N-type semiconductor constructed by quinone synergistic imide as well as preparation method and application of n-type semiconductor

Abstract

The invention discloses an n-type semiconductor constructed by quinone synergistic imide and a preparation method and application thereof, a polymer semiconductor material is obtained by polymerization of a quinone-imide compound, and the obtained polymer semiconductor material is used for constructing the n-type semiconductor; according to the invention, a quinonoid compound is embedded into an imide structure, so that the whole molecular structure has excellent solubility, good planarity and strong electron deficiency characteristic. Therefore, the prepared n-type polymer semiconductor has good performance and shows superexcellent application potential in the fields of organic solar cells, organic field effect transistors, organic thermoelectricity and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of organic optoelectronics, and in particular to a quinone-type synergistic imide-structured n-type semiconductor, and a preparation method and application thereof. Background Art

[0002] Conjugated polymers have excellent solution processability and can be used to prepare low-cost, large-area mechanically flexible electronic devices by printing and other methods. At the same time, low-temperature processing enables the device to be combined with a flexible substrate (such as fabric or plastic) without affecting the flexible function of the substrate. Organic electronic devices (organic field effect transistors (OFETs), organic solar cells (OSCs), organic light-emitting diodes (OLEDs), and organic thermoelectrics (OTEs)) based on conjugated polymers as active layers are expected to become the core technology in the fields of a new generation of flexible displays, wearable electronic devices, flexible solar cells, etc.

[0003] In recent years, compared with p-type polymer materials, the development of n-type polymers with good air stability and high electron mobility is still relatively lagging. Since p-type and n-type polymer semiconductors are indispensable components for constructing pn heterojunctions, complementary logic circuits and hole / electron transport layers, the development of new n-type polymer materials with high mobility and stable device performance in air is of great significance for the industrialization of a new generation of flexible electronic devices. The key to developing high-performance n-type polymers is to design highly electron-deficient building blocks, which are currently mainly naphthalene diimide (NDI), perylene diimide (PDI) and bithiophene diimide (BTI). However, NDI and PDI-based polymers have a distorted skeleton, which limits their electron mobility and absorption in the near-infrared region. For BTI-type polymers, although they have a good planar skeleton structure, their LUMO energy level is relatively high, and they are prone to exhibit p-type characteristics.

[0004] Therefore, it is very important to develop an imide polymer with excellent solubility, good planar skeleton structure and low LUMO energy level. Summary of the invention

[0005] In order to solve the defects of the prior art, the present invention provides a quinone-type synergistic imide to construct an n-type semiconductor and a preparation method and application thereof.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0007] The present invention discloses a method for constructing an n-type semiconductor with quinone-imide synergistically, comprising the following steps: polymerizing a quinone-imide compound to obtain a polymer semiconductor material, and constructing an n-type semiconductor with the obtained polymer semiconductor material;

[0008] The general structural formula of the quinone-imide compound is as shown in the following formula (I) or formula (II):

[0009]

[0010] In the structural formula (I), X is any one of oxygen, sulfur, and selenium atoms; Y1 is any one of oxygen, sulfur, and selenium atoms; A is selected from any one of Br and I; n is an integer of 10-300; R is any one of a straight chain, branched chain, cyclic alkyl chain, ether chain, silane chain, and thioether chain having 1-100 carbon atoms;

[0011] In the structural formula (II), X is any one of oxygen, sulfur, and selenium atoms; Y2 is any one of oxygen, sulfur, and selenium atoms; B is selected from any one of Br and I; n is an integer of 10-300; R is any one of a straight chain, branched chain, cyclic alkyl chain, ether chain, silane chain, and thioether chain of 1-100 carbon atoms.

[0012] As a preferred technical solution of the present invention, the preparation method of the quinone-acylimide compound comprises the following steps:

[0013] Prepared by reaction of intermediate 2 and intermediate 3:

[0014] First, intermediate 2 needs to be prepared. 1 mol of compound 1 is reacted with 1 mol of n-butyl lithium at -78°C for 1 h, and then 1 mol of tributyltin chloride is added and reacted for 1 h to obtain intermediate 2.

