Tetrahydronaphthyl non-fused ring non-fullerene receptor as well as preparation method and application thereof

Abstract

The invention discloses a tetrahydronaphthyl non-fused ring non-fullerene receptor as well as a preparation method and application thereof, and belongs to the field of optoelectronic devices. The chemical structural formula of the tetrahydronaphthyl non-fused ring non-fullerene receptor is shown in the specification. According to the invention, tetrahydronaphthyl side chain substitution is introduced into bithiophene, a bithiophene bridge unit is coupled, and an electron-deficient unit is connected, so that a corresponding small molecule acceptor material is obtained. The acceptor material provided by the invention has good solution processability, and can be used as an active layer for manufacturing an organic photovoltaic cell device. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the field of optoelectronic devices, and in particular relates to a tetrahydronaphthyl non-condensed ring non-fullerene receptor and a preparation method and application thereof. Background Art

[0002] In order to meet the growing demand for energy, humans need to develop and utilize some renewable clean energy to alleviate the crisis of traditional energy depletion while reducing damage to the environment. Solar energy is an inexhaustible, sustainable and environmentally friendly energy. How to better utilize solar energy has become an important scientific issue that scientists around the world are striving for, as well as a technical challenge. The research on organic photovoltaic cells has received increasing attention and has been continuously developed. This device has the advantages of high flexibility, good semi-permeability, and solution processing to obtain a large area of ​​uniform film, so it has attracted much attention.

[0003] The active layer materials of organic solar cells mainly include donor materials and acceptor materials. At present, the acceptors of most high-efficiency systems are mainly based on Y series non-fullerene condensed ring acceptors. Research on organic photovoltaic cells based on this type of acceptor material has made breakthrough progress. However, acceptor materials with condensed ring conjugated skeletons usually have a more complicated synthesis route, which will lead to lower yields. Therefore, it is also very important to develop new non-condensed ring acceptors with low synthesis costs. However, since the non-condensed ring acceptor units are connected by carbon-carbon single bonds, twisting will occur, and the structural stability of the molecules is poor, which ultimately leads to low device efficiency. In order to make up for this defect, there are two main improvement measures. The first is to introduce strong electron-attracting atoms into the molecular structure to form a non-covalent interaction stable structure, and the second is to introduce side chain groups with large steric hindrance into the molecular central skeleton to stabilize the molecular skeleton. Bo Zhishan et al. used thiophene as the central core and introduced diphenylimine with large steric hindrance as the side chain group. By modifying the alkyl side chain on benzene, a new non-condensed ring acceptor 2BTh-2F (C2) was prepared. The three-dimensional molecular conformation brought by the diphenylimine group not only effectively improves the solubility of the molecule, but also prevents excessive molecular aggregation; it also effectively enhances the charge transfer effect within the molecule, causing the absorption spectrum of the material to red-shift. Therefore, it is necessary to further enrich the non-condensed ring receptor system. Summary of the invention

[0004] In order to solve the problems existing in the prior art, the primary purpose of the present invention is to provide a tetrahydronaphthyl non-condensed ring non-fullerene acceptor.

[0005] Another object of the present invention is to provide use of the receptor in preparing solar cells.

[0006] Another object of the present invention is to provide a photovoltaic cell.

[0007] In order to achieve the above object, the present invention provides the following technical solutions:

[0008] A tetrahydronaphthyl non-condensed ring non-fullerene acceptor having the following chemical structure:

[0009]

[0010] Among them, Ar 1 ,Ar 2 ,Ar 3 is an aromatic ring or a conjugated unit, R is C 1 -C 24 The alkyl chain or H of Ar 1 Ar is an electron-donating aromatic ring. 2 is a bridge unit aromatic ring, Ar 3 It is an electron-deficient aromatic ring.

[0011] Preferably, the Ar 1 One of the following structures:

[0012]

[0013] Among them, R 1 -R 3 C 1 -C 24 of an alkyl chain or H.

[0014] Preferably, the Ar 2 One of the following structures:

[0015]

[0016] Among them, R 4 C 1 -C 24 Alkyl chain or H, R 5 C 1 -C 24 Alkyl chain or H, X is H, F, Cl, Br, I, CF 3 , CH 3 O、CH 3 One of the following, Y is H, F, Cl, Br, I, CF 3 , CH 3 O、CH 3 One of them.

