Dimeric electron acceptor material with near-infrared absorption characteristic as well as preparation method and application of dimeric electron acceptor material

Abstract

The invention provides a dimeric electron acceptor material with a near-infrared absorption characteristic as well as a preparation method and application of the dimeric electron acceptor material. The dimeric electron acceptor material has one of the following chemical structural formula: # imgabs0 #, in which R1 is independently CnH2n + 1 when appearing each time, and n is an integer between 1 and 100; r2 is independently CmH2m + 1 at each occurrence, and m is an integer between 1 and 100; x is independently selected at each occurrence from H, F, Cl, I, NO2 or CN. The dimeric electron acceptor material has a near-infrared absorption characteristic; an organic solar cell device prepared from the dimer electron acceptor material has a high filling factor and excellent photoelectric conversion efficiency; an organic photoelectric detector prepared from the dimeric electron acceptor material has excellent light responsivity, external quantum efficiency and specific detection rate in a near-infrared region.

Description

Technical Field

[0001] The present invention relates to the technical field of organic electronic materials and device preparation, and in particular to a dimeric electron acceptor material with near-infrared absorption characteristics, a preparation method and application thereof. Background Art

[0002] In recent years, with the increasing demand for renewable energy and the improvement of environmental protection awareness, organic photovoltaic devices with advantages such as flexibility, low cost and large-scale production have attracted widespread attention. Among them, the active layer is the core part of the organic photovoltaic device, which is usually composed of donor materials and acceptor materials. Among them, the donor material is mainly responsible for absorbing light energy and converting it into excited electron-hole pairs, while the acceptor material completes the current collection by accepting electrons and transferring them to the electrode.

[0003] At present, the receptor materials used mainly include polymer receptor materials, small molecule receptor materials and dimeric electron receptor materials. Among them, polymer receptor materials have good film-forming properties, but have disadvantages such as uncontrollable synthesis and large batch differences. Therefore, polymer receptor materials and their corresponding devices have poor repeatability and batch instability, which is a bottleneck in the commercialization process. Small molecule receptor materials have clear structures and have synthetic controllability, which solves the problem of batch instability. However, since charge transport strongly depends on crystallinity, it is difficult to obtain the best active layer morphology, which affects the performance of its corresponding device. The dimeric electron receptor material between the two has the advantages of both and has become a hot topic of research. For example, the patent technology with publication number CN107304218 A discloses an ortho-bridged perylene diimide dimer and its preparation method and application in organic photovoltaic devices. Perylene diimide (PDI) dimer is obtained by ortho-bridging, and then the PDI dimer is used to prepare an organic solar cell device. The photoelectric conversion efficiency of the photovoltaic cell device is 0.99% to 4.25%. However, the organic solar cell device prepared by using PDI dimer in this patent still has the problem of low photoelectric conversion efficiency (less than 5%).

[0004] In addition, the absorption distribution of most receptor materials is in the visible light region and cannot effectively utilize sunlight in the near-infrared region, which limits their application in image sensing, information transmission, and medical treatment.

[0005] Therefore, developing a dimeric electron acceptor material with near-infrared absorption characteristics is a technical problem that needs to be solved urgently in this field. Summary of the invention

[0006] The present invention provides a dimeric electron acceptor material with near-infrared absorption characteristics. The dimeric electron acceptor material has near-infrared absorption characteristics. An organic solar cell device prepared by using the dimeric electron acceptor material has a high filling factor and excellent photoelectric conversion efficiency. An organic photodetector device prepared by using the dimeric electron acceptor material has excellent light responsiveness, external quantum efficiency and specific detection rate in the near-infrared region.

[0007] The present invention also provides a method for preparing a dimeric electron acceptor material with near-infrared absorption characteristics. The dimeric electron acceptor material with near-infrared absorption characteristics can be prepared by the preparation method.

[0008] The present invention also provides an organic solar cell device, which comprises the above-mentioned dimeric electron acceptor material having near-infrared absorption characteristics, so the organic solar cell device also has near-infrared absorption characteristics, and also has a high filling factor and excellent photoelectric conversion efficiency.

[0009] The present invention also provides an organic photodetection device, which includes the above-mentioned dimeric electron acceptor material with near-infrared absorption characteristics, so that the organic photodetection device also has near-infrared absorption characteristics, and has excellent photoresponsivity, external quantum efficiency and specific detection rate in the near-infrared region.

[0010] The first aspect of the present invention provides a dimeric electron acceptor material having near-infrared absorption characteristics, wherein the dimeric electron acceptor material is a compound DYSe-4A or a compound DYSe-5A, wherein the chemical structure of the compound DYSe-4A is shown in Formula 1, and the chemical structure of the compound DYSe-5A is shown in Formula 2:

[0011]

[0012] In Formula 1 or Formula 2, R 1 C independently at each occurrence n H 2n+1 , n is an integer between 1 and 100; R 2 C independently at each occurrence m H 2m+1 , m is an integer between 1 and 100; X is independently selected from H, F, Cl, I, NO 2 or CN.

[0013] The dimeric electron acceptor material having near-infrared absorption characteristics as described above has an absorption peak in the wavelength range of 600nm to 1000nm.

[0014] The second aspect of the present invention provides a method for preparing the dimeric electron acceptor material having near-infrared absorption characteristics, comprising:

[0015] S1: Compound 1 is subjected to the first aldehyde formation by the Vilsmeier-Hack reaction to obtain compound 2;

[0016] S2: subjecting compound 2 to an aldol condensation reaction to obtain compound 3;

[0017] S3: performing a first reaction on compound 3 and a first terminal compound to generate compound 4-1, or performing a second reaction on compound 3 and a second terminal compound to generate compound 4-2;

[0018] S4: subjecting compound 4-1 to a second aldehyde reaction by using the Vilsmayer-Hack reaction to obtain compound 5-1, or subjecting compound 4-2 to a third aldehyde reaction by using the Vilsmayer-Hack reaction to obtain compound 5-2;

[0019] S5: performing a third reaction on compound 5-1 and a third terminal compound to generate compound 6-1, or performing a fourth reaction on compound 5-2 and a fourth terminal compound to generate compound 6-2;

[0020] S6: subjecting compound 6-1 to a fifth reaction with 2,5-bis(trimethyltinyl)thiophene to generate the compound DYSe-4A, or subjecting compound 6-2 to a sixth reaction with 2,5-bis(trimethyltinyl)thiophene to generate the compound DYSe-5A;

[0021] The chemical structural formula of the compound 1 is shown in Formula 3, the chemical structural formula of the compound 2 is shown in Formula 4, the chemical structural formula of the compound 3 is shown in Formula 5, the chemical structural formula of the first terminal compound or the fourth terminal compound is shown in Formula 6, the chemical structural formula of the second terminal compound or the third terminal compound is shown in Formula 7, the chemical structural formula of the compound 4-1 is shown in Formula 8, the chemical structural formula of the compound 4-2 is shown in Formula 9, the chemical structural formula of the compound 5-1 is shown in Formula 10, the chemical structural formula of the compound 5-2 is shown in Formula 11, the chemical structural formula of the compound 6-1 is shown in Formula 12, and the chemical structural formula of the compound 6-2 is shown in Formula 13:

[0022]

[0023]

[0024] Among them, R 1 C independently at each occurrence n H 2n+1 , n is an integer between 1 and 100; R2 C independently at each occurrence m H 2m+1 , m is an integer between 1 and 100; X is independently selected from H, F, Cl, I, NO 2 or CN.

