Organic photovoltaic device active layer of non-halogenated solvent and preparation method and application thereof

Abstract

The invention provides an organic photovoltaic device active layer of a non-halogenated solvent as well as a preparation method and application of the organic photovoltaic device active layer. The preparation method of the active layer of the organic photovoltaic device comprises the following steps: dissolving a first raw material system comprising a donor material, a first acceptor material and a liquid additive in an o-xylene solvent, and stirring to obtain a first mixed solution; or dissolving a second raw material system comprising the donor material, the first acceptor material, the second acceptor material and the solid additive in the o-xylene solvent, and stirring to obtain a second mixed solution; and spin-coating the first mixed solution or the second mixed solution on a substrate, and annealing to form the active layer of the organic photovoltaic device. The active layer of the organic photovoltaic device prepared by the preparation method does not contain a halogenated solvent, the threat of the toxicity and volatility of the halogenated solvent to the health of operators is avoided, and the pollution to the environment is reduced, so that the preparation method has the advantages of high safety and high environmental friendliness.

Description

Technical Field

[0001] The invention relates to the technical field of organic photovoltaic devices, and in particular to an organic photovoltaic device active layer of a non-halogenated solvent and a preparation method and application thereof. Background Art

[0002] Organic photovoltaic devices are devices that can achieve photoelectric conversion using materials with photoelectric effect. They have attracted widespread attention in the field of solar energy conversion due to their flexibility, low cost, and large-scale production. The active layer is the core part of an organic photovoltaic device, which is usually composed of a donor material and an acceptor material. In this layer, the photoelectric conversion reaction triggered by light causes electrons and holes to separate, thereby generating current. Therefore, the preparation of the active layer is crucial to the performance of organic photovoltaic devices (such as photoelectric conversion efficiency).

[0003] At present, the prior art generally adopts halogenated solvents (such as chloroform, chlorobenzene, etc.) to dissolve donor materials and acceptor materials to prepare the active layer of organic photovoltaic devices. For example, the patent technology with publication number CN 113241412 A discloses a method for preparing the active layer of an organic photovoltaic device and its application, wherein the donor material and the acceptor material are respectively dissolved in a mixed solution of chloroform and o-xylene solvent to obtain an active layer with good film morphology and photoelectric performance, and the photoelectric conversion efficiency of the organic photovoltaic device containing the active layer is 14.29% to 15.20%. However, there are still some problems in preparing the active layer of the organic photovoltaic device by this method: (1) the halogenated solvent (chloroform) has high toxicity and high volatility. In the process of preparing the active layer of the organic photovoltaic device, the volatilization of the halogenated solvent (chloroform) will not only cause potential harm to the health of the operator, but also cause environmental pollution problems; (2) the organic photovoltaic device prepared by using the active layer of the organic photovoltaic device still has the problem of low photoelectric conversion efficiency.

[0004] Therefore, how to obtain an organic photovoltaic device active layer without halogenated solvent is a technical problem to be solved urgently in this field. Summary of the invention

[0005] The present invention provides a method for preparing an active layer of an organic photovoltaic device without a halogenated solvent. The preparation method can be used to prepare an active layer of an organic photovoltaic device without a halogenated solvent, thereby avoiding the threat of toxicity and volatility of halogenated solvents to the health of operators and reducing pollution to the environment. Therefore, the preparation method has the advantages of high safety and high environmental protection. The active layer of the organic photovoltaic device without a halogenated solvent prepared by the preparation method has excellent film morphology, and the organic photovoltaic device containing the active layer of the organic photovoltaic device without a halogenated solvent has a high filling factor and excellent photoelectric conversion efficiency. Therefore, the preparation method has a reference significance for further improving the efficiency of organic photovoltaic devices and large-area preparation.

[0006] The present invention also provides an active layer of an organic photovoltaic device of a non-halogenated solvent, which is prepared by the above-mentioned preparation method. Therefore, the active layer of the organic photovoltaic device of a non-halogenated solvent does not contain a halogenated solvent and has excellent film morphology. In addition, the organic photovoltaic device prepared by using the active layer of the organic photovoltaic device of a non-halogenated solvent has a high filling factor and excellent photoelectric conversion efficiency.

[0007] The present invention also provides an organic photovoltaic device, which comprises the organic photovoltaic device active layer containing the non-halogenated solvent, so the organic photovoltaic device has a high filling factor and excellent photoelectric conversion efficiency.

[0008] The first aspect of the present invention provides a method for preparing an active layer of an organic photovoltaic device in a non-halogenated solvent, comprising:

[0009] Dissolving a first raw material system including a donor material, a first acceptor material, and a liquid additive in an o-xylene solvent, and stirring to obtain a first mixed solution; or dissolving a second raw material system including a donor material, a first acceptor material, a second acceptor material, and a solid additive in an o-xylene solvent, and stirring to obtain a second mixed solution;

[0010] Spin coating the first mixed solution or the second mixed solution on a substrate, and annealing to form an active layer of an organic photovoltaic device of the non-halogenated solvent;

[0011] The first receptor material is one of the compounds shown in Formula 1, Formula 2, and Formula 3:

[0012]

[0013] In the method for preparing an active layer of an organic photovoltaic device using a non-halogenated solvent as described above, during the spin coating, the temperature of the first mixed solution or the second mixed solution is controlled to be 25° C. to 80° C.

[0014] In the method for preparing an active layer of an organic photovoltaic device using a non-halogenated solvent as described above, the substrate is a hole transport layer, and the temperature of the substrate is 25°C to 80°C.

[0015] The method for preparing an active layer of an organic photovoltaic device using a non-halogenated solvent as described above, wherein the stirring treatment is performed at a temperature of 60° C. to 80° C. and for a time of 3 h to 6 h;

[0016] And / or, the annealing temperature is 90°C to 110°C and the time is 6min to 10min;

[0017] and / or, in the first raw material system, the mass ratio of the donor material to the first acceptor material is 1:(1-1.4);

[0018] And / or, in the second raw material system, the mass ratio of the donor material, the first acceptor material and the second acceptor material is 1:(0.6-1):(0.4-0.6).

