Halogen-containing hole transport materials, applications, and perovskite cells

Abstract

The present invention belongs to the technical field of solar energy industry, and specifically relates to a hole transport material containing halogen and its application as an organic hole transport material. The present invention designs a cyanoacetic acid or cyanophosphoric acid as an anchoring group, and introduces halogen into the molecular structure through the self-assembled monolayer strategy, thereby obtaining a new type of hole transport material containing halogen, the purpose of which is to solve the technical problems such as poor stability and poor device performance faced by existing organic small molecule hole transport materials with anchoring groups. In addition, the present invention also relates to a perovskite battery and a flexible perovskite battery prepared using the aforementioned organic hole transport material. The beneficial effect of the present invention is that the introduction of halogen atoms in the material can improve the stability of the perovskite battery and a flexible perovskite battery and extend its service life.

Description

Technical Field

[0001] The present invention belongs to the field of solar energy technology, and more specifically, relates to a halogen-containing hole transport material and its application as an organic hole transport material. Furthermore, the present invention also relates to a perovskite cell and a flexible perovskite cell. Background Art

[0002] Photovoltaic power generation is a way of obtaining energy with great potential and great significance to sustainable development.

[0003] The rapid improvement in the efficiency of perovskite solar cells (PSCs) is closely related to the excellent optoelectronic properties of perovskite active materials and the simple and low-cost preparation process of battery devices. On the one hand, as a direct semiconductor material, perovskite has a suitable adjustable band gap (1.2-2.3eV), a high molar extinction coefficient (>3*10 in the visible light region), and a high molar extinction coefficient (>3*10 in the visible light region). 4 cm -1 ), low exciton binding energy (2-75meV) ] 、High carrier mobility (>10cmV -1 s -1 ), long carrier diffusion distances (2-10μm), and high defect tolerance make them ideal photovoltaic materials with the potential to achieve high photoelectric conversion efficiencies. Furthermore, perovskite cell devices have a simple structure, and high-quality perovskite polycrystalline thin films can be obtained through solution processing. Other cell components (such as charge transport layers) can also be easily prepared. This has attracted a large number of researchers to engage in related research, and the number of published papers has increased exponentially, greatly promoting the development of the PSCs industry, making it one of the most cutting-edge and popular research areas in the new energy field.

[0004] Hole transport materials play a key role in perovskite cells. The use of organic small molecules containing anchoring groups to prepare hole transport layers has been shown to have excellent charge selectivity (Energy Environ. Sci., 2019, 12, 230-237). However, currently developed organic small molecule hole transport materials with anchoring groups face problems such as poor stability and poor device performance. Summary of the Invention

[0005] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a self-assembled monolayer hole transport material with good hole transport properties and strong interface passivation ability, which is suitable for large-scale applications.

[0006] To achieve the above objectives, the present invention designs a novel halogen-containing hole transport material using cyanoacetic acid or cyanophosphoric acid as an anchoring group and introduces halogen into the molecular structure through a self-assembled monolayer strategy. The technical solution of the present invention is as follows:

[0007] A halogen-containing hole transport material having the general chemical formula shown in the following formula (I):

[0008]

[0009] wherein R1-R9 are independently hydrogen, deuterium, halogen, aldehyde, carboxyl, cyano, nitro, amino, sulfonic acid, boric acid, silicon, sulfone, sulfoxide, amide; C1-C30 substituted or unsubstituted alkyl, alkenyl, alkynyl, alkoxy, thioalkoxy; C1-C30 substituted or unsubstituted haloalkyl, C1-C30 substituted or unsubstituted alkylsilyl, C6-C30 substituted or unsubstituted aryl, C3-C30 substituted or unsubstituted heteroaryl; and R1-R8 are at least one halogen;

[0010] R10 represents a phosphate group, a carboxyl group, an aldehyde group, a cyano group, or a sulfonic acid group;

[0011] L represents a C6-C30 substituted or unsubstituted arylene group, or a C3-C30 substituted or unsubstituted heteroarylene group;

[0012] A represents space, single bond, oxygen, sulfur, and selenium.

[0013] Further preferably, formula (I) includes but is not limited to any one of the following compounds 1 to 96:

[0014]

[0015]

[0016]

[0017]

[0018]

[0019]

[0020] Another object of the present invention is to provide a perovskite solar cell, which includes a transparent conductive oxide substrate, an inorganic P-type semiconductor hole transport layer, an organic hole transport layer, a perovskite active layer, an electron transport layer, a hole blocking layer and an electrode layer; or, includes a transparent conductive oxide substrate, an organic hole transport layer, a perovskite active layer, an electron transport layer, a hole blocking layer and an electrode layer arranged in sequence; wherein an Ag back electrode is provided on the transparent conductive oxide electrode layer; and the organic hole transport layer is the above-mentioned hole transport material containing the general formula (I).

