阅读说明：本技术 亚萘酞菁类受体材料及其合成方法和太阳能电池 (Naphthalocyanine acceptor material, synthetic method thereof and solar cell ) 是由 袁忠义 蔡春生 赵晓宏 李莉 胡昱 胡明 张有地 陈义旺 于 2019-09-06 设计创作，主要内容包括：本发明亚萘酞菁类受体材料及其合成方法和太阳能电池,属于有机合成及光电技术领域。以6,7-二氰基萘单酰亚胺类化合物和三氯化硼为原料,在有机溶剂中,一定温度下搅拌反应,生成氯代亚萘酞菁三酰亚胺,以氯代亚萘酞菁三酰亚胺进行氟取代、苯氧基取代或苯硫基取代,最后得到一系列亚萘酞菁分子受体材料。本发明设计将酰亚胺基团引入未取代的亚萘酞菁分子中,合成了一类溶解性好、分离提纯简单、LUMO能级合适的新型受体材料。这类受体材料在器件结构要求简单的体相异质结太阳能电池中,光电转换效率高达6.25％,是亚酞菁、亚萘酞菁、酞菁和萘酞菁类可溶液处理的有机太阳能电池中最高的光电转换效率。(The invention relates to a naphthalocyanine acceptor material, a synthetic method thereof and a solar cell, belonging to the technical field of organic synthesis and photoelectricity. The preparation method comprises the steps of taking 6, 7-dicyanonaphthalene monoimide compounds and boron trichloride as raw materials, stirring the raw materials in an organic solvent at a certain temperature to react to generate chloronaphthalocyanine triacmide, and carrying out fluorine substitution, phenoxy substitution or phenylthio substitution on the chloronaphthalocyanine triacmide to finally obtain a series of naphthalocyanine molecular acceptor materials. The invention designs to introduce an imide group into unsubstituted naphthalocyanine molecules, and synthesizes a novel acceptor material with good solubility, simple separation and purification and proper LUMO energy level. In bulk heterojunction solar cells with simple device structure requirements, the photoelectric conversion efficiency of the acceptor material reaches 6.25 percent, and the acceptor material is the highest photoelectric conversion efficiency in organic solar cells which can be treated by subphthalocyanine, phthalocyanine and naphthalocyanine solution.)

1. A naphthalocyanine receptor material, characterized in that: has the following molecular structural formula

Wherein R is C₄-C₃₀Linear, branched or aromatic hydrocarbons of (a);

x is Cl, F or a substituent group with the structural formula shown below;

phenoxy group:

p-methoxyphenoxy group:

p-carbomethoxyphenoxy:

p-cyanophenoxy group:

pentafluorophenoxy group:

phenylthio:

p-methoxyphenoxythio:

p-carbomethoxyphenylthio acetate:

p-cyanophenylthio group:

pentafluorosulfanyl group:

2. the method for synthesizing a naphthalocyanine receptor material according to claim 1, wherein: when X is Cl for substitution, 6, 7-dicyanonaphthalene monoimide compounds and boron trichloride react for 20min to 3h in an organic solvent at a certain temperature by stirring according to the molar ratio of 1 (1-10) to generate chloronaphthalocyanine triacylimide compounds.

3. The method for synthesizing a naphthalocyanine receptor material according to claim 1, wherein: and when X is F substitution, the chloronaphthalocyanine triacimide compound and silver tetrafluoroborate react for 1 to 24 hours in an organic solvent at room temperature by stirring for 1 to 10 mol ratio to obtain the fluoronaphthalocyanine triacimide compound.

4. The method for synthesizing a naphthalocyanine receptor material according to claim 1, wherein: when X is phenoxy or phenoxy derivative substitution, the chloronaphthalocyanine trisimide compound, phenol or phenol derivative and pyridine are stirred and reacted for 1-48 h at a certain temperature in an organic solvent according to the mol ratio of 1 (1-10) to (1-5) to obtain the phenoxy or phenoxy derivative substitution naphthalocyanine trisimide compound.

5. The method for synthesizing a naphthalocyanine receptor material according to claim 1, wherein: when X is a thiophenyl group or a thiophenyl derivative for substitution, chloronaphthalocyanine triacimide, thiophenol or a thiophenol derivative, silver trifluoromethanesulfonate and N, N-diisopropylethylamine are stirred and reacted for 1h to 48h at a certain temperature in an organic solvent according to the molar ratio of 1 (1-10) to (1-5) to obtain the thiophenyl group or the thiophenyl derivative substituted naphthalocyanine triacimide compound.

6. The method for synthesizing a naphthalocyanine receptor material according to claim 2, wherein: the molecular formula of the 6, 7-dicyanonaphthalene monoimide compound is as follows:

wherein R is C₄-C₃₀Linear, branched or aromatic hydrocarbons.

7. The method for synthesizing a naphthalocyanine receptor material according to claim 4, wherein: the phenoxy derivative is p-methoxyphenoxy, p-carbomethoxyphenoxy, p-cyanophenoxy and pentafluorophenoxy; the phenol derivatives are p-methoxyphenol, p-carbomethoxyphenol, p-cyanophenol and pentafluorophenol.

