CN110746585B - Conjugated polymer of amino functionalized 3, 4-propylene dioxythiophene unit and application thereof - Google Patents

Conjugated polymer of amino functionalized 3, 4-propylene dioxythiophene unit and application thereof Download PDF

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CN110746585B
CN110746585B CN201911198396.4A CN201911198396A CN110746585B CN 110746585 B CN110746585 B CN 110746585B CN 201911198396 A CN201911198396 A CN 201911198396A CN 110746585 B CN110746585 B CN 110746585B
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林凯文
张小宾
王可
林建辉
王悦辉
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University of Electronic Science and Technology of China Zhongshan Institute
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Abstract

The invention discloses a conjugated polymer of amino functionalized 3, 4-propylene dioxythiophene unit and application thereof. The conjugated polymer of the amino functionalized 3, 4-propylene dioxythiophene unit has the following structure, wherein Ar is an electron-withdrawing conjugated unit, specifically is one or more of naphthalimide, perylene imide, pyrrolopyrrole dione, isoindigo, naphthothiadiazole, pyrazinothiadiazole, naphthotriazole, pyridothiadiazole, benzoxadiazole, benzothiadiazole, fluorobenzothiadiazole, difluorobenzothiadiazole, benzotriazol, difluorobenzotriazol, quinoxaline, thienopyrrolodione, thiazole, benzothiazole, pyrazine and derivatives of all the structures; n is a natural number of 1 to 10000. The conjugated polymer has proper water-alcohol solubility, can be used as an electron transport layer to be applied to an organic photoelectric device, and obviously improves the performance of the device.
Figure DDA0003446303160000011

Description

Conjugated polymer of amino functionalized 3, 4-propylene dioxythiophene unit and application thereof
Technical Field
The invention belongs to the field of organic photoelectric materials, and particularly relates to a conjugated polymer of an amino functionalized 3, 4-propylene dioxythiophene unit and application thereof in an organic photoelectric device.
Background
Due to the worldwide annual increase in energy demand, the increasing exhaustion of traditional energy sources such as petroleum and coal, and the need for protecting the ecological environment of the earth, more and more scientists around the world concentrate their research on developing and utilizing inexhaustible renewable clean energy sources such as wind energy, geothermal energy, solar energy, etc.
An organic/polymer solar cell based on an organic/polymer material as a novel thin film photovoltaic cell technology has the advantages of being all solid, capable of realizing translucency, capable of being made into a flexible device and the like. In addition, the organic/polymer solar cell can be processed to prepare large-area devices by adopting a low-cost roll-to-roll processing method. The organic/polymer solar cell is hardly limited by environment and place, has very strong complementarity with an inorganic semiconductor solar cell, and has huge commercial development value and market competitiveness. The photovoltaic performance of the organic/polymer material has wide adjustable range, and the properties of the material, such as electronic energy level, carrier mobility, solution processing and the like, can be effectively regulated and controlled by chemical means. Therefore, research on organic/polymer solar cells has attracted much attention, and scientific research centered on organic/polymer solar cells has become a world-wide competitive advanced research field of materials science.
The core of the current research on a wide range of organic/polymer solar cells is a heterojunction structure in which the photoactive layer of the organic/polymer solar cell is composed of two materials, a donor and an acceptor, based on the bulk heterojunction model proposed in 1995 by Heeger, A J et al (sciences 1995,270, 1789). The structure of such heterojunctions has been a breakthrough in efficiency of 16% -17% (adv. mater.2019, 1901872.; nat. commun.2019,10,2515.Science,2018,361,1094.) due to the development of more than two decades.
The electron transport layer between the active layer and the cathode plays an important role in improving the performance of the device. The good electron transport layer can reduce interface potential barrier and passivate surface defects of the electrode, thereby reducing leakage current, enhancing charge injection and improving open-circuit voltage. Electron transport layers such as PFN, PNDITF3N (chem. soc. rev.2010,39,2500.j.am. chem. soc.2016,138,2004.adv. energy mater.2015,1501534.) are widely accepted electron transport materials. Low cost and high performance electron transport layers in the field of organic photovoltaics have become an important direction of research.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a conjugated polymer of amino functionalized 3, 4-propylene dioxythiophene units.