[0021] Optionally, the organic hole transport layer having structural formula I can be used alone or in combination.

[0022] Optionally, the thickness of the organic hole transport layer is 0.1 nm to 100 um, preferably 1 nm to 10 um;

[0023] Optionally, the halogen-containing hole transport layer material having structural formula I can be prepared by vacuum evaporation, molecular beam evaporation, solvent-dissolved dip coating, spin coating, rod coating or inkjet printing.

[0024] Optionally, the p-type semiconductor hole transport layer of the perovskite cell of the present invention comprises a metal semiconductor, preferably nickel oxide, aluminum copper oxide, iron copper oxide, copper oxide, copper iodide, tungsten oxide, molybdenum oxide, copper sulfide, ferrous sulfide and cuprous thiocyanate.

[0025] Optionally, the electron transport layer of the present invention is selected from [6,6]-phenyl-C71-butyric acid isomethyl ester, C60 or C60 derivatives.

[0026] Optionally, the perovskite cell of the present invention is selected from a single-layer cell or a stacked cell.

[0027] Optionally, the tandem cell may be a perovskite / crystalline silicon tandem cell, a full perovskite tandem cell, a perovskite / organic tandem cell, or a perovskite / CIGS tandem cell, preferably a perovskite / crystalline silicon tandem cell or a full perovskite tandem cell.

[0028] The present invention also provides a flexible perovskite battery, comprising a conductive glass substrate, a perovskite battery body arranged on the conductive glass substrate, an encapsulation layer arranged on the perovskite battery body, and a backplane arranged on the side of the encapsulation layer away from the flexible perovskite battery body; the perovskite battery body is sequentially arranged from bottom to top as a first electrode layer, a first electron transport layer, a perovskite absorption layer, a second electron transport layer, a second electrode layer, a conductive electrode and an encapsulation layer; the first electron transport layer contains the hole transport material represented by the above-mentioned general formula (I).

[0029] Preferably, the thickness of the conductive glass substrate is ≤800 nm.

[0030] Preferably, the absorption spectrum range of the flexible perovskite battery is 300 to 800 nm.

[0031] Preferably, the first electrode layer is disposed close to the chemically strengthened glass substrate.

[0032] Preferably, the flexible perovskite battery further includes a barrier layer, and the barrier layer is arranged between the conductive glass substrate and the first electrode layer.

[0033] Preferably, the material of the barrier layer is at least one selected from silicon dioxide, silicon nitride, and aluminum oxide.

[0034] Preferably, the perovskite battery body includes a plurality of battery cells connected in series in sequence; wherein, each of the battery cells located at both ends is connected to one of the conductive electrodes.

[0035] Preferably, the second electron transport layer is a hole transport layer.

[0036] Preferably, the back plate is made of chemically strengthened glass or polyimide film.

[0037] The organic electron transport material provided by the present invention can also be used to produce organic electroluminescent devices, organic solar cells, organic thin film transistors, organic photodetectors, organic field effect transistors, organic integrated circuits and organic photoreceptors.

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

[0039] (1) The introduction of halogen atoms greatly improves the stability of organic hole transport materials, including photostability, human stability, redox stability, etc., which is beneficial to the long-term stability of the device under working conditions.

[0040] (2) The introduction of halogen atoms can adjust the frontier orbital energy level of the material to make it more compatible with the energy level of the active layer material, thereby improving the efficiency of interface carrier injection and extraction and enhancing device performance.

[0041] (3) The introduction of halogen atoms can passivate the structural defects of the interface, extend the carrier lifetime in the perovskite active layer, and improve the open circuit voltage and fill factor of solar cells.

[0042] (4) The introduction of halogen atoms, due to the hydrophobicity of halogens, can reduce the erosion of water on the perovskite layer on the one hand, and reduce the diffusion of halogens in the perovskite layer on the other hand. Both of these aspects help to improve the stability of the battery and extend the battery life. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 This is a schematic diagram of a battery structure device of the present invention.