[0017] Preferably, the Ar 3 One of the following structures:

[0018]

[0019] Where Z is H, F, Cl, Br, I, CF3 , CH 3 O、CH 3 One of them.

[0020] Preferably, the Ar 1 is a benzene ring, and the substituent on the benzene ring is a methyl group or an octyl group; Ar 2 is a thiophene aromatic ring, and the substituent on the thiophene aromatic ring is an undecyl group; Ar 3 is a dicyanoindanone aromatic ring; the substituent on the dicyanoindanone aromatic ring is F.

[0021] Preferably, the preparation method of the tetrahydronaphthyl non-condensed ring non-fullerene receptor is: after obtaining the tetrahydronaphthyl side chain substituted thiophene, 2 Precursor coupling, and then with Ar 3 The precursor reacts and connects the electron-deficient unit to obtain the tetrahydronaphthyl non-condensed ring non-fullerene acceptor. The structural formula of the tetrahydronaphthyl side chain substituted thiophene is as follows:

[0022]

[0023] Among them, Ar 1 It is an aromatic ring.

[0024] Preferably, the tetrahydronaphthyl side chain substituted thiophene is obtained by Buchwald-Hartwig reaction at 120° C. under inert atmosphere.

[0025] Preferably, the tetrahydronaphthyl side chain substituted thiophene and the bridge unit Ar 2 Precursor coupling was achieved by Stiller coupling reaction at 120 °C under inert atmosphere.

[0026] Preferably, the final acceptor molecule is reacted with the Ar to form the Ar at 60°C by a classical Clauwing condensation reaction. 3 The reaction is obtained by reacting a precursor compound, and an inert atmosphere is used, wherein the inert atmosphere is argon or high-purity nitrogen.

[0027] In the present invention, since the Stiller reaction is a coupling reaction of an organic halide and an organic tin compound under the catalysis of Pd, the tetrahydronaphthyl side chain substituted thiophene needs to undergo a halogenation reaction before coupling with the organic tin compound.

[0028] In the present invention, since the Knoevenagel reaction is a condensation reaction between a compound having an active methylene group and an aldehyde or ketone, it needs to undergo a Vilsmeier-Hack reaction after coupling with the bridge unit, formylate the intermediate product, and then connect the electron-deficient unit.

[0029] More specifically, the inert atmosphere is argon or high-purity nitrogen.

[0030] The present invention also protects the use of the above tetrahydronaphthyl non-condensed ring non-fullerene acceptor in the preparation of photovoltaic cells.

[0031] A photovoltaic cell comprises the above-mentioned tetrahydronaphthyl non-condensed ring non-fullerene acceptor.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] The invention introduces a tetrahydronaphthyl side chain substitution into the thiophene, couples the thiophene bridge unit, and connects the electron-deficient unit to obtain a tetrahydronaphthyl non-condensed ring non-fullerene receptor. The small molecule receptor has good structural stability and greatly enriches the non-condensed ring non-fullerene receptor system. Moreover, the receptor material of the invention has a simple synthesis route, low synthesis cost, good solution processability, and can be used as an active layer for preparing an organic photovoltaic cell device. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 This is the NMR image of Example 1.

[0035] Figure 2 This is the NMR image of Example 2.

[0036] Figure 3 This is the absorption diagram of the small molecule receptor solution prepared in Examples 1 and 2.

[0037] Figure 4 This is the absorption diagram of the small molecule receptor film prepared in Examples 1 and 2.

[0038] Figure 5 This is the electrochemical curve of the small molecule receptor prepared in Example 1.

[0039] Figure 6 This is the electrochemical curve of the small molecule receptor prepared in Example 2.

[0040] Figure 7 This is a device current-voltage curve of the small molecule receptor prepared in Example 1.

