar cells and light-emitting diodes are selected from any one of Ag, Cu, Au, Al, Cr, ITO, IZO, FTO, AZO or C electrodes, and are prepared by methods such as scraper coating, slit coating, screen printing, thermal evaporation, atomic deposition or magnetron sputtering.

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] (1) The cross-structured spiroaromatic phosphonic acid derivatives provided by the present invention have cross-shaped π conjugated planes that produce a highly disordered molecular layer structure. Compared with the crystalline ordered films formed by traditional planar conjugated molecular materials, this type of highly disordered molecular film has better stability under external stimulation conditions (thermal aging and mechanical aging, etc.).

[0040] (2) The high operational stability of the cross-structured spiroaromatic hydrocarbon phosphonic acid derivatives provided by the present invention enables the spiroaromatic hydrocarbon phosphonic acid derivatives to be used in various perovskite or organic optoelectronic devices, thereby increasing the charge extraction rate, reducing the overall series resistance of the device, and improving the photoelectric conversion efficiency of the optoelectronic device. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 This is a cross-sectional SEM image of the perovskite-based solar cell prepared based on SAX in Example 1.

[0042] Figure 2 This is a comparison chart of the JV curves of SAX-based perovskite-based solar cells in Application Example 1.

[0043] Figure 3 This is a comparison chart of the JV curves of SAF-based perovskite-based solar cells in Application Example 2.

[0044] Figure 4 This is a comparison chart of the JV curves of the 4PACz-based perovskite solar cells in Comparative Example 1. DETAILED DESCRIPTION

[0045] The present invention will be described in detail below based on the accompanying drawings and preferred embodiments, and the purpose and effects of the present invention will become more clear. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0046] Example 1 Synthesis of SAF

[0047]

[0048] (1) Synthesis of intermediate A1

[0049] 10H-spiro[aza-9,9'-fluorene] (1.7 g, 5.0 mmol) was dissolved in 1,4-dibromobutane (20.0 eq, 21.6 g, 11.9 mL, 100.0 mmol), followed by the addition of tetrabutylammonium bromide (0.2 eq, 322 mg, 1.0 mmol) and 50% aqueous potassium hydroxide solution (5 eq). The reaction was stirred overnight at 120 ° C. After the reaction was completed, it was extracted with dichloromethane. The combined organic phase was dried over anhydrous sodium sulfate and the solvent was removed by vacuum rotary evaporation. The crude product was purified by column chromatography (petroleum ether: dichloromethane = 5: 1, volume ratio) to obtain 2.1 g (92%) of white powder.

[0050] 1 H NMR (500MHz, CDCl3) δ7.75(d,J=7.5Hz,2H),7.33(td,J=7.0,1.0Hz,2H),7.26(d,J=7.5Hz,2H),7.19–7.14(m,4H),7.03(dd,J=8.5 ,1.0Hz,2H),6.60(td,J=8.0,1.0Hz,2H),6.41(dd,J=7.5,1.5Hz,2H),4.09–4.06(m,2H),3.57-3.55(m,2H),2.14(t,J=3.5Hz,4H).

[0051] 13 C NMR (126MHz, CDCl3) δ153.22,137.74,136.73,125.80,125.32,125.21,125.11 ,124.30,123.12,117.88,117.43,109.99,54.63,42.92,30.54,27.82,21.95.

[0052] HRMS-ESI(m / z):[M+H] + Calcd.for(C 29 H 25 BrN):466.1125, found 466.1170.

[0053] (2) Synthesis of intermediate A2

[0054] Under nitrogen atmosphere, 10-(4-bromobutyl)-10H-spiro[acridine-9,9'-fluorene] (933 mg, 2.0 mmol) was dissolved in triethyl phosphite (20.0 eq, 6.7 g, 6.8 mL, 40.0 mmol), and the reaction mixture was heated at 165 ° C for 24 h. After the reaction was completed, the solvent was removed by vacuum rotary evaporation. The crude product was purified by column chromatography (petroleum ether: ethyl acetate = 1: 1, volume ratio) to obtain 890 mg (85%) of a white oily liquid.

[0055] 1 H NMR(500MHz, CDCl3)δ7.75(d,J=7.5Hz,2H),7.35–7.31(m,2H),7.27–7.25(m,2H),7.20–7.14(m,4H),7.01(dd,J=8.0,1.0Hz,2H),6.59(td,J=7 .5,1.0Hz,2H),6.41(dd,J=7.5,1.5Hz,2H),4.18-4.14(m,4H),4.08–4. 05(m,2H),2.11–2.05(m,2H),1.95–1.89(m,4H),1.37(t,J=7.0Hz,6H).

[0056] 13 C NMR (126MHz, CDCl3) δ155.66,140.22,139.16,128.22,127.72,127.63,127.53,12 6.72,125.56,120.26,119.84,112.42,61.69,57.06,45.78,26.58,20.32,16.56.

[0057] 31 P NMR (203MHz,CDCl3)δ31.54.

[0058] HRMS-ESI(m / z):[M+H] + Calcd.for(C 33 H 35 NO3P):524.2355, found 524.2382.

[0059] (3) Synthesis of compound SAF

[0060] Under nitrogen atmosphere, diethyl (4-(10H-spiro[acridine-9,9'-fluorene]-10-yl)butyl)phosphonate (524mg, 1.0mmol) was dissolved in 1,4-dioxane (20.0mL), and trimethylsilyl bromide (10.0eq, 1.5g 1.3mL, 10.0mmol) was added dropwise. The mixture was stirred for 24 hours, after which the solvent was evaporated under reduced pressure, and the residue was dissolved in methanol (20.0mL), and distilled water was added dropwise until the solution became white and opaque, and stirring was continued for 24h. The product was filtered out, washed with water, and dried to obtain 470mg (80%) of a white solid.