[0025] In the method for preparing the dimeric electron acceptor material having near-infrared absorption characteristics as described above, in S3, the mass ratio of the compound 3 to the first terminal compound is 1:(1.5-2), or the mass ratio of the compound 3 to the second terminal compound is 1:(1.5-2);

[0026] and / or, in S5, the mass ratio of the compound 5-1 to the third terminal compound is 1:(1.5-2), or the mass ratio of the compound 5-2 to the fourth terminal compound is 1:(1.5-2);

[0027] And / or, in S6, the mass ratio of the compound 6-1 to the 2,5-bis(trimethyltinyl)thiophene is 1:(0.47-0.49), or the mass ratio of the compound 6-2 to the 2,5-bis(trimethyltinyl)thiophene is (0.47-0.49).

[0028] The preparation method of the dimeric electron acceptor material with near-infrared absorption characteristics as described above, wherein the first aldehyde reaction is carried out for 6 hours to 7 hours;

[0029] And / or, the aldol condensation reaction is carried out for 10 hours to 12 hours;

[0030] And / or, the temperature for the first reaction or the second reaction is 65-70° C. and the time is 10 h to 12 h;

[0031] And / or, the time for performing the second hydroformylation or the third hydroformylation is 6 h to 7 h;

[0032] And / or, the time for performing the third reaction or the fourth reaction is 0.5h to 1h;

[0033] And / or, the temperature for carrying out the fifth reaction or the sixth reaction is 115° C. to 120° C. and the time is 12 h to 14 h.

[0034] The third aspect of the present invention provides an organic solar cell device, comprising an active layer formed by blending a first donor material and a first acceptor material, wherein the first acceptor material is the dimeric electron acceptor material having near-infrared absorption characteristics.

[0035] The organic solar cell device as described above, wherein the first donor material comprises PBDB-T;

[0036] In the active layer, the mass ratio of the PBDB-T to the dimeric electron acceptor material having near-infrared absorption characteristics is 1:(1-1.6).

[0037] A fourth aspect of the present invention provides an organic photodetector device, comprising an active layer prepared from a raw material system of a second donor material and a second acceptor material, wherein the second acceptor material is a dimeric electron acceptor material having near-infrared absorption characteristics.

[0038] The organic solar cell device as described above, wherein the second donor material comprises PBDB-T;

[0039] In the raw material system, the mass ratio of the PBDB-T to the dimeric electron acceptor material having near-infrared absorption characteristics is 1:(1-1.6).

[0040] The organic solar cell device as described above, wherein the raw material system further comprises a liquid additive, and the liquid additive comprises 1,8-diiodooctane;

[0041] In the raw material system, the volume percentage of the 1,8-diiodooctane is 0.3 vol% to 1 vol%.

[0042] The present invention provides a dimeric electron acceptor material with near-infrared absorption characteristics. The dimeric electron acceptor material has an absorption peak in the near-infrared region, and its chemical structure is shown in Formula 1 or Formula 2. The structure is clear and can effectively avoid the problem of instability between batches, providing a reference method for realizing high-performance organic photovoltaic devices.

[0043] The organic solar cell device provided by the present invention has significant near-infrared absorption characteristics by applying the above-mentioned dimeric electron acceptor material to the organic solar cell device, and has a high fill factor (up to 58.4%) and excellent photoelectric conversion efficiency (up to 11.75%).

[0044] The organic photodetector device provided by the present invention has near-infrared absorption characteristics and excellent photoresponsivity (up to 0.50 AW) in the near-infrared region (850 nm) by applying the above-mentioned dimerized electron acceptor material to the organic photodetector device. -1 ), external quantum efficiency (up to 73.0%) and specific detectivity (up to 4.5×10 13 Jones). BRIEF DESCRIPTION OF THE DRAWINGS

[0045] 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.

[0046] Figure 1 is the product 2A in Example 1 of the present invention 1 H NMR spectrum;

[0047] Figure 2 is the product 3A in Example 1 of the present invention 1 H NMR spectrum;

[0048] Figure 3 is the product 4-1A in Example 1 of the present invention 1 H NMR spectrum;

[0049] Figure 4 is the product 5-1A in Example 1 of the present invention 1 H NMR spectrum;

[0050] Figure 5 is the product 6-1A in Example 1 of the present invention 1 H NMR spectrum;

[0051] Figure 6 The product DYSe-4 in Example 1 of the present invention 1 H NMR spectrum;

[0052] Figure 7 The product DYSe-5 in Example 2 of the present invention 1 H NMR spectrum;

[0053] Figure 8 The UV-visible absorption spectra of the solution and film of DYSe-4 / DYSe-5 of the present invention;

[0054] Fig. 9 The current density-photovoltage curve (JV curve) and the external quantum efficiency (EQE) curve of the organic solar cell device (PBDB-T:DYSe-4) in Application Example 1 and the organic solar cell device (PBDB-T:DYSe-5) in Application Example 6 of the present invention are shown in FIG. Fig. 9 A is the current density-photovoltage curve (JV curve) of the organic solar cell device (PBDB-T:DYSe-4) in Application Example 1 and the organic solar cell device (PBDB-T:DYSe-5) in Application Example 6, Fig. 9B is the external quantum efficiency (EQE) curve of the organic solar cell device (PBDB-T:DYSe-4) in Application Example 1 and the organic solar cell device (PBDB-T:DYSe-5) in Application Example 6;

[0055] Fig.10 The current density-photovoltage curve (JV curve), external quantum efficiency (EQE) curve, responsivity (R) curve and specific detectivity (D*) curve of the organic photodetector device (PBDB-T:DYSe-4) in Application Example 17 of the present invention and the organic photodetector device (PBDB-T:DYSe-5) in Application Example 21 are shown in FIG. Fig.10 A is a current density-photovoltage curve (JV curve) of the organic photodetection device (PBDB-T:DYSe-4) in Application Example 17 and the organic photodetection device (PBDB-T:DYSe-5) in Application Example 21; Fig.10 B is an external quantum efficiency (EQE) curve of the organic photodetector device (PBDB-T:DYSe-4) in Application Example 17 and the organic photodetector device (PBDB-T:DYSe-5) in Application Example 21; Fig.10 C is the responsivity (R) curve of the organic photodetector device (PBDB-T:DYSe-4) in Application Example 17 and the organic photodetector device (PBDB-T:DYSe-5) in Application Example 21; Fig.10 D is the specific detectivity (D*) curve of the organic photodetector device (PBDB-T:DYSe-4) in Application Example 17 and the organic photodetector device (PBDB-T:DYSe-5) in Application Example 21. DETAILED DESCRIPTION

[0056] 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.