Another object of the present invention is to provide a method for preparing the above conjugated polymer of amino-functionalized 3, 4-propylenedioxythiophene units.
The invention further aims to provide application of the conjugated polymer of the amino functionalized 3, 4-propylene dioxythiophene unit in organic photoelectric devices.
The purpose of the invention is realized by the following technical scheme:
a conjugated polymer of amino functionalized 3, 4-propylene dioxythiophene units has the following structure:
Figure GDA0003446303150000021
wherein Ar is an electron-withdrawing conjugated unit; n is a natural number of 1-10000; the electron-withdrawing conjugated unit Ar is one or more of naphthalimide, perylene imide, pyrrolopyrrole dione, isoindigo, naphthothiadiazole, pyrazinothiadiazole, naphthotriazole, pyridothiadiazole, benzooxadiazole, benzothiadiazole, fluorobenzothiadiazole, difluorobenzothiadiazole, benzotriazol, difluorobenzotriazol, quinoxaline, thienopyrrole dione, thiazole, benzothiazole, pyrazine and derivatives of all the structures.
Further, the conjugated unit Ar is selected from the following structures:
Figure GDA0003446303150000031
wherein R is selected from H, C1-C50 linear alkyl or branched alkyl.
Further, the structural formula of the conjugated polymer of the amino functionalized 3, 4-propylene dioxythiophene unit is as follows:
Figure GDA0003446303150000041
wherein n is a natural number of 1-10000.
Further, the molecular weight Mn of the conjugated polymer of amino-functionalized 3, 4-propylenedioxythiophene units is 22788, and Mw is 56238.
The preparation method of the conjugated polymer of the amino functionalized 3, 4-propylene dioxythiophene unit comprises the following steps: under the protection of gas, mixing the calculated mole ratio of the tertiary amino side chain modified 3, 4-ethylenedioxythiophene monomer with other Ar monomers in corresponding ratio, and then adding Pivalic Acid and P (o-CH)3Ph)3、Pd2(dba)3.CHCl3And CsCO3And finally, adding an organic solvent, carrying out C-H activated coupling polymerization, and purifying a product to obtain a corresponding polymer material.
Further, the temperature of the C-H activation coupling polymerization reaction is 110-120 ℃, and the time is 24H.
Further, the molar ratio of the tertiary amine side chain modified 3, 4-ethylenedioxythiophene monomer to the Ar monomer is 1: 1.
further, the organic solvent is at least one of o-xylene, toluene and chlorobenzene.
Further, the purification steps are as follows: and after the reaction is finished, precipitating a polymer in methanol, sequentially extracting the polymer by methanol, acetone and normal hexane, finally extracting the final polymer by chloroform, precipitating the polymer by methanol again, and drying to obtain the conjugated polymer of the amino functionalized 3, 4-propylene dioxythiophene unit.
The conjugated polymer of the amino functionalized 3, 4-propylene dioxythiophene unit is applied as an electron transport layer in an organic photoelectric device.
The conjugated polymer of the amino-functionalized 3, 4-propylene dioxythiophene unit is obtained by a C-H activation coupling method, has proper water-alcohol solubility, low toxicity and low cost, can be used for preparing a high-efficiency stable polymer/polymer solar cell device, and is expected to replace the existing commercial interface material.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention designs a novel polymer material for an electron transport layer.
(2) The invention applies C-H activated coupling polymerization with low toxicity and low cost to the synthesis of an electron transport layer for the first time.
(3) The invention realizes a polymer/polymer solar cell device with excellent performance.
Drawings
FIG. 1 is a NMR spectrum of NDI-ProDOTN prepared in example 1.