[0019] In the method for preparing an active layer of an organic photovoltaic device using a non-halogenated solvent as described above, in the first raw material system, the liquid additive is 1-chloronaphthalene, and the content of the 1-chloronaphthalene is 0.5 vol% to 1.2 vol% based on the total volume of the donor material, the first acceptor material and the o-xylene solvent;

[0020] And / or, in the second raw material system, in the second raw material system, the solid additive is 2-methoxynaphthalene, and the mass of the 2-methoxynaphthalene accounts for 40% to 90% of the total mass of the donor material, the first acceptor material and the second acceptor material.

[0021] The method for preparing an active layer of an organic photovoltaic device using a non-halogenated solvent as described above, wherein the donor material is PM6;

[0022] And / or, the second acceptor material is L8-BO-D.

[0023] The second aspect of the present invention provides an organic photovoltaic device active layer of a non-halogenated solvent, which is prepared by the preparation method.

[0024] The third aspect of the present invention provides an organic photovoltaic device, comprising an ITO conductive substrate and a hole transport layer stacked in sequence, including the organic photovoltaic device active layer of the non-halogenated solvent, wherein the organic photovoltaic device active layer of the non-halogenated solvent is arranged on the surface of the hole transport layer away from the ITO conductive substrate.

[0025] In the organic photovoltaic device as described above, the hole transport layer is one of a self-assembled molecule 3-BPIC-F layer, a PEDOT:PSS-AI4083 layer, a 2PACz layer, a Br-2PACz layer, and a Cl-2PACz layer.

[0026] The organic photovoltaic device as described above further comprises an electron transport layer and a metal electrode;

[0027] The electron transport layer is disposed on a surface of the organic photovoltaic device active layer of the non-halogenated solvent away from the hole transport layer, and the metal electrode is disposed on a surface of the electron transport layer away from the organic photovoltaic device active layer of the non-halogenated solvent.

[0028] The present invention provides a method for preparing an active layer of an organic photovoltaic device of a non-halogenated solvent. The method comprises dissolving a first raw material system including a donor material, a first acceptor material, and a liquid additive in an o-xylene solvent, and obtaining a first mixed solution after stirring; or dissolving a second raw material system including a donor material, a first acceptor material, a second acceptor material, and a solid additive in an o-xylene solvent, and obtaining a second mixed solution after stirring; spin coating the first mixed solution or the second mixed solution on a substrate, and annealing to form an active layer of an organic photovoltaic device of a non-halogenated solvent that does not contain a halogenated solvent. On the one hand, the preparation method avoids the use of halogenated solvents, avoids the threat of toxicity and volatility of halogenated solvents to the health of operators, and reduces pollution to the environment, so the preparation method has the advantages of high safety and high environmental protection; on the other hand, the organic photovoltaic device active layer of the non-halogenated solvent prepared by the preparation method has excellent film morphology, and the organic photovoltaic device containing the organic photovoltaic device active layer of the non-halogenated solvent has a high filling factor and excellent photoelectric conversion efficiency, so the preparation method has a reference significance for further improving the efficiency of organic photovoltaic devices and large-area preparation. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0030] Figure 1 is the mass spectrum of the acceptor material CH8-4 in Example 1 of the present invention;

[0031] Figure 2 is the mass spectrum of the acceptor material CH8-4A in Example 2 of the present invention;

[0032] Figure 3 is the mass spectrum of the acceptor material CH8-4B in Example 3 of the present invention;

[0033] Figure 4 is a schematic structural diagram of an organic photovoltaic device according to Example 4 of the present invention;

[0034] Figure 5 is the chemical structural formula of the self-assembling molecule 3-BPIC-F in Example 4 of the present invention;

[0035] Figure 6 is the chemical structural formula of the acceptor material L8-BO-D in Example 7 of the present invention;

[0036] Figure 7The results of the UV-visible absorption spectrum test of PM6 film, CH8-4 film, CH8-4A film, CH8-4B film and L8-BO-D film are shown in the figure;

[0037] Figure 8 The results of the UV-visible absorption spectrum test of CH8-4 solution, CH8-4A solution and CH8-4B solution at different temperatures are shown in the figure, wherein: Figure 8 A is the result of UV-visible absorption spectrum test of CH8-4 solution at different temperatures. Figure 8 B is the result of UV-visible absorption spectrum test of CH8-4A solution at different temperatures. Figure 8 C is the result of UV-visible absorption spectrum test of CH8-4B solution at different temperatures;

[0038] Fig. 9 This is a graph showing the morphology test results of the active layer of Example 4 of the present invention, wherein: Fig. 9 AFM height map of the active layer PM6:CH8-4 of an organic photovoltaic device in a non-halogenated solvent. Fig. 9 B is the AFM phase image of the active layer PM6:CH8-4 of the organic photovoltaic device with non-halogenated solvent. Fig. 9 IR-AFM image of PM6:CH8-4, the active layer of an organic photovoltaic device in which C is a non-halogenated solvent;

[0039] Fig.10 This is a graph showing the morphology test results of the active layer of Example 5 of the present invention, wherein: Fig.10 AFM height map of the active layer PM6:CH8-4A of an organic photovoltaic device in a non-halogenated solvent. Fig.10 B is the AFM phase image of the active layer PM6:CH8-4A of the organic photovoltaic device with non-halogenated solvent. Fig.10 IR-AFM image of the binary device of PM6:CH8-4A, the active layer of the organic photovoltaic device with C as a non-halogenated solvent;

[0040] Fig.11 This is a graph showing the morphology test results of the active layer of Example 6 of the present invention, wherein: Fig.11 AFM height map of the active layer PM6:CH8-4B of an organic photovoltaic device in a non-halogenated solvent. Fig.11 B is a non-halogenated solvent organic photovoltaic device active layer PM6: CH8-4B AFM phase image, Fig.11 IR-AFM image of PM6:CH8-4B, an active layer of an organic photovoltaic device in which C is a non-halogenated solvent;

[0041] Fig.12This is a graph showing the morphology test results of the active layer of Example 7 of the present invention, wherein: Fig.12 AFM height map of the active layer PM6:CH8-4B:L8-BO-D of an organic photovoltaic device in a non-halogenated solvent. Fig.12 B is the AFM phase image of the active layer PM6:CH8-4B:L8-BO-D of the organic photovoltaic device with non-halogenated solvent. Fig.12 IR-AFM image of the active layer PM6:CH8-4B:L8-BO-D of the organic photovoltaic device with C as a non-halogenated solvent;

[0042] Description of reference numerals:

[0043] 1- Glass substrate (ITO conductive substrate);

[0044] 2-hole transport layer;

[0045] 3-active layer;

[0046] 4-Electron transport layer;

[0047] 5-Metal electrode. DETAILED DESCRIPTION

[0048] In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0049] Unless otherwise specified, the raw materials and reagents used in the following examples can be obtained from commercial sources; the processes used, unless otherwise specified, are conventional processes in the art.