[0057] 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.

[0058] It should be noted that, the descriptions involving “first”, “second”, “third”, “fourth”, “fifth”, “sixth”, etc. in the present invention are only for descriptive purposes and therefore cannot be understood as limiting the present invention.

[0059] The first aspect of the present invention provides a dimeric electron acceptor material having near-infrared absorption characteristics, wherein the dimeric electron acceptor material is a compound DYSe-4A or a compound DYSe-5A, wherein the chemical structure of the compound DYSe-4A is shown in Formula 1, and the chemical structure of the compound DYSe-5A is shown in Formula 2:

[0060]

[0061] In Formula 1 or Formula 2, R 1 C independently at each occurrence n H 2n+1 , n is an integer between 1 and 100; R 2 C independently at each occurrence m H 2m+1 , m is an integer between 1 and 100; X is independently selected from H, F, Cl, I, NO 2 or CN.

[0062] In the present invention, the above-mentioned dimeric electron acceptor material has an absorption peak in the near-infrared region, and its chemical structure is shown in Formula 1 or Formula 2. The structure is clear and can effectively avoid the problem of instability between batches, providing a reference method for realizing high-performance organic photovoltaic devices.

[0063] In a specific embodiment, the dimeric electron acceptor material has an absorption peak in the wavelength range of 600 nm to 1000 nm.

[0064] In the present invention, the absorption peak of the above-mentioned dimeric electron acceptor material is within the above-mentioned wavelength range, which indicates that the dimeric electron acceptor material has near-infrared absorption characteristics.

[0065] The second aspect of the present invention provides a method for preparing a dimeric electron acceptor material having near-infrared absorption characteristics, comprising:

[0066] S1: Compound 1 is subjected to the first aldehyde formation by the Vilsmeier-Hack reaction to obtain compound 2;

[0067] S2: subjecting compound 2 to an aldol condensation reaction to obtain compound 3;

[0068] S3: performing a first reaction on compound 3 and a first terminal compound to generate compound 4-1;

[0069] S4: Compound 4-1 is subjected to a second aldehyde reaction using the Vilsmeier-Hack reaction to obtain compound 5-1;

[0070] S5: subjecting compound 5-1 to a third reaction with a third terminal compound to generate compound 6-1;

[0071] S6: Compound 6-1 is subjected to a fifth reaction with 2,5-bis(trimethyltinyl)thiophene to generate compound DYSe-4A;

[0072] The chemical structural formula of compound 1 is shown in Formula 3, the chemical structural formula of compound 2 is shown in Formula 4, the chemical structural formula of compound 3 is shown in Formula 5, the chemical structural formula of the first terminal compound is shown in Formula 6, the chemical structural formula of the third terminal compound is shown in Formula 7, the chemical structural formula of the compound 4-1 is shown in Formula 8, the chemical structural formula of the compound 5-1 is shown in Formula 10, and the chemical structural formula of the compound 6-1 is shown in Formula 12:

[0073]

[0074]

[0075] Among them, R 1 C independently at each occurrence n H 2n+1 , n is an integer between 1 and 100; R 2 C independently at each occurrence m H 2m+1 , m is an integer between 1 and 100; X is independently selected from H, F, Cl, I, NO 2 or CN.

[0076] In the present invention, the Vilsmeier-Hack reaction refers to the reaction of N,N-dimethylformamide (DMF) and phosphorus oxychloride (POCl 3 ), a reaction in water that converts electron-rich aromatic compounds into the corresponding aromatic aldehydes.

[0077] In the present invention, the aldol condensation reaction refers to a reaction in which an aldehyde having α-H generates a carbon anion under base catalysis, and then the carbon anion acts as a nucleophilic reagent to perform nucleophilic addition on another aldehyde molecule to generate a β-hydroxyaldehyde, and the β-hydroxyaldehyde is dehydrated by heat to generate an unsaturated aldehyde. Through the aldol condensation reaction, a new carbon-carbon bond can be formed in the molecule and the carbon chain can be extended.

[0078] The present invention does not particularly limit the sources of the raw materials for preparing the compound DYSe-4A, which can be purchased through commercial channels or prepared by methods known to those skilled in the art.

[0079] The present invention can prepare the compound DYSe-4A with near-infrared absorption characteristics by the above-mentioned preparation method. The organic solar cell device prepared by using the compound DYSe-4A has a high filling factor (up to 55.1%) and excellent photoelectric conversion efficiency (up to 9.71%); the organic photodetector device prepared by using the dimerized electron acceptor material has excellent light response in the near-infrared region (up to 0.47AW -1 ), external quantum efficiency (up to 68.5%) and specific detectivity (up to 2.9×10 13 Jones).

[0080] In another specific embodiment, the preparation method of the above-mentioned dimeric electron acceptor material having near-infrared absorption characteristics comprises:

[0081] S1: Compound 1 is subjected to the first aldehyde formation by the Vilsmeier-Hack reaction to obtain compound 2;

[0082] S2: subjecting compound 2 to an aldol condensation reaction to obtain compound 3;

[0083] S3: performing a second reaction on compound 3 and a second terminal compound to generate compound 4-2;

[0084] S4: Compound 4-2 is subjected to a third aldehyde reaction by using the Vilsmeier-Hack reaction to obtain compound 5-2;

[0085] S5: subjecting compound 5-2 to a fourth reaction with a fourth terminal compound to generate compound 6-2;

[0086] S6: Compound 6-2 is reacted with 2,5-bis(trimethyltinyl)thiophene to generate compound DYSe-5A;

[0087] The chemical structural formula of compound 1 is shown in the above formula 3, the chemical structural formula of compound 2 is shown in the above formula 4, the chemical structural formula of compound 3 is shown in the above formula 5, the chemical structural formula of the fourth terminal compound is shown in the above formula 6, the chemical structural formula of the second terminal compound is shown in the above formula 7, the chemical structural formula of compound 4-2 is shown in formula 9, and the chemical structural formula of compound 5-2 is shown in

[0088] As shown in Formula 11, the chemical structure of the compound 6-2 is shown in Formula 13:

[0089]

[0090] Among them, R 1 C independently at each occurrence n H 2n+1 , n is an integer between 1 and 100; R 2C independently at each occurrence m H 2m+1 , m is an integer between 1 and 100; X is independently selected from H, F, Cl, I, NO 2 or CN.

[0091] The present invention does not particularly limit the sources of the raw materials for preparing the compound DYSe-5A, which can be purchased through commercial channels or prepared by methods known to those skilled in the art.

[0092] The present invention can prepare the compound DYSe-5A with near-infrared absorption characteristics by the above-mentioned preparation method. The organic solar cell device prepared by using the compound DYSe-5A has a high filling factor (up to 58.4%) and excellent photoelectric conversion efficiency (up to 11.75%); the organic photodetector device prepared by using the dimerized electron acceptor material has excellent light response in the near-infrared region (up to 0.50AW -1 ), external quantum efficiency (up to 73.0%) and specific detectivity (up to 4.5×10 13 Jones).

