CN108101930B

CN108101930B - Micromolecule receptor material containing benzothiadiazolothiophene unit and preparation method and application thereof

Info

Publication number: CN108101930B
Application number: CN201711409334.4A
Authority: CN
Inventors: 陈兴国; 徐寒
Original assignee: Wuhan University WHU
Current assignee: Wuhan University WHU
Priority date: 2017-12-22
Filing date: 2017-12-22
Publication date: 2020-10-30
Anticipated expiration: 2037-12-22
Also published as: CN108101930A

Abstract

The invention provides a micromolecular receptor material containing diazosulfide thiophene units, a preparation method and application thereof.

Description

Micromolecule receptor material containing benzothiadiazolothiophene unit and preparation method and application thereof

Technical Field

The invention relates to a micromolecule receptor material containing diazosulfide thiophene units, and a preparation method and application thereof.

Background

The energy problem is increasingly prominent, and as the non-renewable energy is gradually consumed, the development of new energy becomes a hot spot problem concerned by countries in the world. The solar energy has the advantages of cleanness, environmental protection, huge energy storage and the like, has wide development prospect, and can become a solution for effectively coping with energy crisis by developing and utilizing the solar energy. Up to now, through the design of molecular structures, optimization of device structures and processing technologies, the photoelectric conversion efficiency of organic solar cells prepared based on blending of organic small molecule donors or polymer donors and fullerene receptors has exceeded 11%, indicating a huge application prospect of organic solar cells (see li yong boat acc. chem. res.,2012,45(5), 723-73). However, fullerene derivative receptor materials represented by fullerene receptors (PCBM) have many disadvantages, such as difficulty in synthesis and purification, high price, difficulty in adjustment and control of energy level, low absorption in the visible light region, easiness in aggregation, poor morphology stability, and the like, and therefore, development of small molecule receptor materials for organic solar cells capable of replacing fullerenes is one of the major research directions in this field at present. For organic micromolecular receptor materials, through reasonable molecular design, the energy level of corresponding materials can be effectively adjusted, the absorption range of the materials to sunlight is widened, and the absorption efficiency of the materials to the sunlight is improved, so that the photoelectric conversion efficiency of the solar cell is greatly improved, and the solar cell is industrialized early.

Disclosure of Invention

The invention aims to solve the technical problem of providing a preparation method and application of a micromolecule receptor material containing benzothiadiazolothiophene units.

The technical scheme of the invention can be realized by the following technical measures:

a micromolecular receptor material containing benzothiadiazolothiophene units is disclosed, wherein the chemical structural formula of the receptor material is as follows:

wherein,

x is selected from the following groups:

y is selected from the following groups:

*-H,*-F，

a is an organic acceptor unit with a pi conjugated structure, and is respectively selected from the following groups:

r is a straight chain or branched chain alkyl with 1-20 carbon atoms.

Preferably, the receptor material 1 has the structure:

preferably, the structure of the receptor material 2 is:

preferably, the preparation process of the receptor material 1 comprises:

preferably, the preparation process of the receptor material 2 is as follows:

the small molecule acceptor material containing the benzothiadiazolothiophene unit is blended with PTB7-Th to be used as an active layer of an organic solar cell.

Preferably, the weight ratio of PTB7-Th to the acceptor material is 2: 1-1: 2.

Preferably, the substrate of the organic solar cell is glass; the cathode is ITO; the cathode modification layer is ZnO; the anode modification layer is MoO₃(ii) a The anode is Ag.

Compared with the prior art, the invention has the following beneficial effects:

compared with the traditional IDT-2Br type receptor, the molecule in the invention can effectively adjust the energy level of the corresponding material, broaden the absorption range of the molecule on sunlight and improve the absorption efficiency of the molecule on the sunlight, thereby greatly improving the short-circuit current density and the photoelectric conversion efficiency of the solar cell and providing a new idea for the early industrialization of the solar cell.

Drawings

The invention is further illustrated by means of the attached drawings, the examples of which are not to be construed as limiting the invention in any way.

