A DPP-bridged perylene imide compound, preparation method thereof, and application in organic solar cells
By introducing a DPP bridge structure into peryleneimide compounds, regulating the interaction between molecules, the problem of difficulty in exciton dissociation of peryleneimide compounds in organic solar cells in the prior art is solved, and high efficiency is achieved photoelectric conversion efficiency.
Patent Information
- Application Number
- CN202310096291.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-01-19
- Publication Date
- 2025-02-11
- Estimated Expiration
- 2043-01-19
AI Technical Summary
In organic solar cells, existing peryleneimide compounds have difficulty in dissociating excitons due to strong interactions and large phase separation between molecules, which in turn reduces device performance.
By introducing a DPP bridge structure, two peryleneimide molecules are connected through DPP as bridges, thereby regulating the intermolecular interactions and forming an appropriate molecular configuration to improve exciton dissociation efficiency.
It realizes the improvement of photoelectric conversion efficiency in organic solar cells, combines the advantages of perylimides and pyrrolopyrrole dione compounds, and provides high electron mobility and good exciton dissociation performance.
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Figure CN116354966B_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of heterocyclic compounds, and in particular relates to a DPP-bridged perylene imide compound, a preparation method thereof, and an application thereof in an organic solar cell. Background Art
[0002] Perylene imide compounds have the characteristics of low cost, good photochemical stability, strong light absorption ability, high electron mobility, and easy functionalization to adjust solubility, energy level and molecular configuration, so they have attracted widespread attention from researchers. With the joint efforts of researchers in multiple fields such as material synthesis and device physics, perylene imide materials have made great progress in the field of organic semiconductors and have shown extremely excellent application prospects. Although the larger planar conjugated structure of perylene imide molecules is conducive to the formation of tight π-π stacking, thereby obtaining higher electron mobility. However, when it is used in organic solar cell (OSCs) devices, this aggregation behavior will lead to excessively large phase separation scale, which seriously hinders the efficient dissociation of excitons and greatly reduces the performance of the device. Therefore, achieving a balance between the molecular conjugation size and the degree of distortion to take into account both carrier mobility and exciton dissociation efficiency is an effective way to obtain high-performance perylene imide receptors.
[0003] However, existing perylene imide compounds generally have the following disadvantages: (1) The perylene imide molecules have strong interactions and are prone to self-aggregation. (2) Exciton dissociation is difficult because large phase separation is likely to occur between the donor and acceptor materials. Therefore, further structural modification of perylene imide electron acceptor materials is required. Summary of the invention
[0004] The technical problem to be solved by the present invention is to provide a 2,5-dihydro-1,4-diketopyrrolo[3,4-c]pyrrole (DPP)-bridged perylene imide compound and a preparation method thereof as well as an application in an organic solar cell in view of the above-mentioned deficiencies in the prior art. The compound uses DPP as a bridge D unit connecting two perylene imide molecules to obtain a DPP-bridged perylene imide compound, which combines the advantages of perylene imide and 2,5-dihydro-1,4-diketopyrrolo[3,4-c]pyrrole compounds, and an organic solar cell device prepared with the compound as a semiconductor layer has high photoelectric conversion efficiency.
[0005] In order to solve the above technical problems, the technical solution provided by the present invention is:
[0006] Provided is a DPP-bridged perylene imide compound, the structural formula of which is as follows:
[0007]
[0008] A is
[0009]
[0010] Where R 1 is selected from C1-C20 substituted or unsubstituted alkyl, further selected from unsubstituted C3-C15 alkyl, more preferably octyl, most preferably
[0011] R 2 is selected from C1-C30 substituted or unsubstituted alkyl, further selected from unsubstituted C3-C25 alkyl, more preferably tridecyl, most preferably
[0012] R 3 is selected from C1-C30 substituted or unsubstituted alkyl, further selected from unsubstituted C3-C25 alkyl, more preferably tridecyl, most preferably
[0013] According to the above scheme, the DPP-bridged perylene imide compound has the following structural formula:
[0014]
[0015]
[0016] The present invention also provides a method for preparing the DPP-bridged perylene imide compound, which comprises the following specific steps: dissolving the compound represented by the following formula (1) and DPP in a mixed solvent, carrying out a Suzuki coupling reaction catalyzed by a palladium catalyst in the presence of a base, and then separating and purifying to obtain the DPP-bridged perylene imide compound;
[0017] The structural formula of the compound shown in formula (1) is as follows:
[0018]
[0019] Where A is
[0020]
[0021] The structural formula of DPP is as follows:
[0022]
[0023] Where R 1 is selected from C1-C20 substituted or unsubstituted alkyl, further selected from unsubstituted C3-C15 alkyl, more preferably octyl, most preferably
[0024] R2 is selected from C1-C30 substituted or unsubstituted alkyl, further selected from unsubstituted C3-C25 alkyl, more preferably tridecyl, most preferably
[0025] R 3 is selected from C1-C30 substituted or unsubstituted alkyl, further selected from unsubstituted C3-C25 alkyl, more preferably tridecyl, most preferably
[0026] The reaction formula is as follows:
[0027]
[0028] According to the above scheme, the molar ratio of the compound represented by formula (1) to DPP is 0.1 to 10:1.
