CN107501232B - Organic solar cell small molecule receptor material with naphtho-indene fluorene unit as core and preparation method and application thereof - Google Patents

Organic solar cell small molecule receptor material with naphtho-indene fluorene unit as core and preparation method and application thereof Download PDF

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CN107501232B
CN107501232B CN201710763636.5A CN201710763636A CN107501232B CN 107501232 B CN107501232 B CN 107501232B CN 201710763636 A CN201710763636 A CN 201710763636A CN 107501232 B CN107501232 B CN 107501232B
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应磊
傅登豪
郭婷
杨伟
彭俊彪
曹镛
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South China University of Technology SCUT
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Abstract

The invention discloses an organic solar cell small molecule acceptor material taking a naphtho-indene fluorene unit as a core, and a preparation method and application thereof. The preparation method comprises the steps of taking a naphthoindene fluorene unit containing a polar substituent group as a core, and sequentially connecting electron-withdrawing units to two sides of the naphthoindene fluorene unit through a coupling reaction to obtain the organic solar cell micromolecule acceptor material taking the naphthoindene fluorene unit as the core. And dissolving the organic solar cell micromolecule acceptor material taking the naphthoindene fluorene unit as the core and the donor material in an organic solvent, spin-coating the ITO/PEDOT/PSS surface to form a film, and evaporating to remove the residual organic solvent to obtain the active layer of the organic solar cell. The organic solar cell small molecule acceptor material taking the naphthoindenofluorene unit as the core has the characteristics of simple structure and easiness in processing.

Description

Organic solar cell small molecule receptor material with naphtho-indene fluorene unit as core and preparation method and application thereof
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to an organic solar cell small molecule acceptor material taking a naphthoindene fluorene unit as a core, and a preparation method and application thereof.
Background
Organic solar cells (OPVs) have the advantages of light material weight, easy chemical structure design and synthesis, simple device preparation process, easy realization of large-area/flexible devices and the like, so that the organic solar cells become an important development direction of new-generation solar cells.
A typical device structure of an organic solar cell is composed of an Indium Tin Oxide (ITO) transparent anode, a metal cathode, and a photoactive layer sandwiched therebetween. The working principle of the solar cell is that when sunlight irradiates an active layer through a transparent ITO electrode, a D material and an A material in the active layer absorb photons to generate excitons, the excitons diffuse to a D/A interface to be dissociated into electrons and holes, the electrons are transported to a cathode through an acceptor material and collected, the holes are transported through a donor material and collected at the anode, and therefore current is generated.
Over the last decade, the energy conversion efficiency of solution processed bulk heterojunction organic solar cells has been dramatically increased, from the earliest efficiencies below 1% to the more recently reported efficiencies above 10%. The improvement of organic photovoltaic efficiency is mainly due to the development of many new donor materials. However, the development of electron acceptor materials lags far behind the development of electron donor materials.
Currently, among solution processed bulk heterojunction OPVs, fullerenes and derivatives thereof, especially PC61BM and PC71BM, are the most successful as electron acceptor materials. However, fullerene and its derivatives also have disadvantages such as weak absorption in the visible spectral region, limited spectral width, and difficulty in adjusting the band gap of fullerene by chemical modification. Therefore, the research on non-fullerene acceptor materials is also becoming one of the directions for improving the performance of organic solar cells.
Disclosure of Invention
The invention aims to provide an organic solar cell small molecule acceptor material taking a naphthoindenofluorene unit as a core, which has the characteristics of simple structure and easiness in processing.
The invention also aims to provide a preparation method of the organic solar cell small molecule acceptor material taking the naphthoindenofluorene unit as the core.
The invention also aims to provide application of the organic solar cell small molecule acceptor material taking the naphthoindenofluorene unit as the core.
The purpose of the invention is realized by the following technical scheme.
A small molecule acceptor material of an organic solar cell taking a naphthoindene fluorene unit as a core has the following chemical structural formula:
Figure BDA0001393673160000021
wherein R is H atom, aryl, or C1-20 linear chainOr a branched alkyl group, or an alkoxy group having 1 to 20 carbon atoms; b is1、B2Are all polar substituent groups, B1、B2Are independently selected from the same or different aromatic ring derivatives, conjugated units containing carbon-carbon double bonds or conjugated units containing carbon-carbon triple bonds; a. the1、 A2Are the same or different electron-withdrawing units.