[0050] It should be noted that the descriptions involving “first”, “second”, etc. in the present invention are only for descriptive purposes and therefore cannot be understood as limiting the present invention.

[0051] The first aspect of the present invention provides a method for preparing an active layer of an organic photovoltaic device in a non-halogenated solvent, comprising:

[0052] Dissolving a first raw material system including a donor material, a first acceptor material, and a liquid additive in an o-xylene solvent, and stirring to obtain a first mixed solution; or dissolving a second raw material system including a donor material, a first acceptor material, a second acceptor material, and a solid additive in an o-xylene solvent, and stirring to obtain a second mixed solution;

[0053] Spin coating the first mixed solution or the second mixed solution on a substrate, and annealing to form an active layer of an organic photovoltaic device of the non-halogenated solvent;

[0054] The first receptor material is one of the compounds shown in Formula 1, Formula 2, and Formula 3:

[0055]

[0056] Specifically, the present invention can dissolve a first raw material system including a donor material, a first acceptor material, and a liquid additive in an o-xylene solvent, obtain a first mixed solution after stirring, spin-coat the first mixed solution on a substrate, and anneal to form an active layer of an organic photovoltaic device with a non-halogenated solvent having excellent thin film morphology; or dissolve a second raw material system including a donor material, a first acceptor material, a second acceptor material, and a solid additive in an o-xylene solvent, obtain a second mixed solution after stirring, spin-coat the first mixed solution or the second mixed solution on a substrate, and anneal to form an active layer of an organic photovoltaic device with a non-halogenated solvent having excellent thin film morphology.

[0057] The thickness of the active layer of the organic photovoltaic device prepared by the present invention is not particularly limited and can be selected according to specific needs. In some embodiments, the thickness of the active layer of the organic photovoltaic device prepared by the non-halogenated solvent can be 100nm to 120nm.

[0058] The present invention prepares the non-halogenated solvent organic photovoltaic device active layer by the above method, which does not contain halogenated solvents, avoids the use of halogenated solvents, avoids the threat of toxicity and volatility of halogenated solvents to the health of operators, and reduces pollution to the environment. Therefore, the preparation method has the advantages of high safety and high environmental protection.

[0059] The inventors have shown through research that the preparation method can be used to prepare an organic photovoltaic device active layer containing no halogenated solvents, and the organic photovoltaic device containing the organic photovoltaic device active layer of the non-halogenated solvent has a high filling factor and excellent photoelectric conversion efficiency. The inventors analyzed this and believed that the reasons may be: (1) the use of the preparation method can improve the phase separation degree of the organic photovoltaic device active layer film of the non-halogenated solvent, promote the microscopic phase separation between the donor material and the first acceptor material (or promote the microscopic phase separation between the donor material and the first acceptor material and the second acceptor material), which is beneficial to charge transport and collection, thereby improving the filling factor and photoelectric conversion efficiency of the organic photovoltaic device; (2) the use of the preparation method can optimize the crystallinity of the organic photovoltaic device active layer film of the non-halogenated solvent, reduce the defect state density in the film, reduce charge recombination, and thereby improve the performance of the organic photovoltaic device.

[0060] In a specific embodiment, during the spin coating, the temperature of the first mixed solution or the second mixed solution is controlled to be 25° C. to 80° C.

[0061] The present invention does not particularly limit the specific operation of controlling the temperature of the first mixed solution or the second mixed solution, and the temperature can be controlled according to methods known in the art. In some embodiments, the first mixed solution or the second mixed solution can be heated to 25°C to 80°C to obtain the first mixed solution or the second mixed solution with a temperature of 25°C to 80°C.

[0062] When the parameters for controlling the temperature of the first mixed solution or the second mixed solution are within the above range, it is beneficial to form a uniform non-halogenated solvent organic photovoltaic device active layer after the first mixed solution or the second mixed solution is spin-coated on the substrate, thereby preparing an organic photovoltaic device with a high fill factor and excellent photoelectric conversion efficiency.

[0063] Exemplarily, during the spin coating, the temperature of the first mixed solution or the second mixed solution can be controlled to be any one of 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C or 80°C, or a range consisting of any two of them.

[0064] In a specific embodiment, the substrate is a hole transport layer, and the temperature of the substrate is 25°C to 80°C.

[0065] When the temperature parameters of the substrate are within the above range, it is helpful to prepare a thin film uniform non-halogenated solvent organic photovoltaic device active layer, thereby preparing an organic photovoltaic device with a high fill factor and excellent photoelectric conversion efficiency, which is beneficial to reducing production costs and industrial promotion and application.

[0066] Illustratively, the temperature of the substrate may be any one of 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C or 80°C, or a range consisting of any two of them.

[0067] In a specific embodiment, the stirring treatment is carried out at a temperature of 60° C. to 80° C. and for a time of 3 h to 6 h.

[0068] When the parameters of the temperature and time of the stirring treatment are within the above range, a first mixed solution or a second mixed solution with high uniformity can be prepared, which is conducive to the subsequent formation of a uniform non-halogenated solvent organic photovoltaic device active layer after the first mixed solution or the second mixed solution is spin-coated on the substrate.

[0069] Exemplarily, the temperature of the stirring treatment may be any one of 60°C, 65°C, 70°C, 75°C and 80°C, or a range consisting of any two thereof;

[0070] The time can be any one of 3h, 4h, 5h or 6h, or a range consisting of any two of them.

[0071] In a specific embodiment, the annealing temperature is 90° C. to 110° C. and the time is 6 min to 10 min.

[0072] When the parameters of the temperature and time of the stirring treatment are within the above range, the non-halogenated solvent organic photovoltaic device active layer with excellent film morphology can be formed. The inventors analyzed this and believed that the reason may be that annealing can promote the rearrangement of molecules in the non-halogenated solvent organic photovoltaic device active layer, which has order, thereby improving its crystallinity. This order of molecular arrangement can reduce grain boundaries and defects and improve charge transfer efficiency; in addition, annealing can also promote microscopic phase separation between the donor material and the first acceptor material (or promote microscopic phase separation between the donor material and the first acceptor material and the second acceptor material), reduce the defect state density in the non-halogenated solvent organic photovoltaic device active layer, reduce the charge recombination rate, form a more optimal microscopic phase structure, and facilitate the generation and separation of charges. The prepared non-halogenated solvent organic photovoltaic device active layer has excellent film morphology.

