Polymer, preparation method thereof and organic polymer solar battery

Abstract

The invention provides a polymer, a preparation method thereof and an organic polymer solar battery. The polymer is shown in a formula (I) or a formula (II). Compared with an existing conjugated polymer, the polymer which is shown in the formula (I) or the formula (II) has the advantages that a condensed ring unit of dithieno carbazole serves as a donor and is low in reorganization energy and good in pi electron delocalization; by introducing the condensed ring unit into a conjugated compound, the reorganization energy of the polymer can be effectively reduced, and the conjugation length of the polymer is increased, so that the mobility of the polymer can be improved, and an optical band gap of the polymer is reduced; the optical band gap is reduced to cause the red shift of an absorption band of the polymer, and absorption spectra are matched with solar spectra. Therefore, by the adoption of the polymer, the spectrum absorption range of the polymer can be expanded, and the hole mobility can be improved; fluoro-isoindigo serves as a receptor, so that the highest occupied molecular orbital (HOMO) energy level of the polymer can be reduced, and the open-circuit voltage of the polymer solar battery is improved.

Description

technical field

[0001] The invention belongs to the technical field of semiconductor materials, and in particular relates to a polymer, a preparation method thereof, and an organic polymer solar cell. Background technique

[0002] Compared with traditional silicon solar cells, organic polymer solar cells have attracted much attention due to their advantages of light weight, low cost, large-area processing and flexible devices.

[0003] Organic polymer solar cells are usually composed of positive and negative electrodes and a thin photoactive layer between them. The photoactive thin layer is generally a bulk heterojunction (BHJ) structure composed of a donor (D) and an acceptor (A). . The currently used acceptor materials mainly include CdSe, n-type polymer, C60 and its derivative PCBM, among which PCBM is the most used. The positive and negative electrodes of the BHJ type solar cell are indium tin oxide (ITO) and a metal with a lower functional function, respectively, and ...

Examples

preparation example Construction

[0036] The present invention also provides a preparation method of a polymer represented by formula (I), comprising the following steps: under the condition of inert gas protection, combining a compound having a structure of formula (III-1) with a compound having a structure of formula (IV) The compound is mixed under the action of a catalyst and an auxiliary ligand, and reacted to obtain a polymer represented by formula (I);

[0037]

[0038] Among them, R 1 is an alkyl group; R 2 Is an alkyl group; X is H or a fluorine atom; n is the degree of polymerization.

[0039] In the present invention, the R 1 , R 2 , X and n are the same as above, and will not be repeated here.

[0040] The present invention has no special limitation on the sources of all raw materials, which can be commercially available or self-made.

[0041] The compound with the structure of formula (IV) is preferably prepared according to the following method: S1) The compound with the structure of form...

Embodiment 1

[0062] 1.1 Under argon atmosphere, add 16.39mmol 6-bromoindol-2-one and 16.39mmol 6-bromo-7-fluoroisatin to a 250ml three-necked flask, add 200ml glacial acetic acid and 1.2ml concentrated hydrochloric acid, and heat to 130 React at ℃ for 24 hours, cool to room temperature, filter, wash with water, ethanol, and ether in turn, and the red solid that is drained is 6,6′-dibromo-7-fluoroisoindigo, with a yield of 70%.

[0063] 1.2 Dissolve 2.28mmol of 6,6′-dibromo-7-fluoroisoindigo obtained in 1.1 and 9.13mmol of potassium hydroxide in 40ml of DMF, and add 9.13mmol of 1-iodo-2- Octyldodecane and 40ml THF were slowly dropped into the reaction solution, and after 24 hours of reaction at room temperature, poured into water, extracted with chloroform, and dried the organic layer with anhydrous magnesium sulfate. After washing with petroleum ether and dichloromethane as the eluent, the red solid is N,N'-bis(2-octyldodecyl)-6,6'-dibromo-7-fluoroisoindigo, Yield 42%.

[0064] 1.3 Under...

Embodiment 2

[0073] 2.1 Under argon atmosphere, add 16.39mmol 6-bromoindol-2-one and 16.39mmol 6-bromo-7-fluoroisatin into a 250ml three-necked flask, add 200ml glacial acetic acid and 1.2ml concentrated hydrochloric acid, heat to 130 React at ℃ for 24 hours, cool to room temperature, filter, wash with water, ethanol, and ether in turn, and the red solid that is drained is 6,6′-dibromo-7-fluoroisoindigo, with a yield of 70%.