[0044] Figure 2 The J / V curve of the perovskite cell (i.e., device 1) prepared using the compound 1 provided by the present invention as a hole transport material;

[0045] Figure 3 The J / V curve of the perovskite cell (i.e., device 2) prepared using the compound 2 provided by the present invention as a hole transport material;

[0046] Figure 4 The J / V curve of the perovskite cell (i.e., device 3) prepared using compound 18 provided by the present invention as a hole transport material;

[0047] Figure 5 The J / V curve of the perovskite cell (i.e., device 4) prepared using compound 34 provided by the present invention as a hole transport material;

[0048] Figure 6 The J / V curve of the perovskite cell (i.e., device 5) prepared using compound 38 provided by the present invention as a hole transport material;

[0049] Figure 7 The J / V curve of the perovskite cell (i.e., device 6) prepared using compound 39 provided by the present invention as a hole transport material;

[0050] Figure 8 The J / V curve of the perovskite cell (i.e., device 7) prepared using compound 44 provided by the present invention as a hole transport material;

[0051] Figure 9 The J / V curve of the perovskite cell (i.e., device 8) prepared using the compound 60 provided by the present invention as a hole transport material;

[0052] Figure 10 The J / V curve of the perovskite cell (i.e., device 9) prepared using the compound 66 provided by the present invention as a hole transport material;

[0053] Figure 11 1 is the J / V curve of a perovskite cell (i.e., device 10) prepared using compound 75 provided by the present invention as a hole transport material. Specific implementation methods

[0054] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined purpose of the invention, the specific implementation methods, structures, features and effects of the present invention are described in detail below with reference to the accompanying drawings and preferred embodiments.

[0055] Example 1

[0056] Synthesis of compound 1

[0057]

[0058] Synthesis of Intermediate 1-1: 4,4'-dichlorodiphenylamine (5 g, 0.021 mol), p-fluorobenzaldehyde (2.88 g, 0.023 mol), and potassium carbonate (8.74 g, 0.063 mol) were weighed into a three-necked flask, purged with nitrogen, and 100 mL of DMF was added. The mixture was heated to 130°C and stirred for 4 hours. After the reaction was complete, the mixture was cooled to room temperature and filtered. The filtrate was concentrated, and 10 mL of ethanol was added to precipitate a solid, which was then filtered to obtain the product cake. The product was oven-dried to obtain 5.3 g, with a yield of 74%. 1 H NMR (400MHz, CDCl3): δ9.65(s,1H),7.47-7.52(d,2H),7.32-7.36(d,2H),7.19-7.23(d,4H),7.01-7.04(d,4H).

[0059] Synthesis of Intermediate 1-2: Weigh Intermediate 1-1 (5 g, 0.015 mol) into a three-necked flask and purge with nitrogen. Add 50 mL of toluene, followed by diethyl (cyanomethyl)phosphonate (7.86 g, 0.044 mol) and piperidine (12.46 g, 0.147 mol). Raise the temperature to 110°C and stir for 4 h. After the reaction is complete, cool to room temperature, and spin-dry the toluene solvent. Prepare a sample and pass it through a silica gel column chromatography using a 10 / 10 / 10 / 1 eluent. 4.2 g of the product is obtained as an oil in a 57% yield. 1 H NMR (400MHz, DMSO-d6): δ8.62(s,1H),7.57-7.62(d,2H),7.34-7.38(d,4H),7.11-7.16(m,6H),4.51-4.59(q,4H).1.32-1.35(t,6H).

[0060] Synthesis of Compound 1: Intermediate 1-2 (4 g, 8 mmol) was weighed and dissolved in 40 mL of DCM, purged with nitrogen. Trimethylsilyl bromide (3.65 g, 24 mmol) was added and stirred at room temperature for 24 h. The reaction was terminated and quenched by adding methanol until no white smoke was emitted. The reaction solution was concentrated, washed with 20 mL of water, and extracted with DCM several times. The organic phase was separated, dried over anhydrous sodium sulfate, concentrated, and the precipitated solid was filtered. Drying yielded 1.67 g, with a yield of 47%. 1 HNMR(400MHz, DMSO-d6): δ7.77-7.81(d,2H),7.47(s,1H),7.26-7.32(d,4H),7.11-7.15(m,6H).HRMS(EI,m / z): calcd.for:C 21 H 15Cl2N2O3P,444.0197,found,444.0195.Anal.:calcd.:C,56.65;H,3.40;Cl,15.92;N, 6.29;O,10.78;P,6.96;found:C,56.69;H,3.42;Cl,15.90;N,6.25;O,10.79;P,6.95.

[0061] Example 2

[0062] Synthesis of compound 2

[0063]

[0064] Synthesis of intermediate 2-1: The synthesis steps are similar to those of intermediate 1-1, with a yield of 78%. 1 H NMR (400MHz, CDCl3): δ9.89(s,1H),7.38-7.42(m,6H),7.27-7.31(d,2H),7.01-7.06(d,4H).

[0065] Synthesis of intermediate 2-2: The synthesis steps are similar to those of intermediate 1-2, with a yield of 61%. 1 H NMR (400MHz, DMSO-d6): δ8.67(s,1H),7.57-7.62(d,2H),7.34-7.38(d,4H),7.04-7.06(m,6H),4.51-4.55(q,4H).1.22-1.25(t,6H).