[0061] 1 H NMR(500MHz,DMSO-d6)δ7.92(d,J=7.5Hz,2H),7.38(td,J=7.0,1.5Hz,2H),7.25–7.16(m,8H),6.59(td, J=7.5,1.5Hz,2H),6.22(dd,J=4.0,1.0Hz,2H),4.10-4.07(m,1H),1.98-1.93(m,2H),1.82-1.69(m,4H).

[0062] 13 C NMR (126MHz, DMSO-d6) δ154.43,139.37,137.98,127.74,127.32,127.14,125.89,125. 32,124.51,119.69,119.28,112.57,55.98,44.49,27.25,26.16,25.45,25.34,19.76.

[0063] 31 P NMR (203 MHz, DMSO-d6) δ 26.35.

[0064] HRMS-ESI(m / z):[M+H] + Calcd.for(C 29 H 27 NO3P):468.1729, found 468.1728.

[0065] Example 2 Synthesis of Me-SAF

[0066]

[0067] (1) Synthesis of intermediate A3

[0068] A3 2,7-dimethyl-10H-spiro[acridine-9,9'-fluorene] (1.8 g, 5.0 mmol) was dissolved in 1,4-dibromobutane (20.0 eq, 21.6 g, 11.9 mL, 100.0 mmol), followed by the addition of tetrabutylammonium bromide (0.2 eq, 322 mg, 1.0 mmol) and 50% aqueous potassium hydroxide solution (5.0 eq). The reaction was stirred at 120 ° C overnight. After the reaction was completed, it was extracted with dichloromethane. The combined organic phases were dried over anhydrous sodium sulfate and the solvent was removed by vacuum rotary evaporation. The crude product was purified by column chromatography (petroleum ether: dichloromethane = 5:1, volume ratio) to obtain 2.2 g (90%) of white powder.

[0069] 1 H NMR(500MHz, CDCl3)δ7.77(d,J=7.5Hz,2H),7.36–7.33(m,2H),7.26-7.25(m,4H),7.19(td,J=7.5,1.0Hz ,2H),6.97–6.92(m,4H),6.17(s,2H),4.05(s,2H),3.58(d,J=6.0Hz,2H),2.14-2.12(m,4H),1.99(s,3H).

[0070] 13 C NMR (126MHz, CDCl3) δ150.31,139.17,128.23,128.23,127.42,125.59,119.79,117.08,60.29,33.03,32.51,30.33.

[0071] HRMS-ESI(m / z):[M+H] + Calcd.for(C 31 H 29 BrN):494.1438, found 494.1483.

[0072] (2) Synthesis of intermediate A4

[0073] Under nitrogen atmosphere, 10-(4-bromobutyl)-2,7-dimethyl-10H-spiro[acridine-9,9'-fluorene] (989 mg, 2.0 mmol) was dissolved in triethyl phosphite (20.0 eq, 6.7 g, 6.8 mL, 40.0 mmol), and the reaction mixture was heated at 165 ° C for 24 h. After the reaction was completed, the solvent was removed by vacuum rotary evaporation. The crude product was purified by column chromatography (petroleum ether: ethyl acetate = 1: 1, volume ratio) to obtain 882 mg (80%) of a white oily liquid.

[0074] 1H NMR(500MHz, CDCl3)δ7.76(d,J=7.5Hz,2H),7.34(td,J=7.5,1.0Hz,2H),7.26–7.25(m,2H),7.19(td,J=7.5,1.0Hz,2 H),6.96–6.89(m,4H),6.17(s,2H),4.18–4.13(m,4H),4.03–4.01(m,2H),2.07–1.88(m,12H),1.37(t,J=7.0Hz,6H).

[0075] 13 C NMR (126MHz, CDCl3) δ153.71,137.21,136.13,127.06,126.27,125.86,125.46,1 24.58,123.64,117.83,110.24,59.67,43.73,24.30,23.18,18.41,14.63,14.58.

[0076] 31 P NMR (203MHz,CDCl3)δ31.64.

[0077] HRMS-ESI(m / z):[M+H] + Calcd.for(C 35 H 39 NO3P):552.2668,found 552.2666.

[0078] (3) Synthesis of intermediate MeSAF

[0079] Under nitrogen atmosphere, diethyl (4-(2,7-dimethyl-10H-spiro[acridine-9,9'-fluorene]-10-yl)butyl)phosphonate (551mg, 1.0mmol) was dissolved in 1,4-dioxane (20.0mL), and trimethylsilyl bromide (10.0eq, 1.5g 1.3mL, 10.0mmol) was added dropwise. The mixture was stirred for 24 hours, after which the solvent was evaporated under reduced pressure, and the residue was dissolved in methanol (20.0mL), and distilled water was added dropwise until the solution became white and opaque, and stirring was continued for 24h. The product was filtered out, washed with water, and dried to obtain 370mg (75%) of a white solid.

[0080] 1 H NMR (500 MHz, DMSO-d 6)δ7.92(d,J=7.5Hz,2H),7.38(td,J=7.0,1.0Hz,2H),7.23(td,J=7.5,1.0Hz,2H),7.17(d,J=7.5Hz,2H),7.08(d,J=8 .5Hz,2H),6.97(dd,J=8.0,2.5Hz,2H),5.99(d,J=2.0Hz,2H),4.03(t,J=8.0Hz,2H),3.60-3.38(m,6H),1.91(s,6H).

[0081] 13 C NMR (126MHz, DMSO-d6) δ153.93,153.93,137.51,136.93,127.46,127.29,126.91,126.65,125.52,124 .68,124.09,123.12,119.26,111.96,55.56,43.89,38.95,26.86,25.78,25.06,24.95,19.34,18.99.