Further, B1、B2The structures of (A) are independently selected from any one or two of the following structural formulas:
Figure BDA0001393673160000031
wherein X is an oxygen atom, a sulfur atom or a selenium atom, and Y is a carbon atom or a silicon atom; r2、R3Are selected from H atom, aryl, C1-20 straight chain or branched chain alkyl, or C1-20 alkoxy.
Further, A1、A2The structures of (A) are independently selected from any one or two of the following structural formulas:
Figure BDA0001393673160000041
wherein R is4、R5Are all independently selected from alkyl of C1-C8, R6、R7Are independently selected from H atom, F atom, nitro, cyano, methyl, ester group or trifluoromethyl.
Further, A1、A2The structures of (A) are independently selected from any one or two of the following structural formulas:
Figure BDA0001393673160000042
in the formula (I), the compound is shown in the specification,
Figure BDA0001393673160000043
are all selected from one of the following structuresOne or two of:
Figure BDA0001393673160000044
wherein R is6、R7、R6’、R7' are independently selected from H atom, F atom, nitro, cyano, methyl, ester group or trifluoromethyl; r4’、R5' are all independently selected from alkyl groups of C1-C8.
Even more preferably, A1、A2The structures of (A) are independently selected from any one or two of the following structural formulas:
Figure BDA0001393673160000051
in the formula (I), the compound is shown in the specification,
Figure BDA0001393673160000052
one or two of the following structures:
Figure BDA0001393673160000053
wherein R is6、R7、R6’、R7' are independently selected from H atom, F atom, nitro, cyano, methyl, ester group or trifluoromethyl; r4’、R5' are all independently selected from alkyl groups of C1-C8.
The method for preparing the organic solar cell small molecule acceptor material with the naphthoindenofluorene unit as the core comprises the following steps:
the method comprises the steps of taking a naphthoindene fluorene unit containing a polar substituent group as a core, and sequentially connecting electron-withdrawing units to two sides of the naphthoindene fluorene unit through a coupling reaction to obtain the organic solar cell small molecule acceptor material taking the naphthoindene fluorene unit as the core.
Further, the reaction temperature of the coupling reaction is 60 ℃ to 70 ℃.
Further, the coupling reaction time is 4-6 hours.
The organic solar cell small molecule acceptor material taking the naphtho-indene fluorene unit as the core is applied to preparing an active layer of a solar cell, the organic solar cell small molecule acceptor material taking the naphtho-indene fluorene unit as the core and a donor material are dissolved in an organic solvent, a film is formed on the surface of ITO/PEDOT (PSS) in a spin coating mode, and residual organic solvent is removed by evaporation to obtain the active layer of the organic solar cell.
Further, the mass ratio of the organic solar cell small molecule acceptor material taking the naphthoindenofluorene unit as the core to the donor material is 1.5: 1-1: 1.
further, the organic solvent includes chlorobenzene or o-dichlorobenzene.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the method synthesizes the small-molecule receptor material by using the naphtho-indene fluorene unit as the center for the first time, has simple synthesis method and easy purification, and is beneficial to industrial application;
(2) the organic solar cell micromolecule receptor material taking the naphtho-indene fluorene unit as the core has better solubility and film forming property, so that the process of the active layer based on the material is simpler when the solar cell device is prepared;
(3) the organic solar cell micromolecule acceptor material taking the naphthoindene fluorene unit as the core has a larger conjugated structure, and is beneficial to improving the efficiency of an organic solar cell device.