[0066] Synthesis of compound 2: The synthesis steps are similar to those of compound 1, with a yield of 50%. 1 H NMR(400MHz, DMSO-d6): δ7.73-7.76(d,2H),7.45(s,1H),7.28-7.32(d,4H),7.01-7.05(m,6H).HRMS(EI,m / z): calcd.for:C 21 H 15 Br2N2O3P,531.9187,found,531.9183.Anal.:calcd.:C,47.22;H,2.83;Br,29.92;N ,5.24;O,8.99;P,5.80;found:C,47.26;H,2.80;Br,29.96;N,5.21;O,8.95;P,5.82.

[0067] Example 3

[0068] Synthesis of compound 18

[0069]

[0070] Synthesis of intermediate 18-1: The synthesis steps are similar to those of intermediate 1-1, with a yield of 67%. 1 H NMR (400MHz, CDCl3): δ9.87(s,1H),7.38-7.42(d,2H),7.26-7.28(m,8H).

[0071] Synthesis of intermediate 18-2: The synthesis steps are similar to those of intermediate 1-2, with a yield of 52%. 1 H NMR (400MHz, DMSO-d6): δ8.07(s,1H),7.77-7.79(d,2H),7.24-7.28(m,6H),7.14-7.15(d,2H),4.51-4.52(q,4H).1.22-1.25(t,6H).

[0072] Synthesis of compound 18: The synthesis steps were similar to those of compound 1, with a yield of 37%. 1 H NMR(400MHz, DMSO-d6): δ7.74-7.76(d,2H),7.35(s,1H),7.28-7.30(m,6H),7.13-7.15(m,2H).HRMS(EI,m / z): calcd.for:C 21 H 13 Cl4N2O3P,511.9418,found,511.9412.Anal.:calcd.:C,49.06;H,2.55;Cl,27.58;N ,5.45;O,9.34;P,6.02,found:C,49.02;H,2.53;Cl,27.56;N,5.47;O,9.38;P,6.04.

[0073] Example 4

[0074] Synthesis of compound 34

[0075]

[0076] Synthesis of intermediate 34-1: The synthesis steps are similar to those of intermediate 1-1, with a yield of 70%. 1 H NMR (400MHz, CDCl3): δ9.78(s,1H),7.49-7.51(m,4H),7.24-7.26(m,4H),7.12-7.14(m,4H).

[0077] Synthesis of intermediate 34-2: The synthesis steps are similar to those of intermediate 1-2, with a yield of 55%.1 H NMR (400MHz, DMSO-d6): δ8.12(s,1H),7.26-7.29(m,6H),7.12-7.14(d,4H),6.09-7.01(m,2H),4.51-4.52(q,4H).1.22-1.25(t,6H).

[0078] Synthesis of compound 34: The synthesis steps were similar to those of compound 1, with a yield of 45%. 1 H NMR (400MHz, DMSO-d6): 7.45 (s, 1H), δ7.28-7.32 (m, 6H), 7.12-7.14 (d, 4H), 6.92-6.94 (m, 2H). HRMS (EI, m / z): calcd.for: C 21 H 15 Cl2N2O3P,444.0197,found,444.0195.Anal.:calcd.:C,56.65;H,3.40;Cl,15.92;N, 6.29;O,10.78;P,6.96;found:C,56.61;H,3.44;Cl,15.96;N,6.25;O,10.79;P,6.95.

[0079] Example 5

[0080] Synthesis of compound 38

[0081]

[0082] Synthesis of intermediate 38-1: The synthesis steps are similar to those of intermediate 1-1, with a yield of 72%. 1 H NMR (400MHz, CDCl3): δ9.67(s,1H),7.96-7.98(m,6H),7.32-7.34(m,4H).

[0083] Synthesis of intermediate 38-2: The synthesis steps are similar to those of intermediate 1-2, with a yield of 54%. 1 H NMR (400MHz, DMSO-d6): δ8.15(s,1H),7.80-7.82(m,4H),7.68-7.70(d,2H), 7.48-7.51(d,2H),7.23-7.25(m,2H),4.51-4.52(q,4H).1.22-1.25(t,6H).

[0084] Synthesis of compound 38: The synthesis steps were similar to those of compound 1, with a yield of 48%. 1H NMR(400MHz, DMSO-d6): δ7.78-7.82(m,4H),7.68-7.70(d,2H),7.46(s,1H),7.42-7.44(m,4H).HRMS(EI,m / z): calcd.for:C 21 H 13 Cl2N2O3P,442.0031,found,442.0037.Anal.:calcd.:C,56.91;H,2.96;Cl,16.00;N, 6.32;O,10.83;P,6.99;found:C,56.95;H,2.92;Cl,16.04;N,6.27;O,10.86;P,6.96.

