CN108794779B - Preparation method of molecular-level-thickness polythiophene two-dimensional film - Google Patents
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Abstract
The invention belongs to the technical field of two-dimensional material preparation, and particularly relates to a preparation method of a polythiophene two-dimensional film with a molecular thickness. The method comprises the following steps: firstly, putting a monomer and a metal substrate subjected to annealing treatment into a chemical vapor deposition system, and reacting the monomer and the substrate at a required reaction temperature for a certain time under a specific gas flow; and then, taking out the substrate after the system is cooled, and obtaining the polythiophene two-dimensional film on the substrate. The preparation method has the advantages of simple process, low reaction temperature and low cost, is suitable for large-scale production, and the prepared polythiophene film has molecular-level thickness due to the surface confinement effect of the metal catalytic substrate.
Description
Technical Field
The invention belongs to the technical field of two-dimensional material preparation, and particularly relates to a preparation method of a molecular-level-thickness polythiophene two-dimensional film.
Background
Polythiophene, a common conjugated polymer, was first prepared by Yamamoto et al in 1980 using a metal organic reaction, and has received attention from researchers due to its intrinsic semiconducting properties and good conductivity after doping, as well as designability between structure and performance. The most common preparation methods of polythiophene comprise electrochemical polymerization and chemical polymerization, and a polythiophene film with a certain thickness is obtained by methods such as spin coating, drip coating and lifting when the polythiophene film is used, so that the polythiophene film is widely applied to the fields of organic field effect transistors, organic solar cells, super capacitors and the like.
Chemical vapor deposition is a common deposition technique in the semiconductor industry, and is based on the principle that one or more gaseous substances are introduced into a reaction chamber to undergo a chemical reaction, so as to obtain a new material to be deposited on the surface of a substrate. Surface-assisted Ullmannuciling (surface-assisted Ullmannuciling) is a surface catalysis technology which has emerged in recent years, and the principle of the technology is to utilize a phase interface between a metal substrate with catalytic activity and a reactant as a reaction site, and strictly limit a chemical reaction at a position of a molecular-level thickness of the surface of the substrate so as to accurately control a chemical reaction process and a product. However, no report is available at present for preparing a polythiophene two-dimensional film with large-area molecular scale thickness by a surface-assisted chemical vapor deposition method or a surface-assisted Ullmann coupling reaction.
Disclosure of Invention
The invention aims to provide a method for preparing a molecular-level (molecular scale) thickness polythiophene two-dimensional film, which has the advantages of simple process, low reaction temperature and low cost.
The invention provides a preparation method of a polythiophene two-dimensional film with a molecular thickness, which combines a surface-assisted Ullmann coupling reaction with a chemical vapor deposition method and comprises the following specific steps:
(1) placing the metal substrate subjected to annealing treatment in a chemical vapor deposition reaction system, and continuously introducing specific airflow to stabilize the atmosphere;
(2) respectively heating the monomer and the substrate to the required reaction temperature for reaction;
(3) and stopping heating, taking out the substrate after the system is cooled to room temperature, obtaining the polythiophene two-dimensional film on the substrate, and transferring the polythiophene two-dimensional film to the required substrate through a wet method.
Wherein the monomer is dihalogen thiophene and polyhalogenated aromatic hydrocarbon, and the molar ratio of the two is 100:1 to 1: 10; preferably, the molar ratio of the two is 10:1 to 1: 5.
The introduced gas flow is inert gas and reducing gas, and the gas flow is 1-1000 ml per minute. Inert gases such as argon and nitrogen, and reducing gases such as hydrogen; the volume ratio of the flow rates of the inert gas and the reducing gas is 100:1 to 1: 100; preferably, the volume ratio of the two flow rates is 10:1 to 1: 10.
In the invention, the dihalo-thiophene is selected from 2, 5-dibromothiophene, 2, 3-dibromothiophene and the like, and the polyhalogenated aromatic hydrocarbon is selected from 1,3, 5-tribromobenzene, 2,3, 5-tribromothiophene, 1,3, 5-trichloropyridine, tetrabromothiophene and the like.
In the invention, the metal substrate is selected from a catalytic substrate of gold, silver, copper or iron.
In the invention, the heating temperature of dihalogenated thiophene is 30-100 ℃, the heating temperature of polyhalogenated aromatic hydrocarbon is 40-150 ℃, the heating temperature of a substrate is 150-400 ℃, and the reaction time is 1-60 minutes.
In the present invention, the "wet" transfer is the same as the graphene transfer, and can be referred to in Science, 2009 (5932), 324,1312-1314 (doi: 10.1126/Science, 1171245).