FIG. 2 is a molecular weight test pattern of NDI-ProDOTN prepared in example 1.
Fig. 3 is a schematic structural diagram of a solar cell device in example 2.
FIG. 4 is a current density-voltage curve of the solar cell device in example 2, in which W/O represents a control group having an NDI-ProDOTN coating thickness of 0nm, NDI-ProDOTN (5nm) represents an experimental group having an NDI-ProDOTN coating thickness of 5nm, NDI-ProDOTN (20nm) represents an experimental group having an NDI-ProDOTN coating thickness of 20nm, and NDI-ProDOTN (40nm) represents an experimental group having an NDI-ProDOTN coating thickness of 40 nm.
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.
The practice of the present invention may employ conventional techniques of polymer chemistry within the skill of the 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 were purchased analytically or chromatographically pure and all reactions were carried out under nitrogen atmosphere. All reagents are commercially available unless otherwise indicated.
Example 1
Preparation of conjugated polymer (NDI-ProDOTN for short) of amino functionalized 3, 4-propylene dioxythiophene unit
The chemical reaction flow is shown as follows, and the specific reaction steps and reaction conditions are as follows:
Figure GDA0003446303150000061
(1) the raw materials ProDOTN and NDIBr in the reaction formula2Is purchased from Suzhou Nakai science and technology Co., Ltd, o-Xylene is purchased from Beijing Bailingwei science and technology Co., Ltd, Pivalic Acid, P (o-CH)3Ph)3、CsCO3、Pd2(dba)3.CHCl3Is purchased from companies such as Beijing Yinuoka technologies, Inc.
(2) Under the protection of nitrogen, monomer NDIBr2(97.27mg,0.15mmol)、ProDOTN(40.5mg,0.15mmol)、Pd2(dba)3.CHCl3(6.79mg,7.64μmol)、P(o-CH3Ph)3(4.9mg, 15. mu. mol), Pivalic Acid (7.07mg,0.07mmol) and CsCO3(184mg) was dissolved in 2 ml of o-xylene and stirred at 110 ℃ for 24 hours. After the reaction is finished, precipitating a polymer in methanol, sequentially extracting the polymer by methanol, acetone and normal hexane, finally extracting the final polymer by chloroform, precipitating the final polymer by methanol again, and drying the precipitate to obtain the final blue flocculent polymer NDI-ProDOTN, wherein the yield is 120 mg and 90 percent.
Example 2
The polymer material obtained in example 1 is taken as an example to illustrate the application of the polymer material in a polymer/polymer solar cell device as electron transport
The following examples illustrate the conjugated polymers of amino-functionalized 3, 4-propylenedioxythiophene units and their application processes in organic optoelectronic devices, but the present invention is not limited to these examples.
The specific preparation process of the device is as follows:
and (3) spinning a PEDOT (polymer ethylene terephthalate) (PSS) hole transport layer (anode interface layer) with the thickness of 40 nanometers on the ITO, then spinning a polymer donor/acceptor PTB7-Th (polycarbonate 71) (71 BM) blended optical active layer with the thickness of about 100 nanometers, then spinning an NDI (NDI) -ProDOTN with the thickness of about 5 nanometers as a cathode interface layer, and then evaporating an Ag layer (metal anode) with the thickness of 100 nanometers to finish the preparation of the device.
Referring to the above steps, devices with NDI-ProDOTN spin-coating thicknesses of about 20nm and 40nm were prepared, and a control group without NDI-ProDOTN coating (i.e., coating thickness of 0nm) was prepared.
J-V curve tests were performed and the relevant parameters for the devices prepared above are shown in Table 1. From table 1, it can be seen that the polymer/polymer solar cell device without NDI-ProDOTN as cathode interface layer of PTB7-Th: PC71BM has a device efficiency of only 6.58%; the NDI-ProDOTN with the thickness of 5nm as a cathode interface layer can greatly improve the open-circuit voltage, the short-circuit current and the filling factor, and simultaneously can realize the device efficiency as high as 9.35%. Therefore, the conjugated polymer of the amino functionalized 3, 4-propylene dioxythiophene unit is a good interface material and is a polymer/polymer solar cell material with excellent performance.