[0073] In a specific embodiment, in the first raw material system, the mass ratio of the donor material to the first acceptor material is 1:(1-1.4), and the mass ratio of the donor material to the first acceptor material may preferably be 1:1.4.

[0074] In the first raw material system, when the mass ratio of the donor material to the first acceptor material is within the above range, it is beneficial to prepare an organic photovoltaic device active layer of a non-halogenated solvent with excellent film morphology.

[0075] In another specific embodiment, in the second raw material system, the mass ratio of the donor material, the first acceptor material and the second acceptor material is 1:(0.6-1):(0.4-0.6), and the mass ratio of the donor material, the first acceptor material and the second acceptor material may preferably be 1:0.8:0.6.

[0076] In the second raw material system, when the mass ratio of the donor material, the first acceptor material and the second acceptor material is within the above range, it is beneficial to prepare a non-halogenated solvent organic photovoltaic device active layer with excellent film morphology.

[0077] In a specific embodiment, in the first raw material system, the liquid additive is 1-chloronaphthalene, and based on the total volume of the donor material, the first acceptor material and the o-xylene solvent, the content of the 1-chloronaphthalene is 0.5 vol% to 1.2 vol%, and the content of the 1-chloronaphthalene may preferably be 1 vol%.

[0078] In the first raw material system, when the content of 1-chloronaphthalene is within the above range, the added 1-chloronaphthalene can regulate the pre-aggregation effect of the molecule itself, making the film formation process slower, and helping to form a compact continuous interpenetrating network of the donor material and the first acceptor material and a non-halogenated solvent active layer of an organic photovoltaic device with a better film morphology.

[0079] Illustratively, in the first raw material system, based on the total volume of the donor material, the first acceptor material and the o-xylene solvent, the content of 1-chloronaphthalene can be any one of 0.5 vol%, 0.8 vol%, 1 vol% or 1.2 vol%, and a range consisting of any two of them.

[0080] In a specific embodiment, in the second raw material system, the solid additive is 2-methoxynaphthalene, and the mass of the 2-methoxynaphthalene accounts for 40% to 90% of the total mass of the donor material, the first acceptor material and the second acceptor material.

[0081] In the second raw material system, when the mass of 2-methoxynaphthalene accounts for the total mass of the donor material, the first acceptor material and the second acceptor material within the above range, the added 2-methoxynaphthalene can regulate the pre-aggregation effect of the molecules themselves, making the film formation process slower, and helping to form a compact donor material, a continuous interpenetrating network of the first acceptor material and the second acceptor material and a non-halogenated solvent active layer of an organic photovoltaic device with a better thin film morphology.

[0082] In a specific embodiment, the donor material is PM6.

[0083] The present invention does not particularly limit the specific source of PM6, which can be purchased directly from the market or synthesized according to methods known in the art.

[0084] When PM6 is selected as the donor material, it can provide electrons to the electron acceptor, thereby generating electron-hole pairs under light.

[0085] In one specific embodiment, the second acceptor material is L8-BO-D.

[0086] The present invention does not particularly limit the specific preparation process of L8-BO-D, and it can be synthesized according to conventional methods in the art.

[0087] When L8-BO-D is selected as the second acceptor material, it can help adjust the phase separation degree and morphology between the donor material and the first acceptor material, thereby forming the non-halogenated solvent organic photovoltaic device active layer with excellent film morphology. The non-halogenated solvent organic photovoltaic device active layer has a more ideal microscopic phase separation structure, which helps to improve the charge separation and transfer efficiency.

[0088] The second aspect of the present invention provides an organic photovoltaic device active layer of a non-halogenated solvent, which is prepared by the above-mentioned preparation method.

[0089] Specifically, the non-halogenated solvent organic photovoltaic device active layer provided by the present invention can be prepared by dissolving a first raw material system including a donor material, a first acceptor material, and a liquid additive in an o-xylene solvent, or can be prepared by dissolving a second raw material system including a donor material, a first acceptor material, a second acceptor material, and a solid additive in an o-xylene solvent. The non-halogenated solvent organic photovoltaic device active layer does not contain a halogenated solvent, has excellent film morphology, and the organic photovoltaic device prepared using the non-halogenated solvent organic photovoltaic device active layer has a high fill factor and excellent photoelectric conversion efficiency.

[0090] The third aspect of the present invention provides an organic photovoltaic device, comprising an ITO conductive substrate and a hole transport layer stacked in sequence, including the organic photovoltaic device active layer of the non-halogenated solvent, wherein the organic photovoltaic device active layer of the non-halogenated solvent is arranged on the surface of the hole transport layer away from the ITO conductive substrate.

[0091] The organic photovoltaic device provided by the present invention comprises the organic photovoltaic device active layer of the non-halogenated solvent, so the organic photovoltaic device has a high filling factor and excellent photoelectric conversion efficiency.

[0092] In a specific embodiment, the hole transport layer is one of a self-assembled molecule 3-BPIC-F layer, a PEDOT:PSS-AI4083 layer, a 2PACz layer, a Br-2PACz layer, and a Cl-2PACz layer.

[0093] The present invention does not particularly limit the sources of the materials of the self-assembling molecule 3-BPIC-F layer, PEDOT:PSS-AI4083 layer, 2PACz layer, Br-2PACz layer, and Cl-2PACz layer, which can be directly purchased from the market or synthesized according to methods known in the art.

[0094] When the above hole transport layer is selected, the prepared organic photovoltaic device has a high filling factor and excellent photoelectric conversion efficiency.

[0095] In a specific embodiment, it also includes an electron transport layer and a metal electrode;

[0096] The electron transport layer is disposed on a surface of the organic photovoltaic device active layer of the non-halogenated solvent away from the hole transport layer, and the metal electrode is disposed on a surface of the electron transport layer away from the organic photovoltaic device active layer of the non-halogenated solvent.