The invention combines a chemical vapor deposition method with surface-assisted Ullmann coupling reaction, and catalyzes the surface chemical reaction by gasifying reaction monomers in a chemical vapor deposition system and heating a metal substrate to a certain temperature to obtain a large-surface accumulated thiophene two-dimensional film on the substrate. The preparation method has the advantages of simple process, low reaction temperature and low cost, and is suitable for large-scale production; and the prepared polythiophene film has molecular-level thickness due to the surface confinement effect of the metal catalytic substrate.
Drawings
FIG. 1 is a schematic view of a surface-assisted chemical vapor deposition apparatus.
FIG. 2 is an optical micrograph of a film obtained in example 1.
FIG. 3 is an atomic force microscope photograph obtained in example 1.
FIG. 4 is a transmission electron micrograph and a selected diffraction pattern obtained in example 1.
FIG. 5 shows the results of the Raman spectrum obtained in example 1.
FIG. 6 is the X-ray photoelectron spectroscopy result obtained in example 1.
FIG. 7 shows the results of the UV-VIS absorption spectrum obtained in example 1.
FIG. 8 is an optical micrograph of a film obtained in example 2.
FIG. 9 is an optical micrograph of a film obtained in example 3.
Detailed Description
The present invention is further described below in conjunction with the following embodiments, which are intended to be illustrative only and not limiting.
Example 1
In the first step, 2, 5-dibromothiophene (monomer 1), 1,3, 5-tribromobenzene (monomer 2) and the mixture are retreatedFire treated copper foil (1X 2 cm)2) Respectively placed in the proper positions in the quartz tubes, the quartz tubes are put into the electric furnace, the monomers are aligned to the center of the heating zone at the upstream of the electric furnace, and the copper foil is aligned to the center of the heating zone at the downstream, as shown in fig. 1. Continuously introducing 150sccmH2And 30 sccmAr, and maintaining for 20 min to remove the air in the tube and stabilize the atmosphere;
secondly, heating the copper foil to 200 ℃, then heating the 2, 5-dibromothiophene to 60 ℃, heating the 1,3, 5-tribromobenzene to 100 ℃, and keeping the reaction for 30 min;
thirdly, keeping introducing gas after the reaction is finished, immediately stopping heating, removing a heating source for rapid cooling, taking out the copper foil after the temperature is reduced to room temperature, and transferring the polythiophene two-dimensional film to SiO by using a wet method2On the/Si substrate, a layer of film which is a polythiophene two-dimensional film is observed on the surface of the substrate, the optical microscope photograph is shown as fig. 2, the atomic force microscope photograph is shown as fig. 3, the transmission electron microscope photograph and the selected area diffraction result are shown as fig. 4, the Raman spectrum result is shown as fig. 5, the X-ray photoelectron spectrum result is shown as fig. 6, and the ultraviolet visible absorption spectrum result is shown as fig. 7, so that the obtained film is proved to be the polythiophene two-dimensional film.
Example 2
In the first step, 2, 5-dibromothiophene, 2,3, 5-tribromothiophene and annealed copper foil (1 × 2 cm)2) Respectively placed in the proper positions in the quartz tubes, the quartz tubes are put into the electric furnace, the monomers are aligned to the center of the heating zone at the upstream of the electric furnace, and the copper foil is aligned to the center of the heating zone at the downstream, as shown in fig. 1. Continuously introducing 150sccmH2And 30 sccmAr, and maintaining for 20 min to remove the air in the tube and stabilize the atmosphere;
secondly, heating the copper foil to 200 ℃, then heating the 2, 5-dibromothiophene to 60 ℃, heating the 2,3, 5-tribromothiophene to 70 ℃, and keeping the reaction for 30 min;
thirdly, keeping introducing gas after the reaction is finished, immediately stopping heating, removing a heating source for rapid cooling, taking out the copper foil after the temperature is reduced to room temperature, and transferring the polythiophene two-dimensional film to SiO by using a wet method2On a/Si substrate, a thin film was observed on the surface of the substrateThe film was a polythiophene two-dimensional film, and the optical micrograph thereof is shown in fig. 8.