[0041] Figure 8 This is a device current-voltage curve of the small molecule receptor prepared in Example 2. DETAILED DESCRIPTION

[0042] The present invention is further described below in conjunction with examples. These examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. The experimental methods in the following examples that do not specify specific conditions are usually carried out according to conventional conditions in the art or according to the conditions recommended by the manufacturer; the raw materials, reagents, etc. used, unless otherwise specified, are all raw materials and reagents that can be obtained from commercial channels such as conventional markets. Any non-substantial changes and substitutions made by those skilled in the art on the basis of the present invention belong to the scope of protection claimed by the present invention.

[0043] Example 1

[0044] This embodiment provides a tetrahydronaphthyl non-condensed ring non-fullerene acceptor (named C8Ph-4F), and its chemical structure is as follows:

[0045]

[0046] The synthesis route of the tetrahydronaphthyl non-condensed ring non-fullerene acceptor is as follows:

[0047] Synthesis route of compound 3:

[0048]

[0049] Under argon protection, 6-bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene (20 mmol, 5.34 g), compound 2 (22 mmol, 4.5 g), sodium tert-butoxide (40 mmol, 3.84 g) and Pd 2 (dba) 3 (1mmol, 0.92g), (t-Bu) 3 PBF 4 (4mmol, 1.16g) was dissolved in 30ml of ultra-dry o-xylene and heated at 120℃ for 1h. After the reaction, the mixture was filtered and the solvent was removed by rotary evaporation. The mixture was separated by chromatographic column using petroleum ether and dichloromethane as eluents, and the eluent was PE:DCM=4:1. Finally, an oily liquid (13mmol, 5g, 65%) was obtained. 1 H NMR (500MHz, Chloroform-d), δ (ppm): 7.19 (d, J=8.5Hz, 1H), 7.08-7.04 (m, 2H), 7.00-6.95 (m, 3H), 6.86 (d d, J=8.4, 2.5Hz, 1H), 2.53 (t, J=7.8Hz, 2H), 1.61-1.55 (m, 2H), 1.35-1.24 (m, 26H), 0.89 (d, J=6.6Hz, 3H).

[0050] Synthesis route of compound 5:

[0051]

[0052] Under argon protection, compound 4 (3 mmol, 0.9 g), compound 3 (7.8 mmol, 3 g), sodium tert-butoxide (6.3 mmol, 0.6 g) and Pd 2 (dba) 3 (0.15mmol, 137mg), (t-Bu) 3 PBF4 (0.6mmol, 174mg) was dissolved in 30ml of ultra-dry o-xylene and heated to 120℃ for reflux reaction for 12h. After the reaction, it was dispersed with dichloromethane, filtered by suction, and the solvent was removed by rotary evaporation. The chromatographic column was separated using petroleum ether and dichloromethane as eluents to finally obtain a white solid (1.86mmol, 1.7g, 62%).

[0053] Synthesis route of compound 6:

[0054]

[0055] Under argon protection, compound 5 (1.5mmol, 1.37g) was dissolved in ultra-dry dichloromethane, and NBS (3.15mmol, 0.56g) was added in portions under light-proof conditions and 0°C. The reaction was allowed to react at room temperature for 12h. After the reaction was completed, the reaction was quenched with water, extracted with dichloromethane three times, and the solvent was removed by rotary evaporation. The product was separated and purified by chromatographic column using dichloromethane and petroleum ether as eluents to finally obtain a yellow liquid (1.3mmol, 1.37g, 85%). 1 HNMR (400MHz, Chloroform-d), δ (ppm): 7.17 (d, J=8.5Hz, 2H), 7.10-7.04 (m, 4H), 6.97-6.90 (m, 6H), 6.78 (dd, J=8.5, 2.5Hz, 2H), 2.57 (t, J=7.7Hz, 4H), 1.63-1.58 (m, 4H), 1.34-1.16 (m, 52H), 0.88-0.84 (m, 6H).