[0082] 31 P NMR (203 MHz, DMSO-d6) δ 26.21.

[0083] HRMS-ESI(m / z):[M+H] + Calcd.for(C 31 H 31 NO3P):496.2041, found 496.2038.

[0084] Example 3 Synthesis of Br-SAF

[0085]

[0086] (1) Synthesis of intermediate A5

[0087] 2,7-Dibromo-10H-spiro[acridine-9,9'-fluorene] (2.5 g, 5.0 mool) was dissolved in 1,4-dibromobutane (20.0 eq, 21.6 g, 11.9 mL, 100.0 mmol), followed by the addition of tetrabutylammonium bromide (0.2 eq, 322 mg, 1.0 mmol) and 50% aqueous potassium hydroxide solution (5.0 eq). The reaction was stirred overnight at 120 ° C. After the reaction was completed, it was extracted with dichloromethane. The combined organic phase was dried over anhydrous sodium sulfate, and the solvent was removed by vacuum rotary evaporation. The crude product was purified by column chromatography (petroleum ether: dichloromethane = 5: 1, volume ratio) to obtain 2.7 g (85%) of white powder.

[0088] 1 H NMR (500MHz, CDCl3) δ7.77(d,J=7.5Hz,2H),7.40–7.36(m,2H),7.27–7.22(m,6H),6.90(d,J=9. 5Hz,2H),6.46(d,J=1.0Hz,2H),4.02(t,J=8.0Hz,2H),3.56(t,J=5.5Hz,2H),2.13-2.11(m,4H).

[0089] 13 C NMR (126MHz, CDCl3) δ154.08,139.05,139.00,130.75,129.98,128.84,128.54 ,128.21,125.28,120.28,114.26,112.90,56.58,45.58,32.78,29.96,23.97.

[0090] HRMS-ESI(m / z):[M+H] + Calcd.for(C 29 H 23 Br3N):621.9380, found 621.9378.

[0091] (2) Synthesis of intermediate A6

[0092] Under nitrogen atmosphere, 2,7-dibromo-10-(4-bromobutyl)-10H-spiro[acridine-9,9'-fluorene] (1.2 g, 2.0 mmol) was dissolved in triethyl phosphite (20.0 eq, 6.7 g, 6.8 mL, 40.0 mmol), and the reaction mixture was heated at 165 ° C for 24 h. After the reaction was completed, the solvent was removed by vacuum rotary evaporation. The crude product was purified by column chromatography (petroleum ether: ethyl acetate = 1: 1, volume ratio) to obtain 1.1 g (82%) of a white oily liquid.

[0093] 1 H NMR (500MHz, CDCl3) δ7.77(d,J=8.0Hz,2H),7.40-7.37(m,2H),7.25–7.20(m,6H),6.88(d,J=9.0Hz,2H),6.45(d, J=2.5Hz,2H),4.18–4.14(m,4H),4.01–3.98(m,2H),2.04–2.00(m,2H),1.94–1.87(m,4H),1.37(t,J=7.0Hz,6H).

[0094] 13C NMR (126MHz, CDCl3) δ154.10,139.06,130.72,129.97,128.83,128.54,128.20,125.29,120 .28,114.27,112.85,61.73,61.68,56.59,46.06,26.31,26.19,20.26,20.22,16.59,16.54.

[0095] 31 P NMR (203MHz,CDCl3)δ31.24.

[0096] HRMS-ESI(m / z):[M+H] + Calcd.for(C 33 H 33 Br2NO3P):680.0565, found 680.0563.

[0097] (3) Synthesis of intermediate BrSAF

[0098] Under nitrogen atmosphere, diethyl (4-(2,7-dibromo-10H-spiro[acridine-9,9'-fluorene]-10-yl)butyl)phosphonate (681mg, 1.0mmol) was dissolved in 1,4-dioxane (20.0mL), and trimethylsilyl bromide (10.0eq, 1.5g 1.3mL, 10.0mmol) was added dropwise. The mixture was stirred for 24 hours, after which the solvent was evaporated under reduced pressure, and the residue was dissolved in methanol (20.0mL), and distilled water was added dropwise until the solution became white and opaque, and stirring was continued for 24h. The product was filtered out, washed with water, and dried to obtain 519mg (83%) of white solid.

[0099] 1 H NMR (500MHz, DMSO-d6) δ7.97(d,J=8.0Hz,2H),7.45(td,J=7.5,1.5Hz,2H),7.35(dd,J=9.0,2.5Hz,2H),7.30(td,J= 7.5,1.5Hz,2H),7.25-7.23(m,2H),6.22(d,J=2.5Hz,2H),4.08–4.05(m,2H),1.93-1.87(m,2H),1.80–1.66(m,4H).

[0100] 13C NMR(126MHz,DMSO-d6)δ154.28,139.48,138.84,131.26,129.37,129.01,128.82,1 28.50,125.50,121.26,116.45,111.98,56.56,45.74,28.27,27.18,26.05,20.72.

[0101] 31 P NMR (203 MHz, DMSO-d6) δ 26.17.

[0102] HRMS-ESI(m / z):[M+H] + Calcd.for(C 29 H 25 Br2NO3P):623.9939, found 623.9933.