[0029] According to the above scheme, the mixed solvent is composed of toluene, ethanol and water in a volume ratio of 1:0.05 to 0.5:
[0030] The mass volume ratio of DPP to the mixed solvent is 1 g / 50-100 mL.
[0031] According to the above scheme, the base is one or more of potassium carbonate, sodium carbonate, potassium acetate, cesium carbonate, sodium acetate, and potassium phosphate, and the molar ratio of DPP to the base is 1:50-150.
[0032] According to the above scheme, the palladium catalyst is one or more of palladium acetate, palladium chloride, palladium bromide, tetrakistriphenylphosphine palladium, 1,1'-bis(diphenylphosphinodiphenylferrocene)palladium dichloride, and the molar ratio of DPP to palladium catalyst is 1:0.05-0.8.
[0033] According to the above scheme, the temperature of the Suzuki coupling reaction is 50-100°C, and the reaction time is 4-8h.
[0034] The present invention also provides the use of the DPP-bridged perylene imide compound, which is used in the preparation of an organic solar cell device. Further, the DPP-bridged perylene imide compound is used as a semiconductor layer in an organic solar cell device.
[0035] The present invention synthesizes the above-mentioned DPP-bridged perylene imide compounds for the first time. The compounds are used as electron acceptor materials in organic solar cells. There is a large difference in the molecular surface electrostatic potential between the compounds and the electron donor. The corresponding intermolecular electric field provides the driving force for exciton dissociation, promotes the efficient generation of charges, and thus improves the efficiency of organic solar cells.
[0036] The beneficial effects of the present invention are as follows: 1. The DPP-bridged perylene imide compound provided by the present invention has good photochemical stability, strong light absorption ability, and high electron mobility, and is used as a semiconductor layer in an organic solar cell device. The organic solar cell device prepared with the DPP-bridged perylene imide compound as the semiconductor layer has high photoelectric conversion efficiency. 2. The preparation method of the present invention has a simple synthesis route, mild reaction conditions, relatively low raw material cost, and high yield. BRIEF DESCRIPTION OF THE DRAWINGS
[0037] Figure 1 This is the hydrogen spectrum of PMI-DPP-PMI prepared in Example 1 of the present invention;
[0038] Figure 2 The mass spectrum of PMI-DPP-PMI prepared in Example 1;
[0039] Figure 3 This is the hydrogen spectrum of PDI-DPP-PDI prepared in Example 2;
[0040] Figure 4 is the mass spectrum of PDI-DPP-PDI prepared in Example 2;
[0041] Figure 5 is a JV curve of an organic solar cell based on PMI-DPP-PMI prepared in Example 1;
[0042] Figure 6 : is the JV curve of the organic solar cell based on PDI-DPP-PDI prepared in Example 2. DETAILED DESCRIPTION
[0043] In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention is further described in detail below with reference to the accompanying drawings.
[0044] Example 1
[0045] Preparation of PMI-DPP-PMI:
[0046] Compound 5 (139 mg), compound DPP (75 mg), tetrakistriphenylphosphine palladium (22 mg), and sodium carbonate (1.06 g) were added to the reaction flask in sequence. After nitrogen was pumped for 30 min, deoxygenated water (1 mL), ethanol (1 mL) and toluene (4 mL) were added and heated under reflux at 80 ° C for 6 h. After the reaction was completed, it was extracted with dichloromethane, dried, concentrated under reduced pressure, and then purified by column chromatography to obtain a red target compound PMI-DPP-PMI (116 mg, yield 69%). The hydrogen spectrum and mass spectrum of PMI-DPP-PMI are shown in Figure 1 and Figure 2 .
[0047] The specific reaction formula is as follows:
[0048]
[0049] Example 2
[0050] Preparation of PDI-DPP-PDI:
[0051] Compound 6 (195 mg), compound DPP (75 mg), tetrakistriphenylphosphine palladium (22 mg), and sodium carbonate (1.06 g) were added to the reaction flask in sequence. After nitrogen was pumped for 30 min, deoxygenated water (1 mL), ethanol (1 mL) and toluene (4 mL) were added and heated under reflux at 80 ° C for 6 h. After the reaction was completed, it was extracted with dichloromethane, dried, concentrated under reduced pressure, and separated and purified to obtain the red target compound PDI-DPP-PDI (118 mg, yield 53%). The hydrogen spectrum and mass spectrum of PDI-DPP-PDI are shown in Figure 3 and Figure 4 .