FIG. 1 is a UV-visible absorption spectrum of a receptor material 1 prepared in example 1 in chloroform and thin film states, showing that the absorption range of the receptor material 1 in a solution state is mainly 300nm to 850nm, the absorption in a thin film state is mainly 300nm to 1000nm, and the absorption wavelength range in the thin film state is broader and red-shifted compared to that in the solution state;

FIG. 2 is a UV-visible absorption spectrum of the receptor material 2 prepared in example 2 in chloroform and thin film states, which shows that the absorption range of the receptor material 2 in the solution state is mainly 300nm-800nm, the absorption in the thin film state is mainly 300nm-900nm, and the thin film state has a broader absorption wavelength range and is red-shifted compared to the solution state;

FIG. 3 is a J-V plot of the solar cell devices obtained in examples 3-5. The figure shows that the device efficiency is highest under the condition that the two materials PTB7-Th and the acceptor material 1 in the active layer of the solar cell of the structure are 1:1, and the short-circuit current, the open-circuit voltage and the conversion efficiency are respectively 14.80mA/cm2, 0.83V and 7.30 percent;

FIG. 4 is a J-V plot of the solar cell device obtained in example 6, under which the short-circuit current, open-circuit voltage and conversion efficiency were 17.46mA/cm2, 0.82V and 8.46%, respectively;

fig. 5 is a J-V plot of the solar cell devices constructed as examples 7-9, showing that the two materials PTB7-Th and acceptor material 2 in the active layer of the solar cell of this construction had the highest device efficiencies at 1:1, with short circuit currents, open circuit voltages and conversion efficiencies of 13.60mA/cm2, 0.96V and 6.54%, respectively.

Detailed Description

In order that the invention may be more readily understood, specific embodiments thereof will be described further below.

Example 1

The preparation process of the small molecule receptor material 1 is as follows:

(1) synthesis of Compound 1: a250 mL Hilbert flask was charged with 10.8g of 1-bromo-2, 4-difluoro-3-toluene, evacuated, and then purged with argon, and the operation was repeated three times. Adding the redistilled tetrahydrofuran, dropwise adding 1.2eq mol of N-butyllithium at-78 ℃, reacting for 30 minutes at-78 ℃, then adding 2eq mol of redistilled N, N-dimethylformamide, and reacting at room temperature overnight. After the reaction is finished, liquid separation is carried out by chloroform, and the crude product is obtained by washing and spin-drying the solvent. And (3) separating and purifying the obtained crude product by silica gel column chromatography to obtain a colorless liquid compound, namely the compound 1, with the yield of 80%.

The nmr spectrum of compound 1 was:¹h NMR (400MHz, CDCl3) (ppm)10.29(s,1H),7.75(s,1H),6.97(s,1H),2.26(t, J ═ 1.9Hz, 3H). (1.3g of 2, 4-difluoro-3-methylbenzaldehyde).

(2) Synthesis of Compound 2: adding the compound 1 into a 250mL single-mouth bottle, adding 30mL concentrated sulfuric acid, slowly dropwise adding 0.2mL concentrated nitric acid at the temperature of minus 10 ℃ for reacting for 2 hours at the temperature of minus 10 ℃, extracting with chloroform after the reaction is finished, separating liquid, washing with water, and spin-drying the solvent to obtain a crude product. The obtained crude product is separated and purified by silica gel column chromatography to obtain a colorless liquid compound, namely the compound 2. The yield was 78%.

The nmr spectrum of compound 2 was:¹H NMR：(400MHz,CDCl3):(ppm)10.31(s,1H),8.50(t,J＝7.7Hz,1H),2.38(t,J＝2.1Hz,3H)。¹³c NMR (100MHz, CDCl3) (ppm)184.17,184.16,184.12,184.10,166.72,166.63,164.07,163.98,159.46,159.35,156.75,156.65,134.83,124.04,123.99,120.26,120.22,120.15,120.11,118.33,118.12,117.91,77.39,77.08,76.76,7.59,7.55, 7.51. (2, 4-difluoro-3-nitrobenzaldehyde).

(3) Synthesis of Compound 3: 3.4g of concentrated aqueous ammonia was added to a 250mL single-neck flask, and then 3.9g of Compound 2 dissolved in tetrahydrofuran was added dropwise to the single-neck flask under ice-bath conditions. After one hour of reaction, concentrated hydrochloric acid was added to the single-neck flask again until the solution was acidic. After the reaction is finished, chloroform is used for extraction, liquid separation and water washing, and the solvent is dried in a spinning mode to obtain a crude product. The obtained crude product is separated and purified by silica gel column chromatography to obtain a light yellow liquid compound, namely the compound 3. The yield was 92%.

The nmr spectrum of compound 3 was:¹H NMR(400MHz,DMSO):(ppm)9.91(d,J＝5.2Hz,1H),8.47(d,J＝7.6Hz,1H),8.05(s,2H),2.12(d,J＝2.4Hz,3H)。¹³C NMR(100MHz,CDCl3):(ppm)186.11,186.09,164.39,161.81,150.29,150.18,128.85,128.78,128.36,113.74,113.60,112.05,111.86,40.56,40.36,40.15,39.94,39.73,39.52,39.31,9.37,9.31. (4-amino-2-fluoro-3-methyl-5-nitrobenzaldehyde).

