CN109161003B - N-type conjugated polymer containing thiazole bridged naphthalene diimide, preparation thereof and application thereof in organic thin film transistor and photovoltaic device - Google Patents

N-type conjugated polymer containing thiazole bridged naphthalene diimide, preparation thereof and application thereof in organic thin film transistor and photovoltaic device Download PDF

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CN109161003B
CN109161003B CN201810720470.3A CN201810720470A CN109161003B CN 109161003 B CN109161003 B CN 109161003B CN 201810720470 A CN201810720470 A CN 201810720470A CN 109161003 B CN109161003 B CN 109161003B
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thiazole
naphthalene diimide
conjugated polymer
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段春晖
张龙
黄飞
曹镛
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South China University of Technology SCUT
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Abstract

The invention relates to an n-type conjugated polymer containing thiazole bridged naphthalene diimide, and preparation and application thereof in organic thin film transistors and photovoltaic devices. The structural formula of the n-type conjugated polymer containing the thiazole bridged naphthalene diimide is shown as follows, wherein Ar1 and Ar2 are aromatic groups; the R0, R1 and R2 are H, C1~50Alkyl straight or branched chains; and n is a natural number of 1-10000. The polymer has higher electron transfer performance, shows single n-type transmission when being applied to an organic thin film transistor, has high electron mobility and switching ratio and low threshold voltage, and can well inhibit p-type transfer characteristics; in addition, the polymer can also be applied to organic photovoltaic devices, and the devices have good photoelectric response performance. Therefore, the n-type conjugated polymer containing the thiazole bridged naphthalene diimide has larger commercial practical application value.

Description

N-type conjugated polymer containing thiazole bridged naphthalene diimide, preparation thereof and application thereof in organic thin film transistor and photovoltaic device
Technical Field
The invention relates to the field of organic semiconductor materials, in particular to an n-type conjugated polymer containing thiazole bridged naphthalene diimide, and preparation and application thereof in organic thin film transistors and photovoltaic devices.
Background
The conjugated polymer is soluble in solution processing, has good mechanical property and good compatibility with a plastic substrate, and is expected to be used as a candidate material for preparing a large-area flexible electronic device with low cost and light weight. Organic thin film transistors and organic/polymer solar cells are two of the more popular research fields, and organic thin film transistors have great potential to drive the development of next-generation electronic products, such as flexible displays, radio identification tags, sensors, wearable electronic devices and the like; the organic/polymer solar cell is used as a novel thin-film photovoltaic cell energy technology, and has the advantages of translucency, capability of preparing flexible devices and the like. In addition, the large-area device can be processed and prepared by adopting low-cost ink-jet printing, roll-to-roll processing and other modes. The organic/polymer solar cell as a solar energy technology using clean energy can improve the limitation and ecological environment problems caused by the use of traditional fossil energy, is expected to solve the problem of increasing global energy demand, and has great commercial development value and market competitiveness.
For organic thin film transistors, a number of currently developed p-type polymers have been reported to achieve more than 10 square centimeters/(volt-seconds) in organic thin film transistors, which is superior to amorphous-based silicon-based thin film transistors. In contrast, the development of n-type polymers is relatively delayed. However, n-type conjugated polymers are also an essential part in the fabrication of similar complementary metal oxide logic circuit structures that are very important and widely used in integrated circuits. In a class of conjugated polymers containing naphthalene diimide, although the materials show a high electron transport capability in an organic thin film transistor device, the organic thin film transistor device based on the materials is difficult to realize pure electron transport, and has a certain p-type transport characteristic below a threshold voltage to a greater or lesser extent, which is not favorable for realizing single n-type electron transport.
Disclosure of Invention
In order to overcome the defect that the conventional conjugated polymer containing a naphthalene diimide unit is difficult to inhibit the p-type transmission characteristic, the invention aims to prepare a structural unit which has the p-type transmission characteristic and realizes single n-type transmission to construct an n-type conjugated polymer material, and the structural unit is applied to an organic thin film transistor to prepare a device which has higher electron mobility and is represented as single polarity.