[0103] Example 4 Synthesis of Br-U-SAF

[0104]

[0105] (1) Synthesis of intermediate A7

[0106] 2',7'-Dibromo-10H-spiro[acridine-9,9'-fluorene] (2.5 g, 5.0 mool) was dissolved in 1,4-dibromobutane (20.0 eq, 21.6 g, 11.9 mL, 100.0 mmol), followed by the addition of tetrabutylammonium bromide (0.2 eq, 322 mg, 1.0 mmol) and 50% aqueous potassium hydroxide solution (5.0 eq). The reaction was stirred overnight at 120 ° C. After the reaction was completed, it was extracted with dichloromethane. The combined organic phases were dried over anhydrous sodium sulfate, and the solvent was removed by vacuum rotary evaporation. The crude product was purified by column chromatography (petroleum ether: dichloromethane = 5: 1, volume ratio) to give 2.6 g (82%) of white powder.

[0107] 1 H NMR (500MHz, CDCl3) δ7.58(d,J=8.1Hz,2H),7.46(dd,J=8.2,1.7Hz,2H),7.35(d,J=1.7Hz,2H),7.24–7.20(m,2H),7.06(d, J=8.3Hz,2H),6.65(t,J=7.4Hz,2H),6.38(d,J=7.7Hz,2H),4.09(d,J=7.7Hz,2H),3.59–3.56(m,2H),2.15(d,J=3.7Hz,2H).

[0108] 13C NMR (126MHz, CDCl3) δ157.29,139.93,137.09,131.05,128.89,128.31,127.69,124.9 2,122.21,121.33,120.53,112.84,57.17,53.42,45.21,32.92,30.21,30.17,24.29.

[0109] HRMS-ESI(m / z):[M+H] + Calcd.for(C 29 H 23 Br3N):621.9380, found 621.9395.

[0110] (2) Synthesis of intermediate A8

[0111] Under nitrogen atmosphere, 2',7'-dibromo-10-(4-bromobutyl)-10H-spiro[acridine-9,9'-fluorene] (1.2 g, 2.0 mmol) was dissolved in triethyl phosphite (20.0 eq, 6.7 g, 6.8 mL, 40.0 mmol), and the reaction mixture was heated at 165 ° C for 24 h. After the reaction was completed, the solvent was removed by vacuum rotary evaporation. The crude product was purified by column chromatography (petroleum ether: ethyl acetate = 1: 1, volume ratio) to obtain 1.0 g (75%) of a white oily liquid.

[0112] 1 H NMR(500MHz, CDCl3)δ7.58(d,J=8.1Hz,2H),7.46(dd,J=8.1,1.8Hz,2H),7.35(d,J=1.8Hz,2H),7.22-7.19(m,2H),7.04(dd,J=8.4,1.0Hz,2H),6 .66–6.63(m,2H),6.37(dd,J=7.8,1.6Hz,2H),4.21-4.12(m,4H),4.08-4 .05(m,2H),2.10-2.03(m,2H),1.97-1.87(m,4H),1.37(t,J=7.1Hz,6H).

[0113] 13C NMR (126MHz, CDCl3) δ155.64,138.30,129.38,127.23,126.62,126.00,123.22,120.54,119.65,118.8 1,111.17,60.02,59.97,55.50,44.01,24.90,24.77,24.52,23.40,18.63,18.59,14.92,14.87,14.84.

[0114] 31 P NMR (203MHz,CDCl3)δ31.47.

[0115] HRMS-ESI(m / z):[M+H] + Calcd.for(C 33 H 33 Br2NO3P):680.0565, found 680.0571.

[0116] (3) Synthesis of intermediate Br-U-SAF

[0117] Under nitrogen atmosphere, diethyl (4-(2',7'-dibromo-10H-spiro[acridine-9,9'-fluorene]-10-yl)butyl)phosphonate (681mg, 1.0mmol) was dissolved in 1,4-dioxane (20.0mL), and trimethylsilyl bromide (10.0eq, 1.5g 1.3mL, 10.0mmol) was added dropwise. The mixture was stirred for 24 hours, after which the solvent was evaporated under reduced pressure, and the residue was dissolved in methanol (20.0mL), and distilled water was added dropwise until the solution became white and opaque, and stirring was continued for 24h. The product was filtered out, washed with water, and dried to obtain 494mg (79%) of white solid.

[0118] 1 H NMR(500MHz,DMSO-d6)δ7.95(d,J=8.2Hz,2H),7.61(dd,J=8.2,1.9Hz,2H),7.27(d,J=21.6Hz,4H ),6.67-6.64(m,2H),6.25-6.23(m,2H),4.21-4.08(m,2H),1.96-1.81(m,2H),1.79-1.71(m,4H).

[0119] 13C NMR(126MHz,DMSO-d6)δ157.51,140.16,137.34,131.65,128.99,128.30,127.08,124.61, 123.33,122.00,120.74,114.07,57.23,45.49,28.29,27.21,26.44,26.32,20.79,20.75.

[0120] 31 P NMR (203 MHz, DMSO-d6) δ 26.40.

[0121] HRMS-ESI(m / z):[M+H] + Calcd.for(C 29 H 25 Br2NO3P):623.9939, found 623.9943.

[0122] Example 5 Synthesis of SAX

[0123]

[0124] (1) Synthesis of intermediate A9

[0125] 10H-spiro[acridine-9,9'-xanthene] (1.7 g, 5.0 mool) was dissolved in 1,4-dibromobutane (20.0 eq, 21.6 g, 11.9 mL, 100.0 mmol), followed by the addition of tetrabutylammonium bromide (0.2 eq, 322 mg, 1.0 mmol) and 50% aqueous potassium hydroxide solution (5.0 eq). The reaction was stirred overnight at 120 ° C. After the reaction was completed, it was extracted with dichloromethane. The combined organic phases were dried over anhydrous sodium sulfate, and the solvent was removed by vacuum rotary evaporation. The crude product was purified by column chromatography (petroleum ether: dichloromethane = 5: 1, volume ratio) to give 2.2 g (90%) of white powder.