8. The method for synthesizing a naphthalocyanine receptor material according to claim 5, wherein: the phenylthio derivatives are p-methoxy phenylthio, p-carbomethoxyphenylthio acetate, p-cyano phenylthio and pentafluorophenylthio; the thiophenol derivatives are p-methoxy thiophenol, p-methyl acetate thiophenol, p-cyano thiophenol and pentafluorothiophenol.

9. The method for synthesizing a receptor material of the naphthalocyanine family according to any one of claims 2 to 8, wherein: the organic solvent is o-xylene, o-dichlorobenzene, p-xylene, m-xylene, mesitylene or a mixed solvent of p-xylene and mesitylene with the volume ratio of 1 (0.5-2); the certain temperature is from room temperature to the reflux temperature of the solvent.

10. A solar cell, characterized in that: the active material layer of the bulk heterojunction solar cell is prepared by using the polymer PTQ10 as a donor, the naphthalocyanine compound as the acceptor, and the additive, wherein the additive is 0.5% of 1, 8-diiodooctane and 0.5% of diphenyl ether in volume ratio.

Technical Field

The invention relates to the technical field of organic synthesis and photoelectricity, in particular to a naphthalocyanine acceptor material, a synthesis method thereof and a solar cell.

Background

With the development of society, non-renewable resources such as coal, petroleum and the like are gradually reduced, and inexhaustible, clean and pollution-free solar energy is paid attention to by people. Solar cells have been rapidly developed in recent years as devices capable of efficiently converting solar energy into electric energy. Although the inorganic solar cell has been commercialized, the energy conversion efficiency is about 8% to 18%, the further popularization and application of the inorganic solar cell is limited due to the problems of complex production process, high cost, poor portability, high energy consumption in the production process of raw materials and the like. The organic bulk heterojunction solar cell has low-cost solution processing, can be used for preparing flexible wearable equipment, and has the advantages of various types and various properties, so that the organic bulk heterojunction solar cell is highly valued by people.

The active layer of the organic solar cell is a core part of the whole device, and important processes such as absorption of photons, generation and diffusion separation of excitons, and transmission of carriers are performed in the active layer, so that a great deal of research and development is devoted to developing efficient active layer materials. The active layer material is divided into an acceptor material and a donor material, the donor material has multiple types and excellent performance, the acceptor material matched with the donor material has fewer types and poor performance, and the development of the organic solar cell is restricted by the lack of the excellent acceptor material.

Subphthalocyanine is a phthalocyanine compound with a bowl-shaped conjugated skeleton, which is composed of three isoindole units, and the central atom is boron (Chinese patent, publication number: CN 109824709A). The periphery of the sub-naphthalocyanine molecular structure is connected with three naphthalene rings instead of benzene rings, and the structure is completely different from that of the sub-phthalocyanines. Although their central structural units are similar, the naphthalocyanines have completely different properties due to the ability of the peripheral aromatic rings to participate in conjugation. The naphthalocyanine molecules have aromaticity, high stability and strong near infrared absorption. The photoelectric conversion efficiency of the three-layer heterojunction solar cell based on the naphthalocyanine is as high as 8.4%, but the active layer material adopts complicated vapor deposition under high temperature and high vacuum in the preparation of a cell device. High device preparation requirements greatly limit the application of the naphthalocyanine as an organic acceptor material in the photoelectric field. The use of the prior art synthetic naphthalocyanines as solution processable receptor materials has the following disadvantages: 1) a high LUMO energy level (lowest unoccupied orbital) results in a mismatch with many excellent donors; 2) the solubility is poor, and when the composite is applied to a solar cell, the synthesis and the device processing are difficult; 3) the synthesis process in the prior art is complex and is difficult to separate and obtain a high-purity target product. Therefore, the development of a naphthalocyanine acceptor material without the defects has important significance for the application of the naphthalocyanine acceptor material in the organic solar cell.

Disclosure of Invention

The first object of the present invention is: a naphthalocyanine acceptor material with low LUMO energy level and good solubility is provided.

The second object of the present invention is: provides a method for synthesizing a naphthalocyanine receptor material with simple process.

The third object of the present invention is: a solar cell containing the above-mentioned naphthalocyanine receptor material is provided.