[0085] Example 6

[0086] Synthesis of compound 39

[0087]

[0088] Synthesis of intermediate 39-1: The synthesis steps are similar to those of intermediate 1-1, with a yield of 76%. 1 H NMR (400MHz, CDCl3): δ9.65(s,1H),7.91-7.93(m,6H),7.36-7.38(m,4H).

[0089] Synthesis of intermediate 39-2: The synthesis steps are similar to those of intermediate 1-2, with a yield of 55%. 1 H NMR (400MHz, DMSO-d6): δ8.13(s,1H),7.82-7.84(m,4H),7.65-7.67(d,2H), 7.47-7.49(d,2H),7.26-7.28(m,2H),4.51-4.52(q,4H).1.22-1.25(t,6H).

[0090] Synthesis of compound 39: The synthesis steps were similar to those of compound 1, with a yield of 52%. 1 H NMR(400MHz, DMSO-d6): δ7.73-7.75(m,4H),7.65-7.67(d,2H),7.44(s,1H),7.32-7.35(m,4H).HRMS(EI,m / z): calcd.for:C 21 H 13Br2N2O3P,529.9031,found,529.9039.Anal.calcd.:C,47.40;H,2.46;Br,30.03;N ,5.26;O,9.02;P,5.82;found:C,47.42;H,2.44;Br,30.09;N,5.23;O,9.05;P,5.77.

[0091] Example 7

[0092] Synthesis of compound 44

[0093]

[0094] Synthesis of intermediate 44-1: The synthesis steps are similar to those of intermediate 1-1, with a yield of 80%. 1 H NMR (400MHz, CDCl3): δ8.92(s,1H),8.29-8.30(m,1H),7.91-7.93(m,5H),7.71-7.72(m,1H),7.45-7.52(m,3H),7.21-7.22(m,1H).

[0095] Synthesis of intermediate 44-2: The synthesis steps are similar to those of intermediate 1-2, with a yield of 60%. 1 H NMR (400MHz, DMSO-d6): δ8.29-8.30(d,1H),8.06(s,1H),7.93(d,1H),7.68-7.72(m ,3H),7.46-7.52(m,5H),7.21-7.22(t,1H),4.23-4.25(q,4H).1.32-1.335(t,6H).

[0096] Synthesis of compound 44: The synthesis steps were similar to those of compound 1, with a yield of 52%. 1 H NMR(400MHz, DMSO-d6): δ8.73-8.75(d,2H),7.65(s,1H),7.67-7.69(m,3H),7.42-7.45(m,6H).HRMS(EI,m / z): calcd.for:C 21 H 14 I2N2O3P,499.8787,found,499.8789.Anal.calcd.:C,50.42;H,2.82;I,25.37;N, 5.60;O,9.59;P,6.19;found:C,50.42;H,2.78;I,25.42;N,5.65;O,9.57;P,6.16.

[0097] Example 8

[0098] Synthesis of compound 60

[0099]

[0100] Synthesis of Intermediate 60-1: The synthesis steps are similar to those of Intermediate 1-1, with a yield of 70%. 1 H NMR (400MHz, CDCl3): δ8.87(s,1H),7.88-7.89(m,5H),7.66(s,1H),7.42(s,2H).

[0101] Synthesis of intermediate 60-2: The synthesis steps are similar to those of intermediate 1-2, with a yield of 52%. 1 H NMR (400MHz, DMSO-d6): δ8.01(s,1H),7.95(s,1H),7.64-7.65(m,3H),7.44-7.46(m,3H),4.21-4.34(q,4H).1.22-1.25(t,6H).

[0102] Synthesis of compound 60: The synthesis steps were similar to those of compound 1, with a yield of 37%. 1 H NMR (400MHz, DMSO-d6): δ7.95 (s, 1H), 7.66-7.68 (m, 3H), 7.44-7.46 (m, 5H). HRMS (EI, m / z): calcd.for: C 21 H 11 Br4N2O3P,685.7241,found,685.7246.Anal.:calcd.:C,36.56;H,1.61;Br,46.33;N ,4.06;O,6.96;P,4.49;found:C,36.54;H,1.63;Br,46.30;N,4.09;O,6.98;P,4.46.

[0103] Example 9

[0104] Synthesis of compound 66

[0105]

[0106] Synthesis of intermediate 66-1: The synthesis steps are similar to those of intermediate 1-1, with a yield of 72%. 1H NMR (400MHz, CDCl3): δ8.78(s,1H),8.52(s,1H),8.17(t,1H),8.02(s,1H),7.78-7.82(m,4H),7.44-7.46(m,2H),

[0107] 7.22-7.24 (m, 1H).