[0056] Synthesis route of compound 7:

[0057]

[0058] Under argon protection, compound 6 (1mmol, 1.1g), tributyl (6-undecylthieno [3,2-B] thiophene-2-yl) stannane (2.5mmol, 1.45g), tetrakis (triphenylphosphine) palladium (0.05mmol, 57mg) were dissolved in ultra-dry o-xylene and reacted at 120°C for 12h. After the reaction, it was poured into water to quench, extracted with dichloromethane three times, the solvent was removed by rotary evaporation, and column chromatography was performed with dichloromethane and petroleum ether as eluents to separate and purify, and finally a yellow-green solid (0.65mmol, 0.98g, 65%) was obtained. 1H NMR (400MHz, Chloroform-d), δ (ppm): 7.10 (dd, J=7.9, 5.4Hz, 6H), 7.05 (s, 8H), 6.85-6.82 (m, 4H), 2.55 (dt, J=10.6, 7.7Hz, 8H), 1.60 (d, J=8.2Hz, 8H), 1.26 (dt, J=15.9, 10.6Hz, 72H), 1.15 (s, 12H), 0.89-0.85 (m, 12H).

[0059] Synthesis route of compound 8:

[0060]

[0061] Under argon protection, compound 7 (0.64mmol, 0.96g) was dissolved in 20ml of ultra-dry 1,2-dichloroethane, and then 10ml of ultra-dry DMF was added thereto. At 0°C, 0.8ml of phosphorus oxychloride was slowly added dropwise. After reacting for 2h, the temperature was raised to 85°C and reacted for 16h. After the reaction was completed, the reactant was slowly poured into an icy sodium hydroxide aqueous solution, extracted three times with dichloromethane, and the solvent was removed by rotary evaporation. After separation and purification by column chromatography, an orange solid (0.47mmol, 0.73g, 73%) was finally obtained. 1 H NMR (500MHz, Chloroform-d), δ (ppm): 9.98 (s, 2H), 7.13 (d, J=8.6Hz, 2H), 7.09-7.04 (m, 12H), 6.82 (dd, J=8.5, 2.6Hz, 2H), 2.94 (t, J=7.6Hz, 4H), 2.58-2.53 (m, 4H), 1.57 (d, J=12.9Hz, 8H), 1.32-1.20 (m, 72H), 1.15 (s, 12H), 0.87 (t, J=7.1Hz, 12H).

[0062] The final synthetic route of the receptor:

[0063]

[0064] Under argon protection, compound 8 (0.2mmol, 312mg) and 5,6-difluoro-3-(dicyanomethylene)indone (0.8mmol, 184mg) were added to 30ml of chloroform, and then 1ml of ultra-dry pyridine was added dropwise, and the mixture was refluxed at 60 degrees Celsius in the dark for 12h. After the reaction, the mixture was poured into methanol and allowed to stand, filtered, and then further purified by silica gel chromatography using a mixed solution of dichloromethane and petroleum ether as eluent, and the product was recrystallized in methanol, ethanol, and isopropanol as solvents, and finally a blue-black solid product C8Ph-4F (0.15mmol, 297mg, 75%) was obtained. 1 H NMR (500MHz, Chloroform-d), δ (ppm): 8.98 (s, 2H), 8.53 (dd, J=10.0, 6.4Hz, 2H) , 7.64 (t, J=7.5Hz, 2H), 7.19 (d, J=8.6Hz, 2H), 7.14 (s, 2H), 7.12-7.07 (m, 6H), 7. 05 (d, J = 8.6 Hz, 4H), 6..85 (dd, J = 8.6, 2.5 Hz, 2H), 2.98 (t, J = 7.9 Hz, 4H), 2.56 (t, J = 7.8 Hz, 4H), 1.55 (s, 20H), , 1.36-1.15 (m, 72H), 0.85 (dt, J = 15.0, 6.9 Hz, 12H). The specific NMR is shown in Figure 1 shown.

[0065] Example 2

[0066] This embodiment provides a tetrahydronaphthyl non-condensed ring non-fullerene acceptor (named MePh-4F), and its chemical structure is as follows:

[0067]

[0068] The synthesis route of the tetrahydronaphthyl non-condensed ring non-fullerene acceptor is as follows:

[0069] Synthesis route of compound 3:

[0070]

[0071] Under argon protection, 6-bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene (20 mmol, 5.34 g), compound 2 (22 mmol, 2.35 g), sodium tert-butoxide (40 mmol, 3.84 g) and Pd 2 (dba) 3 (1mmol, 0.92g), (t-Bu) 3 PBF 4(4mmol, 1.16g) was dissolved in 30ml of ultra-dry o-xylene and heated at 120℃ for 1h. After the reaction, it was filtered, rotary evaporated, separated by chromatographic column, and petroleum ether and dichloromethane were used as eluents to finally obtain a white solid (12.8mmol, 12.8g, 64%). 1 H NMR (400MHz, Chloroform-d), δ (ppm): 7.18 (d, J=8.4Hz, 1H), 7.06 (d, J=7.9Hz, 2H), 7.02-6.8 9 (m, 3H), 6.84 (d, J=8.4Hz, 1H), 2.29 (s, 3H), 1.67 (d, J=14.3Hz, 4H), 1.26 (d, J=3.4Hz, 12H).