(4) Synthesis of Compound 4: in a 20mL microwave reaction flask, 1.1g of Compound 3, 0.75g of ethyl thioglycolate and 1.2g of anhydrous potassium carbonate were added, 15mL of dimethyl sulfoxide was added, a seal cap was added, and the mixture was placed in a microwave reactor and reacted at 80 ℃ for 1.5 hours. After the reaction is finished, pouring the solution in the microwave reaction bottle into ice water, performing suction filtration, and drying to obtain brick red solid, namely the compound 4. The yield was 85%.

The nmr spectrum of compound 4 was:¹H NMR(400MHz,CDCl3):(ppm)8.62(s,1H),7.94(s,1H),6.11(s,2H),4.40(q,J＝7.1Hz,2H),2.41(s,3H),1.42(t,J＝7.1Hz,3H)。¹³c NMR (100MHz, CDCl3) (ppm)162.31,149.92,140.00,132.35,131.66,128.61,121.94,116.07,61.79,15.90, 14.35. (6-amino-7-methyl-5-nitrobenzothiophene-2-carboxylic acid ethyl ester).

(5) Synthesis of Compound 5: in a 500mL single-neck flask, 2.9g of Compound 4 and 8g of stannous chloride monohydrate were added, and 200mL of tetrahydrofuran was added and reacted at 70 ℃ for 12 hours. And after the reaction is finished, extracting and separating by using ethyl acetate, and spin-drying the solvent to obtain a product, namely a yellow solid compound 5. The yield was 76%.

The nmr spectrum of compound 5 was:¹H NMR(400MHz,CDCl3):(ppm)7.86(s,1H),7.10(s,1H),4.37(d,J＝7.1Hz,2H),3.78(br,4H),2.37(s,3H),1.40(t,J＝7.1Hz,3H)。¹³c NMR (100MHz, CDCl3) (ppm)163.36,137.73,135.42,133.74,130.99,130.80,129.10,114.20,109.71,61.14,15.36, 14.43. (5, 6-diamino-7-methylbenzene [ b ]]Thiophene-2-carbonate ethyl ester).

(6) Synthesis of Compound 6: in a 250mL single-neck flask, 1.1g of compound 5, 100mL of dichloromethane and 1.46g of triethylamine were added, 3.43g of thionyl chloride was added dropwise under an ice bath condition, and after the addition, the ice bath was removed, and the reaction was carried out at 50 ℃ for 12 hours. After the reaction is finished, chloroform is used for extraction, liquid separation and water washing, and the solvent is dried in a spinning mode to obtain a crude product. The obtained crude product is separated and purified by silica gel column chromatography to obtain a yellow solid compound, namely the compound 6. The yield was 70%.

The nmr spectrum of compound 6 was:¹H NMR(400MHz,CDCl3):(ppm)8.40(s,2H),8.10(s,2H),4.45(d,J＝7.1Hz,4H),3.09–2.91(m,6H),1.45(t,J＝7.1Hz,7H)。¹³c NMR (100MHz, CDCl3) (ppm)162.10,152.99,141.81,141.41,137.42,130.63,123.98,114.30,62.14,16.59, 14.33. (4-methyl-benzo [1, 2-c)][1,2,5]Thiadiazole-o [2',3':4,5]]Thiophene-6-carboxylic acid ethyl ester).

(7) Synthesis of compound 7: the compound 6 is dissolved in chloroform and heated and refluxed with liquid bromine for 12 h. After the reaction is finished, chloroform is used for extraction, liquid separation and water washing, and the solvent is dried in a spinning mode to obtain a crude product. The obtained crude product is separated and purified by silica gel column chromatography to obtain a yellow solid compound, namely the compound 7. The yield was 90%.

The nmr spectrum of compound 7 was:¹h NMR (400MHz, CDCl3) (ppm)8.26(s,3H),4.47(d, J ═ 7.1Hz,7H),2.94(s,9H),1.47(t, J ═ 7.1Hz, 11H). (8-bromo-4-methylbenzo [1, 2-c)][1,2,5]Thiadiazole-o [2',3':4,5]]Thiophene-6-carboxylic acid ethyl ester).