[0015] Then, 2 mol of intermediate 2 and 1 mol of intermediate 3 were reacted by Stille coupling reaction at 110°C overnight to obtain compound 4. Finally, compound 4 was reacted with excess liquid bromine and iodine in chloroform solvent overnight to obtain general formula (I);

[0016]

[0017] As a preferred technical solution of the present invention, the preparation method of the quinone-acylimide compound comprises the following steps:

[0018] Prepared by reaction of intermediate 2 with 6:

[0019] First, intermediate 2 needs to be prepared. 1 mol of compound 1 is reacted with 1 mol of n-butyl lithium at -78°C for 1 hour, and then 1 mol of tributyltin chloride is added to react for 1 hour to obtain intermediate 2.

[0020] Then, 2 mol of intermediate 2 and 1 mol of intermediate 6 were reacted by Stille coupling at 110°C overnight to obtain compound 7. Finally, compound 7 was reacted with excess liquid bromine and iodine in chloroform solvent to obtain general formula (II);

[0021]

[0022] As a preferred technical solution of the present invention, the quinone-imide compound is selected from but not limited to any one of QI1-QI18:

[0023]

[0024] A method for preparing a quinone-type synergistic imide-constructed n-type semiconductor, which is used to prepare the polymer semiconductor material in the above-mentioned method for constructing an n-type semiconductor with a quinone-type synergistic imide, comprises the following steps:

[0025] The compound of formula (I) and the copolymer unit Ar having a conjugated structure are reacted by Stille coupling to synthesize a polymer semiconductor material as shown in formula (III);

[0026] Or the compound of formula (II) and the copolymer unit Ar having a conjugated structure are reacted by Stille coupling to synthesize a polymer semiconductor material as shown in formula (IV);

[0027] The reaction formula is as follows:

[0028]

[0029] In the structural formula (III), X is any one of oxygen, sulfur and selenium atoms; Y1 is any one of oxygen, sulfur and selenium atoms; n is an integer of 10-300; R is a straight chain, branched chain or cyclic alkyl chain, ether chain or thioether chain of 1-100 carbon atoms; Ar is selected from vinyl, ethynyl, and substituted or unsubstituted C4-C100 aryl or heteroaryl, wherein the heteroaryl contains at least one heteroatom selected from B, N, O, S, Si and P;

[0030] In the structural formula (IV), X is any one of oxygen, sulfur and selenium atoms; Y2 is any one of oxygen, sulfur and selenium atoms; n is an integer of 10-300; R is a straight chain, branched chain or cyclic alkyl chain, ether chain or thioether chain of 1-100 carbon atoms; Ar is selected from vinyl, ethynyl, and substituted or unsubstituted C4-C100 aromatic or heteroaromatic groups, wherein the heteroaromatic group contains at least one heteroatom selected from B, N, O, S, Si and P.

[0031] As a preferred technical solution of the present invention, the polymer semiconductor material is selected from any one of P1-P36:

[0032]

[0033] As a preferred technical solution of the present invention, a use of the quinone-imide compound or the polymer semiconductor material according to the above claim in an N-type polymer semiconductor.

[0034] As a preferred technical solution of the present invention, an application, the above-mentioned N-type polymer semiconductor is applied to any one of an organic field effect transistor, an organic thermoelectric device, an organic solar cell, and an organic light emitting diode.

[0035] As a preferred technical solution of the present invention, an intermediate 2 for preparing the quinone-acylimide compound shown in formula (I) or (II) or an application of the quinone-acylimide compound shown in formula (I) or (II) in organic optoelectronic materials.

[0036] As a preferred technical solution of the present invention, the quinone-acylimide compound represented by formula (I) or (II) is used in a receptor structural unit in an organic photoelectric material.

[0037] The beneficial effects of the present invention are:

[0038] 1. The quinone-imide structure in the present invention is a quinone compound embedded in the imide structure, so that the entire molecular structure has excellent solubility, good planarity and strong electron-deficient properties. As a result, the prepared n-type polymer semiconductor has good performance and has shown excellent application potential in the fields of organic solar cells, organic field effect transistors, organic thermoelectrics, etc.

[0039] 2. The present invention utilizes quinone-acylimide compounds to copolymerize with copolymerization units Ar to obtain a series of conjugated polymers. The copolymerization units are optimized to obtain high-performance polymer semiconductor materials, thereby promoting the development of the field of organic semiconductors. The preparation method of the quinone-acylimide compounds provided by the present invention also has the advantages of simple synthesis and low cost, which provides a prerequisite for large-scale production and industrialization. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] The accompanying drawings are used to provide further understanding of the present invention and constitute a part of the specification. They are used to explain the present invention together with the embodiments of the present invention and do not constitute a limitation of the present invention.