[0072] Synthesis route of compound 5:

[0073]

[0074] Under argon protection, compound 4 (3 mmol, 0.9 g), compound 3 (7.8 mmol, 2.28 g), sodium tert-butoxide (6.3 mmol, 0.6 g) and Pd 2 (dba) 3 (0.15mmol, 137mg), (t-Bu) 3 PBF 4 (0.6mmol, 174mg) was dissolved in 30ml of ultra-dry o-xylene and heated to 120℃ for reflux reaction for 12h. After the reaction, the mixture was filtered and the solvent was removed by rotary evaporation. The mixture was separated by a chromatographic column using petroleum ether and dichloromethane as eluents to finally obtain a white solid compound 5 (1.83mmol, 1.32g, 61%). 1 H NMR (400MHz, Chloroform-d), δ (ppm): 7.23-6.88 (m, 14H), 6.83 (dd, J=8.5, 2.3Hz, 2H), 2.32 (s, 6H), 1.66 (s, 7H), 1.26 (s, 12H), 1.16 (s, 12H).

[0075] Synthesis route of compound 6:

[0076]

[0077] Under argon protection, compound 5 (1.5 mmol, 1.08 g) was dissolved in ultra-dry dichloromethane, and NBS (3.15 mmol, 0.56 g) was added in portions under light-proof conditions and at 0°C. The reaction was allowed to react at room temperature for 12 h. After the reaction was completed, the reaction was quenched with water, extracted three times with dichloromethane, and the solvent was removed by rotary evaporation. The product was separated and purified by a silica gel column with petroleum ether and dichloromethane as eluents to finally give a yellow liquid (1.35 mmol, 1.19 g, 90%). 1 H NMR (400MHz, Chloroform-d), δ (ppm): 7.17 (d, J=8.4Hz, 2H), 7.07 (d, J=8.2Hz, 4H), 7.00-6.88 (m, 6H), 6.76 (dd, J=8.6, 2.5Hz, 2H), 2.31 (d, J=3.1Hz, 6H), 1.67 (s, 8H), 1.27 (s, 12H), 1.16 (d, J=4.1Hz, 12H).

[0078] Synthesis route of compound 7:

[0079]

[0080] Under argon protection, compound 6 (1mmol, 0.88g), tributyl (6-undecylthieno [3,2-B] thiophene-2-yl) stannane (2.5mmol, 1.45g), tetrakis (triphenylphosphine) palladium (0.05mmol, 57mg) were dissolved in ultra-dry o-xylene and reacted at 120°C for 12h. After the reaction, it was poured into water for quenching, extracted with dichloromethane three times, the solvent was removed by rotary evaporation, and column chromatography was performed with dichloromethane and petroleum ether as eluents to separate and purify, and finally a yellow-green liquid (0.55mmol, 0.72g, 55%) was obtained. 1 H NMR (400MHz, Chloroform-d), δ (ppm): 7.13-7.09 (m, 6H), 7.05 (s, 8H), 6.85-6.80 (m, 4H), 2.57 (t, J=7.6Hz, 4H), 2.29 (s, 6H), 1.56 (d, J=4.7Hz, 8H), 1.29-1.23 (m, 36H), 1.18 (d, J=24.5Hz, 24H), 0.88 (t, J=6.7Hz, 6H).