[0097] The present invention does not specifically limit the materials for preparing the electron transport layer and the metal electrode, and materials well known in the art can be used for preparation. In some embodiments, the material for preparing the electron transport layer can be PNDIT-F3N, and the material for preparing the metal electrode can be silver (Ag).

[0098] The present invention is further described below through specific embodiments.

[0099] The self-assembling molecule 3-BPIC-F used in the following embodiments is synthesized according to the method in the reference (Dipole Moments Regulation of Biphosphonic Acid Molecules for Self-assembled Monolayers Boosts the Efficiency of Organic Solar Cells Exceeding 19.7%, Journal of the American Chemical Society 2024 146 (20), 14287-14296); the acceptor material L8-BO-D is synthesized according to the method for synthesizing L8-BO in the reference (Non-fullerene acceptors with branched side chains and improved molecular packing to exceed 18% efficiency in organic solar cells, Nature Energy, 6, 605–613 (2021)), except that: 1-bromo-2-ethylhexane (1-bromo-2-ethylhexane) in the literature is replaced by 1-bromo-2-decyltetradecane (CAS No.: 732276-63-0).

[0100] Example 1

[0101] This embodiment provides a method for preparing the acceptor material CH8-4 shown in Formula 1:

[0102]

[0103]

[0104] S1: Under argon protection, compound 1 (1.51 g, 1.06 mmol, CAS No.: 2410998-39-7, purchased from Shenzhen Ruixun Organic Solar Cell Co., Ltd.) was dissolved in tetrahydrofuran (70 mL), and lithium aluminum hydride (LiAlH4, 4.25 mL) was added in an ice-water bath to obtain a reaction mixture; after the reaction mixture was reacted at 80° C. for 12 hours, 2 mol / L dilute hydrochloric acid was added in an ice-water bath to quench the reaction to obtain a product, and the product was extracted with ethyl acetate and dried to remove the solvent to obtain a brown solid compound 2 (1.39 g, yield 94%); the synthetic route for preparing compound 2 is as follows:

[0105]

[0106] S2: Compound 2 (509 mg, 0.37 mmol) was dissolved in chloroform (40 mL) to obtain a solution, and then 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (91 mg, 0.4 mmol) and 4-bromo-5-fluorobenzene-1,2-diamine (358 mg, 1.75 mmol) were added to the solution in sequence, and the mixture was reacted at room temperature for 6 hours to obtain a solution after reaction, and the solution after reaction was distilled and dried to obtain a reaction product; finally, the reaction product was purified by column chromatography using petroleum ether as an eluent to obtain a purple-red solid compound 3 (406 mg, with a yield of 71%); the synthetic route for preparing compound 3 is as follows:

[0107]

[0108] S3: Under argon protection, phosphorus oxychloride (POCl3, 0.25 mL), N,N-dimethylformamide (DMF, 0.25 mL) and compound 3 (400 mg, 0.25 mmol) were added to 1,2-dichloroethane (40 mL) to obtain a mixed solution, which was reacted at 80°C and condensed and refluxed for 12 hours, followed by addition of saturated sodium acetate solution (45 mL) for quenching, and stirred at room temperature for 2 hours to obtain the product; the product was extracted with dichloromethane, dried with anhydrous sodium sulfate to remove the solvent, and then purified by column chromatography using petroleum ether / dichloromethane (v / v=3:2) as an eluent to obtain a red solid compound 4 (345 mg, yield 83%); the synthetic route for preparing compound 4 is as follows:

[0109]

[0110] S4: Compound 4 (300 mg, 0.19 mmol), 2,5-bis(trimethyltinyl)thiophene (36 mg, 0.09 mmol) and tetrakis(triphenylphosphine)palladium (Pd(PPh3)4, 46 mg, 0.04 mmol) were added to ultra-dry toluene (20 mL) to obtain a reactant solution; under argon protection, the reactant solution was heated and stirred at 120° C. for 24 h, and cooled to room temperature to obtain a reaction product; the reaction product was dried with anhydrous sodium sulfate to remove the solvent, and then the dried reaction product was purified by column chromatography using petroleum ether / dichloromethane (v / v=3 / 2) as an eluent to obtain a red solid compound 5 (290 mg, yield 49%); the synthetic route for preparing compound 5 is as follows:

[0111]

[0112] S5: Under argon protection, compound 5 (150 mg, 0.047 mmol), 2-(5,6-dichloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (100 mg, 0.38 mmol) and chloroform (CHCl3, 25 mL) were added to a double-necked round-bottom flask to obtain a mixture solution; pyridine (0.3 mL) was added dropwise to the mixture solution to obtain a reaction mixture; the reaction mixture was reacted at 75°C for 12 hours, and after cooling to room temperature, a reaction solution was obtained, and the reaction solution was dried with anhydrous sodium sulfate to remove the solvent to obtain a product; then, petroleum ether / chloroform (v / v=1 / 1) was used as an eluent, and the product was purified by column chromatography, the purified product was subjected to low-pressure distillation and spin-dried, and then dissolved in chloroform and precipitated in methanol to obtain a black solid compound CH8-4 (108 mg, yield 56%) shown in Formula 1, and its mass spectrum is shown as follows Figure 1 The synthetic route for preparing compound CH8-4 is shown below:

[0113]

[0114] Example 2

[0115] This embodiment provides a method for preparing the acceptor material CH8-4A shown in Formula 2:

[0116]

[0117] The preparation of CH8-4A shown in Formula 2 provided in this embodiment is basically the same as that in Example 1, except that:

[0118] S2: 4-bromo-5-fluorobenzene-1,2-diamine was replaced by 4-bromo-3-fluorobenzene-1,2-diamine.

[0119] S5: Obtain a black solid compound CH8-4A (108 mg, yield 56%) as shown in Formula 2. Its mass spectrum is as follows: Figure 2 shown.

[0120] Example 3

[0121] This embodiment provides a method for preparing the acceptor material CH8-4B shown in Formula 3:

[0122]

[0123] The preparation of CH8-4B shown in Formula 3 provided in this embodiment is basically the same as that in Example 1, except that:

[0124] S2: 4-bromo-5-fluorobenzene-1,2-diamine was replaced by 4-bromo-6-fluorobenzene-1,2-diamine.

[0125] S5: Obtain a black solid compound CH8-4B (108 mg, yield 56%) as shown in Formula 3, and its mass spectrum is as follows: Figure 3 shown.