[0041] In the attached picture:

[0042] Figure 1 This is the H NMR spectrum of QⅠ1.

[0043] Figure 2 This is the NMR carbon spectrum of QⅠ1. DETAILED DESCRIPTION

[0044] The preferred embodiments of the present invention are described below in conjunction with the accompanying drawings. It should be understood that the preferred embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0045] Embodiment: A method for constructing an n-type semiconductor by quinone-imide synergistically according to the present invention is characterized by comprising the following steps: polymerizing a quinone-imide compound to obtain a polymer semiconductor material, and constructing an n-type semiconductor with the obtained polymer semiconductor material;

[0046] The general structural formula of the quinone-imide compound is as shown in the following formula (I) or formula (II):

[0047]

[0048] In the structural formula (I), X is any one of oxygen, sulfur, and selenium atoms; Y1 is any one of oxygen, sulfur, and selenium atoms; A is selected from any one of Br and I; n is an integer of 10-300; R is any one of a straight chain, branched chain, cyclic alkyl chain, ether chain, silane chain, and thioether chain having 1-100 carbon atoms;

[0049] In the structural formula (II), X is any one of oxygen, sulfur, and selenium atoms; Y2 is any one of oxygen, sulfur, and selenium atoms; B is selected from any one of Br and I; n is an integer of 10-300; R is any one of a straight chain, branched chain, cyclic alkyl chain, ether chain, silane chain, and thioether chain of 1-100 carbon atoms.

[0050] The preparation method of the quinone-acylimide compound comprises the following steps:

[0051] Prepared by reaction of intermediate 2 and intermediate 3:

[0052] First, intermediate 2 needs to be prepared. 1 mol of compound 1 is reacted with 1 mol of n-butyl lithium at -78°C for 1 h, and then 1 mol of tributyltin chloride is added and reacted for 1 h to obtain intermediate 2.

[0053] Then, 2 mol of intermediate 2 and 1 mol of intermediate 3 were reacted by Stille coupling reaction at 110°C overnight to obtain compound 4. Finally, compound 4 was reacted with excess liquid bromine and iodine in chloroform solvent overnight to obtain general formula (I);

[0054]

[0055] The preparation method of the quinone-acylimide compound comprises the following steps:

[0056] Prepared by reaction of intermediate 2 with 6:

[0057] First, intermediate 2 needs to be prepared. 1 mol of compound 1 is reacted with 1 mol of n-butyl lithium at -78°C for 1 hour, and then 1 mol of tributyltin chloride is added to react for 1 hour to obtain intermediate 2.

[0058] Then, 2 mol of intermediate 2 and 1 mol of intermediate 6 were reacted by Stille coupling at 110°C overnight to obtain compound 7. Finally, compound 7 was reacted with excess liquid bromine and iodine in chloroform solvent to obtain general formula (II);

[0059]

[0060] Wherein, the quinone-imide compound is selected from but not limited to any one of QI1-QI18:

[0061]

[0062] like Figure 1 , Figure 2 As shown, the quinone-imide compound in this embodiment is selected as QⅠ1, Figure 1 is the H NMR spectrum of QⅠ1; Figure 2 This is the NMR carbon spectrum of QⅠ1.

[0063] Among them, a method for preparing a quinone-type cooperative imide-constructed n-type semiconductor is used to prepare a polymer semiconductor material in the method for constructing an n-type semiconductor with a quinone-type cooperative imide, comprising the following steps:

[0064] The compound of formula (I) and the copolymer unit Ar having a conjugated structure are reacted by Stille coupling to synthesize a polymer semiconductor material as shown in formula (III);

[0065] Or the compound of formula (II) and the copolymer unit Ar having a conjugated structure are reacted by Stille coupling to synthesize a polymer semiconductor material as shown in formula (IV);

[0066] 20 mmol of the general formula (I) or (II) and 20 mmol of a tin reagent or borate ester having a conjugated structure Ar are reacted in 5 ml of a toluene solution at 110° C. overnight.