[0081] Synthesis route of compound 8:

[0082]

[0083] Under argon protection, compound 7 (0.64mmol, 0.84g) was dissolved in 20ml of ultra-dry 1,2-dichloroethane, and 10ml of ultra-dry DMF was added thereto. At 0°C, 0.8ml of phosphorus oxychloride was slowly added dropwise. After reacting for 2h, the temperature was raised to 85°C and reacted for 16h. After the reaction was completed, the reactant was slowly poured into an icy sodium hydroxide aqueous solution to quench, extracted three times with dichloromethane, and the solvent was removed by rotary evaporation. The product was further purified by a silica gel chromatography column with petroleum ether and dichloromethane as eluents to obtain an orange solid (0.52mmol, 0.72g). 1 H NMR (400MHz, Chloroform-d), δ (ppm): 9.98 (s, 2H), 7.15-7.11 (m, 4H), 7.09-7.04 (m, 10H), 6.80 (dd, J=8.5, 2.5Hz , 2H), 2.94 (t, J=7.6Hz, 4H), 2.31 (s, 6H), 1.30-1.22 (m, 36H), 1.21 (s, 12H), 1.16 (s, 12H), 0.88 (t, J=6.7Hz, 6H).

[0084] Synthesis route of compound MePh-F:

[0085]

[0086] Under argon protection, compound 8 (0.2mmol, 272mg) and 5,6-difluoro-3-(dicyanomethylidene)indone (0.8mmol, 184mg) were added to 30ml of chloroform, and then 1ml of ultra-dry pyridine was added dropwise, and the mixture was refluxed at 60 degrees Celsius in the dark for 12h. After the reaction, the mixture was poured into methanol and allowed to stand, filtered, and then further purified by silica gel chromatography using a mixed solution of dichloromethane and petroleum ether as eluent. The product was recrystallized in methanol, ethanol, and isopropanol as solvents, and finally a blue-black solid product MePH-4F (0.16mmol, 289mg, 81%) was obtained. The specific NMR is shown in the figure below. Figure 2 shown.

[0087] The receptors prepared in Examples 1 and 2 were subjected to absorption tests. The test results are as follows: Figure 3 as well as Figure 4 As shown. Figure 3 It can be seen that the maximum absorption peaks of the acceptor solution and film obtained in Example 1 are 738 nm and 797 nm, respectively, and the maximum absorption peaks of the small molecule solution and film obtained in Example 2 are 733 nm and 794 nm, respectively.

[0088] The receptors prepared in Examples 1 and 2 were subjected to electrochemical tests, with ferrocene used as a reference test. The test results are as follows: Figure 5 and Figure 6 The electrochemical energy levels HOMO and LUMO of the small molecule receptor obtained in Example 1 calculated by the formula are -5.51 eV and -3.84 eV respectively, and the electrochemical energy levels HOMO and LUMO of the small molecule receptor obtained in Example 2 are -5.48 eV and -3.83 eV respectively.

[0089] Example 3

[0090] Preparation and performance of organic photovoltaic cell devices using ITO as anode

[0091] The structure of the organic photovoltaic cell device with ITO as the anode is: ITO / PEDOT:PSS / polymer donor PM6: small molecule acceptor based on tetrahydronaphthyl-substituted thiophene prepared in Example 1 = 1:1.2 / PDINN / Ag. The device manufacturing process is: using the pre-cleaned ITO glass as the anode, spin-coating PEDOT:PSS on the ITO substrate by spin coating at a speed of 3000rpm for 30s. Annealing at 150°C in an air atmosphere for 12min to form a dense anode interface layer film. Then spin-coat a photovoltaic active layer (PM6 and small molecule acceptor based on tetrahydronaphthyl-substituted thiophene prepared in Example 1) with a thickness of about 110 nanometers. Anneal at 120°C for 10 minutes, and after cooling, spin-coat 1.5mg / mL PDINN methanol solution on the active layer at a speed of 3000rpm for 30s, without annealing. After the solvent evaporates naturally, a Ag electrode with a thickness of about 100 nm is deposited by high vacuum thermal evaporation to obtain the organic solar cell. A bias voltage is applied between the ITO and Ag metal electrodes, and the cell characteristics are measured under the irradiation of AM 1.5 simulated sunlight with a 100 mW / cm2 irradiation. The open circuit voltage of the cell device is 0.90 volts, the short circuit current is 20.46 mA / cm2, the fill factor is 60.05%, and the energy conversion efficiency is 10.98%. The specific JV curve is as follows Figure 7 shown.