Example 3
In the first step, 2, 5-dibromothiophene, tetrabromothiophene and annealed copper foil (1X 2 cm)2) Respectively placed in the proper positions in the quartz tubes, the quartz tubes are put into the electric furnace, the monomers are aligned to the center of the heating zone at the upstream of the electric furnace, and the copper foil is aligned to the center of the heating zone at the downstream, as shown in fig. 1. Continuously introducing 150sccmH2And 30 sccmAr, and maintaining for 20 min to remove the air in the tube and stabilize the atmosphere;
secondly, heating the copper foil to 200 ℃, then heating the 2, 5-dibromothiophene to 60 ℃, heating the tetrabromothiophene to 100 ℃, and keeping the reaction for 30 min;
thirdly, keeping introducing gas after the reaction is finished, immediately stopping heating, removing a heating source for rapid cooling, taking out the copper foil after the temperature is reduced to room temperature, and transferring the polythiophene two-dimensional film to SiO by using a wet method2On the/Si substrate, a film on the surface of the substrate can be observed, the film is a polythiophene two-dimensional film, and an optical microscope photo is shown in FIG. 9.
The foregoing is merely an example of the present invention and various modifications and changes will occur to those skilled in the art. 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 present invention.
Claims (4)
1. A method for preparing a molecular-level thickness polythiophene two-dimensional film is characterized by adopting a method combining surface-assisted Ullmann coupling reaction and chemical vapor deposition, and comprises the following specific steps:
(1) placing the metal substrate subjected to annealing treatment in a chemical vapor deposition reaction system, and continuously introducing specific airflow to stabilize the atmosphere;
(2) respectively heating the monomer and the metal substrate to the required reaction temperature for reaction;
(3) stopping heating, taking out the metal substrate after the system is cooled to room temperature, obtaining a polythiophene two-dimensional film on the metal substrate, and transferring the polythiophene two-dimensional film to a required substrate by a wet method;
wherein the monomer is dihalogen thiophene and polyhalogenated aromatic hydrocarbon, and the molar ratio of the two is 100:1 to 1: 10;
the introduced gas flow is inert gas and reducing gas, and the gas flow is 1-1000 ml per minute; the flow volume ratio of the inert gas to the reducing gas is 100:1 to 1: 100;
the polyhalogenated aromatic hydrocarbon is selected from 1,3, 5-tribromobenzene, 2,3, 5-tribromothiophene, 1,3, 5-trichloropyridine and tetrabromothiophene;
the metal substrate is a catalytic substrate, and the catalytic substrate is selected from gold, silver, copper or iron;
heating dihalothiophene at 30-100 ℃, polyhalogenated aromatic hydrocarbon at 40-150 ℃ and substrate at 150-400 ℃; the reaction time is 1-60 minutes.
2. The method according to claim 1, wherein the dihalothiophene is selected from the group consisting of 2, 5-dibromothiophene and 2, 3-dibromothiophene.
3. The method according to claim 1, wherein the inert gas is selected from argon and nitrogen, and the reducing gas is hydrogen.
4. A two-dimensional film of polythiophene having a molecular thickness, which is produced by the production method according to any one of claims 1 to 3.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0987849A (en) * | 1995-09-29 | 1997-03-31 | Fujitsu Ltd | Production of conjugated polymer film and conjugated organic polymer film |
| CN102219773A (en) * | 2010-04-16 | 2011-10-19 | 中国科学院化学研究所 | X-type two-dimensional or three-dimensional conjugated molecules based on oligomerized thiophene as well as preparation method and application thereof |
| CN103824615A (en) * | 2014-02-18 | 2014-05-28 | 南京邮电大学 | Method for preparing flexible transparent electrode through vapor phase polymerization poly(3,4-ethylenedioxythiophene) and graphene lamination |
| CN104525049A (en) * | 2013-12-30 | 2015-04-22 | 北京大学 | Reaction container and method for preparing composite material by filling polyethylenedioxythiophene |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0987849A (en) * | 1995-09-29 | 1997-03-31 | Fujitsu Ltd | Production of conjugated polymer film and conjugated organic polymer film |
| CN102219773A (en) * | 2010-04-16 | 2011-10-19 | 中国科学院化学研究所 | X-type two-dimensional or three-dimensional conjugated molecules based on oligomerized thiophene as well as preparation method and application thereof |
| CN104525049A (en) * | 2013-12-30 | 2015-04-22 | 北京大学 | Reaction container and method for preparing composite material by filling polyethylenedioxythiophene |
| CN103824615A (en) * | 2014-02-18 | 2014-05-28 | 南京邮电大学 | Method for preparing flexible transparent electrode through vapor phase polymerization poly(3,4-ethylenedioxythiophene) and graphene lamination |
Non-Patent Citations (1)
| Title |
|---|
| "Step-by-step growth of epitaxially aligned polythiophene by surface-confined reaction";J. A. Lipton-Duffin et al;《PNAS》;20100622;第107卷(第25期);第11200-11203页 * |
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