[0093] In a specific embodiment, in the above S3, the mass ratio of compound 3 to the first terminal compound is 1:(1.5-2).

[0094] When the mass ratio of compound 3 to the first terminal compound is within the above range, the first reaction can be sufficiently carried out to obtain compound 4-1 with a high yield.

[0095] In another specific embodiment, in the above S3, the mass ratio of compound 3 to the second terminal compound is 1:(1.5-2).

[0096] When the mass ratio of compound 3 to the second terminal compound is within the above range, the second reaction can be fully carried out to obtain compound 4-2 with a high yield.

[0097] In a specific embodiment, in the above S5, the mass ratio of compound 5-1 to the third terminal compound is 1:(1.5-2).

[0098] When the mass ratio of compound 5-1 to the third terminal compound is within the above range, the third reaction can be sufficiently carried out to obtain compound 6-1 with a high yield.

[0099] In another specific embodiment, in the above S5, the mass ratio of compound 5-2 to the fourth terminal compound is 1:(1.5-2).

[0100] When the mass ratio of compound 5-2 to the fourth terminal compound is within the above range, the fourth reaction can be sufficiently carried out to obtain compound 6-2 with a high yield.

[0101] In a specific embodiment, in the above S6, the mass ratio of compound 6-1 to 2,5-bis(trimethyltinyl)thiophene is 1:(0.47-0.49).

[0102] When the mass ratio of compound 6-1 to 2,5-bis(trimethyltinyl)thiophene is within the above range, the fifth reaction can be fully performed to obtain compound DYSe-4 with a high yield.

[0103] In another specific embodiment, in the above S6, the mass ratio of compound 6-2 to 2,5-bis(trimethyltinyl)thiophene is 1:(0.47-0.49).

[0104] When the mass ratio of compound 6-2 to 2,5-bis(trimethyltinyl)thiophene is within the above range, the sixth reaction can be fully carried out to obtain compound DYSe-5 with high yield.

[0105] In a specific embodiment, the time for the first aldehyde reaction is 6 h to 7 h;

[0106] And / or, the time for the aldol condensation reaction is 10h to 12h;

[0107] And / or, the temperature for the first reaction or the second reaction is 65-70° C. and the time is 10 h to 12 h;

[0108] And / or, the time for the second hydroformylation or the third hydroformylation is 6 h to 7 h;

[0109] And / or, the time for performing the third reaction or the fourth reaction is 0.5h to 1h;

[0110] And / or, the temperature for carrying out the fifth reaction or the sixth reaction is 115° C. to 120° C. and the time is 12 h to 14 h.

[0111] When the time for the first formaldehyde reaction, the temperature and time for the first reaction or the second reaction, the time for the second formaldehyde reaction or the third formaldehyde reaction, the time for the third reaction or the fourth reaction, and the temperature and time for the fifth reaction or the sixth reaction are respectively within the above ranges, each reaction in S1 to S6 can be carried out more smoothly and efficiently, thereby obtaining a target product (compound DYSe-4A or compound DYSe-5A) with high yield and infrared absorption characteristics, laying the foundation for the subsequent preparation of high-performance organic photovoltaic devices.

[0112] The third aspect of the present invention provides an organic solar cell device, comprising an active layer formed by blending a first donor material and a first acceptor material, wherein the first acceptor material is the above-mentioned dimeric electron acceptor material having near-infrared absorption characteristics.

[0113] The present invention does not particularly limit the specific material of the first donor material, and the material known to those skilled in the art can be selected according to actual needs.

[0114] In the present invention, the organic solar cell device comprises the dimeric electron acceptor material having near-infrared absorption characteristics, so the organic solar cell device has near-infrared absorption characteristics, and also has a high fill factor and excellent photoelectric conversion efficiency.

[0115] In a specific embodiment, the first donor material includes PBDB-T;

[0116] In the active layer, the mass ratio of PBDB-T to the dimeric electron acceptor material having near-infrared absorption characteristics is 1:(1-1.6).

[0117] When the mass ratio of PBDB-T to the dimeric electron acceptor material having near-infrared absorption characteristics in the active layer is within the above range, an organic solar cell device having a high fill factor and excellent photoelectric conversion efficiency can be prepared.

[0118] Exemplarily, in the active layer, the mass ratio of PBDB-T to the dimeric electron acceptor material having near-infrared absorption characteristics can be any one of 1:1, 1:2, 1:3, 1:4, 1:5 or 1:6 or a range consisting of any two of them.

[0119] A fourth aspect of the present invention provides an organic photodetector device, comprising an active layer prepared from a raw material system of a second donor material and a second acceptor material, wherein the second acceptor material is the above-mentioned dimeric electron acceptor material having near-infrared absorption characteristics.

[0120] The present invention does not particularly limit the specific material of the second donor material, and the material known to those skilled in the art can be selected according to actual needs.

[0121] In the present invention, the organic photodetection device includes the dimerized electron acceptor material having near-infrared absorption characteristics, so the organic photodetection device also has near-infrared absorption characteristics and has excellent photoresponsivity, external quantum efficiency and specific detectivity in the near-infrared region.

[0122] In one specific embodiment, the second donor material includes PBDB-T;

[0123] In the raw material system, the mass ratio of PBDB-T to the dimeric electron acceptor material with near-infrared absorption characteristics is 1:(1-1.6).

[0124] When the mass ratio of PBDB-T to the dimeric electron acceptor material having near-infrared absorption characteristics in the raw material system is within the above range, an organic photodetection device having excellent photoresponsivity, external quantum efficiency and specific detectivity in the near-infrared region can be prepared.

[0125] Exemplarily, in the raw material system, the mass ratio of PBDB-T to the dimeric electron acceptor material having near-infrared absorption characteristics can be any one of 1:1, 1:2, 1:3, 1:4, 1:5, 1:6 or a range consisting of any two of them.

[0126] In a specific embodiment, the raw material system further includes a liquid additive, and the liquid additive is 1,8-diiodooctane;

[0127] In the raw material system, the volume percentage of 1,8-diiodooctane is 0.3 vol% to 1 vol%.

[0128] When the content of 1,8-diiodooctane in the raw material system is within the above range, an organic photodetection device having excellent photoresponsivity, external quantum efficiency and specific detectivity in the near-infrared region can be prepared.

[0129] For example, the content of 1,8-diiodooctane may be any one of 0.3 vol%, 0.4 vol%, 0.5 vol%, 0.6 vol%, 0.7 vol%, 0.8 vol%, 0.9 vol%, 1 vol%, or any two of them.

[0130] Furthermore, when the content of 1,8-diiodooctane in the raw material system is 0.3 vol%, an organic photodetection device having better photoresponsivity, external quantum efficiency and specific detectivity in the near-infrared region can be prepared.

[0131] The present invention is further described below through specific embodiments.