[0126] Example 4

[0127] Figure 4 is a schematic structural diagram of an organic photovoltaic device according to Example 4 of the present invention; Figure 4 As shown, the method for preparing the organic photovoltaic device of this embodiment includes the following steps:

[0128] (1) An ITO conductive substrate (a glass substrate with an ITO transparent conductive film) having a thickness of 130 nm was sequentially cleaned in an ultrasonic bath in an ultrasonic machine using a conductive glass cleaning solution, deionized water, and isopropyl alcohol for 20 min, and then dried with nitrogen gas. The surface of the ITO conductive substrate was then treated in an ultraviolet-ozone chamber for 15 min to obtain a treated ITO conductive substrate 1;

[0129] (2) The self-assembling molecule 3-BPIC-F (whose chemical structure is as follows) Figure 5 After being dissolved in chromatographic grade anhydrous ethanol, the mixture was placed on a magnetic stirrer and stirred for 2 h at room temperature to obtain a self-assembling molecule 3-BPIC-F solution with a concentration of 0.8 mg / mL;

[0130] The self-assembled molecule 3-BPIC-F solution was spin-coated on the upper surface of the treated ITO conductive substrate 1 at a rotation speed of 3000 r / min using a coating machine, and then placed on an annealing table at 100° C. for annealing for 10 minutes to form a self-assembled molecule 3-BPIC-F layer, i.e., a hole transport layer 2;

[0131] (3) dissolving the donor material PM6 (CAS No.: 1802013-83-7) and the acceptor material CH8-4 in a mass ratio of 1:1.4 and 1-chloronaphthalene in an o-xylene solvent having a concentration of 8 mg / mL (detected by high performance liquid chromatography, the content of the o-xylene solvent is greater than 96%) to obtain a mixed solution, wherein the content of 1-chloronaphthalene is 1 vol% based on the total volume of PM6, CH8-4 and o-xylene solvent;

[0132] The mixed solution was placed on a magnetic stirring heating table at a temperature of 60° C. and stirred for 4 hours to obtain a fully dissolved mixed solution;

[0133] The fully dissolved mixed solution is heated to 60° C. to obtain a mixed solution with a temperature of 60° C.; the hole transport layer 2 prepared in step (2) is placed on a hot plate with a temperature of 60° C. for heating treatment to obtain a hole transport layer 2 substrate with a temperature of 60° C.;

[0134] On the surface of the hole transport layer 2 substrate at a temperature of 60°C away from the ITO conductive substrate 1, a mixed solution at 60°C was spin-coated at a rotation speed of 1500 r / min, and a smooth and uniform film was formed after waiting for 30 seconds, and then placed on an annealing table at 100°C for annealing for 8 minutes to form an active layer 3 with a thickness of 100 nm (i.e., the organic photovoltaic device active layer PM6: CH8-4 of the non-halogenated solvent);

[0135] (4) dissolving PNDIT-F3N (CAS No.: 1800206-46-5) in a mixed solvent of chromatographic grade methanol and chromatographic grade acetic acid (prepared according to 99.7 vol% chromatographic grade methanol and 0.3 vol% chromatographic grade acetic acid) at a concentration of 1 mg / mL to obtain a PNDIT-F3N solution;

[0136] At room temperature, the PNDIT-F3N solution was placed on a magnetic stirring table and stirred for 5 h to obtain a fully dissolved PNDIT-F3N solution;

[0137] Use a coating machine to spin-coat a fully dissolved PNDIT-F3N solution on the surface of the active layer 3 away from the hole transport layer 2 to form an electron transport layer 4;

[0138] (5) After the electron transport layer 4 is formed, the substrate is moved into the physical vapor deposition chamber, and the vacuum system is started until the pressure in the physical vapor deposition chamber drops to 2×10 -6 When Pa, a silver (Ag) target is heated, and a metal electrode 5 (Ag electrode) with a thickness of 150 nm is prepared on the surface of the electron transport layer 4 away from the active layer 3 to form an organic photovoltaic device.

[0139] Example 5

[0140] The preparation of the organic photovoltaic device provided in this embodiment is basically the same as that in embodiment 4, except that:

[0141] (3) The acceptor material CH8-4 is replaced by the acceptor material CH8-4A, and finally an active layer with a thickness of 100 nm is prepared (ie, the active layer PM6 of the organic photovoltaic device of the non-halogenated solvent: CH8-4A).

[0142] Example 6

[0143] The preparation of the organic photovoltaic device provided in this embodiment is basically the same as that in embodiment 4, except that:

[0144] (3) The acceptor material CH8-4 is replaced by the acceptor material CH8-4B, and finally an active layer with a thickness of 100 nm is prepared (ie, the active layer PM6 of the organic photovoltaic device of the non-halogenated solvent: CH8-4B).

[0145] Example 7

[0146] The preparation of the organic photovoltaic device provided in this embodiment is basically the same as that in embodiment 4, except that:

[0147] (3) The donor material PM6 (CAS No.: 1802013-83-7), the acceptor material CH8-4 and the acceptor material L8-BO-D (whose chemical structure is as follows) are added. Figure 6 As shown in the figure, 2-methoxynaphthalene was dissolved in an o-xylene solvent with a concentration of 8 mg / mL (detected by high performance liquid chromatography, the content of o-xylene solvent was greater than 96%) according to a mass ratio of 1:0.8:0.6 to obtain a mixed solution, in which the mass of 2-methoxynaphthalene accounted for 80% of the total mass of PM6, CH8-4 and L8-BO-D, and finally an active layer with a thickness of 100 nm was prepared (i.e., the active layer of an organic photovoltaic device of a non-halogenated solvent, PM6:CH8-4:L8-BO-D).

[0148] Example 8

[0149] The preparation of the organic photovoltaic device provided in this embodiment is basically the same as that in embodiment 7, except that:

[0150] (2) PEDOT:PSS-AI4083 (CAS No.: 155090-83-8) and distilled water were mixed uniformly in a volume ratio of 1:1, and a PEDOT:PSS-AI4083 solution was obtained after filtration;

[0151] The PEDOT:PSS-AI4083 solution was spin-coated on the upper surface of the treated ITO conductive substrate at a rotation speed of 4400 r / min using a coating machine, and then placed on an annealing table at 150°C for annealing for 30 minutes to form a PEDOT:PSS-AI4083 layer, i.e., a hole transport layer.