(8) Synthesis of compound 8: a250 mL single-neck flask was charged with 1.6g of ethyl 8-bromo-4-methylbenzo [1,2-c ] [1,2,5] thiadiazolo [2',3':4,5] thiophene-6-carboxylate (7), 2.5g of bromosuccinimide and 0.22g of benzoyl peroxide, and then 100mL of chlorobenzene was added and reacted at 80 ℃ for 24 hours. After the reaction is finished, chloroform is used for extraction, liquid separation and water washing, and the solvent is dried in a spinning mode to obtain a crude product. The obtained crude product is separated and purified by silica gel column chromatography to obtain a yellow solid compound, namely the compound 8. The yield was 88%.

The nmr spectrum of compound 8 was:¹H NMR(400MHz,CDCl3):(ppm)8.37(s,1H),8.00(s,1H),4.51(q,J＝7.1Hz,2H),1.49(t,J＝7.1Hz,3H)。¹³c NMR (100MHz, CDCl3) (ppm)161.50,150.92,147.80,143.12,139.64,129.55,124.30,111.54,62.65,31.51, 14.36. (8-bromo-4- (dibromomethyl) benzo [1, 2-c)][1,2,5]Thiadiazole-o [2',3':4,5]]Thiophene-6-carboxylic acid ethyl ester).

(9) Synthesis of compound 9: in a 250mL single-neck flask, 1.5g of Compound 8 is added and heated with formic acid to 110 ℃ under reflux for 12 h. After the reaction is finished, the solvent is dried by spinning, washed by sodium sulfite aqueous solution, filtered and dried to obtain a yellow solid, namely the compound 9. The yield was 95%.

The nmr spectrum of compound 9 was: the nuclear magnetic spectrum is¹H NMR(400MHz,CDCl3):(ppm)11.21(s,1H),8.38(s,1H),4.49(q,J＝7.1Hz,2H),1.48(t,J＝7.1Hz,3H)。¹³C NMR (100MHz, CDCl3) (ppm)187.65,161.69,152.64,152.08,144.19,142.77,142.36,128.61,118.36,117.79,62.54, 14.31. (8-bromo-4-formylbenzo [1, 2-c)][1,2,5]Thiadiazole-o [2',3':4,5]]Thiophene-6-carboxylic acid ethyl ester).

(10) Synthesis of compound 10: a100 mL Hilbenk flask was charged with 0.25g of Compound 9, 0.21g of n-octyl IDT tin reagent, and 15mg of Tetratriphenylphosphine palladium catalyst, evacuated, and then purged with argon, and the operation was repeated three times. Adding the redistilled toluene, and carrying out oil bath at 110 ℃ for reaction for 48 h. After the reaction is finished, the solvent is dried by spinning to obtain a crude product. The obtained crude product is separated and purified by silica gel column chromatography to obtain a blue solid compound, namely the compound 10. The yield was 70%.

The nmr spectrum of compound 10 was:¹H NMR(400MHz,CDCl₃):(ppm)11.18(s,1H),8.81(s,1H),8.06(s,1H),7.56(s,1H),4.50(d,J＝7.1Hz,2H),2.19(dt,J₁＝13.0Hz,J₂＝6.7Hz,2H),2.03(td,J₁＝13.3Hz,J₂＝4.6Hz,2H),1.49(t,J＝7.1Hz,3H),1.19(d,J＝15.2Hz,19H),1.13–0.92(m,4H),0.79(t,J＝6.8Hz,6H).。¹³C NMR(100MHz,CDCl₃):(ppm)187.28,162.17,156.94,154.59,154.23,151.49,148.99,146.32,140.09,138.23,137.68,136.50,130.98,129.41,128.16,116.43,114.57,62.20,54.56,39.19,31.83,30.12,29.40,29.30,24.58,22.64,14.38,14.11。

(11) synthesis of Small molecule receptor Material 1: 100mg of compound 10 and 120mg of etofenhexamine are added into a 100mL single-mouth bottle, 30mL of chloroform is added, three drops of anhydrous triethylamine are added dropwise, and the reaction is carried out for 12 hours at the temperature of 75 ℃. After the reaction is finished, the solvent is dried by spinning to obtain a crude product. The resulting crude product was reprecipitated with methanol to remove excess etorhodanine. And (3) performing suction filtration to obtain a crude product, and performing chromatographic separation and purification on the obtained crude product by using a silica gel column to obtain a green solid compound, namely the receptor material micromolecule receptor material 1 with the yield of 70%.