The core technology of the invention is an n-type conjugated polymer containing thiazole bridging naphthalene diimide, which is different from the existing polymer material containing naphthalene diimide, the Bay position of a naphthalene diimide unit is coupled with the No. 2 position of thiazole, and the No. 5 positions of the thiazole on two sides are brominated to prepare a core construction unit, so that the polymer containing thiazole bridging naphthalene diimide has a more planar molecular structure, the front line track energy level is relatively low, the charge transmission in a molecular chain and between chains can be improved, the potential barrier of hole injection is increased, and finally a single n-type organic thin film transistor device with an ideal transmission curve can be prepared. In addition, the n-type conjugated polymer containing the thiazole bridged naphthalene diimide can be used as an electron acceptor material and matched with an electron donor material to be used as a photoactive layer to prepare a polymer/polymer solar cell device, and good performance can be realized. Therefore, the n-type conjugated polymer containing the thiazole bridged naphthalene diimide has larger commercial practical application value.
The purpose of the invention is realized by the following scheme:
an n-type conjugated polymer containing thiazole bridged naphthalene diimide, which is characterized by having the following structure:
Figure BDA0001718536290000031
wherein n is a natural number of 1-10000; 0 is described<x＝<1，0<＝y<1, x + y ═ 1; ar1 and Ar2 are conjugated units constituting a conjugated polymer; the conjugated unit is more than one of thiophene, furan, selenophene, benzene, fluorene, carbazole, silafluorene, benzodithiophene, benzodiselenophene, benzodifuran, benzothiadiazole, phenothiazine, phenoxazine, bithiophene, thienocyclopentadiene, thienopyrrole, thienosilole, indofluorene, indolocarbazole, pyrrole, pyrrolopyrrole dione, naphthalimide, perylene imide and derivatives thereof; the R0, R1 and R2 are H, C1～50Alkyl groups are straight or branched.
Further wherein the conjugated units Ar1 and Ar2 have one or more coupled structures of the following structure:
Figure BDA0001718536290000041
the preparation method of the n-type conjugated polymer containing the thiazole bridged naphthalene diimide comprises the following steps: and mixing dibromo monomers of thiazole bridged naphthalene diimide with Ar1 and Ar2 monomers, polymerizing under the catalysis of a palladium catalyst, and purifying to obtain the corresponding polymer material.
The n-type conjugated polymer containing the thiazole bridged naphthalene diimide is applied as an organic semiconductor material in an organic thin film transistor and an electron acceptor material in an organic photovoltaic device.
Compared with the prior art, the invention has the following advantages:
(1) the invention designs a novel n-type conjugated polymer material containing thiazole bridged naphthalene diimide;
(2) the invention realizes the organic thin film transistor device with higher electron mobility and single polarity;
(3) the invention realizes the n-type transmission curve which is close to the ideal type in the organic thin film transistor;
(4) the invention realizes the application of the n-type conjugated polymer containing the thiazole bridged naphthalene diimide as an electron acceptor in an organic photovoltaic device;
(5) the invention shows the practical application potential of the n-type conjugated polymer containing the thiazole bridged naphthalene diimide in organic semiconductors.
Drawings
FIG. 1 is a schematic diagram of a synthetic scheme representing an n-type conjugated polymer material PNDI-Tz2FT embodying a thiazole bridged naphthalene diimide.
FIG. 2 is a schematic diagram of a representative n-type polymer PNDI-Tz2FT molecular structural formula containing thiazole bridged naphthalene diimide and a related organic thin film transistor device structure.
Fig. 3 is an output characteristic curve and a transfer characteristic curve of an organic thin film transistor device prepared based on a representative polymer PNDI-Tz2FT as an active semiconductor layer.
FIG. 4 is a schematic diagram of a synthetic scheme representing an n-type conjugated polymer material PNDI2OD-Tz10 embodying a thiazole bridged naphthalene diimide
FIG. 5 is a schematic diagram of a polymer structure of an active layer of a polymer/polymer (PBDT-TAZ/PNDI2OD-Tz10) solar cell and a structure of a corresponding organic solar cell device.
FIG. 6 is a current density-voltage curve for a polymer/polymer (PBDT-TAZ/PNDI2OD-Tz10) solar cell device.
Detailed Description
The invention is further illustrated in detail below by means of specific examples, the purpose of which is to help a better understanding of the contents of the invention, including in particular the synthesis of polymeric materials and the method of device fabrication, but these specific embodiments do not in any way limit the scope of protection of the invention.
The practice of the present invention may employ conventional techniques of polymer chemistry within the skill of the relevant art. In the following examples, efforts are made to ensure accuracy with respect to numbers used (including amounts, temperature, reaction time, etc.) but some experimental errors and deviations should be accounted for. The temperatures used in the following examples are expressed in degrees Celsius and the pressures are at or near atmospheric. The solvents used are either analytically pure or chromatographically pure and all reactions are carried out under an inert gas atmosphere. All reagents were obtained commercially unless otherwise indicated.