Drawings
FIG. 1 is a graph of UV-VIS absorption curves for compounds NFIC and NFIC-M;
FIG. 2 is a thermogravimetric plot of compounds NFIC and NFIC-M;
FIG. 3 is an electrochemical plot of compound NFIC;
FIG. 4 is an electrochemical plot of compound NFIC-M;
fig. 5 is a graph of current-voltage (J-V) characteristics of photovoltaic devices based on compounds NFIC and NFIC-M.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example 1
Preparation of 2-borate-9, 9-dioctylfluorene
The chemical reaction equation is as follows:
Figure BDA0001393673160000071
2-bromo-9, 9-dioctylfluorene (15g, 31.95mmol) was dissolved in 200mL of purified Tetrahydrofuran (THF) under an argon atmosphere, and 1.6mol.L was gradually added dropwise at-78 deg.C-139.9mL of n-butyllithium (N-butyllithium), followed by addition of 7.73g of 2-isopropoxy-4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborane, reaction at-78 ℃ for 1 hour, and then heating to room temperature for 24 hours; pouring the reaction mixture into water, extracting with ethyl acetate, completely washing the organic layer with saline, and drying with anhydrous magnesium sulfate; after concentration of the solution, a crude product is obtained in the form of a pale yellow viscous product which is purified by column chromatography on silica gel (the eluent is selected from petroleum ether/ethyl acetate 15/1, v/v), and the product is left for a long time in a refrigerator to give a white solid in 70% yield.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
Example 2
Preparation of methyl 1-bromodinaphthoate
The chemical reaction equation is as follows:
Figure BDA0001393673160000081
adding 1-bromo-2-naphthoic acid (10g, 39.83mmol) into a two-neck bottle under argon atmosphere, adding 100mL of methanol, dropwise adding concentrated sulfuric acid (39.06mg, 398.29umol), heating to 110 ℃, and reacting for 18 h; pouring the reaction mixture into water, extracting with ethyl acetate, and adding common salt to the organic layerAfter water is completely washed, anhydrous magnesium sulfate is added for drying; after concentration of the solution, crude white solid was obtained and purified by column chromatography on silica gel (eluent selected from petroleum ether/dichloromethane: 3/1, v/v), and the product was kept in a refrigerator for a long time to obtain white solid with a yield of 85%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was the target product.
Example 3
Preparation of Compound M1
The chemical reaction equation is as follows:
Figure BDA0001393673160000082
under argon atmosphere, 2-boronate-9, 9-dioctylfluorene (8.5g, 16.45mmol) and methyl 1-bromodinaphthoate (6.11g, 23.03mmol) were added to a two-necked flask, 150ml of toluene was added to dissolve, sodium carbonate (8.72g, 82.27mmol) and 50mg of tetrabutylammonium bromide were added, palladium tetratriphenylphosphine (950.65g, 0.823mmol) was added, and the mixture was reacted at 110 ℃ for 18 hours; pouring the reaction mixture into water, extracting with ethyl acetate, completely washing the organic layer with saline, and drying with anhydrous magnesium sulfate; after concentration of the solution, purification by column chromatography on silica gel (eluent selected from petroleum ether/dichloromethane: 5/1, v/v) gave a white solid in 70% yield.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was M1 as the objective product.
Example 4
Preparation of Compound M2
The chemical reaction equation is as follows:
Figure BDA0001393673160000091
under an argon atmosphere, compound M1(5.5g, 9.57mmol) was added to a single-neck flask, and 50ml of anhydrous THF was added until completely dissolved; reacting the reaction solution at 0 ℃ for 1h, and then dropwise adding 1.6mol.L-1N-octyl magnesium bromide (C)8H17MgBr, 17.9ml), reacting the mixed solution at room temperature for 18 h; adding water into the reaction solution to quench the reaction, extracting with ethyl acetate, completely washing the organic layer with saline, and drying with anhydrous magnesium sulfate; concentrating the solution, and purifying by silica gel column chromatography (the eluent is selected from petroleum ether/dichloromethane (3/1), v/v); the product was kept in a refrigerator for a long time to give a white solid with a yield of 80%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was M2 as the objective product.
Example 5
Preparation of Compound M3
The chemical reaction equation is as follows:
Figure BDA0001393673160000101
under argon atmosphere, compound M2(3.0g, 3.89mmol) was dissolved in 50ml of dichloromethane, 1ml of a diethyl ether solution of 46.5% boron trifluoride was added dropwise at room temperature, and the reaction was carried out for 18 hours; extracting with ethyl acetate, washing the organic layer with saline, adding anhydrous magnesium sulfate, and drying; after concentration of the solution, it was purified by column chromatography on silica gel (eluent selected from petroleum ether), and the product was left in a refrigerator for a long time to obtain a white solid with a yield of 90%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was M3 as the objective product.