The nuclear magnetic spectrum of the receptor material 1 was:¹H NMR(400MHz,CDCl₃):(ppm)8.77(s,1H),8.20(s,1H),7.95(s,1H),7.52(s,1H),7.27(s,1H),4.49(q,J＝7.1Hz,2H),4.26(q,J＝7.1Hz,2H),2.16(dt,J₁＝12.9Hz,J₂＝6.6Hz,2H),2.01(td,J₁＝13.2Hz,J₂＝4.5Hz,2H),1.48(t,J＝7.1Hz,3H),1.36(t,J＝7.1Hz,3H),1.28–1.11(m,24H),1.10–0.84(m,5H),0.79(t,J＝6.7Hz,6H)。¹³C NMR(100MHz,CDCl₃):(ppm)194.82,167.88,161.59,156.69,154.39,151.72,150.66,148.92,147.83,138.40,137.21,136.39,136.35,130.93,128.00,127.31,127.04,125.47,117.19,114.31,62.39,54.46,39.96,39.17,31.81,30.12,29.71,29.39,29.29,24.55,22.61,14.33,14.09,12.39。

the synthetic route is as follows:

example 2

(1) Synthesis of compound 11: 1.03g of the compound 6 obtained in example 1, 1.55g of lithium hydroxide monohydrate and 100mL of tetrahydrofuran were added into a 250mL single-neck flask, and the mixture was reacted at 50 ℃ for 6 hours, after the reaction was completed, diluted hydrochloric acid was added until the solution was acidic, and a yellow solid, i.e., the compound 11, was obtained by suction filtration. The yield was 92%.

The nmr spectrum of compound 11 was:¹h NMR (400MHz, CDCl3) (ppm)8.59(s,1H),8.23(s,1H),2.95(s, 3H). (4-methyl-benzo [1, 2-c)][1,2,5]Thiadiazole-o [2',3':4,5]]Thiophene-6-carboxylic acid).

(2) Synthesis of compound 12: and (3) adding 1.026g of the compound 11, 684mg of silver acetate and 567mg of anhydrous potassium carbonate into a 200mL Hilbenzhu bottle, pumping argon for three times, adding 50mL of N-methylpyrrolidone, reacting for 24 hours at 150 ℃, extracting with ethyl acetate, separating liquid, washing with water, and spin-drying the solvent to obtain a crude product. The obtained crude product is separated and purified by silica gel column chromatography to obtain a yellow solid compound, namely the compound 12. The yield was 78%.

The nmr spectrum of compound 12 was:¹H NMR(400MHz,CDCl3):(ppm)8.27(s,1H),7.51(d, J ═ 5.6Hz,1H),7.37(d, J ═ 5.6Hz,1H),2.98(s, 3H). (4-methyl-benzo [1, 2-c)][1,2,5]Thiadiazole-o [2',3':4,5]]Thiophene).

(14) Synthesis of compound 13: and adding 0.566g of the compound 12, 1.97g N-bromosuccinimide and 50mL of chloroform into a 150mL single-neck bottle, reacting for 24h at 80 ℃, spin-drying the solvent, adding 60mg of benzoyl peroxide and 50mL of chlorobenzene into the solution, continuing reacting for 24h at 80 ℃, and spin-drying the solvent to obtain a crude product, and separating and purifying the crude product by silica gel column chromatography to obtain a yellow solid compound, namely the compound 13. The yield was 86%.

The nmr spectrum of compound 13 was:¹H NMR(400MHz,CDCl3):(ppm)11.23(s,1H),7.84(d,J＝5.6Hz,1H),7.69(d,J＝5.6Hz,1H).¹³c NMR (100MHz, CDCl3) (ppm)187.79,152.03,151.89,143.77,136.22,122.69,120.59,117.58,115.31. (8-bromo-4-formylbenzo [1, 2-c)][1,2,5]Thiadiazole-o [2',3':4,5]]Thiophene).

(15) Synthesis of compound 14: in a 100mL siderk bottle, 0.22g of compound 15, 0.23g of phenyl n-hexyl idttin reagent and 16mg of tetratriphenylphosphine palladium catalyst were added, and the operation was repeated three times by introducing argon after evacuation. Adding the redistilled toluene, and carrying out oil bath at 110 ℃ for reaction for 48 h. After the reaction is finished, the solvent is dried by spinning to obtain a crude product. The obtained crude product is separated and purified by silica gel column chromatography to obtain a blue solid compound, namely the compound 14. The yield was 72%.