TABLE 1 Performance parameters of ITO/PEDOT: PSS/PTB7-Th: PC71BM/NDI-ProDOTN/Al organic solar cell devices
Figure GDA0003446303150000071
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 (10)

1. A conjugated polymer of amino functionalized 3, 4-propylene dioxythiophene units is characterized by having the following structure:
Figure FDA0003446303140000011
wherein Ar is an electron-withdrawing conjugated unit; n is a natural number of 1-10000; the electron-withdrawing conjugated unit Ar is more than one of naphthalimide, perylene imide, pyrrolopyrrole dione, isoindigo, naphthothiadiazole, pyrazinothiadiazole, naphthotriazole, pyridothiadiazole, benzooxadiazole, benzothiadiazole, fluorobenzothiadiazole, benzotriazole, difluorobenzotriazole, quinoxaline, thienopyrrole dione, thiazole, benzothiazole and pyrazine.
2. The conjugated polymer of amino-functionalized 3, 4-propylenedioxythiophene units according to claim 1, wherein the electron-withdrawing conjugated unit Ar is selected from the following structures:
Figure FDA0003446303140000021
，
wherein R is selected from H, C1-C50 straight chain alkyl or branched chain alkyl.
3. The amino-functionalized conjugated polymer of 3, 4-propylenedioxythiophene units of claim 1, wherein the amino-functionalized conjugated polymer of 3, 4-propylenedioxythiophene units has the following structural formula:
Figure FDA0003446303140000031
wherein n is a natural number of 1-10000.
4. The conjugated polymer of amino-functionalized 3, 4-propylenedioxythiophene units of claim 3, wherein the conjugated polymer of amino-functionalized 3, 4-propylenedioxythiophene units has a molecular weight of Mn 22788 and Mw 56238.
5. Conjugated polymerization of amino-functionalized 3, 4-propylenedioxythiophene units according to any of claims 1 to 4The preparation method of the compound is characterized by comprising the following steps: under the protection of gas, mixing the calculated mole ratio of the tertiary amine side chain modified 3, 4-ethylenedioxythiophene monomer with other Ar monomers in corresponding proportion, and then adding pivalic acid and P (o-CH)3Ph)3、Pd2(dba)3.CHCl3And CsCO3And finally, adding an organic solvent, carrying out C-H activated coupling polymerization, and purifying to obtain the conjugated polymer of the amino functionalized 3, 4-propylene dioxythiophene unit.
6. The method for preparing the conjugated polymer of amino-functionalized 3, 4-propylenedioxythiophene units according to claim 5, wherein the temperature of the C-H activated coupling polymerization reaction is 110-120 ℃ and the time is 24H.
7. The method for preparing the conjugated polymer of amino-functionalized 3, 4-propylene dioxythiophene unit according to claim 5, wherein the molar ratio of the tertiary amine group side chain modified 3, 4-ethylene dioxythiophene monomer to the Ar monomer is 1: 1.
8. the method for preparing the conjugated polymer of amino-functionalized 3, 4-propylenedioxythiophene units according to claim 5, wherein the organic solvent is at least one of o-xylene, toluene, and chlorobenzene.
9. The method of claim 5, wherein the purification step comprises: and after the reaction is finished, precipitating a polymer in methanol, sequentially extracting the polymer by methanol, acetone and normal hexane, finally extracting the final polymer by chloroform, precipitating the polymer by methanol again, and drying to obtain the conjugated polymer of the amino functionalized 3, 4-propylene dioxythiophene unit.
10. Use of a conjugated polymer of amino-functionalized 3, 4-propylenedioxythiophene units according to any of claims 1 to 4 as an electron transport layer in an organic opto-electronic device.
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