[0074] 2.2 Dissolve 2.28mmol of 6,6′-dibromo-7-fluoroisoindigo obtained in 2.1 and 9.13mmol of potassium hydroxide in 40ml of DMF, and add 9.13mmol of 1-iodo-2- Butyl octane and 40ml THF were slowly dripped into the reaction liquid, and after reacting at room temperature for 24 hours, they were poured into water, extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate. After rinsing with ether and dichloromethane as the eluent, a red solid was obtained which was N,N'-bis(2-butyloctyl)-6,6'-dibromo-7-fluoroisoindigo, and the yield w...

technical field

[0001] The invention belongs to the technical field of semiconductor materials, and in particular relates to a polymer, a preparation method thereof, and an organic polymer solar cell. Background technique

[0002] Compared with traditional silicon solar cells, organic polymer solar cells have attracted much attention due to their advantages of light weight, low cost, large-area processing and flexible devices.

[0003] Organic polymer solar cells are usually composed of positive and negative electrodes and a thin photoactive layer between them. The photoactive thin layer is generally a bulk heterojunction (BHJ) structure composed of a donor (D) and an acceptor (A). . The currently used acceptor materials mainly include CdSe, n-type polymer, C60 and its derivative PCBM, among which PCBM is the most used. The positive and negative electrodes of the BHJ type solar cell are indium tin oxide (ITO) and a metal with a lower functional function, respectively, and ...

Examples

preparation example Construction

[0036] The present invention also provides a preparation method of a polymer represented by formula (I), comprising the following steps: under the condition of inert gas protection, combining a compound having a structure of formula (III-1) with a compound having a structure of formula (IV) The compound is mixed under the action of a catalyst and an auxiliary ligand, and reacted to obtain a polymer represented by formula (I);

[0037]

[0038] Among them, R 1 is an alkyl group; R 2 Is an alkyl group; X is H or a fluorine atom; n is the degree of polymerization.

[0039] In the present invention, the R 1 , R 2 , X and n are the same as above, and will not be repeated here.

[0040] The present invention has no special limitation on the sources of all raw materials, which can be commercially available or self-made.

[0041] The compound with the structure of formula (IV) is preferably prepared according to the following method: S1) The compound with the structure of form...

Embodiment 1

[0062] 1.1 Under argon atmosphere, add 16.39mmol 6-bromoindol-2-one and 16.39mmol 6-bromo-7-fluoroisatin to a 250ml three-necked flask, add 200ml glacial acetic acid and 1.2ml concentrated hydrochloric acid, and heat to 130 React at ℃ for 24 hours, cool to room temperature, filter, wash with water, ethanol, and ether in turn, and the red solid that is drained is 6,6′-dibromo-7-fluoroisoindigo, with a yield of 70%.

[0063] 1.2 Dissolve 2.28mmol of 6,6′-dibromo-7-fluoroisoindigo obtained in 1.1 and 9.13mmol of potassium hydroxide in 40ml of DMF, and add 9.13mmol of 1-iodo-2- Octyldodecane and 40ml THF were slowly dropped into the reaction solution, and after 24 hours of reaction at room temperature, poured into water, extracted with chloroform, and dried the organic layer with anhydrous magnesium sulfate. After washing with petroleum ether and dichloromethane as the eluent, the red solid is N,N'-bis(2-octyldodecyl)-6,6'-dibromo-7-fluoroisoindigo, Yield 42%.

[0064] 1.3 Under...

Embodiment 2

[0073] 2.1 Under argon atmosphere, add 16.39mmol 6-bromoindol-2-one and 16.39mmol 6-bromo-7-fluoroisatin into a 250ml three-necked flask, add 200ml glacial acetic acid and 1.2ml concentrated hydrochloric acid, heat to 130 React at ℃ for 24 hours, cool to room temperature, filter, wash with water, ethanol, and ether in turn, and the red solid that is drained is 6,6′-dibromo-7-fluoroisoindigo, with a yield of 70%.

[0074] 2.2 Dissolve 2.28mmol of 6,6′-dibromo-7-fluoroisoindigo obtained in 2.1 and 9.13mmol of potassium hydroxide in 40ml of DMF, and add 9.13mmol of 1-iodo-2- Butyl octane and 40ml THF were slowly dripped into the reaction liquid, and after reacting at room temperature for 24 hours, they were poured into water, extracted with chloroform, and the organic layer was dried over anhydrous magnesium sulfate. After rinsing with ether and dichloromethane as the eluent, a red solid was obtained which was N,N'-bis(2-butyloctyl)-6,6'-dibromo-7-fluoroisoindigo, and the yield w...

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