[0152] Example 9

[0153] The preparation of the organic photovoltaic device provided in this embodiment is basically the same as that in embodiment 7, except that:

[0154] (2) 2PACz (CAS No.: 20999-38-6) was dissolved in chromatographic grade anhydrous ethanol and stirred on a magnetic stirrer at room temperature for 2 h to obtain a 2PACz solution with a concentration of 0.25 mg / mL;

[0155] A 2PACz solution was spin-coated on the upper surface of the treated ITO conductive substrate at a rotation speed of 3000 r / min using a coating machine, and then placed on an annealing table at 100° C. for annealing for 10 minutes to form a 2PACz layer, namely a hole transport layer.

[0156] Example 10

[0157] The preparation of the organic photovoltaic device provided in this embodiment is basically the same as that in embodiment 7, except that:

[0158] (2) Br-2PACz (CAS No.: 2762888-11-7) was dissolved in chromatographic grade anhydrous ethanol and stirred on a magnetic stirrer at room temperature for 2 h to obtain a Br-2PACz solution with a concentration of 0.25 mg / mL;

[0159] The Br-2PACz solution was spin-coated on the upper surface of the treated ITO conductive substrate at a rotation speed of 3000 r / min using a coating machine, and then placed on an annealing table at 100° C. for annealing for 10 minutes to form a Br-2PACz layer, i.e., a hole transport layer.

[0160] Embodiment 11

[0161] The preparation of the organic photovoltaic device provided in this embodiment is basically the same as that in embodiment 7, except that:

[0162] (2) Dissolving Cl-2PACz (CAS No.: 3036926-72-1) in chromatographic grade anhydrous ethanol, stirring the mixture on a magnetic stirrer at room temperature for 2 h to obtain a Cl-2PACz solution with a concentration of 0.25 mg / mL;

[0163] The Cl-2PACz solution was spin-coated on the upper surface of the treated ITO conductive substrate at a rotation speed of 3000 r / min using a coating machine, and then placed on an annealing table at 100° C. for annealing for 10 minutes to form a Cl-2PACz layer, i.e., a hole transport layer.

[0164] Example 12

[0165] The preparation of the organic photovoltaic device provided in this embodiment is basically the same as that in embodiment 7, except that:

[0166] (3) The hole transport layer prepared in step (2) of this embodiment is placed on a hot plate at a temperature of 25° C. for heating treatment to obtain a hole transport layer substrate at a temperature of 25° C.

[0167] Embodiment 13

[0168] The preparation of the organic photovoltaic device provided in this embodiment is basically the same as that in embodiment 7, except that:

[0169] (3) The hole transport layer prepared in step (2) of this embodiment is placed on a hot plate at a temperature of 40° C. for heating treatment to obtain a hole transport layer substrate at a temperature of 40° C.

[0170] Embodiment 14

[0171] The preparation of the organic photovoltaic device provided in this embodiment is basically the same as that in embodiment 7, except that:

[0172] (3) The hole transport layer prepared in step (2) of this embodiment is placed on a hot plate at a temperature of 80° C. for heating treatment to obtain a hole transport layer substrate at a temperature of 80° C.

[0173] Embodiment 15

[0174] The preparation of the organic photovoltaic device provided in this embodiment is basically the same as that in embodiment 7, except that:

[0175] (3) The fully dissolved mixed solution is heated to 25°C to obtain a mixed solution with a temperature of 25°C.

[0176] Example 16

[0177] The preparation of the organic photovoltaic device provided in this embodiment is basically the same as that in embodiment 7, except that:

[0178] (3) heating the fully dissolved mixed solution to 25°C to obtain a mixed solution at a temperature of 25°C; placing the hole transport layer prepared in step (2) of this embodiment on a hot plate at a temperature of 25°C for heating treatment to obtain a hole transport layer substrate at a temperature of 25°C.

[0179] Performance Testing

[0180] 1. UV-visible absorption spectrum test

[0181] PM6, CH8-4, CH8-4A, CH8-4B and L8-BO-D were made into thin films respectively, and then the PM6 film, CH8-4 film, CH8-4A film, CH8-4B film and L8-BO-D film were tested by UV-visible absorption spectra. The results are as follows: Figure 7 shown.

[0182] Depend on Figure 7 It can be seen that the acceptor materials (CH8-4, CH8-4A, CH8-4B and L8-BO-D) show strong absorption in the range of 600nm to 800nm, which is complementary to the absorption range of the donor material PM6.

[0183] 2. Aggregation effect test

[0184] The acceptor material CH8-4, the acceptor material CH8-4A, and the acceptor material CH8-4B were dissolved in o-xylene solvent at a concentration of 0.002 mg / mL to obtain CH8-4 solution, CH8-4A solution, and CH8-4B solution, respectively. Then, the CH8-4 solution, CH8-4A solution, and CH8-4B solution were tested at different temperatures using a Cary5000 UV-Vis spectrophotometer. The test results are shown in FIG. Figure 8 As shown in AC.

[0185] Depend on Figure 8 The AC of CH8-4 shows that the shoulder peak near 800 nm is the solution pre-aggregation peak of the receptor material of the present invention. The aggregation degree of CH8-4, CH8-4A and CH8-4B is calculated to be CH8-4B. <CH8-4<CH8-4A。

[0186] 3. Morphology test of active layer

[0187] The active layers in Examples 4 to 7 were tested using a BRUKER Anasys nano IR3 nano-infrared atomic force microscope. The results are as follows: Figure 9-12 shown.

[0188] Depend on Figure 9-12It can be seen that the active layers in Examples 4 to 7 all exhibit smooth surfaces and continuous phase separation, with the root mean square (RMS) roughness value between 1.16 nm and 1.25 nm, which is conducive to establishing effective ohmic contact with the electron transport layer. The active layer in Example 4 (PM6: CH8-4) and the active layer in Example 6 (PM6: CH8-4B) exhibit an obvious co-continuous interpenetrating network, which is conducive to exciton dissociation and charge transport. For the active layer in Example 5 (CH8-4A), due to the excessive pre-aggregation and crystallinity of the acceptor material, the donor material PM6 is dispersed into very small domains and wrapped by the domains of the acceptor material, lacking sufficient donor-acceptor interface. In summary, the active layer provided by the present invention has excellent film morphology.