[0108] Synthesis of intermediate 66-2: The synthesis steps are similar to those of intermediate 1-2, with a yield of 51%. 1 H NMR (400MHz, DMSO-d6): δ8.31(m,1H),8.05-8.06(m,2H),7.80-7.83(m,3H), 7.42-7.44(m,4H),7.09-7.11(m,1H),4.11-4.12(q,4H).1.42-1.45(t,6H).

[0109] Synthesis of compound 66: The synthesis steps were similar to those of compound 1, with a yield of 39%. 1 H NMR (400MHz, DMSO-d6): 8.21 (m, 1H), 8.05 (s, 1H), δ7.88-7.92 (m, 3H), 7.42-7.44 (m, 5H), 7.22-7.24 (m, 1H). HRMS (EI, m / z): calcd.for: C 21 H 13 Br2N2O3P,529.9031,found,529.9034.Anal.:calcd.:C,47.40;H,2.46;Br,30.03;N ,5.26;O,9.02;P,5.82;found:C,47.46;H,2.40;Br,30.04;N,5.25;O,9.06;P,5.79.

[0110] Example 10

[0111] Synthesis of compound 75

[0112]

[0113] Synthesis of intermediate 75-1: The synthesis steps are similar to those of intermediate 1-1, with a yield of 50%. 1 H NMR (400MHz, CDCl3) δ8.89(s,1H),7.87-7.81(m,2H),7.35-7.29(m,4H),6.95(d,2H),6.90(d,2H).

[0114] Synthesis of intermediate 75-2: The synthesis steps are similar to those of intermediate 1-2, with a yield of 45%. 1 H NMR (400MHz, DMSO-d6):7.99(s,1H),7.70-7.64(m,2H),7.33(dd,2H),7.11-7.05(m,2H),6.95(d,2H),6.90(d,2H),4.15(p,4H),1.29(td,6H).

[0115] Synthesis of compound 75: The synthesis steps were similar to those of compound 1, with a yield of 34%. 1 H NMR(400MHz, DMSO-d6): δ8.00(s,1H),7.70-7.64(m,2H),7.33(dd,2H),7.11-7.05(m,2H),6.95(d,2H),6.90(d,2H).HRMS(EI,m / z): calcd.for:C 21 H 13 Br2N2O4P,545.8980,found,545.8984.Anal.:calcd.:C,46.02;H,2.39;Br,29.16;N, 5.11;O,11.68;P,5.65;found:C,46.08;H,2.36;Br,29.13;N,5.15;O,11.67;P,5.61.

[0116] Example 11

[0117] Synthesis of compound 87

[0118]

[0119] Synthesis of intermediate 87-1: The synthesis steps are similar to those of intermediate 1-1, with a yield of 50%. 1 H NMR (400MHz, CDCl3) δ8.89(s,1H),7.77-7.71(m,2H),7.47(dd,2H),7.37-7.32(m,2H),7.20(d,2H),7.09(d,2H).

[0120] Synthesis of intermediate 87-2: The synthesis steps are similar to those of intermediate 1-2, with a yield of 45%. 1 H NMR(400MHz, DMSO-d6):7.99(s,1H),7.70-7.64(m,2H),7.47(dd,2H),7.20(d,2H),7.11-7.05(m,4H),4.15(p,4H),1.29(td,6H).

[0121] Synthesis of compound 87: The synthesis steps were similar to those of compound 1, with a yield of 34%. 1 H NMR(400MHz, DMSO-d6): δ8.00(s,1H),7.60-7.64(m,2H),7.48(dd,2H),7.20(d,2H),7.11-7.05(m,4H).HRMS(EI,m / z): calcd.for:C 21 H 13 Br2N2O3PS,561.8751,found,561.8755.Anal.:calcd.:C,44.71;H,2.32;Br,28.33;N,4.97; O,8.51;P,5.49;S,5.68;found:C,44.74;H,2.29;Br,28.37;N,4.93;O,8.53;P,5.47;S,5.67.

[0122] The following is a further detailed description of the uses and effects of the compounds of the present invention through the preparation process and performance test results analysis of perovskite solar cell devices 1 to 11 prepared from the compounds of the present invention.

[0123] Device 1

[0124] The preparation of perovskite cells is as follows:

[0125] 1) Cleaning of ITO conductive glass substrate;

[0126] 2) Preparation of hole transport layer (ETL): Compound 1 was dissolved in ethanol solvent, spin-coated on ITO, and annealed at 120°C for 20 min to remove adsorbed water molecules;

[0127] 3) Preparation of perovskite film (perovskite layer): The solubility of the perovskite precursor solution is 1.2M, and the perovskite film is prepared by the anti-solvent one-step method. The spin coating is divided into two stages, the first stage speed is 1000 rpms -1 , spin coating for 10 s, acceleration of 200 rpm s -2 , the second stage is 5000rpm s -1 , spin coating for 30s, acceleration of 2000rpm s -1 20 seconds before the end of the second stage, 600 μL of toluene was added as an antisolvent in the center of the perovskite film, and finally heated at 100 °C for 10 min to obtain the final perovskite film;

[0128] 3) Preparation of electron transport layer (HTL) and hole blocking layer: Use chlorobenzene to prepare PCBM solution with a concentration of 20 mg / mL-1 , two-step spin coating (800rmp s -1 , 10s; 4000rmp s -1 , 30s), annealing at 80℃ for 10min.