[0126] 1 H NMR (500MHz, CDCl3) δ7.15–7.11(m,6H),6.97(dd,J=8.0,1.6Hz,4H),6.89-6.86(m,2H),6.82(dd,J=8. 0,1.5Hz,2H),6.71(td,J=8.0,1.5Hz,2H),4.05-4.02(m,2H),3.58(t,J=5.5Hz,2H),2.16-2.09(m,4H).

[0127] 13C NMR (126MHz, CDCl3) δ148.36,138.05,132.63,131.67,131.22,131.20,127.54 ,127.49,123.54,120.53,115.84,111.81,45.27,44.75,32.98,30.12,24.74.

[0128] HRMS-ESI(m / z):[M+H] + Calcd.for(C 29 H 25 Bn O ):482.1119, found 482.1074.

[0129] (2) Synthesis of intermediate A10

[0130] Under nitrogen atmosphere, 10-(4-bromobutyl)-10H-spiro[acridine-9,9'-xanthene] (960 mg, 2.0 mmol) was dissolved in triethyl phosphite (20.0 eq, 6.7 g, 6.8 mL, 40.0 mmol), and the reaction mixture was heated at 165 ° C for 24 h. After the reaction was completed, the solvent was removed by vacuum rotary evaporation. The crude product was purified by column chromatography (petroleum ether: ethyl acetate = 1: 1, volume ratio) to obtain 920 mg (85%) of a white oily liquid.

[0131] 1 H NMR (500MHz, CDCl3) δ7.15–7.11(m,6H),6.98-6.94(m,4H),6.87(td,J=7.0,2.0Hz,2H),6.81(dd,J=8.0,1.5 Hz,2H),6.70(t,J=75Hz,0H),4.19-4.11(m,4H),4.02–3.99(m,2H),2.06–1.85(m,6H),1.36(t,J=7.0Hz,6H).

[0132] 13 C NMR (126MHz, CDCl3) δ148.35,138.09,132.60,131.67,131.20,127.53,127.46,123.54,120.47,11 5.83,111.81,61.69,61.64,45.69,44.74,27.04,26.91,26.26,25.14,20.22,20.18,16.58,16.53.

[0133] 31P NMR(203MHz,Chloroform-d)δ31.52.

[0134] HRMS-ESI(m / z):[M+H] + Calcd.for(C 33 H 35 NO4P):540.2303, found 540.2292.

[0135] (3) Synthesis of intermediate SAX

[0136] Under nitrogen atmosphere, diethyl (4-(10H-spiro[acridine-9,9'-xanthen]-10-yl)butyl)phosphonate (540mg, 1.0mmol) was dissolved in 1,4-dioxane (20.0mL), and trimethylsilyl bromide (10.0eq, 1.5g1.3mL, 10.0mmol) was added dropwise. The mixture was stirred for 24 hours, after which the solvent was evaporated under reduced pressure, and the residue was dissolved in methanol (20.0mL), and distilled water was added dropwise until the solution became white and opaque, and stirring was continued for 24h. The product was filtered out, washed with water, and dried to obtain 410mg (85%) of white solid.

[0137] 1 H NMR(500MHz,DMSO-d6)δ7.21–7.11(m,8H),6.95-6.92(m,2H),6.87–6.86(m,2H),6.69(td,J=7.0 ,1.5Hz,2H),6.61(d,J=4.0Hz,2H),4.03(t,J=8,0Hz,2H),1.93-1.87(m,2H),1.77–1.66(m,4H).

[0138] 13 C NMR(126MHz,DMSO-d6)δ145.84,136.02,130.03,129.70,129.30,128.70,126.10,125.94,122 .02,118.38,113.94,110.85,46.84,43.08,42.38,26.16,25.08,24.64,24.52,18.53,18.49.

[0139] 31 P NMR (203 MHz, DMSO-d6) δ 26.24.

[0140] HRMS-ESI(m / z):[M+H] + Calcd.for(C 29 H27 NO4P):484.1678, found 484.1673.

[0141] Example 6 Synthesis of SAT

[0142]

[0143] (1) Synthesis of intermediate A11

[0144] A11 spiro[acridine-9(10H),9'-[9H]thioxanthene (1.8 g, 5.0 mol) was dissolved in 1,4-dibromobutane (20.0 eq, 21.6 g, 11.9 mL, 100.0 mmol), followed by the addition of tetrabutylammonium bromide (0.2 eq, 322 mg, 1.0 mmol) and 50% aqueous potassium hydroxide solution (5.0 eq). The reaction was stirred at 120 ° C overnight. After the reaction was completed, it was extracted with dichloromethane. The combined organic phases were dried over anhydrous sodium sulfate, and the solvent was removed by vacuum rotary evaporation. The crude product was purified by column chromatography (petroleum ether: dichloromethane = 5:1, volume ratio) to give 2.2 g (87%) of white powder.

[0145] 1 H NMR (500MHz, CDCl3) δ7.20 (dd, J=8.0, 1.0Hz, 2H), 7.12 (td, J=7.5, 1.5H, 2H), 7.04-6.90 (m,10H),6.72–6.68(m,2H),4.04-4.01(m,2H),3.58(t,J=6.0Hz,2H),2.15–2.10(m,4H).

[0146] 13 C NMR (126MHz, CDCl3) δ142.41,137.12,133.94,132.89,132.51,127.56,126.79 ,126.15,126.12,124.44,120.63,111.77,49.76,45.23,33.03,30.11,24.94.

[0147] HRMS-ESI(m / z):[M+H] + Calcd.for(C 29 H 25 BrNS):498.0891, found 498.0883.