Example 6
Preparation of Compound M4
The chemical reaction equation is as follows:
Figure BDA0001393673160000102
under argon atmosphere, compound M3(2g, 2.66mmol) was dissolved in 50mL of dichloromethane, iron powder (148.28mg, 2.66mmol) was added, and liquid bromine (1.06g, 6.64mmol) was added dropwise and reacted at room temperature for 18 h; extracting with ethyl acetate, washing the organic layer with saline, adding anhydrous magnesium sulfate, and drying; solutions ofAfter concentration, the mixture was purified by silica gel column chromatography (eluent selected from petroleum ether) with a yield of 75%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was M4 as the objective product.
Example 7
Preparation of Compound M5
The chemical reaction equation is as follows:
Figure BDA0001393673160000111
compound M4(1.8g, 1.98mmol) was added to a 100ml two-necked flask under an argon atmosphere, dissolved in 30ml of toluene, compound M5(4.4g, 9.88mmol) was added dropwise, palladium tetrakistriphenylphosphine (456.63mg, 0.395mmol) was further added, and after 18 hours of reaction at 110 ℃, tetrahydrofuran THF and a dilute aqueous hydrochloric acid solution (2 mol. L) were added-1) Acidifying 5ml of mixed solution for 6 hours; pouring the reaction mixture into water, extracting with ethyl acetate, completely washing the organic layer with saline, and drying with anhydrous magnesium sulfate; after concentration of the solution, purification by column chromatography on silica gel (eluent selected from petroleum ether/dichloromethane: 2/1, v/v) gave a yellow-green solid with a yield of 70%.1H NMR、13The results of C NMR, MS and elemental analysis showed that the obtained compound was M6 as the objective product.
Example 8
Preparation of Compound NFIC
The chemical reaction equation is as follows:
Figure BDA0001393673160000121
under an argon atmosphere, compound M6(200mg, 0.205mmol) and compound M7(319.16mg, 1.64mmol) were added to a 100ml two-necked flask, dissolved in 12ml chloroform, and 1ml pyridine was added to react at 65 ℃ for 4 h; pouring the reaction mixture into water, extracting with ethyl acetate, completely washing the organic layer with saline, and drying with anhydrous magnesium sulfate; the solution is concentrated and purified by column chromatography over silica gel (eluent)Choice of petroleum ether/dichloromethane-2/1, v/v) finally gave a bluish violet solid in 80% yield.1H NMR、13The results of C NMR, MS and elemental analysis show that the obtained compound is the target product NFIC.
Example 9
Preparation of Compound NFIC-M
The chemical reaction equation is as follows:
Figure BDA0001393673160000131
under an argon atmosphere, compound M6(200mg, 0.205mmol) and compound M8(342.22mg, 1.64mmol) were added to a 100ml two-necked flask, dissolved in 12ml chloroform, and 1ml pyridine was added to react at 65 ℃ for 4 h; pouring the reaction mixture into water, extracting with ethyl acetate, completely washing the organic layer with saline, and drying with anhydrous magnesium sulfate; after concentration of the solution, purification by column chromatography on silica gel (eluent selected from petroleum ether/dichloromethane: 2/1, v/v) gives a violet solid in 85% yield.1H NMR、13C NMR, MS and element analysis results show that the obtained compound is the target product NFIC-M.
The ultraviolet-visible light absorption curve graphs of the receptor material compounds NFIC and NFIC-M are shown in figure 1, the difference of absorption curves of the two receptor materials in a chlorobenzene solution state is small, and the NFIC-M have double absorption of 300-400 nm and 500-700 nm.
In N2In an atmosphere of (2), a temperature rise rate is 20 ℃/min, and a temperature at which a weight loss reaches 5% is taken as a decomposition temperature TdThe thermogravimetric plots of the compounds NFIC and NFIC-M are shown in fig. 2, and it can be seen from fig. 2 that the decomposition temperatures Td of the compounds NFIC and NFIC-M are 353 ℃ and 347 ℃, indicating that both NFIC and NFIC-M receptor materials have good thermal stability, are stable enough for use in device fabrication and use characterization, and are capable of performing relevant thermal treatments.
The electrochemical profiles of the compound NFIC and the compound NFIC-M are shown in FIGS. 3 and 4, respectively, and it can be seen from FIGS. 3 and 4 that the compound NFIC and the compound NFIC-M haveThe initial reduction potentials are-1.50V and-1.55V respectively, so that the obtained LUMO energy level values are-2.92 eV and-2.87 eV respectively; the LUMO energy level of NFIC-M is slightly higher than that of NFIC, which is comparable to the-CH on the indanone unit of NFIC-M3In connection with this, the introduction of a methyl structure can control the electron-withdrawing ability of the acceptor unit and thus the LUMO level of the material.