[0129] 4) Preparation of hole blocking layer: Finally, 120 μL of BCP isopropyl alcohol solution was drop-coated to prepare the hole blocking layer (ITO);

[0130] 5) Back electrode preparation: Use vacuum evaporation apparatus (<5×10 -4 Pa) evaporate 100nm silver to form the negative electrode;

[0131] Figure 1 The perovskite cell prepared in Example 1 of the present invention has a structure including a transparent conductive oxide substrate / organic hole transport layer / perovskite active layer / electron transport layer / hole blocking layer and an electrode layer; wherein an Ag back electrode is provided on the transparent conductive oxide electrode layer, and the organic hole transport layer contains the hole transport material shown in Compound 1.

[0132] Device 2

[0133] The preparation method and process are the same as those of device 1, except that a layer of hole transport material (compound 2) provided by the present invention is prepared on the ITO;

[0134] Device 3

[0135] The preparation method and process are the same as those of device 1, except that a layer of hole transport material (Compound 18) provided by the present invention is prepared on ITO;

[0136] Device 4

[0137] The preparation method and process are the same as those of device 1, except that a layer of hole transport material (compound 34) provided by the present invention is prepared on the ITO;

[0138] Device 5

[0139] The preparation method and process are the same as those of device 1, except that a layer of hole transport material (Compound 38) provided by the present invention is prepared on the ITO;

[0140] Device 6

[0141] The preparation method and process are the same as those of device 1, except that a layer of hole transport material (Compound 39) provided by the present invention is prepared on the ITO;

[0142] Device 7

[0143] The preparation method and process are the same as those of device 1, except that a layer of hole transport material (Compound 44) ​​provided by the present invention is prepared on the ITO;

[0144] Device 8

[0145] The preparation method and process are the same as those of device 1, except that a layer of hole transport material (Compound 60) provided by the present invention is prepared on the ITO;

[0146] Device 9

[0147] The preparation method and process are the same as those of device 1, except that a layer of hole transport material (Compound 66) provided by the present invention is prepared on the ITO;

[0148] Device 10

[0149] The preparation method and process are the same as those of device 1, except that a layer of hole transport material (Compound 75) provided by the present invention is prepared on the ITO;

[0150] Device 11

[0151] The preparation method and process are the same as those of device 1, except that a layer of hole transport material (Compound 87) provided by the present invention is prepared on the ITO;

[0152] Comparative Example

[0153] The preparation method and process are the same as those of device 1, except that the hole transport material prepared on the ITO is Ref, and the structural formula of Ref is as follows:

[0154]

[0155] Perovskite cell performance test: The volt-ampere characteristic (IV) curve of the solar cell was recorded by a Keithley 2400 digital source meter. The light source was a xenon lamp (Osram XBO 450) simulating AM 1.5 sunlight with an intensity of 1000W / m 2 , calibrated with silicon cells, and tested at 25°C. The incident photon-to-electron conversion efficiency (IPCE), also known as external quantum efficiency (EQE), was measured using an oriel-74125 system, a 300W xenon lamp (ILC Technology, USA), and a modulation frequency of 2Hz. The JV data for the tested cells are shown in Table 1 and Figures 1-10 .

[0156] Stability test of perovskite solar cells: After the prepared perovskite solar cell device was placed under a relative humidity (RH) of 85% and a temperature of 50° for 240 h, the relative value of its photoelectric conversion efficiency compared to the original efficiency is shown in Table 1.

[0157] Table 1

[0158]

[0159]

