阅读说明：本技术 一类主链含金属元素的a-d-a型聚合物及制备方法与其应用 (A-D-A type polymer with main chain containing metal element, preparation method and application thereof ) 是由 应磊 钟知鸣 彭沣 黄飞 曹镛 于 2018-06-29 设计创作，主要内容包括：本发明公开了一类主链含金属元素的A-D-A型聚合物及制备方法与其应用。该制备方法以A-D-A单元为核心,以炔-金属化合物-炔单元为纽带,将金属原子引入到共聚物中,制备的聚合物具有宽光谱范围的吸收和高的载流子迁移率。本发明基于此类主链含金属元素的A-D-A型聚合物可作为活性层,应用在有机/聚合物光电探测器或有机/聚合物太阳电池或有机/聚合物场效应晶体管中。(The invention discloses an A-D-A type polymer with a main chain containing metal elements, a preparation method and application thereof. The preparation method takes the A-D-A unit as a core, takes the alkyne-metal compound-alkyne unit as a ligament, introduces metal atoms into the copolymer, and the prepared polymer has wide spectral range absorption and high carrier mobility. The A-D-A type polymer with the main chain containing metal elements can be used as an active layer and applied to an organic/polymer photoelectric detector, an organic/polymer solar cell or an organic/polymer field effect transistor.)

1. A-D-A type polymer with a main chain containing metal elements is characterized in that the chemical structural formula satisfies the following general formula:

wherein n is the number of repeating units, and n is 2-1000;

a is an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 2 to 60 carbon atoms;

m is selected from a group containing a metal atom, being a mercury atom or a platinum group Pt with a phosphorus ligand (P (R)¹)₃)₂Wherein R is¹Is a linear alkyl group having 1 to 60 carbon atoms, a branched or cyclic alkyl group having 3 to 60 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, two or more groups R¹Can be linked to each other and form a ring;

the electron donating group D is selected from an aromatic organic group having 6 to 80 carbon atoms or a heteroaromatic organic group having 3 to 100 carbon atoms.

2. The a-D-a type polymer with main chain containing metal element of claim 1, wherein the a group is the following structure or the halogenated, deuterated, alkyl substituted derivative of the following structure:

wherein X is selected from C-R²A group or an N atom;

R²selected from H, D, F, Cl, CN, NO₂、C(＝O)R³,Si(R³)₃,N(R³)₂,P(＝O)(R³)₂,P(＝S)(R³)₂,OR³,SR³,S(＝O)R³,S(＝O)₂R³A 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 R is²May contain one or more-CHs₂The radical being able to be substituted by-R³C＝CR³-,-C≡C-,Si(R³)₂,C＝O,C＝NR³,-C(＝O)O-,-C(＝O)NR³-,NR³,P(＝O)(R³),P(＝S)(R³) O, S, S (═ O) or SO₂Replacing; two or more radicals R²Can be linked to each other and form a ring;

R³selected from a linear alkyl group having 1 to 60 carbon atoms, a branched or cyclic alkyl group having 3 to 60 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; two or more radicals R³Can be linked to each other and form a ring.

3. The A-D-A type polymer with main chain containing metallic elements as claimed in claim 1, wherein the electron donor unit D is one or more of the following structures or the halogenated, deuterated, alkyl, alkoxy, alkylthio substituted derivatives of the following structures:

wherein K is C (R)⁴)₂,NR⁴,BR⁴,C(R⁴)₂O,Si(R⁴)₂,Ge(R⁴)₂,R⁴C＝CR⁴,C(R⁴)₂C(R⁴)₂,C＝O,C＝NR⁴,C(＝O)O,C(＝O)NR⁴,P(＝O)(R⁴),P(＝S)(R⁴) O, S, Se, Te, S (═ O) or SO₂(ii) a Z is as defined above;

wherein R is⁴Selected from the group consisting of those having 1 to 60 carbon atomsA linear alkyl group, a branched or cyclic alkyl group having 3 to 60 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 R is⁴May contain one or more-CHs₂The radical being able to be substituted by-R⁵C＝CR⁵-,-C≡C-,Si(R⁵)₂,C＝O,C＝NR⁵,-C(＝O)O-,-C(＝O)NR⁵-,NR⁵,P(＝O)(R⁵),P(＝S)(R⁵) O, S, S (═ O) or SO₂Replacing; r⁵Selected from a linear alkyl group having 1 to 60 carbon atoms, a branched or cyclic alkyl group having 3 to 60 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; two or more radicals R⁴、R⁵Can be linked to each other and form a ring.

4. The A-D-A type polymer containing metal element in main chain according to claim 1, wherein the molecular dipoles of two A units in each A-D-A repeating unit are oriented oppositely.