Example 10
Preparation and characterization of organic solar cell based on naphtho-indene fluorene small molecule acceptor material
The BHJ-OPV device adopts a traditional sandwich structure, namely ITO/PEDOT: PSS/active layer/PFNDI-Br/Al, specifically, ITO is a positive electrode, Al is a negative electrode, PEDOT: PSS is a hole transport layer, and PFNDI-Br is an electron transport layer.
The preparation method of the BHJ-OPV device specifically comprises the following steps:
(1) firstly, ultrasonically cleaning ITO glass by using acetone, a detergent, deionized water and isopropanol in sequence, wherein the cleaning time is 10min each time; spin-coating a PEDOT: PSS (1:1, w/w) aqueous solution on the cleaned ITO glass at the rotating speed of 2000rpm, wherein the film thickness is 30nm, then drying in the air at 150 ℃ for 15min, and removing the residual aqueous solvent in the PEDOT: PSS to obtain an ITO/PEDOT: PSS film;
(2) PSS film is transferred into a nitrogen glove box, and the preparation of the active layer donor and acceptor blending solution and the spin coating film forming are carried out in the glove box; the donor material is PTB7-Th (PCE10), and the chemical structure of PCE10 is shown as follows (n is polymerization degree):
Figure BDA0001393673160000151
dichlorobenzene solutions of NFIC and NFIC-M (mass ratio of donor material to acceptor material NFIC and NFIC-M is selected from 1:1 and 1: 1.5, respectively, and concentration is set to 8.5 mg/ml-1) Spin-coating the surface of an ITO/PEDOT film by using a spin coater to prepare a film with the thickness of 30nm, annealing the film for 15min at 110 ℃ in a nitrogen atmosphere, and removing the residual aqueous solvent to obtain an active layer;
in the thin film UV-VIS absorption test for NFIC and NFIC-M, phasesCompared with solution absorption, the film absorption has wider absorption range, and the maximum absorption peaks of the films of NFIC and NFIC-M have more obvious red shifts compared with the solution absorption, which respectively reach 27nm and 33nm, which are caused by intermolecular aggregation in a film state; in film absorption, the absorption band edge of both NFIC and NFIC-M is about 700nm, so Eg optThe optical bandgaps of NFIC and NFIC-M available at 1240/λ are both about 1.78 eV.
(3) Mixing 1 mg/ml-1Attaching a methanol solution of PFNDI-Br on the active layer at 3000rpm for 30s to obtain an electron transport layer with the thickness of 10 nm; finally, Al cathode is at constant voltage of 5X 10-4And (3) evaporating the mixture on an electron transport layer under the condition of Pa, wherein the thickness of the Al cathode layer is 100nm, and thus obtaining the BHJ-OPV device.
The area of the active layer of the prepared BHJ-OPV device was calculated to be 5.7mm2(ii) a Current-voltage (J-V) characteristics of the prepared BHJ-OPV device were measured by Keithley 2602 at an illumination intensity of 100mW cm-2The measured current-voltage (J-V) characteristic curve of the BHJ-OPV device is shown in fig. 5, and it can be seen from fig. 5 that: for the PTB7-Th/NFIC device, the mass ratio of donor to acceptor was 1:1 hour, measured open loop voltage VOC0.91V, current density JSC＝8.28mA·cm-2The filling coefficient FF is 32.07 percent and the PCE is 2.42 percent; for the PTB7-Th/NFIC-M device, the mass ratio of donor to acceptor was 1: open loop voltage V measured at 1.5OC1.01V, current density JSC4.92 mA/cm-2, the filling coefficient FF is 28.51 percent and the PCE is 1.42 percent.
In addition, the mass ratio of the donor material to the acceptor material NFIC is 1: 1.5 hours later, the device was tested and the open loop voltage V was measuredOC0.92V, current density JSC＝9.01mA·cm-2The fill factor FF is 33.34% and the PCE is 2.76%.
The above embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention. Any replacement, modification, combination or simplification made by those skilled in the art without changing the spirit of the present invention will fall within the protection scope of the present invention.