In order to achieve the first object, the present invention provides a naphthalocyanine receptor material, which has a general structural formula as shown in the following formula:

wherein R is C₄-C₃₀Linear, branched alkanes or aromatic hydrocarbons of (a);

x is Cl, F or a substituent group with the structural formula shown below;

phenoxy group:

p-methoxyphenoxy group:

p-carbomethoxyphenoxy:

p-cyanophenoxy group:

pentafluorophenoxy group:

phenylthio:

p-methoxyphenylthio:

p-carbomethoxyphenylthio acetate:

p-cyanophenylthio group:

pentafluorosulfanyl group:

in order to achieve the second object, the present invention provides a method for synthesizing a naphthalocyanine acceptor material, comprising the following steps:

when X is Cl for substitution, 6, 7-dicyanonaphthalene monoimide compounds and boron trichloride react for 20min to 3h in an organic solvent at a certain temperature by stirring for 1 (1-10) to generate chloronaphthalocyanine triacylimide compounds; when X is F substitution, the chloronaphthalocyanine triacimide compound and silver tetrafluoroborate react for 1 to 24 hours in an organic solvent at room temperature by stirring for 1 to 10 mol ratio to obtain the fluoronaphthalocyanine triacimide compound; when X is phenoxy or phenoxy derivative substitution, the chloronaphthalocyanine trisimide compound, phenol or phenol derivative and pyridine are stirred and react for 1-48 h at a certain temperature in an organic solvent according to the mol ratio of 1 (1-10) to (1-5) to obtain the phenoxy or phenoxy derivative substitution naphthalocyanine trisimide compound; when X is a thiophenyl group or a thiophenyl derivative for substitution, the chloronaphthalocyanine triacylimide compound, thiophenol or a thiophenol derivative, silver trifluoromethanesulfonate and N, N-diisopropylethylamine are stirred and reacted for 1-48 h at a certain temperature in an organic solvent according to the molar ratio of 1 (1-10) to (1-5) to obtain the thiophenyl group or the thiophenyl derivative for substituting the naphthalocyanine triacylimide compound.

Further, the phenoxy derivative is p-methoxyphenoxy, p-carbomethoxyphenoxy, p-cyanophenoxy, or pentafluorophenoxy; the phenol derivatives are p-methoxyphenol, p-carbomethoxyphenol, p-cyanophenol and pentafluorophenol.

Further, the thiophenyl derivatives are p-methoxyphenylthio, p-carbomethoxythiophenyl acetate, p-cyanophenylthio, pentafluorothiophenyl; the phenol derivatives are p-methoxy thiophenol, p-carbomethoxy thiophenol acetate, p-cyano thiophenol and pentafluorothiophenol.

Further, the organic solvent is o-xylene, o-dichlorobenzene, p-xylene, m-xylene, mesitylene or a mixed solvent of p-xylene and mesitylene with the volume ratio of 1 (0.5-2).

Further, the certain temperature means a temperature from room temperature to a reflux temperature of the solvent used.

In order to achieve the third object, the solar cell containing the naphthalocyanine acceptor material uses the polymer PTQ10 as a donor, naphthalocyanine as an acceptor, and 0.5% by volume of 1, 8-diiodooctane and 0.5% by volume of diphenyl ether as additives as active material layers of a bulk heterojunction solar cell.

The invention has the beneficial effects that:

1. the naphthalocyanine receptor material prepared by the invention introduces three imide groups on a conjugated parent of naphthalocyanine for the first time, so that the LUMO energy level is reduced from-3.60 eV to (-3.79 to-3.90 eV).

2. The solubility of the molecule is adjusted by changing the alkyl chain on the N atom of the imide group, so that the solubility of the naphthalocyanine triacimide molecule in common organic solvents such as chloroform, chlorobenzene and the like is good, the separation and purification and the solution processing of the target molecule are facilitated, and the purity of the prepared naphthalocyanine triacimide molecule is higher.

3. Compared with the prior art, the synthesis process has the advantages of simple operation, less energy consumption and low cost, and is more favorable for large-scale production.

4. The bulk heterojunction solar cell using the naphthalocyanine triacimide molecule as an acceptor material has the photoelectric conversion efficiency as high as 6.25 percent, and is the highest photoelectric conversion efficiency in the bulk heterojunction solar cells of the naphthalocyanine, the phthalocyanine and the naphthalocyanine.

Drawings

Fig. 1 is a solar cell device structure of example 13.

FIG. 2 is a J-V plot of an organic solar cell device based on the polymer PTQ10: Compound 2 of example 13.

Detailed Description

The following examples are provided to further illustrate the present invention, the method for synthesizing the receptor material, and the solar cell, but the scope of the present invention is not limited thereto.

The starting materials 1, 2-xylene, boron trichloride, silver tetrafluoroborate, phenol or phenol derivatives and thiophenol or thiophenol derivatives, etc., used in the present invention are commercially available, and 6, 7-dicyanonaphthylimide is prepared according to the literature methods (org. Lett.2014,16, 5442-42-type 5445; org. Lett.2019,21, 3382-type 3386).

The invention introduces imide group on the basis of the method for synthesizing naphthalocyanine acceptor in the prior art. The imide group has strong electron withdrawing ability and high stability, can effectively reduce the LUMO energy level of molecules, thereby increasing the stability of the molecules, and the N end of the imide can be connected with different solubilizing groups, can adjust the crystallinity and the solubility of the molecules, and is a common and excellent organic semiconductor molecule modification unit. Based on the method, three imide groups are introduced into a naphthalocyanine conjugate parent body, a series of naphthalocyanine imide compounds with different substituents at the positions of a B atom and an imide N end are synthesized, and the optical property, the electricity property and the application on solar batteries are researched.