[0132] Example 1

[0133] In this embodiment, the compound DYSe-4 shown in Formula 14 is prepared by the following process:

[0134]

[0135] S1: 1 g of compound 1A (12,13-bis(2-hexyldecyl)-3,9-heneicosyl-12,13-dihydroseleno[2″,3″:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2-g]seleno[2′,3′:4,5]thieno[3,2-b][1,2,5]thiadiazo[3,4-e]indole) and 30 mL of 1,2-dichloroethane were added to a two-necked reaction bottle. Under an argon atmosphere, 0.2 mL of N,N-dimethylformamide (DMF) and 0.2 mL of phosphorus oxychloride (POCl 3 ) was subjected to a Vilsmayer-Hack reaction at room temperature for 6 hours, and then a saturated sodium acetate aqueous solution was added and stirred at room temperature for 1 hour to obtain a reaction product 1. The reaction product 1 was extracted with dichloromethane, dried over anhydrous sodium sulfate, and then eluted by column chromatography with an organic eluent (petroleum ether and dichloromethane in a volume ratio of 3:1) to obtain a product 2A, namely compound 2A (0.97 g, yield 95%). 1 HNMR spectrum Figure 1 As shown;

[0136]

[0137] S2: 0.97 g of compound 2A, 0.35 g of tributyl(1,3-dioxane-2-ylmethyl)phosphonium bromide and 30 mL of tetrahydrofuran (THF) were added to a two-necked flask, 30 mg of sodium hydride (NaH) was added under an argon atmosphere and an ice-water bath to obtain a mixture, the mixture was subjected to aldol condensation reaction at room temperature for 12 h, and then quenched with 10% by mass hydrochloric acid (HCl) to obtain a reaction product 2, the reaction product 2 was extracted with ethyl acetate, dried over anhydrous sodium sulfate, and then eluted with an organic eluent (petroleum ether and dichloromethane in a volume ratio of 3:1) by column chromatography to obtain a product 3A, namely compound 3A (0.75 g, yield 70%), and the product 3A 1 H NMR spectrum Figure 2 As shown;

[0138]

[0139] S3: Add 0.3 g of compound 3A to the reaction flask and add chloroform (CHCl 3) as a solvent, 100 mg of the terminal compound (CAS: 2083617-82-5) and 0.3 mL of pyridine were added under an argon protective atmosphere to obtain a mixture, the mixture was reacted at 70°C for 12 hours, and then precipitated with methanol to obtain a reaction product 3, and the reaction product 3 was eluted with an organic eluent (petroleum ether and dichloromethane in a volume ratio of 2:1) by column chromatography to obtain the product 4-1A, i.e., compound 4-1A (0.41 g, yield 90%), and the 1 H NMR spectrum Figure 3 As shown;

[0140]

[0141] S4: 0.41 g of compound 4-1A and 40 mL of 1,2-dichloroethane were added to a two-necked reaction bottle, and 0.2 mL of N,N-dimethylformamide (DMF) and 0.1 mL of phosphorus oxychloride (POCl) were added under an argon atmosphere. 3 ), and then subjected to Vilsmayer-Hack reaction at room temperature for 12 hours, and then added with saturated sodium acetate aqueous solution and stirred at room temperature for 1 hour to obtain reaction product 4. The reaction product 4 was extracted with dichloromethane, dried over anhydrous sodium sulfate, and then eluted with an organic eluent (petroleum ether and dichloromethane in a volume ratio of 2:1) by column chromatography to obtain product 5-1A, i.e., compound 5-1A (0.38 g, yield of 87%). 1 H NMR spectrum Figure 4 As shown;

[0142]

[0143] S5: Add 0.38 g of compound 5-1A and 80 mg of terminal compound (CAS: 2304026-60-4) into a single-mouth reaction bottle, use 25 mL of toluene as solvent, add 0.1 mL of acetic anhydride (Ac 2 O) reagent and 0.1 mL of boron trifluoride etherate (BF 3 OE 2 ) solution to obtain a mixture, the mixture was reacted at room temperature for 0.5h to obtain a reaction product 5, and the reaction product 5 was eluted by column chromatography with an organic eluent (petroleum ether and dichloromethane in a volume ratio of 1:1) to obtain the product 6-1A, i.e., compound 6-1A (0.35g, yield 85%), and the 1 H NMR spectrum Figure 5 As shown;

[0144]

[0145] S6: 0.35 g of compound 6-1A and 0.34 g of 2,5-bis(trimethyltinyl)thiophene were added to a double-necked reaction bottle, 20 mL of toluene was used as solvent, and 0.3 g of tetrakis(triphenylphosphine)palladium (Pd(PPh 3 ) 4 ) to obtain a mixture, and the mixture was reacted at 120°C for 12h to obtain a reaction product 6. The reaction product 6 was extracted with dichloromethane, dried over anhydrous sodium sulfate, and then eluted by column chromatography with an organic eluent (petroleum ether and dichloromethane in a volume ratio of 1:2) to obtain the product DYSe-4, i.e., compound DYSe-4 (0.15 g, yield 50%). 1 HNMR spectrum Figure 6 As shown;

[0146]

[0147] Example 2

[0148] In this embodiment, the compound DYSe-5 shown in Formula 15 is prepared by the following process:

[0149]

[0150] The preparation of compound DYSe-5 in this example is basically the same as that in Example 1, except that:

[0151] S3: Add 0.3 g of compound 3A to the reaction flask and add chloroform (CHCl 3 ) as a solvent, 100 mg of another terminal compound (CAS: 2304026-60-4) and 0.5 mL of pyridine were added under an argon atmosphere to obtain a mixture, the mixture was reacted at 70° C. for 12 h, and then precipitated with methanol to obtain a reaction product 3, and the reaction product 3 was eluted with an organic eluent (petroleum ether and dichloromethane in a volume ratio of 2:1) by column chromatography to obtain the product 4-2A, i.e., compound 4-2A (0.38 g, yield 87%);

[0152]

[0153] S4: Compound 4-2A of this example was used to prepare product 5-2A, namely compound 5-2A (0.33 g, yield 93%);

[0154]

[0155] S5: Compound 5-2A of this example was used to prepare product 6-2A, namely compound 6-2A (0.35 g, yield 85%);

[0156]

[0157] S6: Compound 6-2A of this example was used to prepare the product DYSe-5, namely compound DYSe-5 (0.13 g, yield 45%). 1 H NMR Figure 7 As shown;

[0158]

[0159] Application Example 1

[0160] The method for preparing the organic solar cell device of this application example comprises the following steps:

[0161] (1) ultrasonically cleaning an ITO conductive glass substrate with detergent, deionized water and isopropyl alcohol solvent in an ultrasonic machine for 20 minutes each, and treating the cleaned ITO conductive glass substrate in a UV-ozone chamber for 15 minutes to obtain a treated ITO conductive glass substrate;

[0162] (2) PEDOT:PSS (Clevios P ​​VP Al 4083) and deionized water were mixed in a volume ratio of 1:1 to obtain a PEDOT:PSS solution;

[0163] The PEDOT:PSS solution was spin-coated on the upper surface of the treated ITO conductive glass substrate at 4400 rpm / 20 s using a coating machine, and then placed on a hot plate at 160° C. for thermal annealing for 15 min to form an anode modification layer with a thickness of 15 nm;