[0189] 4. Organic photovoltaic device performance test

[0190] Under standard sunlight (AM 1.5G) irradiation conditions, the following tests were performed on the organic photovoltaic devices of Examples 4 to 16 using a computer-controlled Keithley 2400 digital source meter. The test results are shown in Table 1.

[0191] (1) Open circuit voltage (V oc ): The voltage of the organic photovoltaic device when it is disconnected under light conditions, in volts (V), and the formula is as follows:

[0192]

[0193] In the formula, e is the elementary charge, E LUMO -E HOMO It is called the effective band gap between the donor and acceptor materials, ΔE represents the energy loss in the photoelectric conversion process, V oc is the open circuit voltage;

[0194] (2) Short-circuit current (J sc ): Short-circuit current refers to the output current when the voltage difference between the two sides of the organic photovoltaic device is zero under standard test conditions of temperature and irradiance. In the JV curve, it is shown as the current at the intersection between the curve and the y-axis.

[0195] (3) Fill factor (FF): The fill factor is the ratio of the maximum output power of an organic photovoltaic device to its limit power. The formula is as follows:

[0196]

[0197] In the formula, J max is the current density corresponding to the maximum output power of the organic photovoltaic device, V max is the output voltage corresponding to the maximum output power of the organic photovoltaic device, J sc is the short-circuit current, V ocis the open circuit voltage, and FF is the fill factor.

[0198] (4) Photovoltaic conversion efficiency (PCE): The energy conversion efficiency is used to characterize the ability of organic photovoltaic devices to convert light energy into electrical energy. The formula is as follows:

[0199]

[0200] Where FF is the filling factor, J sc is the short-circuit current, V oc is the open circuit voltage, P in is the incident light intensity, and PCE is the photoelectric conversion efficiency.

[0201] Table 1 Test results

[0202]

[0203]

[0204] As shown in Table 1, the organic photovoltaic device prepared by doping the o-xylene solvent in the active layer (i.e., the organic photovoltaic device prepared in Examples 4-16) has the advantages of high open circuit voltage, high filling factor, and high photoelectric conversion efficiency. The open circuit voltage can reach 0.920V, the filling factor can reach 79.6%, and the photoelectric conversion efficiency can reach 20.0%. By comparing Example 7 with Example 8-Example 11, it can be seen that when the hole transport layer is a self-assembled molecule 3-BPIC-F layer, the filling factor and photoelectric conversion efficiency of the organic photovoltaic device are significantly improved. By comparing Example 7 with Example 12-Example 16, it can be seen that when the temperature of the mixed solution is 60°C and the temperature of the hole transport layer substrate is 60°C, the filling factor and photoelectric conversion efficiency of the organic photovoltaic device are significantly improved.

[0205] In summary, the organic photovoltaic device prepared by the present invention has a high open circuit voltage, a high fill factor and an excellent photoelectric conversion efficiency, which shows that the method of the present invention can be used to prepare a high-performance organic photovoltaic device.

[0206] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing an active layer of an organic photovoltaic device using a non-halogenated solvent, characterized in that: include: Dissolving a first raw material system including a donor material, a first acceptor material, and a liquid additive in an o-xylene solvent, and stirring to obtain a first mixed solution; or dissolving a second raw material system including a donor material, a first acceptor material, a second acceptor material, and a solid additive in an o-xylene solvent, and stirring to obtain a second mixed solution; Spin coating the first mixed solution or the second mixed solution on a substrate, and annealing to form an active layer of an organic photovoltaic device of the non-halogenated solvent; The first receptor material is one of the compounds shown in Formula 1, Formula 2, and Formula 3:

2. The method for preparing an active layer of an organic photovoltaic device using a non-halogenated solvent according to claim 1, characterized in that: During the spin coating, the temperature of the first mixed solution or the second mixed solution is controlled to be 25° C. to 80° C.

3. The method for preparing an active layer of an organic photovoltaic device using a non-halogenated solvent according to claim 1, characterized in that: The substrate is a hole transport layer, and the temperature of the substrate is 25°C to 80°C.

4. The method for preparing an active layer of an organic photovoltaic device using a non-halogenated solvent according to claim 1, characterized in that: The stirring treatment is performed at a temperature of 60°C to 80°C and for a time of 3h to 6h; And / or, the annealing temperature is 90°C to 110°C and the time is 6min to 10min; and / or, in the first raw material system, the mass ratio of the donor material to the first acceptor material is 1:(1-1.4); And / or, in the second raw material system, the mass ratio of the donor material, the first acceptor material and the second acceptor material is 1:(0.6-1):(0.4-0.6).

5. The method for preparing an active layer of an organic photovoltaic device using a non-halogenated solvent according to claim 1, characterized in that: In the first raw material system, the liquid additive is 1-chloronaphthalene, and the content of the 1-chloronaphthalene is 0.5 vol% to 1.2 vol% based on the total volume of the donor material, the first acceptor material and the o-xylene solvent; And / or, in the second raw material system, the solid additive is 2-methoxynaphthalene, and the mass of the 2-methoxynaphthalene accounts for 40% to 90% of the total mass of the donor material, the first acceptor material and the second acceptor material.

6. The method for preparing an active layer of an organic photovoltaic device using a non-halogenated solvent according to claim 1, characterized in that: The donor material is PM6; And / or, the second acceptor material is L8-BO-D.

7. An organic photovoltaic device active layer of a non-halogenated solvent, characterized in that: It is prepared by the preparation method according to any one of claims 1 to 6.

8. An organic photovoltaic device, comprising an ITO conductive substrate and a hole transport layer stacked in sequence, characterized in that: An organic photovoltaic device active layer comprising the non-halogenated solvent according to claim 7, wherein the organic photovoltaic device active layer comprising the non-halogenated solvent is arranged on a surface of the hole transport layer away from the ITO conductive substrate.

9. The organic photovoltaic device according to claim 8, characterized in that: The hole transport layer is one of a self-assembled molecule 3-BPIC-F layer, a PEDOT:PSS-AI4083 layer, a 2PACz layer, a Br-2PACz layer, and a Cl-2PACz layer.

10. The organic photovoltaic device according to claim 8, characterized in that: It also includes an electron transport layer and a metal electrode; The electron transport layer is disposed on a surface of the organic photovoltaic device active layer of the non-halogenated solvent away from the hole transport layer, and the metal electrode is disposed on a surface of the electron transport layer away from the organic photovoltaic device active layer of the non-halogenated solvent.

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