Claims (10)

1. The organic solar cell small molecule acceptor material with the naphtho-indene fluorene unit as the core is characterized by having the following chemical structural formula:
Figure FDA0003127306180000011
wherein R is H atom, aryl, straight chain or branched chain alkyl with 1-20 carbon atoms, or alkoxy with 1-20 carbon atoms; b is1、B2Are all polar substituent groups, B1、B2Are independently selected from the same or different aromatic ring derivatives, conjugated units containing carbon-carbon double bonds or conjugated units containing carbon-carbon triple bonds; a. the1、A2Are the same or different electron-withdrawing units.
2. The organic solar cell small molecule acceptor material with the naphthoindenofluorene unit as the core according to claim 1, wherein B is1、B2Each structure of (a) is independently selected from any one of the following structural formulas:
Figure FDA0003127306180000012
Figure FDA0003127306180000021
wherein X is an oxygen atom, a sulfur atom or a selenium atom, and Y is a carbon atom or a silicon atom; r2、R3Are selected from H atom, aryl, C1-20 straight chain or branched chain alkyl, or C1-20 alkoxy.
3. The organic solar cell small molecule acceptor material with the naphthoindenofluorene unit as the core as claimed in claim 1, characterized in thatIn, A1、A2Each structure of (a) is independently selected from any one of the following structural formulas:
Figure FDA0003127306180000022
wherein R is4、R5Are all independently selected from alkyl of C1-C8, R6、R7Are independently selected from H atom, F atom, nitro, cyano, methyl, ester group or trifluoromethyl.
4. The organic solar cell small molecule acceptor material with the naphthoindenofluorene unit as the core according to claim 1, wherein A is1、A2Each structure of (a) is independently selected from any one of the following structural formulas:
Figure FDA0003127306180000031
in the formula (I), the compound is shown in the specification,
Figure FDA0003127306180000032
are all independently selected from one of the following structures:
Figure FDA0003127306180000033
wherein R is6、R7、R6’、R7' are independently selected from H atom, F atom, nitro, cyano, methyl, ester group or trifluoromethyl; r4’、R5' are all independently selected from alkyl groups of C1-C8.
5. The organic solar cell small molecule acceptor material with the naphthoindenofluorene unit as the core according to claim 1, wherein A is1、A2The structures of (A) are all independently selected from any one of the following structural formulasThe method comprises the following steps:
Figure FDA0003127306180000034
in the formula (I), the compound is shown in the specification,
Figure FDA0003127306180000041
one selected from the following structures:
Figure FDA0003127306180000042
wherein R is6、R7、R6’、R7' are all selected from H atom, F atom, nitro, cyano, methyl, ester group or trifluoromethyl; r4’、R5' are all selected from C1-C8 alkyl.
6. The method for preparing the organic solar cell small molecule acceptor material taking the naphthoindenofluorene unit as the core as claimed in any one of claims 1 to 5 is characterized by comprising the following steps:
the method comprises the steps of taking a naphthoindene fluorene unit containing a polar substituent group as a core, and sequentially connecting electron-withdrawing units to two sides of the naphthoindene fluorene unit through a coupling reaction to obtain the organic solar cell small molecule acceptor material taking the naphthoindene fluorene unit as the core.
7. The preparation method of the organic solar cell small molecule acceptor material with the naphthoindenofluorene unit as the core according to claim 6, wherein the temperature of the coupling reaction is 60-70 ℃; the coupling reaction time is 4-6 hours.
8. The application of the organic solar cell small molecule acceptor material taking the naphtho-indene fluorene unit as the core in preparing the active layer of the solar cell as claimed in any one of claims 1 to 5 is characterized in that the organic solar cell small molecule acceptor material taking the naphtho-indene fluorene unit as the core and a donor material are dissolved in an organic solvent, a film is formed on the surface of ITO/PEDOT PSS through spin coating, and the residual organic solvent is removed through evaporation to obtain the active layer of the organic solar cell.
9. The application of the organic solar cell small molecule acceptor material with the naphthoindenofluorene unit as the core to the donor material according to the mass ratio of 1.5: 1-1: 1.
10. use according to claim 8, wherein the organic solvent comprises chlorobenzene or o-dichlorobenzene.
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