阅读说明：本技术 一种n型有机半导体材料及其制备方法和应用 (N-type organic semiconductor material and preparation method and application thereof ) 是由 孙文彬 钟知鸣 于 2020-06-01 设计创作，主要内容包括：本发明公开了一种窄带隙n型有机半导体材料及其制备方法和在电子器件中的应用。所述的一类窄带隙n型有机半导体材料以方酸菁衍生物为核,化学稳定性及化学修饰性强；其方酸基团具有较强的拉电子特性,可以调节电子云分布,有利降低化合物的LUMO能级,从而调节其半导体材料的光学和载流子传输特性。(The invention discloses a narrow-bandgap n-type organic semiconductor material, a preparation method thereof and application thereof in electronic devices. The narrow-band-gap n-type organic semiconductor material takes squaraine derivatives as cores, and has strong chemical stability and chemical modification; the squarylium group has strong electron withdrawing property, can adjust electron cloud distribution, is favorable for reducing the LUMO energy level of the compound, and thus adjusts the optical and carrier transmission properties of the semiconductor material.)

1. An n-type organic semiconductor material with squaraine derivatives as cores is characterized in that the compound has the following chemical structural formula (1)

Wherein the radicals E are selected, identically or differently on each occurrence, from the group which may be substituted by one or more radicals R¹Substituted aromatic ring systems having from 5 to 30 aromatic ring atoms or which may be substituted by one or more radicals R¹A substituted group of a heteroaromatic ring system having 3 to 30 aromatic ring atoms;

wherein R is¹Each occurrence, identically or differently, of H, D, F, Cl, CN, C (═ O) R²,Si(R²)₃,N(R²)₂,OR²,SR²,S(＝O)R²,C(＝S)、C＝C(CN)₂A linear alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic organic group having 6 to 60 carbon atoms or a heteroaromatic organic group having 3 to 60 carbon atoms, wherein one or more-CH in the above-mentioned groups₂The radical may be represented by-R³C＝CR³-,-C≡C-,Si(R³)₂,C＝O,C＝NR³,-C(＝O)O-,-C(＝O)NR³-,NR³O, S, S (═ O) or SO₂Replacing; two or more radicals R¹May be linked to each other and may form a ring;

R²、R³each occurrence being the same or different and selected from a straight chain alkyl group having 1 to 60 carbon atoms, a branched or cyclic alkyl group having 3 to 22 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic organic group having 6 to 14 carbon atoms, or a heteroaromatic organic group having 3 to 14 carbon atoms; two or more radicals R²、R³May be linked to each other and may form a ring.

2. The squaraine derivative-cored n-type organic semiconductor material of claim 1, wherein the group E is represented by the following structure or one or more groups R at each occurrence¹Substituted derivatives of the following formula (2)An organism or a combination:

wherein X, which are identical or different, are selected from CR¹N; z, which may be identical or different, is selected from: c (R)¹)₂、NR¹、C(R¹)₂O、Si(R¹)₂O, S; wherein R is¹、R²、R³Is defined as in formula (1) and R¹、R²、R³The same definition is applied.

3. A polymer comprising an n-type organic semiconductor material cored by squaraine derivatives according to any one of claims 1-2, comprising an oligomer, polymer or dendrimer, wherein the n-type organic semiconductor material has one or more bonds to the polymer, oligomer or dendrimer which may be located in formula (1) as R¹、R²Or R³At the position of substitution.

4. A process for preparing the above polymer, the process comprising the steps of:

(a) reacting a compound having a pyrrole aldehyde derivative with a hydrazine derivative (R)¹)₂N-NH₂Reaction to obtain

(b) The above product (R)¹)₂N-N ═ CH-L by reaction with squaric acid derivatives

(c) Hydrolyzing the above product to obtain

(d) And (3) reacting the product with an E derivative to obtain the compound with the chemical structural formula (1).

5. A formulation, characterized by: the formulation comprises at least one polymer macromolecule according to claim 3 and at least one solvent.

6. Use of a polymer macromolecule according to claim 3 in an electronic device comprising at least one of an organic thin film transistor (OFET), an Organic Solar Cell (OSC), an Organic Photodiode (OPD), an Organic Light Emitting Diode (OLED); the method is characterized in that: the electronic device comprises at least one polymeric macromolecule according to claim 3.