[0164] (3) 6 mg / mL of donor material PBDB-T (CAS: 1415929-80-4) and acceptor material DYSe-4 (compound DYSe-4 prepared in Example 1) were mixed in a mass ratio of 1:1 to obtain a mixture, and the mixture was dissolved in chloroform and placed on a hot plate and stirred at room temperature for 4 h to obtain a mixed solution;

[0165] The mixed solution was spin-coated on the surface of the anode modification layer away from the ITO conductive glass substrate at 2000 rpm / 20 s using a coating machine, and then placed on a hot plate at 100° C. for thermal annealing for 5 min to form an active layer with a thickness of 100 nm;

[0166] (4) PNDIT-F3N (CAS No.: 1800206-46-5) was dissolved in a mixed solvent of methanol and glacial acetic acid (prepared according to a volume percentage of 99.7 vol% methanol and a volume percentage of 0.3 vol% glacial acetic acid) at a concentration of 1 mg / mL for 3 h to obtain a PNDIT-F3N solution;

[0167] Use a spin coater to spin coat the PNDIT-F3N solution on the surface of the active layer away from the anode modification layer at 3300 rpm / 20 s to form a cathode interface layer with a thickness of 5 nm;

[0168] (5) A metal electrode Ag (Ag electrode) with a thickness of 120 nm was evaporated on the surface of the cathode interface layer away from the active layer to form an organic solar cell device.

[0169] Referring to the process of Application Example 1, organic solar cell devices of Application Examples 2-8 were prepared respectively.

[0170] The donor material, the acceptor material, and the mass ratio of the donor material to the acceptor material in the organic solar cell devices in Application Examples 1-8 are summarized in Table 1;

[0171] Table 1 Donor materials, acceptor materials, and mass ratio of donor materials to acceptor materials in organic solar cell devices in Application Examples 1-8

[0172] project Donor material Receptor material The mass ratio of donor material to acceptor material Application Example 1 PBDB-T DYSe-4 PBDB-T:DYSe-4=1:1 Application Example 2 PBDB-T DYSe-4 PBDB-T:DYSe-4=1:1.2 Application Example 3 PBDB-T DYSe-4 PBDB-T:DYSe-4=1:1.4 Application Example 4 PBDB-T DYSe-4 PBDB-T:DYSe-4=1:1.6 Application Example 5 PBDB-T DYSe-5 PBDB-T:DYSe-5=1:1 Application Example 6 PBDB-T DYSe-5 PBDB-T:DYSe-5=1:1.2 Application Example 7 PBDB-T DYSe-5 PBDB-T:DYSe-5=1:1.4 Application Example 8 PBDB-T DYSe-5 PBDB-T:DYSe-5=1:1.6

[0173] In Table 1, the acceptor material DYSe-5 is the compound DYSe-5 prepared in Example 2.

[0174] Application Example 9

[0175] The method for preparing the organic photodetector device of this application example comprises the following steps:

[0176] (1) ultrasonically cleaning an ITO conductive glass substrate with detergent, deionized water, acetone and isopropanol solvent in an ultrasonic machine for 20 minutes each, drying the cleaned ITO conductive glass substrate with a nitrogen gun and then treating it in a UV-ozone chamber for 20 minutes to obtain a treated ITO conductive glass substrate;

[0177] (2) PEDOT:PSS (Clevios P ​​VP Al 4083) and deionized water were mixed in a volume ratio of 1:1 to obtain a PEDOT:PSS solution;

[0178] The PEDOT:PSS solution was spin-coated on the upper surface of the treated ITO conductive glass substrate at 4400 rpm / 20 s using a coating machine, and then placed on a hot plate at 160° C. for thermal annealing for 15 min to form an anode modification layer with a thickness of 15 nm;

[0179] (3) 6 mg / mL of donor material PBDB-T (CAS: 1415929-80-4) and acceptor material DYSe-4 (compound DYSe-4 prepared in Example 1) were mixed in a mass ratio of 1:1, 1,8-diiodooctane (DIO) was added as a liquid additive to obtain a mixture, the mixture was dissolved in chloroform and placed on a hot plate and stirred at room temperature for 4 h to obtain a mixed solution;

[0180] The mixed solution was spin-coated on the surface of the anode modification layer away from the ITO conductive glass substrate at 2000 rpm / 20 s using a coating machine, and then placed on a hot plate at 100° C. for thermal annealing for 5 min to form an active layer with a thickness of 100 nm;

[0181] (4) PNDIT-F3N (CAS No.: 1800206-46-5) was dissolved in a mixed solvent of methanol and glacial acetic acid (prepared according to a volume percentage of 99.7 vol% methanol and a volume percentage of 0.3 vol% glacial acetic acid) at a concentration of 1 mg / mL for 3 h to obtain a PNDIT-F3N solution;

[0182] Use a spin coater to spin coat the PNDIT-F3N solution on the surface of the active layer away from the anode modification layer at 3300 rpm / 20 s to form a cathode interface layer with a thickness of 5 nm;

[0183] (5) A metal electrode Ag (Ag electrode) with a thickness of 120 nm was deposited on the surface of the cathode interface layer away from the active layer to form an organic photodetection device.

[0184] Referring to the process of Application Example 9, organic photodetection devices of Application Examples 10-24 were prepared respectively.

[0185] The donor material, the acceptor material, the mass ratio of the donor material to the acceptor material, and the volume percentage of 1,8-diiodooctane (DIO) in the organic photodetector devices in Application Examples 9-24 are summarized in Table 2;

[0186] Table 2 Donor materials, acceptor materials, mass ratio of donor materials to acceptor materials and volume percentage of DIO in organic photodetector devices in application examples 9-24

[0187]

[0188]

[0189] Performance Testing

[0190] (1) Absorption spectrum test of compound DYSe-4 and compound DYSe-5

[0191] The compound DYSe-4 in Example 1 was dissolved in a chloroform solution to obtain a DYSe-4 solution; the DYSe-4 solution was spun on the surface of a quartz plate at 1200 rpm to obtain a DYSe-4 film, and the DYSe-4 solution (DYSe-4-sol) and the DYSe-4 film (DYSe-4-film) were tested for UV-visible absorption spectra; the compound DYSe-5 in Example 2 was dissolved in a chloroform solution to obtain a DYSe-5 solution; the DYSe-5 solution was spun on the surface of a quartz plate at 1200 rpm to obtain a DYSe-5 film, and the DYSe-5 solution (DYSe-5-sol) and the DYSe-5 film (DYSe-5-film) were tested for UV-visible absorption spectra, and the results are as follows: Figure 8 shown.