[0148] (2) Synthesis of intermediate A12

[0149] Under nitrogen atmosphere, 10-(4-bromobutyl)-10H-spiro[acridine-9,9'-thioxanthene] (1.0 g, 2.0 mmol) was dissolved in triethyl phosphite (20.0 eq, 6.7 g, 6.8 mL, 40.0 mmol), and the reaction mixture was heated at 165 ° C for 24 h. After the reaction was completed, the solvent was removed by vacuum rotary evaporation. The crude product was purified by column chromatography (petroleum ether: ethyl acetate = 1: 1, volume ratio) to obtain 911 mg (82%) of white oily liquid.

[0150] 1 H NMR (500MHz, CDCl3) δ7.19 (dd, J=8.0, 1.5Hz, 2H), 7.11 (td, J=8.0, 1.5Hz, 2H), 7.03–6.89 (m, 10H), 6.71–6.67(m,2H),4.18-4.13(m,4H),4.01–3.98(m,2H),2.05–1.86(m,6H),1.36(t,J=7.0Hz,6H).

[0151] 13 C NMR(126MHz, CDCl3)δδ142.38,137.12,133.91,132.82,132.45,127.49,126.73,126.10,126.07,124.3 9,120.53,111.73,61.68,61.63,49.72,45.61,27.21,27.09,26.24,25.12,20.19,20.15,16.57,16.52.

[0152] 31 P NMR (203MHz,CDCl3)δ31.49.

[0153] HRMS-ESI(m / z):[M+H] + Calcd.for(C 33 H 35 NO3PS):556.2075, found 556.2072.

[0154] (3) Synthesis of intermediate SAT

[0155] SAT Under nitrogen atmosphere, diethyl (4-(10H-spiro [acridine-9,9'-thioxanthine]-10-yl) butyl) phosphonate (540mg, 1.0mmol) was dissolved in 1,4-dioxane (20.0mL), and trimethylsilyl bromide (10.0eq, 1.5g1.3mL, 10.0mmol) was added dropwise. The mixture was stirred for 24 hours, after which the solvent was evaporated under reduced pressure, and the residue was dissolved in methanol (20.0mL), and distilled water was added dropwise until the solution became white and opaque, and stirring was continued for 24h. The product was filtered out, washed with water, and dried to obtain 410mg (85%) of white solid.

[0156] 1 H NMR(500MHz,DMSO-d6)δ7.28(d,J=8.0Hz,2H),7.14–7.06(m,6H),6.99(t,J=8.0Hz,2H),6.86(d,J=8.0Hz,2H ),6.76(d,J=8.0Hz,2H),6.67(t,J=7.5Hz,2H),4.01(t,J=8.0Hz,2H),1.92–1.86(m,2H),1.79–1.66(m,4H).

[0157] 13 C NMR(126MHz,DMSO-d6)δ141.50,136.19,133.07,131.35,131.22,127.09,125.80,125.67, 125.09,123.76,119.53,111.93,48.46,44.10,27.32,26.23,25.93,25.82,19.63,19.59.

[0158] 31 P NMR (203 MHz, DMSO-d6) δ 26.24.

[0159] HRMS-ESI(m / z):[M+H] + Calcd.for(C 29 H 27 NO3PS):500.1449, found 500.1442.

[0160] Example 7 Synthesis of SAA

[0161]

[0162] (1) Synthesis of intermediate A13

[0163] A13 10H,10'H-spiro[acridine-9,9'-anthracene]-10'-one (1.8 g, 5.0 mool) was dissolved in 1,4-dibromobutane (20.0 eq, 21.6 g, 11.9 mL, 100.0 mmol), followed by the addition of tetrabutylammonium bromide (0.2 eq, 322 mg, 1.0 mmol) and 50% aqueous potassium hydroxide solution (5.0 eq). The reaction was stirred overnight at 120 ° C. After the reaction was completed, it was extracted with dichloromethane. The combined organic phases were dried over anhydrous sodium sulfate and the solvent was removed by vacuum rotary evaporation. The crude product was purified by column chromatography (petroleum ether: dichloromethane = 5: 1, volume ratio) to give 2.0 g (80%) of light yellow powder.

[0164] 1 H NMR (500MHz, CDCl3) δ8.38 (dd, J=7.9, 1.6Hz, 2H), 7.44-7.41 (m, 2H), 7.35 (ddd, J=8.3, 7.1, 1.3Hz, 2H), 7.22 (dd, J= 8.1,1.2Hz,2H),7.16(ddd,J=8.6,7.0,1.6Hz,2H),7.06-7.04(m,2H),4.10(t,J=7.4Hz,2H),3.63-3.60(m,2H),2.19 -2.17(m,4H).

[0165] 13 C NMR (126MHz, CDCl3) δ184.09,153.26,138.46,134.05,131.97,131.75,128.75,12 8.31,127.90,126.69,126.36,120.54,112.59,48.45,45.34,33.01,30.08,24.86.

[0166] HRMS-ESI(m / z):[M+H] + Calcd.for(C 30 H 25 BrNO):494.1075, found 494.1119.

[0167] (2) Synthesis of intermediate A14

[0168] Under nitrogen atmosphere, 10-(4-bromobutyl)-10H,10'H-spiro[acridine-9,9'-anthracene]-10'-one (989mg, 2.0mmol) was dissolved in triethyl phosphite (20.0eq, 6.7g, 6.8mL, 40.0mmol), and the reaction mixture was heated at 165°C for 24h. After the reaction was completed, the solvent was removed by rotary evaporation under reduced pressure. The crude product was purified by column chromatography (petroleum ether: ethyl acetate = 1:1, volume ratio) to obtain 827mg (75%) of a white oily liquid.