[0052] The specific reaction formula is as follows:
[0053]
[0054] Example 3
[0055] The inverted structure (ITO / ZnO / PM1:PMI-DPP-PMI or PM1:PMI-DPP-PMI / MoO) with good stability is used in the present invention. 3 / Ag) to prepare an organic solar cell device, the specific preparation process is as follows: first, a ZnO electron transport layer is spin-coated on a clean ITO-glass substrate, the spin coating speed and duration are 5000 rpm and 30 s respectively, and then it is placed on a hot stage for annealing at 150°C for 1 h, and then the acceptor materials PMI-DPP-PMI, PDI-DPP-PDI prepared in Example 1-2 and the donor material PM1 (Shuolun Organic Optoelectronics (Beijing) Technology Co., Ltd.) are dissolved in a chlorobenzene solvent at a mass ratio of 1:1, and the mass volume ratio of the acceptor material to the solvent is 15 mg / mL. The active layer solution is stirred at 60°C overnight to prepare a film, and the active layer solution is subsequently spin-coated into a film, the spin coating speed and duration are 1000 rpm and 50 s respectively, and the film is thermally annealed at 110°C for 10 minutes to obtain an ideal film morphology. Finally, the substrate coated with the active layer is placed in a mask and transferred to a vacuum coating machine. When the cavity pressure is lower than 1×10 -4 Pa, the hole transport layer MoO was deposited. 3 , the evaporation rate is The film thickness is 8nm; then the anode Ag is evaporated at a rate of The film thickness is 100 nm, and finally the organic solar cells based on PMI-DPP-PMI and PDI-DPP-PDI are obtained, with an effective area of 0.0625 cm 2 .
[0056] The test results of the current density and voltage characteristic curve (JV curve) of organic solar cells based on PMI-DPP-PMI and PDI-DPP-PDI are shown in Figure 5 and Figure 6 The main parameters extracted from the JV curve, including short-circuit current density Jsc, open-circuit voltage Voc, energy conversion efficiency PCE, and fill factor FF, are shown in Table 1.
[0057] Table 1 Photoelectric parameters of organic solar cells based on PMI-DPP-PMI and PDI-DPP-PDI
[0058] <![CDATA[J SC (mAcm -2 )]]> <![CDATA[V OC (V)]]> PCE(%) FF(%) PMI-DPP-PMI 14.05 0.709 4.03 0.405 PDI-DPP-PDI 7.51 0.791 2.61 0.439
[0059] Tests on organic solar devices show that the organic solar cells prepared using the DPP-bridged perylene imide compounds prepared in Examples 1-2 as acceptor materials all achieved relatively high photoelectric conversion efficiencies, among which the PMI-DPP-PMI-based device achieved a higher photoelectric conversion efficiency (PCE = 4.03%), which is at a relatively high level among the existing DPP-based solar cell acceptor materials.
[0060] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by any technician familiar with the technical field within the technical scope disclosed by the present invention should be covered within the protection scope of the present invention.
Claims
1. A DPP-bridged perylene imide compound, characterized in that: Its structural formula is as follows:
2. A method for preparing the DPP-bridged perylene imide compound according to claim 1, characterized in that: The specific steps are as follows: dissolving the compound represented by the following formula (1) and DPP in a mixed solvent, carrying out a Suzuki coupling reaction catalyzed by a palladium catalyst in the presence of a base, and then separating and purifying to obtain a DPP-bridged perylene imide compound; The structural formula of the compound shown in formula (1) is as follows: Where A is The structural formula of DPP is as follows: Where R 1 for R 2 for 3. The method for preparing the DPP-bridged perylene imide compound according to claim 2, characterized in that: The molar ratio of the compound represented by formula (1) to DPP is 0.1 to 10:
1.
4. The method for preparing the DPP-bridged perylene imide compound according to claim 2, characterized in that: The mixed solvent is obtained by mixing toluene, ethanol and water in a volume ratio of 1:0.05-0.5:0.05-0.5, and the mass volume ratio of DPP to the mixed solvent is 1g / 50-100mL.
5. The method for preparing the DPP-bridged perylene imide compound according to claim 2, characterized in that: The base is one or more of potassium carbonate, sodium carbonate, potassium acetate, cesium carbonate, sodium acetate, and potassium phosphate, and the molar ratio of DPP to the base is 1:50-150.
6. The method for preparing the DPP-bridged perylene imide compound according to claim 2, characterized in that: The palladium catalyst is one or more of palladium acetate, palladium chloride, palladium bromide, tetrakistriphenylphosphine palladium, and 1,1'-bis(diphenylphosphino)ferrocenepalladium dichloride. The molar ratio of DPP to the palladium catalyst is 1:0.05-0.
8.
7. The method for preparing the DPP-bridged perylene imide compound according to claim 2, characterized in that: The temperature of the Suzuki coupling reaction is 50-100°C, and the reaction time is 4-8 hours.
8. The use of the DPP-bridged perylene imide compound according to claim 1, characterized in that: The DPP-bridged perylene imide compound is used for preparing an organic solar cell device.