The nmr spectrum of compound 14 was:¹H NMR(400MHz,CDCl3):(ppm)11.21(s,1H),7.91(d,J＝6.0Hz,1H),7.89(s,1H),7.72(d,J＝6.0Hz,1H),7.63(s,1H),7.29(d,4H),7.14(d,4H),2.58(t,J＝7.6Hz,4H),1.34-1.26(m,16H),0.88-0.84(m,7H).¹³C NMR(100MHz,CDCl3):(ppm)187.47,156.88,154.14,153.34,151.42,146.88,145.24,141.96,141.44,139.51,139.43,135.76,134.62,129.73,128.62,128.10,127.90,127.76,122.49,118.49,116.67,63.27,35.61,31.75,31.42,29.17,22.64,14.15。

(16) synthesis of small molecule receptor material 2: in a 100mL single-neck flask, 100mg of compound 16, 240mg of hexylrhodanine, 30mL of chloroform, three drops of anhydrous triethylamine were added dropwise, and the mixture was reacted at 75 ℃ for 12 hours. After the reaction is finished, the solvent is dried by spinning to obtain a crude product. The resulting crude product was reprecipitated with methanol to remove excess hexylrhodanine. And (3) performing suction filtration to obtain a crude product, and performing chromatographic separation and purification on the obtained crude product by using a silica gel column to obtain a green solid compound, namely the receptor material micromolecule receptor material 2 with the yield of 73%.

The nuclear magnetic spectrum of the receptor material 2 was:¹H NMR(400MHz,CDCl3):(ppm)8.37(s,1H)，7.91(d,J＝6.0Hz,1H)，7.85(s,1H),7.62(s,1H),7.56(d,J＝6.0Hz,1H)，7.28(d,4H)，7.13(d,4H)，4.27(q,J＝8.0Hz,2H)，2.85(q,J＝8.0Hz,4H)，1.81-1.78(m,2H)1.63-1.56(m,4H)，1.47-1.56(m,22H),0.91-0.84(m,9H).¹³C NMR(100MHz,CDCl3):(ppm)166.99,166.94,156.89,154.10,151.60,149.92,149.24,146.55,141.92,141.38,139.55,138.65,135.72,130.10,129.26,128.57,127.84,127.49,125.32,124.51,120.86,118.38,116.23,113.26,112.57,63.21,55.37,45.41,35.57,31.73,31.71,31.39,29.13,29.07,28.82,26.01,22.62,22.60,14.11。

the synthetic route is as follows:

example 3

And (3) carrying out ultrasonic oscillation cleaning on the transparent conductive glass with the strip-shaped ITO (anode) etched on the surface sequentially by using a cleaning agent, deionized water, acetone and isopropanol, and then drying. And then spinning and coating a 2-methoxy ethanol solution of zinc acetate on the surface of the conductive glass at the rotating speed of 4000r/min, and drying at 200 ℃ for 30 minutes to obtain the cathode modification layer ZnO. Then, in a glove box, a mixed solution of PTB7-Th and the small molecule receptor material 1 is spin-coated, the rotating speed is 1000r/min, the total concentration of the solution is 20mg/mL, and the solvent is o-dichlorobenzene. The weight ratio of PTB7-Th to small molecule receptor material 1 was 1.5: 1. The spin coating time was 60 s. Then, at a pressure below 1X 10^-4Vacuum evaporating a layer of 3.7nm MoO on the upper layer under Pa₃Finally, in MoO₃And a layer of Al with the thickness of 100nm is evaporated on the cathode. Thereby obtaining a complete organic solar cell device. The illumination intensity is 100mW/cm²The AM1.5 is used for testing the device under the irradiation of simulated sunlightThe current-voltage curve of the device is obtained, so that the open-circuit voltage is 0.82V, and the short-circuit current density is 15.40mA/cm²The fill factor was 50.73%, and the photoelectric energy conversion efficiency was 6.44%.

Example 4

And (3) carrying out ultrasonic oscillation cleaning on the transparent conductive glass with the strip-shaped ITO (cathode) etched on the surface sequentially by using a cleaning agent, deionized water, acetone and isopropanol, and then drying. And then spinning and coating a 2-methoxy ethanol solution of zinc acetate on the surface of the conductive glass at the rotating speed of 4000r/min, and drying at 200 ℃ for 30 minutes to obtain the cathode modification layer ZnO. Then, in a glove box, a mixed solution of PTB7-Th and the small molecule receptor material 1 is spin-coated, the rotating speed is 1000r/min, the total concentration of the solution is 20mg/mL, and the solvent is o-dichlorobenzene. The weight ratio of PTB7-Th to small molecule receptor material 1 was 1:1. The spin coating time was 60 s. Then, at a pressure below 1X 10^-4Vacuum evaporating a layer of 3.7nm MoO on the upper layer under Pa₃Finally, in MoO₃And then a layer of Al with the thickness of 100nm is evaporated on the anode. Thereby obtaining a complete organic solar cell device. The current-voltage curve of the device is tested under the irradiation of AM1.5 simulated sunlight with the illumination intensity of 100mW/cm2, so that the open-circuit voltage is 0.83V, the short-circuit current density is 14.80mA/cm2, the filling factor is 59.51%, and the photoelectric energy conversion efficiency is 7.30%.