5. A-D-A type polymer with main chain containing metal element as claimed in any one of claims 1 to 4, which is prepared by the following steps:

(1) performing Stille coupling on the D unit containing the dialkyl tin functional group and dibromo or iodo Ar to obtain dibromo or iodo A-D-A unit;

(2) reacting dibromo or iodo A-D-A units with trialkyl acetylene silicon in a solvent to obtain di (trialkyl silicon) acetylene end group A-D-A units; reacting the A-D-A unit of the di (trialkylsilyl) acetylene end group with an alkali solution to obtain an A-D-A unit of a diacetylene end group;

(3) and reacting the A-D-A unit of the diacetylene end group with a metal compound to obtain the A-D-A type polymer with the main chain containing metal elements.

6. The preparation method according to claim 5, wherein the molar ratio of the D containing the dialkyltin functional group to the dibromo or iodo Ar unit in the step (1) is 1:2 to 1: 4; the Stille coupling reaction solvent in the step (1) is toluene, xylene, chlorobenzene or tetrahydrofuran, and a reaction catalytic system is preferably tetrakis (triphenylphosphine) palladium or a mixture of the tetrakis (triphenylphosphine) palladium and the tetrahydrofuran in a mass ratio of 1: 1-1: 3 palladium acetate: tri-tert-butylphosphine or 1: 1-1: 3 tris (dibenzylideneacetone) dipalladium: the reaction temperature of the tri (o-methyl phenylphosphine) is 20-140 ℃.

7. The method according to claim 5, wherein the molar ratio of the dibromo or iodo A-D-A unit to the trialkylethylene silicon in step (2) is 1:2 to 1:10, the reaction solvent is diisopropylamine, toluene, xylene, chlorobenzene, tetrahydrofuran, water, methanol, ethanol or isopropanol, and the reaction temperature is 0 to 150 ℃.

8. The preparation method according to claim 5, wherein the step (3) specifically comprises the following steps:

(a) under the protection of inert gas, dissolving the A-D-A monomer with the diacetylene end group in an organic solvent, then adding a metal compound, and reacting for 0.1-36 hours at the temperature of 0-100 ℃;

(b) adding an alkaline solution, adopting a solution of hydroxide of alkali metal or alkaline earth metal, and continuously reacting for 0.1-36 hours;

(c) and after the reaction is finished, purifying the obtained precipitate to obtain the target product.

9. The method for preparing A-D-A type polymers containing metal elements in the main chain according to claim 8, wherein: the organic solvent in the step (a) is at least one of ethanol, isopropanol, glycerol, acetic acid, acetone, carbon disulfide, diethyl ether, ethyl acetate, pyridine, tetrahydrofuran, methyltetrahydrofuran, chlorobenzene and dichlorobenzene.

10. The method for preparing A-D-A type polymers containing metal elements in the main chain according to claim 8, wherein: the amount of the A-D-A monomer with diacetylene end groups and the metal compound monomer in the step (a) is such that the total molar amount of the monomers containing diacetylene functional groups is equal to the total molar amount of the metal compound monomer; the solute dosage of the alkaline solution in the step (b) is 0.1-100 times of the molar total amount of the A-D-A monomer of the diacetylene end group.

11. The method for preparing A-D-A type polymers containing metal elements in the main chain according to claim 8, wherein: and (c) purifying, namely drying the obtained precipitate without filtration to obtain a crude product, dissolving the crude product with a solvent, filtering again, concentrating, precipitating in a methanol solution after concentrating, filtering, and drying to obtain the target product.

12. Use of a polymer of type a-D-a with a main chain containing a metal element according to any one of claims 1 to 4 for the manufacture of an electronic device, characterized in that: the electronic device comprises an organic thin film transistor OFET, an organic light emitting transistor OLET, an organic solar cell OSC, an organic photodiode OPD, an organic phototransistor OPT, an organic light emitting electrochemical cell OLEC and an organic electroluminescent diode device OLED.

13. Use of a-D-a type polymer having a main chain containing a metal element according to any one of claims 1 to 4 for the preparation of an electronic device according to claim 12, wherein: the A-D-A type polymer with the main chain containing the metal element is dissolved in an organic solvent and then is subjected to spin coating, ink-jet printing or printing to form a film.

Technical Field

The invention belongs to the field of organic semiconductors, and particularly relates to an A-D-A type polymer with a main chain containing metal elements, a preparation method and application thereof in organic/polymer photodetectors, organic/polymer solar cells, organic/polymer diodes and organic/polymer field effect transistors.

Background

The photoelectric detector is a component for converting optical signals into electric signals based on the photoelectric effect, and has important application in the fields of optical communication, image sensing, biomedical sensing, environmental monitoring, meteorology, military and the like. The photodetectors commonly used today are based essentially on inorganic semiconductor materials, such as Si-based, Ge-based, and InGaAs, etc.