[0160] From Table 1 and Figures 1-10 It can be seen that: (1) the halogen-containing cyanoacetic acid compound of the present invention is used as a hole transport material in a perovskite battery, and the short-circuit density of the battery is greater than 24 mA / cm 2 , the open circuit voltage is greater than 1.18V, and the fill factor is greater than 81%. The photoelectric conversion efficiency under the simulated sunlight intensity of 1.5AM is greater than 24%, and even reaches 25%. Compared with the reference compounds, they all show higher photoelectric conversion efficiency. This is mainly due to the introduction of halogen atoms, which adjusts the frontier orbital energy level of the material to make it more compatible with the energy level of the active layer material, improves the interface carrier injection and extraction efficiency, and improves the device efficiency. In addition, it can passivate the structural defects of the interface, extend the carrier lifetime in the perovskite active layer, and improve the open circuit voltage and fill factor of the perovskite battery. (2) Due to the introduction of halogen atoms, the light stability and redox stability of the hole transport material can be improved. It can be seen from Table 1 that after being placed under high temperature and high humidity conditions for 240 hours, the perovskite battery using the compound of the present invention as the hole transport material still has a good photoelectric conversion efficiency. Compared with the original value, it is higher than 80%, while the reference device is only 35%, showing that the battery of the present invention shows good stability. In addition to increasing the stability of the material, halogens can also increase the material's hydrophobicity, reducing the erosion of moisture in the air on the perovskite layer during operation, thereby extending the battery's service life. Furthermore, since perovskites themselves contain halogens, halogen-containing hole transport materials can help reduce the migration of halogens in the perovskite, which also helps improve the stability of perovskite cells.

Claims

1. A halogen-containing hole transport material having the general chemical formula shown in the following formula (I): wherein R1-R8 are independently hydrogen, halogen, methyl, phenyl, methoxy, trifluoromethoxy, tert-butyl, or cyano; and at least one of R1-R8 is halogen; R9 represents hydrogen; R 10 Expressed as a phosphate group; L represents a C6 arylene group; A represents space, single bond, oxygen, or sulfur.

2. A halogen-containing hole transport material, characterized in that Any one of the following compounds 1 to 96:

3. A perovskite solar cell comprising at least a transparent conductive oxide substrate, an inorganic p-type semiconductor hole transport layer, an organic hole transport layer, a perovskite active layer, an electron transport layer, a hole blocking layer, and an electrode layer arranged in sequence; or comprising a transparent conductive oxide substrate, an organic hole transport layer, a perovskite active layer, an electron transport layer, a hole blocking layer, and an electrode layer arranged in sequence; wherein: An Ag back electrode is provided on the transparent conductive oxide electrode layer; and the organic hole transport layer comprises the hole transport material according to any one of claims 1 or 2.

4. The perovskite solar cell according to claim 3, wherein The hole transport materials are used alone or in combination.

5. The perovskite solar cell according to claim 3, wherein The thickness of the organic hole transport layer is 0.1 nm to 100 um.

6. The perovskite solar cell according to claim 3, wherein The hole transport layer material is prepared by vacuum evaporation, molecular beam evaporation, solvent-dissolved dip coating, spin coating, rod coating or inkjet printing.

7. The perovskite solar cell according to claim 3, wherein The hole transport layer is a double-layer structure, wherein the upper layer is a P-type semiconductor hole transport layer, the lower layer is an organic hole transport layer, and the perovskite layer is located between the organic hole transport layer and the electron transport layer.

8. The perovskite solar cell according to claim 7, wherein The p-type semiconductor hole transport layer material is a metal-containing semiconductor, and the metal-containing semiconductor is any one of nickel oxide, aluminum copper oxide, iron copper oxide, copper oxide, copper iodide, molybdenum oxide, copper sulfide, ferrous sulfide and cuprous thiocyanate.

9. The perovskite solar cell according to claim 3, wherein The electron transport layer is selected from any one of [6,6]-phenyl-C71-butyric acid isomethyl ester and C60.

10. The perovskite solar cell according to claim 3, wherein: The perovskite cell is selected from a single-layer cell or a stacked cell; when it is a stacked cell, the perovskite cell is any one of a perovskite / crystalline silicon stacked cell, a full perovskite stacked cell, a perovskite / organic stacked cell, and a perovskite / CIGS stacked cell.

11. A flexible perovskite cell, comprising a conductive substrate, a perovskite cell body arranged on the conductive substrate, an encapsulation layer arranged on the perovskite cell body, and a backplane arranged on a side of the encapsulation layer away from the flexible perovskite cell body; the perovskite cell body is sequentially arranged from bottom to top as a first electrode layer, a first electron transport layer, a perovskite absorption layer, a second electron transport layer, a second electrode layer, a conductive electrode, and an encapsulation layer; the first electron transport layer contains the hole transport material according to any one of claims 1 or 2.

12. The flexible perovskite battery according to claim 11, wherein: The perovskite battery body includes a plurality of battery cells connected in series in sequence; wherein, each of the battery cells located at both ends is connected to one of the conductive electrodes.

13. The flexible perovskite battery according to claim 11, wherein: The second electron transport layer is a hole transport layer.

14. The flexible perovskite battery according to claim 11, wherein: The back plate is made of chemically strengthened glass or polyimide film.

15. The flexible perovskite battery according to any one of claims 12 to 14, characterized in that The flexible perovskite cell further includes a barrier layer disposed between the conductive glass substrate and the first electrode layer.

Images