Example 5

And (3) carrying out ultrasonic oscillation cleaning on the transparent conductive glass with the strip-shaped ITO (cathode) etched on the surface sequentially by using a cleaning agent, deionized water, acetone and isopropanol, and then drying. And then spinning and coating a 2-methoxy ethanol solution of zinc acetate on the surface of the conductive glass at the rotating speed of 4000r/min, and drying at 200 ℃ for 30 minutes to obtain the cathode modification layer ZnO. Then, in a glove box, spin coating the mixed solution of PTB7-Th and the small molecule receptor material 1 at the rotation speed of 1000r/min, the total concentration of the solution is 20mg/mL, and the solvent is o-dichlorobenzene. The weight ratio of PTB7-Th to small molecule receptor material 1 was 1: 1.5. The spin coating time was 60 s. Then, at a pressure below 1X 10^-4Vacuum evaporating a layer of 3.7nm MoO on the upper layer under Pa₃Finally, in MoO₃And then a layer of Al with the thickness of 100nm is evaporated on the anode. Thereby obtaining a complete organic solar energyA battery device. The illumination intensity is 100mW/cm²The AM1.5 of (1) is used for testing the current-voltage curve of the device under the irradiation of simulated sunlight, so that the open-circuit voltage is 0.84V, and the short-circuit current density is 7.98mA/cm²The fill factor was 47.50%, and the photoelectric energy conversion efficiency was 3.17%.

Example 6

And (3) carrying out ultrasonic oscillation cleaning on the transparent conductive glass with the strip-shaped ITO (cathode) etched on the surface sequentially by using a cleaning agent, deionized water, acetone and isopropanol, and then drying. And then spinning and coating a 2-methoxy ethanol solution of zinc acetate on the surface of the conductive glass at the rotating speed of 4000r/min, and drying at 200 ℃ for 30 minutes to obtain the cathode modification layer ZnO. Then, in a glove box, spin-coating a mixed solution of PTB7-Th and the small molecule receptor material 1 at the rotation speed of 1000r/min, the total concentration of the solution is 20mg/mL, and the solvent is o-dichlorobenzene: 1-chloronaphthalene is 1: 0.8% (volume ratio) of mixed solvent. The weight ratio of PTB7-Th to small molecule receptor material 1 was 1:1. The spin coating time was 60 s. Then, at a pressure below 1X 10^-4Vacuum evaporating a layer of 3.7nm MoO on the upper layer under Pa₃Finally, in MoO₃And then a layer of Al with the thickness of 100nm is evaporated on the anode. Thereby obtaining a complete organic solar cell device. The current-voltage curve of the device is tested under the irradiation of AM1.5 simulated sunlight with the illumination intensity of 100mW/cm2, so that the open-circuit voltage is 0.82V, and the short-circuit current density is 17.46mA/cm²The fill factor was 58.77%, and the photoelectric energy conversion efficiency was 8.46%.

Example 7

And (3) carrying out ultrasonic oscillation cleaning on the transparent conductive glass with the strip-shaped ITO (cathode) etched on the surface sequentially by using a cleaning agent, deionized water, acetone and isopropanol, and then drying. And then spinning and coating a 2-methoxy ethanol solution of zinc acetate on the surface of the conductive glass at the rotating speed of 4000r/min, and drying at 200 ℃ for 30 minutes to obtain the cathode modification layer ZnO. Then, in a glove box, spin coating the mixed solution of PTB7-Th and the small molecule receptor material 2 at the rotation speed of 1500r/min, the total concentration of the solution is 20mg/mL, and the solvent is o-dichlorobenzene. The weight ratio of PTB7-Th to small molecule receptor material 2 was 1.5: 1. The spin coating time was 60 s. Then, at a pressure below 1X 10^-4Vacuum of PaLower layer is evaporated with upper layer of 3.7nm MoO₃Finally, in MoO₃And then a layer of Al with the thickness of 100nm is evaporated on the anode. Thereby obtaining a complete organic solar cell device. The illumination intensity is 100mW/cm²The AM1.5 of (1) is used for testing the current-voltage curve of the device under the irradiation of simulated sunlight, so that the open-circuit voltage is 0.92V, and the short-circuit current density is 12.12mA/cm²The fill factor was 42.83%, and the photoelectric energy conversion efficiency was 4.77%.