Compared with inorganic materials, the organic/polymer material has the advantages of low cost, easy adjustment of absorption wavelength, film formation through a solution method and the like, so that the organic/polymer photodiode has the advantages of simple manufacturing process, low production cost, light weight, easy large-area preparation, realization of flexible devices and wide application prospect. Gong et al utilize a narrow-band conjugated polymer PDDTT and a fullerene derivative PC₆₁BM blending to prepare a full-color photodetector with a spectral response range of 300-1150 nm, wherein the detection rate of the detector under zero bias voltage exceeds 10¹³cm Hz^1/2W^-1The overall performance of the device is superior to that of silicon-based devices [ Science,2009,325(5948): 1665-1667-]。

The A-D-A type polymer with the main chain containing the metal element has good energy level structure and solution processing characteristics, and is beneficial to meeting the requirement that an organic light detector works in short wave infrared, so that the A-D-A type polymer has great development potential and prospect in the field of organic light detectors.

Disclosure of Invention

In order to solve the defects and shortcomings of the prior art, the invention mainly aims to provide an A-D-A type polymer with a main chain containing metal elements. The introduction of metal atoms can provide intermetallic supramolecular action, induce molecular aggregation, and combine the strong D-A action of an electron supply D unit to effectively adjust the absorption spectrum of the polymer, thereby improving the external quantum efficiency of the polymer. The regular structure of the A-D-A type enables polymer molecules to be more ordered, is more beneficial to the accumulation of the polymer molecules, can further improve the mobility and red shift of an absorption spectrum, and is beneficial to improving the molecular weight and batch stability of the polymer.

Another object of the present invention is to provide a method for preparing the A-D-A type polymer containing metal element in the main chain.

The invention further aims to provide application of the A-D-A type polymer with the main chain containing the metal element in the field of organic semiconductor devices.

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

A-D-A type polymer with a main chain containing metal elements has a chemical structural formula which satisfies the following general formula:

wherein n is the number of repeating units, and n is a positive integer of 2-1000;

a is an aromatic hydrocarbon group having 6 to 60 carbon atoms or an aromatic heterocyclic group having 2 to 60 carbon atoms;

m is selected, identically or differently on each occurrence, from a group containing a metal atom, preferably a mercury atom or a platinum group Pt with a phosphorus ligand (P (R)¹)₃)₂；

R¹Is a linear alkyl group having 1 to 60 carbon atoms, a branched or cyclic alkyl group having 3 to 60 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, two or more groups R¹May be linked to each other and may form a ring;

d is selected from aromatic organic groups with 6-80 carbon atoms or heteroaromatic organic groups with 3-100 carbon atoms, which are the same or different at each occurrence.

Further, the a group is preferably a halogenated, deuterated, alkyl-substituted derivative of the following structure or of the following structure:

wherein X is selected, identically or differently on each occurrence, from C-R²A group or an N atom;

R²each occurrence being the same or different and selected from H, D, F, Cl, CN, NO₂、C(＝O)R³,Si(R³)₃,N(R³)₂,P(＝O)(R³)₂,P(＝S)(R³)₂,OR³,SR³,S(＝O)R³,S(＝O)₂R³A 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 R is²One or more-CH groups may contain₂The radical may be represented by-R³C＝CR³-,-C≡C-,Si(R³)₂,C＝O,C＝NR³,-C(＝O)O-,-C(＝O)NR³-,NR³,P(＝O)(R³),P(＝S)(R³) O, S, S (═ O) or SO₂Replacing; two or more radicals R²May be linked to each other and may form a ring;

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 60 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; two or more radicals R³May be linked to each other and may form a ring.

Furthermore, the electron donor units D are preferably one or more of the following structures or halogenated, deuterated, alkyl, alkoxy, alkylthio-substituted derivatives of the following structures, respectively:

wherein K is C (R)⁴)₂,NR⁴,BR⁴,C(R⁴)₂O,Si(R⁴)₂,Ge(R⁴)₂,R⁴C＝CR⁴,C(R⁴)₂C(R⁴)₂,C＝O,C＝NR⁴,C(＝O)O,C(＝O)NR⁴,P(＝O)(R⁴),P(＝S)(R⁴) O, S, Se, Te, S (═ O) or SO₂(ii) a Z is as defined above.

Wherein R is⁴Each occurrence identically or differently selected from a straight-chain alkyl group having 1 to 60 carbon atoms, a branched or cyclic alkyl group having 3 to 60 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 R is⁴May contain one or more-CHs₂The radical may be represented by-R⁵C＝CR⁵-,-C≡C-,Si(R⁵)₂,C＝O,C＝NR⁵,-C(＝O)O-,-C(＝O)NR⁵-,NR⁵,P(＝O)(R⁵),P(＝S)(R⁵) O, S, S (═ O) or SO₂Replacing; r⁵Each 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 60 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; two or more radicals R⁴、R⁵May be linked to each other and may form a ring.