[0192] Depend on Figure 8 It can be seen that DYSe-4 solution and DYSe-5 solution have good absorption in the wavelength range of 300nm to 1000nm, the maximum absorption peak position of DYSe-4 solution is 793 nanometers (nm), and the maximum absorption peak position of DYSe-5 solution is 790nm; DYSe-4 film has an obvious red shift relative to DYSe-4 solution and has a wider absorption range, and DYSe-5 film has an obvious red shift relative to DYSe-5 solution and has a wider absorption range, the maximum absorption peak position of DYSe-4 film is 865nm, and the maximum absorption peak position of DYSe-5 film is 872nm, which shows that the compound DYSe-4 prepared in Example 1 and the compound DYSe-5 prepared in Example 2 have near-infrared absorption characteristics.

[0193] (2) Performance testing of organic solar cell devices

[0194] Under standard sunlight (AM 1.5G) irradiation conditions, the open circuit voltage (V oc ), short circuit current (J sc ), integrated short-circuit current (J sc cal ), fill factor (FF) and photoelectric conversion efficiency (PCE) tests, the test results are shown in Table 3;

[0195] Table 3 Test results

[0196] project <![CDATA[V oc (V)]]> <![CDATA[J sc (mA cm -2 )]]> <![CDATA[J sc cal (mA cm -2 )]]> FF(%) PCE(%) Application Example 1 0.728 24.63 23.84 54.2 9.71 Application Example 2 0.727 23.54 / 55.1 9.42 Application Example 3 0.724 25.51 / 51.0 9.40 Application Example 4 0.714 24.51 / 50.0 8.74 Application Example 5 0.761 26.79 / 57.3 11.66 Application Example 6 0.759 26.56 26.06 58.4 11.75 Application Example 7 0.754 27.56 / 54.1 11.21 Application Example 8 0.753 27.70 / 50.5 10.52

[0197] In Table 3, “ / ” means that the short-circuit current is not integrated.

[0198] Fig. 9 The current density-photovoltage curve (JV curve) and the external quantum efficiency (EQE) curve of the organic solar cell device (PBDB-T:DYSe-4) in Application Example 1 and the organic solar cell device (PBDB-T:DYSe-5) in Application Example 6 of the present invention are shown in FIG. Fig. 9 A is the current density-photovoltage curve (JV curve) of the organic solar cell device (PBDB-T:DYSe-4) in Application Example 1 and the organic solar cell device (PBDB-T:DYSe-5) in Application Example 6, Fig. 9 B is the external quantum efficiency (EQE) curve of the organic solar cell device in Application Example 1 (PBDB-T:DYSe-4) and the organic solar cell device in Application Example 6 (PBDB-T:DYSe-5).

[0199] As can be seen from Table 3, the organic solar cell device prepared by using the compound DYSe-4 in Example 1 of the present invention or the compound DYSe-5 in Example 2 (i.e., the organic solar cell device prepared in Application Examples 1-8) has the advantages of high filling factor and high photoelectric conversion efficiency, the filling factor can reach 58.4%, and the photoelectric conversion efficiency can reach 11.75%.

[0200] Depend on Fig. 9 It can be seen that the organic solar cell device prepared by using the compound DYSe-4 in Example 1 or the compound DYSe-5 in Example 2 of the present invention has a better open circuit voltage and short circuit current, and the external quantum efficiency is more than 70%, so this material can be used to prepare high-efficiency organic solar cell devices.

[0201] (3) Performance test of organic photodetection devices

[0202] Under standard sunlight (AM 1.5G) irradiation conditions, a computer-controlled Keithley 2400 digital source meter was used to measure the dark current (J) of the organic photodetector devices in Examples 9-22. dark ), external quantum efficiency (EQE), photoresponsivity (R 850 nm ) and specific detection rate (D*) tests, the test results are shown in Table 4;

[0203] Table 4 Test results

[0204] project <![CDATA[J dark (Acm -2 )]]> <![CDATA[EQE 850 nm (%)]]> <![CDATA[R 850 nm (AW -1 )]]> <![CDATA[D* 850nm (Jones)]]> Application Example 9 <![CDATA[9.3×10 -9 ]]> 65.7 0.45 <![CDATA[8.3×10 12 ]]> Application Example 10 <![CDATA[9.2×10 -9 ]]> 66.8 0.46 <![CDATA[8.4×10 12 ]]> Application Example 11 <![CDATA[8.8×10 -9 ]]> 67.0 0.46 <![CDATA[8.7×10 12 ]]> Application Example 12 <![CDATA[9.5×10 -9 ]]> 66.6 0.46 <![CDATA[8.3×10 12 ]]> Application Example 13 <![CDATA[5.2×10 -9 ]]> 70.6 0.48 <![CDATA[1.2×10 13 ]]> Application Example 14 <![CDATA[8.3×10 -9 ]]> 71.4 0.49 <![CDATA[9.5×10 12 ]]> Application Example 15 <![CDATA[6.2×10 -9 ]]> 71.8 0.49 <![CDATA[1.1×10 13 ]]> Application Example 16 <![CDATA[5.2×10 -9 ]]> 72.1 0.49 <![CDATA[1.2×10 13 ]]> Application Example 17 <![CDATA[8.2×10 -10 ]]> 68.5 0.47 <![CDATA[2.9×10 13 ]]> Application Example 18 <![CDATA[8.4×10 -10 ]]> 67.9 0.47 <![CDATA[2.8×10 13 ]]> Application Example 19 <![CDATA[8.8×10 -10 ]]> 67.4 0.46 <![CDATA[2.8×10 13 ]]> Application Example 20 <![CDATA[9.6×10 -10 ]]> 67.2 0.46 <![CDATA[2.6×10 13 ]]> Application Example 21 <![CDATA[3.8×10 -10 ]]> 73.0 0.50 <![CDATA[4.5×10 13 ]]> Application Example 22 <![CDATA[4.8×10 -10 ]]> 72.8 0.50 <![CDATA[4.0×10 13 ]]> Application Example 23 <![CDATA[5.5×10 -10 ]]> 72.5 0.50 <![CDATA[3.7×10 13 ]]> Application Example 24 <![CDATA[7.3×10 -10 ]]> 72.0 0.49 <![CDATA[3.2×10 13 ]]>

[0205] Fig.10 The current density-photovoltage curve (JV curve), external quantum efficiency (EQE) curve, responsivity (R) curve and specific detectivity (D*) curve of the organic photodetector device (PBDB-T:DYSe-4) in Application Example 17 of the present invention and the organic photodetector device (PBDB-T:DYSe-5) in Application Example 21 are shown in FIG. Fig.10 A is a current density-photovoltage curve (JV curve) of the organic photodetection device (PBDB-T:DYSe-4) in Application Example 17 and the organic photodetection device (PBDB-T:DYSe-5) in Application Example 21; Fig.10 B is an external quantum efficiency (EQE) curve of the organic photodetector device (PBDB-T:DYSe-4) in Application Example 17 and the organic photodetector device (PBDB-T:DYSe-5) in Application Example 21; Fig.10 C is the responsivity (R) curve of the organic photodetector device (PBDB-T:DYSe-4) in Application Example 17 and the organic photodetector device (PBDB-T:DYSe-5) in Application Example 21; Fig.10 D is the specific detectivity (D*) curve of the organic photodetector device (PBDB-T:DYSe-4) in Application Example 17 and the organic photodetector device (PBDB-T:DYSe-5) in Application Example 21.