Technical Field

The invention belongs to the technical field of organic photoelectricity, and particularly relates to an n-type organic semiconductor material taking squaraine derivatives as cores, and a preparation method, a preparation and application of the material.

Background

Since the invention of conducting polymers by alanj, heeger et al (acquired by nobel chemical prize in 2000) at the end of the last 70 s century, organic/polymeric semiconductors have attracted much attention due to their potential in the fabrication of low-cost, large-area optoelectronic devices. The success of more and more novel photoelectric products in recent years shows great commercial application prospect. Organic/polymer semiconductor materials not only have the electronic properties of metals or semiconductors, but are also easier to process than metals or crystalline semiconductors, and the possibility of processing electronic materials at low temperatures opens up the possibility of processing electronic devices inexpensively. More importantly, solution processable conjugated polymer semiconductor materials can be used as electronic "inks" which, in combination with conventional printing techniques (inkjet printing, offset printing, roll-to-roll printing, etc.), revolutionize the manufacture of electronic devices, while electronic devices based on organic/polymer semiconductor materials can also be used for applications requiring specific mechanical properties (e.g. flexible devices). Due to these special advantages, the academic circles and the industrial circles both at home and abroad are increasing the investment in this field, so that the organic/polymer semiconductor electronics field is rapidly developed.

Organic/polymer solar cells based on the "photoelectric conversion" characteristics of polymer semiconductor materials are hot spots of international research and are an important development direction of new-generation, low-cost solar cells. As a novel thin film photovoltaic technology, the organic/polymer solar cell has the outstanding advantages of all solid state, wide adjustable range of photovoltaic material properties, semi-transparency, capability of being made into flexible cell devices, large-area low-cost preparation and the like. The basic physical process is that an organic donor and an acceptor material are blended to form a light absorption active layer, the energy level difference between the donor and the acceptor is utilized, after sunlight is absorbed, charge separation is generated between the donor and the acceptor interface, and the charge reaches different electrodes through selective transmission of the charge in the material, so that photocurrent is generated to realize photoelectric conversion. Compared with inorganic semiconductor materials, the organic/polymer photovoltaic materials are low in price, low in toxicity (or non-toxic), and high in light absorption coefficient, and the effective absorption of sunlight can be achieved when the thickness of a common film is hundreds of nanometers. The organic/polymer solar cell can be processed by adopting methods such as printing, printing and the like, a large-area and flexible thin-film solar cell can be manufactured by a roll-to-roll rolling processing flow similar to that for manufacturing photographic film by taking reference to the processing technology of traditional plastics, and the manufacturing cost of the photovoltaic cell can be effectively reduced by the production technology. In addition, the characteristics of flexibility and light weight of the organic/polymer solar cell greatly expand the application range and environmental compatibility of the solar cell, can gradually expand the installation and use modes of the solar cell from a fixed plane installation mode to more flexible different curved surface installation modes, and is favorable for realizing portable multiple applications.

The n-type organic semiconductor material taking the squarylium cyanine derivatives as the core, and the preparation method and the application thereof have great development potential and prospect in the field of organic photoelectric devices because of having better energy level structure, absorption characteristic and processing characteristic and being beneficial to realizing the requirement of organic photoelectric conversion.

Disclosure of Invention

In order to overcome the defects and shortcomings in the prior art, the invention mainly aims to provide an n-type organic semiconductor material taking squaraine derivatives as cores. The squaric acid derivative unit has stronger electricity absorption performance, can effectively adjust the absorption spectrum and the molecular orbital energy level of molecules, and meanwhile, the unit connected on the squaric acid derivative also has stronger electricity absorption performance and chemical modification.

The invention also aims to provide a preparation method of the n-type organic semiconductor material taking the squaraine derivative as the core.

The invention also aims to provide application of the n-type organic semiconductor material taking the squarylium cyanine derivative as the core in the field of organic semiconductors.