Example 1
Preparation of thiazole-bridged naphthalene diimide-containing monomer (compound 4)
The chemical synthesis flow is shown as follows, and the specific reaction steps and reaction conditions are as follows:
Figure BDA0001718536290000061
(1) the starting materials or intermediate reactants, starting materials 1 and 2, were prepared according to literature reported methods and tetrakis-triphenylphosphine palladium, liquid bromine, sodium carbonate and various solvents were purchased commercially.
(2) Preparation of Compound 3
Starting material 1(2.2 g) and starting material 2(3.0 g) were dissolved in 30 ml of toluene under an inert atmosphere of argon, and after two purging cycles, the catalyst tetrakis-triphenylphosphine palladium (185 mg) was added, followed by two purging cycles and subsequent refluxing overnight reaction. After the reaction was complete, the solvent was removed, purified on a silica gel column and recrystallized to give 1.9 g of compound 3 in 87% yield.
(3) Preparation of Compound 4
Under the protection of inert gas argon, compound 3(553 mg) and anhydrous sodium carbonate (500 mg) were dissolved in a mixed solvent of chloroform (8 ml) and N, N-dimethylformamide (2 ml), and liquid bromine (1 ml) was slowly added in a low speed under an ice bath, followed by heating to 40 ℃, and the reaction was stopped after the point panel showed that the initial raw materials were substantially reacted. After removal of excess liquid bromine by addition of aqueous sodium thiosulfate, the solvent was removed, purified on silica gel column and recrystallized to give 300 mg of compound 4 in 48% yield.
Example 2
Preparation of n-type conjugated polymer representative material (PNDI-Tz 2FT for short) containing thiazole bridged naphthalene diimide
The chemical reaction flow is shown as follows, and the specific reaction steps and reaction conditions are as follows:
Figure BDA0001718536290000071
(1) the starting materials or intermediate reactants, monomer 5, tris (dibenzylideneacetone) dipalladium, tris (o-tolyl) phosphine, and solvent were all commercially available.
(2) Compound 4(126.4 mg, 0.1 mmol), compound 5(44.6 mg, 0.1 mmol), tris (dibenzylideneacetone) dipalladium (1.8 mg), and tris (o-tolyl) phosphine (4.9 mg) were dissolved in a mixed solvent of o-xylene (2 ml) and N, N-dimethylformamide (0.4 ml) under a nitrogen atmosphere, stirred at 115 ℃ for 24 hours, and after thiophene capping, the reaction was terminated. Precipitating the polymer in methanol, extracting with methanol, acetone, n-hexane, dichloromethane and chloroform, heating with chlorobenzene to extract the final polymer, precipitating with methanol again, and oven drying to obtain the final polymer PNDI-Tz2FT, 112 mg, 92% yield.
Example 3
The application of the polymer material PNDI-Tz2FT as an organic semiconductor in an organic thin film transistor device is illustrated by taking the polymer representative material PNDI-Tz2FT obtained in example 2 as an example
The following examples will represent the material PNDI-Tz2FT for the n-type conjugated polymer containing thiazole bridged naphthalene diimide and its application in organic thin film transistor device
The preparation process of the organic thin film transistor device is as follows:
firstly, evaporating and plating gold source/drain electrodes of 25 nanometers on a highly n-type doped silicon/silicon dioxide sheet; then under the condition of heating the substrate by a heating table at 120 ℃, spin-coating an organic polymer semiconductor film, then thermally annealing for 10 minutes at 200 ℃ in a nitrogen environment, then spin-coating a polymethyl methacrylate layer about 500 nanometers on the semiconductor layer to be used as a dielectric layer, and then heating for 30 minutes at 100 ℃ for drying; finally, about 80 nm of gold is evaporated on the substrate to form a gate electrode.
And after the device is prepared, carrying out device transmission performance test. The obtained device-related performance parameters are shown in the table one, and it can be seen from the table one that an organic thin film transistor device prepared by using the n-type conjugated polymer containing the thiazole bridging naphthalene diimide as the organic semiconductor layer shows a single-polarity n-type transmission characteristic, can obtain an electron mobility of 0.57 square centimeters/(volt-seconds), a high on-off ratio and a low threshold voltage, and the p-type transmission characteristic of the organic thin film transistor device is well inhibited, and the organic thin film transistor device is one of systems with higher performance based on the n-type conjugated polymer containing the naphthalene diimide unit. Therefore, the n-type conjugated polymer material containing the thiazole bridged naphthalene diimide is a single n-type material with excellent performance and is applied to organic thin film transistor devices.