[0169] 1 H NMR (500MHz, CDCl3) δ8.36 (dd, J=8.0, 1.4Hz, 2H), 7.41 (td, J=7.6, 1.5Hz, 2H), 7. 33(td,J=7.5,7.1,1.2Hz,2H),7.19(dd,J=8.0,1.1Hz,2H),7.13(ddd,J=8.6,7.1 ,1.6Hz,2H),7.00(d,J=8.4Hz,2H),6.62–6.59(m,2H),6.45(dd,J=7.9,1.5Hz,2H ),4.19-4.14(m,4H),4.07–4.04(m,2H),2.11–1.90(m,6H),1.37(t,J=7.0Hz,6H).

[0170] 13 C NMR (126MHz, CDCl3) δ184.08,153.24,138.47,134.02,131.95,131.71,128.72,128.27,127.84,126.66,12 6.33,120.46,112.56,61.70,61.66,48.42,45.74,27.13,27.03,26.17,25.23,20.22,20.18,16.59,16.55.

[0171] 31 P NMR (203MHz,CDCl3)δ31.40.

[0172] HRMS-ESI(m / z):[M+H] + Calcd.for(C 34 H 35 NO4P):552.2303,found 552.2329.

[0173] (3) Synthesis of intermediate SAA

[0174] Under nitrogen atmosphere, diethyl (4-(10'-oxo-10H, 10'H-spiro[acridine-9,9'-anthracene]-10-yl)butyl)phosphonate (551mg, 1.0mmol) was dissolved in 1,4-dioxane (20.0mL), and trimethylsilyl bromide (10.0eq, 1.5g 1.3mL, 10.0mmol) was added dropwise. The mixture was stirred for 24 hours, after which the solvent was evaporated under reduced pressure, and the residue was dissolved in methanol (20.0mL), and distilled water was added dropwise until the solution became white and opaque, and stirring was continued for 24h. The product was filtered out, washed with water, and dried to obtain 430mg (87%) of light yellow solid.

[0175] 1 H NMR (500MHz, DMSO-d6) δ8.21(dd,J=7.9,1.5Hz,2H),7.54(ddd,J=8.2,7.2,1.5Hz,2H),7.47-7.36(m,2H),7.22(d,J=8.8Hz,2H),7. 13(dd,J=8.1,1.3Hz,2H),6.66-6.49(m,2H),6.30(dd,J=7.8,1.6Hz,2H),4.10-4.06(m,2H),1.97-1.91(m,2H),1.81-1.68(m,4H).

[0176] 13 C NMR (126MHz, DMSO-d6) δ183.32,153.61,138.68,134.82,132.44,131.42,128.47,127.98, 127.36,126.13,120.59,113.85,48.35,45.33,28.43,27.34,26.98,26.86,20.76,20.72.

[0177] 31 P NMR (203 MHz, DMSO-d6) δ 26.23.

[0178] HRMS-ESI(m / z):[M+H] + Calcd.for(C 30 H 27 NO4P):496.1678, found 496.1699.

[0179] Application Example 1

[0180] The SAX prepared in Example 5 was used as a hole selective contact layer to prepare a perovskite-based solar cell. Figure 1As shown, the structure of perovskite-based solar cells is ITO / SAX / perovskite / C 60 / BCP / Ag.

[0181] The preparation method of perovskite-based solar cells includes the following steps: ultrasonically cleaning the ITO conductive glass with glass cleaning agent, pure water, acetone and isopropanol for 30 minutes in sequence. After the ITO glass is cleaned with an N2 air gun, it is treated with ultraviolet ozone for 30 minutes. The SAX prepared in Example 1 is used as a hole selective contact layer, and the SAX solution is prepared to have a concentration of 0.6 mg mL -1 50 μL of SAX solution was added to the ITO glass and then rotated at 1000 rpm for 6 seconds, 3000 rpm for 30 seconds, and annealed at 130°C for 20 minutes. 0.05 (FA 0.98 MA 0.02 ) 0.95 Pb(I 0.98 Br 0.02 )3 The perovskite solution was spin-coated onto the SAX surface and thermally annealed at 110°C for 20 minutes. After cooling, 30 nm C 60 and 6nm 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP). Finally, 100nm of Ag was vacuum-evaporated as the top electrode to complete the preparation of the perovskite-based solar cell device with an effective area of ​​0.1cm 2 .

[0182] Application Example 2

[0183] The only difference between the perovskite-based solar cell in this application example and that in application example 1 is that SAF is used instead of SAX to prepare the hole-selective contact layer.

[0184] Comparative Example 1

[0185] The difference between the perovskite-based solar cell in this comparative example and that in Application Example 1 is that 4-(9H-carbazole-9-yl)butyl]phosphonic acid (4PACZ) is used instead of SAX to prepare the hole-selective contact layer.

[0186] Results Analysis

[0187] After the devices of Application Example 1, Application Example 2 and Comparative Example 1 were prepared, a xenon lamp solar simulator was used to test the light source intensity of AM 1.5G (100 mW cm -2 ), the current-voltage (JV) characteristic curve of the inverted perovskite solar cell device was tested, and the test results included open circuit voltage, short circuit current, fill factor and photoelectric conversion efficiency.

[0188] The current-voltage (JV) characteristic curve of the perovskite-based solar cell device performance prepared in Application Example 1 is shown in Figure 2 The open circuit voltage (V oc ) is 1.16V, the short-circuit current density J sc 25.8 mA cm -2 , the filling factor FF is 81.4% and the photoelectric conversion efficiency is 24.4%.