[0092] The tetrahydronaphthyl-substituted thiophene small molecule acceptor prepared in Example 2 was used, and the polymer D18 was used as the donor. The organic photovoltaic cell device was prepared according to the same process as above, and the cell device performance was: open circuit voltage of 0.91 volts, short circuit current of 20.99 milliamperes per square centimeter, fill factor of 64.98%, and energy conversion efficiency of 12.55%. The specific JV curve is shown in the figure below. Figure 8 The small molecule receptors of Examples 1 and 2 are shown in Table 1.

[0093] Table 1. Photovoltaic performance of small molecule acceptors based on tetrahydronaphthyl-substituted thiophene prepared in Examples 1 and 2

[0094] Receptor material <![CDATA[V oc (V)]]> <![CDATA[J sc (mA / cm 2 )]]> FF(%) PCE(%) C8Ph-4F 0.90 20.46 60.05 10.98 MePh-4F 0.91 20.99 64.98 12.55

[0095] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A tetrahydronaphthyl non-condensed ring non-fullerene acceptor, characterized in that: It has the following chemical structure: Wherein, Ar1, Ar2, Ar3 are aromatic rings or conjugated units, and R is C1-C 24 Ar1 is an electron-donating aromatic ring, Ar2 is a bridge unit aromatic ring, and Ar3 is an electron-deficient aromatic ring.

2. The tetrahydronaphthyl non-condensed ring non-fullerene acceptor according to claim 1, characterized in that: The Ar1 is one of the following structures: Where R1-R3 is C1-C 24 of an alkyl chain or H.

3. The tetrahydronaphthyl non-condensed ring non-fullerene acceptor according to claim 1, characterized in that: The Ar2 is one of the following structures: Where R4 is C1-C 24 Alkyl chain or H, R5 is C1-C 24 An alkyl chain or H, X is one of H, F, Cl, Br, I, CF3, CH3O, CH3, and Y is one of H, F, Cl, Br, I, CF3, CH3O, CH3.

4. The tetrahydronaphthyl non-condensed ring non-fullerene acceptor according to claim 1, characterized in that: The Ar3 is one of the following structures: Wherein, Z is one of H, F, Cl, Br, I, CF3, CH3O, and CH3.

5. The tetrahydronaphthyl non-condensed ring non-fullerene acceptor according to claim 1, characterized in that: Ar1 is a benzene ring, and the substituent on the benzene ring is methyl or octyl; Ar2 is a thiophene aromatic ring, and the substituent on the thiophene aromatic ring is undecyl; Ar3 is a dicyanoindanone aromatic ring; and the substituent on the dicyanoindanone aromatic ring is F.

6. The tetrahydronaphthyl non-condensed ring non-fullerene acceptor according to claim 1, characterized in that: The preparation method of the tetrahydronaphthyl non-condensed ring non-fullerene receptor is as follows: after obtaining a tetrahydronaphthyl side chain substituted thiophene, coupling it with a bridge unit aromatic ring Ar2 precursor, and then reacting it with an Ar3 precursor to connect an electron-deficient unit to obtain the tetrahydronaphthyl non-condensed ring non-fullerene receptor; The structural formula of the tetrahydronaphthyl side chain substituted thiophene is as follows: Wherein, Ar1 is an aromatic ring.

7. The tetrahydronaphthyl non-condensed ring non-fullerene acceptor according to claim 6, characterized in that: The tetrahydronaphthyl side chain substituted thiophene is obtained by Buchwald-Hartwig reaction at 120° C. under an inert atmosphere.

8. The tetrahydronaphthyl non-condensed ring non-fullerene acceptor according to claim 6, characterized in that: The coupling of the tetrahydronaphthyl side chain substituted thiophene with the bridge unit Ar2 precursor is achieved by Stiller coupling reaction at 120° C. under inert atmosphere.

9. Use of the tetrahydronaphthyl non-condensed ring non-fullerene acceptor according to any one of claims 1 to 5 in the preparation of photovoltaic cells.

10. A photovoltaic cell, characterized in that: It comprises the tetrahydronaphthyl non-condensed ring non-fullerene acceptor as described in any one of claims 1 to 5.

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