[0206] From Table 4 and Fig.10 It can be seen that the organic photodetector device prepared by using the compound DYSe-4 in Example 1 or the compound DYSe-5 in Example 2 of the present invention (i.e., the organic photodetector device prepared by Application Examples 9-24) has excellent photoresponsivity, external quantum efficiency and specific detection rate in the near-infrared region (850nm), and the photoresponsivity can reach 0.50AW -1 , the external quantum efficiency can reach 73.0%, and the specific detectivity can reach 4.5×10 13 Jones.

[0207] In summary, the organic solar cell device prepared by using the compound DYSe-4 or the compound DYSe-5 in the embodiment of the present invention as a novel acceptor material has near-infrared absorption characteristics, and its PCE can reach up to 11.75%. In addition, the organic photodetector device prepared by using the compound DYSe-4 or the compound DYSe-5 in the embodiment of the present invention as a novel acceptor material has outstanding performance, which can reach up to 4.5×10 13In addition, the compound DYSe-4 or the compound DYSe-5 in the embodiment of the present invention has the advantages of precise molecular weight, controllable structure and easy purification, and is therefore suitable for preparing an organic solar cell device with good stability, flexibility and large area, and an organic photoelectric detection device with high detection rate, good stability and flexibility.

[0208] 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 dimeric electron acceptor material having near-infrared absorption characteristics, characterized in that: The dimeric electron acceptor material is a compound DYSe-4A or a compound DYSe-5A. The chemical structure of the compound DYSe-4A is shown in Formula 1, and the chemical structure of the compound DYSe-5A is shown in Formula 2: In Formula 1 or Formula 2, R1 is independently C at each occurrence. n H 2n+1 , n is an integer between 1 and 100; R2 is independently C at each occurrence m H 2m+1 , m is an integer between 1 and 100; X is independently selected from H, F, Cl, I, NO2 or CN at each occurrence.

2. The dimeric electron acceptor material having near-infrared absorption characteristics according to claim 1, characterized in that: The dimeric electron acceptor material has an absorption peak in the wavelength range of 600nm to 1000nm.

3. A method for preparing a dimeric electron acceptor material having near-infrared absorption characteristics according to claim 1 or 2, characterized in that: include: S1: Compound 1 is subjected to the first aldehyde formation by the Vilsmeier-Hack reaction to obtain compound 2; S2: subjecting compound 2 to an aldol condensation reaction to obtain compound 3; S3: performing a first reaction on compound 3 and a first terminal compound to generate compound 4-1, or performing a second reaction on compound 3 and a second terminal compound to generate compound 4-2; S4: subjecting compound 4-1 to a second aldehyde reaction by using the Vilsmayer-Hack reaction to obtain compound 5-1, or subjecting compound 4-2 to a third aldehyde reaction by using the Vilsmayer-Hack reaction to obtain compound 5-2; S5: performing a third reaction on compound 5-1 and a third terminal compound to generate compound 6-1, or performing a fourth reaction on compound 5-2 and a fourth terminal compound to generate compound 6-2; S6: subjecting compound 6-1 to a fifth reaction with 2,5-bis(trimethyltinyl)thiophene to generate the compound DYSe-4A, or subjecting compound 6-2 to a sixth reaction with 2,5-bis(trimethyltinyl)thiophene to generate the compound DYSe-5A; The chemical structural formula of the compound 1 is shown in Formula 3, the chemical structural formula of the compound 2 is shown in Formula 4, the chemical structural formula of the compound 3 is shown in Formula 5, the chemical structural formula of the first terminal compound or the fourth terminal compound is shown in Formula 6, the chemical structural formula of the second terminal compound or the third terminal compound is shown in Formula 7, the chemical structural formula of the compound 4-1 is shown in Formula 8, the chemical structural formula of the compound 4-2 is shown in Formula 9, the chemical structural formula of the compound 5-1 is shown in Formula 10, the chemical structural formula of the compound 5-2 is shown in Formula 11, the chemical structural formula of the compound 6-1 is shown in Formula 12, and the chemical structural formula of the compound 6-2 is shown in Formula 13: Where R1 is independently C at each occurrence n H 2n+1 , n is an integer between 1 and 100; R2 is independently C at each occurrence m H 2m+1 , m is an integer between 1 and 100; X is independently selected from H, F, Cl, I, NO2 or CN at each occurrence.

4. The method for preparing a dimeric electron acceptor material having near-infrared absorption characteristics according to claim 3, characterized in that: In S3, the mass ratio of the compound 3 to the first terminal compound is 1:(1.5-2), or the mass ratio of the compound 3 to the second terminal compound is 1:(1.5-2); and / or, in S5, the mass ratio of the compound 5-1 to the third terminal compound is 1:(1.5-2), or the mass ratio of the compound 5-2 to the fourth terminal compound is 1:(1.5-2); And / or, in S6, the mass ratio of the compound 6-1 to the 2,5-bis(trimethyltinyl)thiophene is 1:(0.47-0.49), or the mass ratio of the compound 6-2 to the 2,5-bis(trimethyltinyl)thiophene is (0.47-0.49).

5. The method for preparing the dimeric electron acceptor material having near-infrared absorption characteristics according to claim 3, characterized in that: The time for the first aldehyde reaction is 6 to 7 hours; And / or, the aldol condensation reaction is carried out for 10 hours to 12 hours; And / or, the temperature for the first reaction or the second reaction is 65-70° C. and the time is 10 h to 12 h; And / or, the time for performing the second hydroformylation or the third hydroformylation is 6 h to 7 h; And / or, the time for performing the third reaction or the fourth reaction is 0.5h to 1h; And / or, the temperature for carrying out the fifth reaction or the sixth reaction is 115° C. to 120° C. and the time is 12 h to 14 h.

6. An organic solar cell device, characterized in that: An active layer is formed by blending a first donor material and a first acceptor material, wherein the first acceptor material is the dimeric electron acceptor material having near-infrared absorption characteristics as claimed in claim 1 or 2.

7. The organic solar cell device according to claim 6, characterized in that: The first donor material includes PBDB-T; In the active layer, the mass ratio of the PBDB-T to the dimeric electron acceptor material having near-infrared absorption characteristics is 1:(1-1.6).

8. An organic photodetector device, characterized in that: An active layer prepared from a raw material system comprising a second donor material and a second acceptor material, wherein the second acceptor material is the dimeric electron acceptor material having near-infrared absorption characteristics as claimed in claim 1 or 2.

9. The organic solar cell device according to claim 8, characterized in that: The second donor material includes PBDB-T; In the raw material system, the mass ratio of the PBDB-T to the dimeric electron acceptor material having near-infrared absorption characteristics is 1:(1-1.6).

10. The organic solar cell device according to claim 9, characterized in that: The raw material system also includes a liquid additive, and the liquid additive includes 1,8-diiodooctane; In the raw material system, the volume percentage of the 1,8-diiodooctane is 0.3 vol% to 1 vol%.

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