[0189] The current-voltage (JV) characteristic curve of the perovskite-based solar cell device performance prepared in Application Example 2 is shown in Figure 3 The open circuit voltage (V oc ) is 1.14V, the short-circuit current density J sc 25.2 mA cm -2 The filling factor FF is 81.2%, and the photoelectric conversion efficiency can reach 23.2%.

[0190] like Figure 4 As shown in Comparative Example 1, the photoelectric conversion efficiency of the 4PACZ-based perovskite-based solar cell device is very low, only 21.0%, and the open circuit voltage (V oc ) is 1.11V, the short-circuit current density J sc 25.5 mA cm -2 , the filling factor FF is 73.7%.

[0191] In summary, the spiroaromatic phosphonic acid derivatives of the present invention are used as self-assembled hole selection materials for preparing perovskite-based solar cells, and a photoelectric conversion efficiency of >23% can be obtained. Compared with the traditional material 4PACZ, the SAX and SAF of the present invention as molecular hole selection contact layers of perovskite-based solar cells greatly increase the charge extraction speed, and improve the photoelectric conversion efficiency and stability of perovskite-based solar cells.

[0192] Those skilled in the art can understand that the above are only preferred examples of the invention and are not intended to limit the invention. Although the invention is described in detail with reference to the above examples, those skilled in the art can still modify the technical solutions recorded in the above examples or replace some of the technical features therein with equivalents. Any modification, equivalent replacement, etc. made within the spirit and principle of the invention shall be included in the protection scope of the invention.

Claims

1. A spiroaromatic phosphonic acid derivative containing a cross structure, characterized in that: Its structure is as follows: In formula (I-1) and formula (I-2), n is an integer of 1 to 6, and R is selected from any one of a halogen atom, an alkyl group, an alkoxy group, an alkoxy group substituted with a substituent, an aryl group, and an aryl group substituted with a substituent; In formula (I-2), X is selected from any one of an oxygen atom, a sulfur atom, a selenium atom, a carbonyl group, a sulfinyl group, a sulfyl group, and a thiocarbonyl group.

2. The spiroaromatic phosphonic acid derivative containing a cross structure according to claim 1, characterized in that: The halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; The alkyl group is a C1-C20 alkyl group; The alkoxy group is a C1-C20 alkoxy group; The substituents in the substituted aryl and the substituted alkoxy are selected from any one of methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, methoxy, ethoxy, propoxy, methylthio, ethylthio, propylthio, hydroxyl, carboxyl and thiol.

3. The spiroaromatic phosphonic acid derivative containing a cross structure according to claim 1, characterized in that: The spiroaromatic phosphonic acid derivatives containing a cross structure are Me-SAF, SAF, Br-SAF, Br-U-SAF, SAX, SAT, and SAA, respectively, as shown in the following formulas:

4. A method for preparing a spiroaromatic phosphonic acid derivative containing a cross structure, characterized in that: The method comprises the following steps: Step 1: Under an inert gas atmosphere, compound 1 and dibromide are mixed at a molar ratio of 1:20, and tetrabutylammonium bromide and potassium hydroxide aqueous solution are added to allow the compound 1 to react with the dibromide to obtain compound 2; Step 2: Under an inert gas atmosphere, the compound 2 is reacted with triethyl phosphite at a molar ratio of 1:20 to obtain compound 3; Step 3: Under an inert gas atmosphere, the compound 3 is dissolved in 1,4-dioxane, and trimethylsilyl bromide is added, and the mixture is stirred until the spiroaromatic hydrocarbon phosphonate derivative is completely reacted; then, the 1,4-dioxane is evaporated under reduced pressure, and the residue is dissolved in methanol, and distilled water is added until the solution becomes white and opaque, and stirring is continued until the impurities are dissolved in the methanol; finally, the product is filtered out, washed with water, and dried to obtain a spiroaromatic hydrocarbon phosphonic acid derivative containing a cross structure; The compound 1 is a spiroaromatic hydrocarbon raw material, and its structural formula is: or In formula (a) and formula (b), R is selected from any one of a halogen atom, an alkyl group, an alkoxy group, an alkoxy group substituted with a substituent, an aryl group, and an aryl group substituted with a substituent; In formula (b), X is selected from any one of an oxygen atom, a sulfur atom, a selenium atom, a carbonyl group, a sulfinyl group, a sulfyl group, and a thiocarbonyl group; The dibromide structural formula is Wherein, n is an integer from 1 to 6; The structural formula of the compound 2 is The structural formula of the compound three is 5. The method for preparing the spiroaromatic hydrocarbon phosphonic acid derivative according to claim 4, characterized in that: The potassium hydroxide aqueous solution is a potassium hydroxide aqueous solution with a mass ratio of 50%, the reaction temperature of the compound 1 and the dibromide is 120° C., and the reaction time is 24 hours.

6. The method for preparing the spiroaromatic hydrocarbon phosphonic acid derivative according to claim 4, characterized in that: The reaction temperature of the compound 2 and triethyl phosphite is 165° C., and the reaction time is 24 hours.

7. Use of the spiroaromatic phosphonic acid derivative containing a cross structure as claimed in claim 1 in optoelectronic devices.

8. The use according to claim 7, characterized in that: The optoelectronic device is a single-junction perovskite solar cell, an organic solar cell, a stacked solar cell, a perovskite light-emitting diode, an organic light-emitting diode, a perovskite photodetector or an organic photodetector; The stacked solar cell is a perovskite-crystalline silicon stacked cell, a full perovskite stacked cell, a perovskite-Cu(InGa)Se2 stacked cell or a perovskite-organic stacked cell.

9. The use according to claim 8, characterized in that: The hole selective contact layer of the optoelectronic device is made of the spiroaromatic phosphonic acid derivative containing a cross structure as claimed in claim 1.

Images