[0067] The reaction formula is as follows:

[0068]

[0069] In the structural formula (III), X is any one of oxygen, sulfur and selenium atoms; Y1 is any one of oxygen, sulfur and selenium atoms; n is an integer of 10-300; R is a straight chain, branched chain or cyclic alkyl chain, ether chain or thioether chain of 1-100 carbon atoms; Ar is selected from vinyl, ethynyl, and substituted or unsubstituted C4-C100 aryl or heteroaryl, wherein the heteroaryl contains at least one heteroatom selected from B, N, O, S, Si and P;

[0070] In the structural formula (IV), X is any one of oxygen, sulfur, and selenium atoms; Y2 is any one of oxygen, sulfur, and selenium atoms; n is an integer of 10-300; R is a straight chain, branched chain, cyclic alkyl chain, ether chain, and thioether chain of 1-100 carbon atoms; Ar is selected from vinyl, ethynyl, and substituted or unsubstituted C4-C100 aryl or heteroaryl, wherein the heteroaryl contains at least one heteroatom selected from B, N, O, S, Si, and P. The present invention relates to the field of organic synthesis and organic electronics, and mainly relates to the design route, preparation method, and application of the combination of quinone and imide. The general structural formula of the quinone-imide is shown in the structure: and The quinone-imide structure in the present invention is a quinone compound embedded in the imide structure, so that the entire molecular structure has excellent solubility, good planarity and strong electron-deficient properties. As a result, the prepared n-type polymer semiconductor has good performance and has shown excellent application potential in the fields of organic solar cells, organic field effect transistors, organic thermoelectrics, etc.

[0071] The present invention develops a new type of soluble strongly electron-deficient structural unit quinone-imide compound and a preparation method thereof by combining quinone and imide units. This series of strongly electron-deficient units has excellent solubility, planarity and strong electron-deficient characteristics, and can be used as N-type semiconductor materials in the field of organic electronics.

[0072] The present invention utilizes quinone-imide compounds and conjugated structural units for copolymerization to obtain a series of conjugated polymers. The copolymerization units are optimized to obtain high-performance polymer semiconductor materials, thereby promoting the development of the field of organic semiconductors.

[0073] After electrochemical testing, the LUMO energy level of the developed quinone-imide compound was as low as -4.1eV, indicating that this is a type of strong electron-deficient unit. In addition, it provides a new acceptor unit for the development of N-type polymer semiconductors, promoting the development of N-type organic semiconductors.

[0074] The preparation method of the quinone-acylimide compound provided by the invention also has the advantages of simple synthesis and low cost, and provides a prerequisite for large-scale production and industrialization.

[0075] Wherein, the polymer semiconductor material is selected from any one of P1-P36:

[0076]

[0077] Among them, an application of the above-mentioned quinone-imide compound or the polymer semiconductor material in an N-type polymer semiconductor. The N-type polymer semiconductor is applied to any one of an organic field effect transistor, an organic thermoelectric device, an organic solar cell, and an organic light-emitting diode. The strongly electron-deficient quinone unit is added to the imide with a soluble side chain, so that the polymer LUMO energy level is reduced, and excellent device performance is exhibited in the organic field effect transistor, the organic thermoelectric and the organic solar cell.

[0078] An intermediate 2 for preparing a quinone-acylimide compound of formula (I) or (II) or the use of the quinone-acylimide compound of formula (I) or (II) in an organic photoelectric material, and the use of the quinone-acylimide compound of formula (I) or (II) in a receptor structural unit in an organic photoelectric material.

[0079] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for constructing an n-type semiconductor using quinone-type synergistic imide, characterized in that: The following steps are involved: A polymer semiconductor material is obtained by polymerizing a quinone-imide compound, and an n-type semiconductor is constructed by using the obtained polymer semiconductor material; The general structural formula of the quinone-imide compound is as shown in the following formula (I) or formula (II): In the structural formula (I), X is any one of oxygen, sulfur, and selenium atoms; Y1 is any one of oxygen, sulfur, and selenium atoms; A is selected from any one of Br and I; n is an integer of 10-300; R is any one of a straight chain, branched chain, cyclic alkyl chain, ether chain, silane chain, and thioether chain having 1-100 carbon atoms; In the structural formula (II), X is any one of oxygen, sulfur, and selenium atoms; Y2 is any one of oxygen, sulfur, and selenium atoms; B is selected from any one of Br and I; n is an integer of 10-300; R is any one of a straight chain, branched chain, cyclic alkyl chain, ether chain, silane chain, and thioether chain of 1-100 carbon atoms.