In order to achieve the purpose, the invention adopts the following technical scheme:

an n-type organic semiconductor material taking squarylium cyanine derivatives as cores is characterized by having the following chemical structural formula (I):

where the following applies to the symbols appearing:

the radicals E, which are identical or different on each occurrence, are selected from the group consisting of¹Substituted aromatic ring systems having from 5 to 30 aromatic ring atoms or which may be substituted by one or more radicals R¹A substituted group of a heteroaromatic ring system having 3 to 30 aromatic ring atoms;

wherein R is¹Identical in each occurrence orVariously selected from H, D, F, Cl, CN, C (═ O) R²,Si(R²)₃,N(R²)₂,OR²,SR²,S(＝O)R²,C(＝S)、C＝C(CN)₂A linear alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic organic group having 6 to 60 carbon atoms or a heteroaromatic organic group having 3 to 60 carbon atoms, wherein one or more-CH in the above-mentioned groups₂The radical may be represented by-R³C＝CR³-,-C≡C-,Si(R³)₂,C＝O,C＝NR³,-C(＝O)O-,-C(＝O)NR³-,NR³O, S, S (═ O) or SO₂Replacing; two or more radicals R¹May be linked to each other and may form a ring;

R²、R³each occurrence being the same or different and selected from a straight chain alkyl group having 1 to 60 carbon atoms, a branched or cyclic alkyl group having 3 to 22 carbon atoms, an alkenyl or alkynyl group having 2 to 20 carbon atoms, an aromatic organic group having 6 to 14 carbon atoms, or a heteroaromatic organic group having 3 to 14 carbon atoms; two or more radicals R²、R³May be linked to each other and may form a ring;

furthermore, the n-type organic semiconductor material taking the squaraine derivative as the core is characterized in that the E unit preferably has the following structure or one or more groups R at each occurrence¹A substituted derivative or combination of the following structures (wavy bond being the junction):

wherein X, which are identical or different, are selected from CR¹N; z, which may be identical or different, is selected from: c (R)¹)₂、NR¹、C(R¹)₂O、Si(R¹)₂O, S; wherein R is¹、R²、R³Is defined as in formula 1¹、R²、R³Definition of (1)The same is true.

An oligomer, polymer or dendrimer containing the above compound, wherein one or more of the bonds to the polymer, oligomer or dendrimer may be located in formula (I) as R¹、R²Or R³At any desired position of substitution.

A method of making the above-described compound, oligomer, polymer or dendrimer, the method comprising the steps of:

(a) reacting a compound having a pyrrole aldehyde derivative with a hydrazine derivative (R)¹)₂N-NH₂Reaction to obtain

(b) The above product (R)¹)₂N-N ═ CH-L by reaction with squaric acid derivatives

(c) Hydrolyzing the above product to obtain

(d) Reacting the product with an E derivative to obtain a structural formula 1;

a formulation comprising at least one of the above compounds, oligomers, polymers or dendrimers and at least one solvent.

An electronic device selected from the group consisting of: organic thin film transistors (OFETs), Organic Solar Cells (OSCs), Organic Photodiodes (OPDs), Organic Light Emitting Diodes (OLEDs) the electronic device comprises at least one of the above-mentioned organic compounds, oligomers, polymers or dendrimers.

An array of the above devices.

Advantageous effects

Compared with the prior art, the invention has the following advantages:

the squaric acid derivative unit based on the invention has strong chemical stability and chemical modification, and the band gap and the energy level can be conveniently adjusted; the squarylium acid derivative unit based on the method has good electricity absorption performance, and is favorable for realizing a high-mobility n-type semiconductor material; the squaric acid derivative unit based on the invention has narrow band gap and is beneficial to the application of broadband light detection and photovoltaic.

Drawings

FIG. 1 is a chemical reaction equation for the preparation of Compound 1;

FIG. 2 is a chemical reaction equation for preparing Compound 2;

FIG. 3 is a chemical reaction equation for preparing Compound 3;

FIG. 4 is a chemical reaction equation for the preparation of Compound 4;

FIG. 5 is a chemical reaction equation for the preparation of compound M1;

FIG. 6 shows a chemical reaction equation for preparing an electron acceptor type compound M2;

FIG. 7 shows a chemical reaction equation for preparing an electron acceptor type compound M3;

FIG. 8 is a chemical reaction equation for preparing the electron acceptor type compound P1;

fig. 9 shows the signal response of two devices under irradiation of monochromatic light (wavelength 750 nm) with a switching frequency of 500 hz. It can be seen that the M1-based device is aligned to an optical signal ratio PC of 750 nm₆₁The strength of the BM.

Detailed Description

The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.