TABLE Performance parameters for organic thin film transistor devices fabricated with the Polymer PNDI-Tz2FT as the semiconductor layer
Figure BDA0001718536290000081
Example 4
The preparation chemical reaction flow of the representative n-type conjugated polymer (PNDI 2OD-Tz10 for short) containing the thiazole bridged naphthalene diimide is shown as follows, and the specific reaction steps and reaction conditions are as follows:
Figure BDA0001718536290000091
(1) the starting materials or intermediate reactants, monomer 6, monomer 7, tris (dibenzylideneacetone) dipalladium, tris (o-tolyl) phosphine, and related solvents were all commercially available.
(2) Monomer 4(12.64 mg, 0.01 mmol), monomer 6(88.6mg, 0.09 mmol), monomer 7(49.2 mg, 0.1 mmol), tris (dibenzylideneacetone) dipalladium (1.8 mg), and tris (o-tolyl) phosphine (4.9 mg) were dissolved in a mixed solvent of o-xylene (2 ml) and N, N-dimethylformamide (0.4 ml) under a nitrogen atmosphere, stirred at 115 ℃ for 24 hours, and the reaction was terminated after thiophene capping. Precipitating the polymer in methanol, extracting with methanol, acetone, n-hexane, dichloromethane and chloroform, heating with chlorobenzene to extract the final polymer, precipitating with methanol again, and oven drying to obtain the final polymer PNDIOD-Tz10, 88 mg, yield 86%.
Example 5
The polymer material obtained in example 4 is used as an example to represent PNDIOD-Tz10 to illustrate the application of the polymer material as a polymer acceptor in a polymer/polymer solar cell device
The following examples illustrate representative n-type conjugated polymers of thiazole-bridged naphthalene diimides and their use in organic opto-electronic devices, but the invention is not limited thereto.
The specific preparation process of the device is as follows:
and (3) a 40-nanometer PEDOT (polymer ethylene terephthalate) (PSS) hole transport layer is spin-coated on the ITO, a mixed optical active layer of a polymer donor PBDT-TAZ with the size of about 100 nanometers and PNDIOD-Tz10 is spin-coated, quaternary ammonium bromide salt (PFN-Br) of amino polyfluorene with the size of about 5 nanometers is spin-coated as a cathode interface layer, and a 100-nanometer Ag layer is evaporated to complete the preparation of the device. J-V curve test is carried out, and the relevant parameters of the obtained device are shown in the table II. As can be seen from the table II, 4.7% of energy conversion efficiency can be obtained in the polymer/polymer solar cell device of PBDT-TAZ/PNDIOD-Tz10 with PNDIOD-Tz10 as a polymer acceptor, and the potential application value of the n-type conjugated polymer containing the thiazole bridged naphthalene diimide as a polymer acceptor material in the polymer/polymer solar cell material is shown.
Performance parameters of the epi-dimeric polymer solar cell device ITO/PEDOT: PSS/PCE10/PNDIOD-Tz10/PFNBr/Ag
Figure BDA0001718536290000101
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (4)

1. An n-type conjugated polymer containing thiazole bridged naphthalene diimide, which is characterized by having the following structure:
Figure FDA0002882480270000011
wherein n is a natural number of 1-10000; 0 is described<x＝<1，0<＝y<1, x + y ═ 1; ar1 and Ar2 are conjugated units constituting a conjugated polymer; the conjugated unit is more than one of furan, thiophene, selenophene, bithiophene, benzodithiophene, benzodifuran, benzodiselenophene, benzene and derivatives thereof; the R0, R1 and R2 are H, C1～50Alkyl groups are straight or branched.
2. The n-type conjugated polymer of claim 1, wherein the conjugated units Ar1 and Ar2 have one or more of the following structures:
Figure FDA0002882480270000012
3. the method for preparing the n-type conjugated polymer containing the thiazole-bridged naphthalene diimide of any one of claims 1 to 2, which comprises the following steps: and mixing dibromo monomers of thiazole bridged naphthalene diimide with Ar1 and Ar2 monomers, polymerizing under the catalysis of a palladium catalyst, and purifying to obtain the corresponding polymer material.
4. The use of the n-type conjugated polymer containing a thiazole bridged naphthalene diimide according to any one of claims 1 to 2 as an organic semiconductor material in an organic thin film transistor and as an electron acceptor material in an organic photovoltaic device.
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