2. The method for constructing an n-type semiconductor using quinone-type synergistic imide according to claim 1, characterized in that: The preparation method of the quinone-acylimide compound comprises the following steps: Prepared by reaction of intermediate 2 and intermediate 3: First, intermediate 2 needs to be prepared. 1 mol of compound 1 is reacted with 1 mol of n-butyl lithium at -78°C for 1 h, and then 1 mol of tributyltin chloride is added and reacted for 1 h to obtain intermediate 2. Then, 2 mol of intermediate 2 and 1 mol of intermediate 3 were reacted by Stille coupling reaction at 110°C overnight to obtain compound 4. Finally, compound 4 was reacted with excess liquid bromine and iodine in chloroform solvent overnight to obtain general formula (I); 3. The method for constructing an n-type semiconductor using quinone-type synergistic imide according to claim 1, characterized in that: The preparation method of the quinone-acylimide compound comprises the following steps: Prepared by reaction of intermediate 2 with 6: First, intermediate 2 needs to be prepared. 1 mol of compound 1 is reacted with 1 mol of n-butyl lithium at -78°C for 1 hour, and then 1 mol of tributyltin chloride is added to react for 1 hour to obtain intermediate 2. Then, 2 mol of intermediate 2 and 1 mol of intermediate 6 were reacted by Stille coupling at 110°C overnight to obtain compound 7. Finally, compound 7 was reacted with excess liquid bromine and iodine in chloroform solvent to obtain general formula (II); 4. The method for constructing an n-type semiconductor using quinone-type synergistic imide according to claim 1, 2 or 3, characterized in that: The quinone-imide compound is selected from but not limited to any one of QI1-QI18:

5. A method for preparing a quinone-type synergistic imide-constructed n-type semiconductor, for preparing a polymer semiconductor material in a method for constructing an n-type semiconductor with a quinone-type synergistic imide as claimed in any one of claims 1 to 4, comprising the following steps: The compound of formula (I) and the copolymer unit Ar having a conjugated structure are reacted by Stille coupling to synthesize a polymer semiconductor material as shown in formula (III); Or the compound of formula (II) and the copolymer unit Ar having a conjugated structure are reacted by Stille coupling to synthesize a polymer semiconductor material as shown in formula (IV); The reaction formula is as follows: In the structural formula (III), X is any one of oxygen, sulfur and selenium atoms; Y1 is any one of oxygen, sulfur and selenium atoms; n is an integer of 10-300; R is a straight chain, branched chain or cyclic alkyl chain, ether chain or thioether chain of 1-100 carbon atoms; Ar is selected from vinyl, ethynyl, and substituted or unsubstituted C4-C100 aryl or heteroaryl, wherein the heteroaryl contains at least one heteroatom selected from B, N, O, S, Si and P; In the structural formula (IV), X is any one of oxygen, sulfur and selenium atoms; Y2 is any one of oxygen, sulfur and selenium atoms; n is an integer of 10-300; R is a straight chain, branched chain or cyclic alkyl chain, ether chain or thioether chain of 1-100 carbon atoms; Ar is selected from vinyl, ethynyl, and substituted or unsubstituted C4-C100 aromatic or heteroaromatic groups, wherein the heteroaromatic group contains at least one heteroatom selected from B, N, O, S, Si and P.

6. The method for preparing a quinone-type synergistic imide-constructed n-type semiconductor according to claim 5, characterized in that: The polymer semiconductor material is selected from any one of P1-P36:

7. Use of the quinone-imide compound according to claim 1, 2, 3 or 4, or the polymer semiconductor material according to claim 5 or 6 in an N-type polymer semiconductor.

8. The use according to claim 8, characterized in that: The N-type polymer semiconductor is applied to any one of an organic field effect transistor, an organic thermoelectric device, an organic solar cell, and an organic light emitting diode.

9. An intermediate 2 for preparing a quinone-acylimide compound of formula (I) or (II) according to claim 1, 2, 3 or 4, or use of a quinone-acylimide compound of formula (I) or (II) in an organic optoelectronic material.

10. The use according to claim 9, characterized in that: Application of quinone-acylimide compounds represented by formula (I) or (II) in receptor structural units in organic photoelectric materials.

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