Further, in the A-D-A type polymer having a main chain containing a metal element, the molecular dipoles of the two A units in each A-D-A repeating unit are oriented oppositely.

The invention also provides a preparation method of the A-D-A type polymer with the main chain containing the metal element, which comprises the following steps:

(1) performing Stille coupling on the D unit containing the dialkyl tin functional group and dibromo or iodo Ar to obtain dibromo or iodo A-D-A unit;

(2) reacting dibromo or iodo A-D-A units with trialkyl acetylene silicon in a solvent to obtain di (trialkyl silicon) acetylene end group A-D-A units; reacting the A-D-A unit of the di (trialkylsilyl) acetylene end group with an alkali solution to obtain an A-D-A unit of a diacetylene end group;

(3) and reacting the A-D-A unit of the diacetylene end group with a metal compound to obtain the A-D-A type polymer with the main chain containing metal elements.

Furthermore, the molar ratio of the D containing the dialkyl tin functional group to the A unit of the dibromo or iodo group is 1: 2-1: 4, the reaction solvent includes but is not limited to toluene, xylene, chlorobenzene, tetrahydrofuran, and the like, the reaction catalyst includes but is not limited to tetrakis (triphenylphosphine) palladium, palladium acetate/tri-tert-butylphosphine, tris (dibenzylideneacetone) dipalladium/tris (o-tolylphosphine), and the like, and the reaction temperature is 20-140 ℃.

Further, the molar ratio of the dibromo or iodo a-D-a unit to the trialkylethylene silicon in the step (2) is 1:2 to 1:10, the reaction solvent includes, but is not limited to, diisopropylamine, toluene, xylene, chlorobenzene, tetrahydrofuran, water, methanol, ethanol, isopropanol, and the like, and the reaction temperature is 0 to 150 ℃.

Further, the method for synthesizing a-D-a type polymer with a main chain containing a metal element in step (3) above comprises the following steps:

(a) under the protection of inert gas, dissolving the A-D-A monomer with the diacetylene end group in an organic solvent, then adding a metal compound, and reacting for 0.1-36 hours at the temperature of 0-100 ℃;

(b) adding an alkaline solution, preferably a solution of hydroxide of alkali metal or alkaline earth metal, and continuously reacting for 0.1-36 hours;

(c) and after the reaction is finished, purifying the obtained precipitate to obtain the target product.

Further, the organic solvent in the step (a) includes, but is not limited to, at least one of ethanol, isopropanol, glycerol, acetic acid, acetone, carbon disulfide, diethyl ether, ethyl acetate, pyridine, tetrahydrofuran, methyl tetrahydrofuran, chlorobenzene, and dichlorobenzene.

Further, the diacetylene-terminated A-D-A monomers and metal compound monomers described in step (a) are used in amounts such that the total molar amount of diacetylene-functional group-containing monomers and the total molar amount of metal compound monomers are equal.

Further, the amount of the alkali used in the step (b) is 0.1-100 times of the total molar amount of the reaction monomers.

Further, the purification in step (c) means that the obtained precipitate is dried without filtration to obtain a crude product, the crude product is dissolved by a solvent and then filtered again, concentrated and precipitated in a methanol solution after concentration, filtered and dried to obtain the target product.

An electronic device selected from the group consisting of: organic thin film transistors (OFET), Organic Light Emitting Transistors (OLET), Organic Solar Cells (OSC), Organic Photodiodes (OPD), Organic Phototransistors (OPT), organic light emitting electrochemical cells (OLEC), organic electroluminescent diode devices (OLED), said electronic device comprising at least one of the above-mentioned a-D-a type polymers having a main chain containing a metal element.

Further, the A-D-A type polymer with the main chain containing the metal element is used for preparing an electronic device, and the A-D-A type polymer with the main chain containing the metal element is dissolved in an organic solvent and then is subjected to spin coating, ink-jet printing or printing to form a film.

Compared with the prior art, the invention has the following advantages and technical effects:

(1) the introduction of metal atoms can provide potential supramolecular action, inducing molecular aggregation.

(2) The A-D-A regular structure is beneficial to the accumulation of polymer molecules, the mobility is further improved, and the absorption spectrum is red-shifted, and in addition, the regular structure is beneficial to the improvement of the molecular weight and batch stability of the polymer.

Drawings

Fig. 1 is a graph of current density-voltage characteristics of an organic/polymer photodetector device based on polymer P1.

FIG. 2 is a graph of the spectral responsivity characteristics of an organic/polymer photodetector device based on polymer P1 under a-0.1V bias.

Detailed Description

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