Example 8

And (3) carrying out ultrasonic oscillation cleaning on the transparent conductive glass with the strip-shaped ITO (cathode) etched on the surface sequentially by using a cleaning agent, deionized water, acetone and isopropanol, and then drying. And then spinning and coating a 2-methoxy ethanol solution of zinc acetate on the surface of the conductive glass at the rotating speed of 4000r/min, and drying at 200 ℃ for 30 minutes to obtain the cathode modification layer ZnO. Then, in a glove box, spin coating the mixed solution of PTB7-Th and the small molecule receptor material 2 at the rotation speed of 1500r/min, the total concentration of the solution is 20mg/mL, and the solvent is o-dichlorobenzene. The weight ratio of PTB7-Th to small molecule receptor material 2 was 1:1. The spin coating time was 60 s. Then, at a pressure below 1X 10^-4Vacuum evaporating a layer of 3.7nm MoO on the upper layer under Pa₃Finally, in MoO₃And then a layer of Al with the thickness of 100nm is evaporated on the anode. Thereby obtaining a complete organic solar cell device. The illumination intensity is 100mW/cm²The AM1.5 of (1) was tested for a current-voltage curve under simulated sunlight irradiation, thereby obtaining an open circuit voltage of 0.96V and a short circuit current density of 13.60mA/cm²The fill factor is 49.94%, and the photoelectric energy conversion efficiency is 6.54%.

Example 9

And (3) carrying out ultrasonic oscillation cleaning on the transparent conductive glass with the strip-shaped ITO (cathode) etched on the surface sequentially by using a cleaning agent, deionized water, acetone and isopropanol, and then drying. And then spinning and coating a 2-methoxy ethanol solution of zinc acetate on the surface of the conductive glass at the rotating speed of 4000r/min, and drying at 200 ℃ for 30 minutes to obtain the cathode modification layer ZnO. Then, in a glove box, spin coating the mixed solution of PTB7-Th and the small molecule receptor material 2 at the rotation speed of 1500r/min, the total concentration of the solution is 20mg/mL, and the solvent is o-dichlorobenzene. PTB7-ThAnd the weight ratio of the small molecule acceptor material 2 is 1: 1.5. The spin coating time was 60 s. Then, at a pressure below 1X 10^-4Vacuum evaporating a layer of 3.7nm MoO on the upper layer under Pa₃Finally, in MoO₃And then a layer of Al with the thickness of 100nm is evaporated on the anode. Thereby obtaining a complete organic solar cell device. The illumination intensity is 100mW/cm²The AM1.5 of (1) was subjected to a test of the current-voltage curve of the device under the irradiation of simulated sunlight, thereby obtaining an open-circuit voltage of 0.94V and a short-circuit current density of 11.37mA/cm²The fill factor was 47.16%, and the photoelectric energy conversion efficiency was 5.07%.

Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims

1. A micromolecular receptor material containing diazosulfide thiophene units is characterized in that the chemical structural formula of the receptor material is as follows:

wherein,

x is selected from the following groups:

y is selected from the following groups:

*-H,

r is a straight chain or branched chain alkyl with 1-20 carbon atoms.

2. The small molecule receptor material containing benzothiadiazolothiophene units of claim 1, wherein the receptor material has the structure:

3. the small molecule receptor material containing benzothiadiazolothiophene units of claim 1, wherein the receptor material has the structure:

4. the preparation method of the small molecule receptor material containing the benzothiadiazolothiophene unit according to claim 2, characterized in that the preparation process is as follows:

5. the preparation method of the small molecule receptor material containing the benzothiadiazolothiophene unit according to claim 3, characterized in that the preparation process is as follows:

6. use of a small molecule acceptor material containing benzothiadiazolothiophene units according to any one of claims 1 to 3, characterised in that it is blended with PTB7-Th as an active layer of an organic solar cell.

7. The application of the small molecule acceptor material containing the benzothiadiazolothiophene unit according to claim 6, wherein the weight ratio of PTB7-Th to the acceptor material is 2: 1-1: 2.

8. The use of the benzothiadiazolothiophene unit-containing small molecule acceptor material as claimed in claim 6, wherein the substrate of the organic solar cell is glass; the cathode is ITO; the cathode modification layer is ZnO; the anode modification layer is MoO₃(ii) a The anode is Ag.