CN108794779A - A kind of preparation method of molecular level thickness polythiophene two-dimensional film - Google Patents
A kind of preparation method of molecular level thickness polythiophene two-dimensional film Download PDFInfo
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- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
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- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C08G2261/10—Definition of the polymer structure
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- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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Abstract
The invention belongs to two-dimensional material preparing technical fields, the specially preparation method of molecular level thickness polythiophene two-dimensional film.The method of the present invention includes：First, monomer and the metal substrate by making annealing treatment are put into chemical gas-phase deposition system, monomer and substrate is made to reach the reaction temperature of needs under particular airflow, react certain time；Then, substrate is taken out after system cooling, obtains polythiophene two-dimensional film on substrate.The preparation method of the present invention is simple for process, and reaction temperature is low, of low cost, is suitable for large-scale production, and due to the surface confinement effect of metal catalytic substrate, prepared polythiophene film has molecular level thickness.
Description
Technical field
The invention belongs to two-dimensional material preparing technical fields, and in particular to the preparation of molecular level thickness polythiophene two-dimensional film
Method.
Background technology
Polythiophene is a kind of common conjugated polymer, first using Organometallic Reac- tion in 1980 by Yamamoto et al.
It first prepares, due to setting between good electric conductivity and structure and performance after the semiconductor property of its eigenstate and doping
Meter property, it is interested to researchers.The most common preparation method of polythiophene is electrochemical polymerization and chemical polymerization, and when use is usual
It obtains that there is certain thickness polythiophene film with the methods of spin coating, instillation, lifting, is widely used in organic effect crystal
The fields such as pipe, organic solar batteries, ultracapacitor.
Chemical vapour deposition technique is a kind of deposition technique very common in semi-conductor industry, and principle is will be a kind of or more
Kind of gaseous material introduces reative cell and is chemically reacted, and obtains a kind of new material and is deposited on substrate surface.Surface assists Wu Er
Graceful coupling reaction（SurfaceassistedUllmanncoupling）It is a kind of surface catalysis technology of rising in recent years, it is former
Reason is using the boundary between metal substrate and reactant with catalytic activity as reacting environment, strictly by chemical reaction
The position for being limited in substrate surface molecular level thickness carries out, to accurately control chemical reaction process and product.But at present
There are no assist Liv Ullmann coupling reaction to prepare by surface auxiliary chemical vapor deposition method or surface to have large area molecule ruler
Spend the report of thickness polythiophene two-dimensional film.
Invention content
The purpose of the present invention is to provide it is a kind of it is simple for process, reaction temperature is low, low-cost molecular level（That is molecule ruler
Degree）The preparation method of thickness polythiophene two-dimensional film.
The preparation method of molecular level thickness polythiophene two-dimensional film provided by the invention is even using surface auxiliary Liv Ullmann
Connection reaction is combined with chemical vapour deposition technique, is as follows：
（1）It will be placed in chemical vapour deposition reaction system by the metal substrate of annealing, and be continually fed into specific gas
Stream, makes atmosphere stablize；
（2）Monomer and substrate are separately heated to required reaction temperature, reacted；
（3）Stop heating, after system is cooled to room temperature, takes out substrate, obtain polythiophene two-dimensional film on substrate, pass through
" wet method " is transferred to required substrate.
Wherein, the monomer is dihalothiophene and polyhalo aromatic hydrocarbons, and the two dosage molar ratio is 100:1 to 1:10；
Both preferential dosage molar ratio is 10:1 to 1:5.
The air-flow being passed through is inert gas and reducibility gas, and gas flow is 1 ~ 1000 milliliter per minute.The indifferent gas
Body such as argon gas, nitrogen, the reducibility gas such as hydrogen；The volume ratio of inert gas and reducibility gas flow is 100:1 to
1:100；It is preferred that the volume ratio of the two flow is 10:1 to 1:10.
In the present invention, the dihalothiophene is selected from 2,5- dibromo thiophenes, 2,3- dibromo thiophenes etc., the polyhalo aromatic hydrocarbons
Selected from 1,3,5- tribromo-benzenes, tri- bromothiophenes of 2,3,5-, 1,3,5- trichloropyridines, tetrabromothiophene etc..
In the present invention, the metal substrate is selected from the catalytic substrates such as gold, silver, copper or iron.
In the present invention, dihalothiophene heating temperature is 30 ~ 100 DEG C, and polyhalo aromatic hydrocarbons heating temperature is 40 ~ 150 DEG C, lining
Bottom heating temperature is 150 ~ 400 DEG C, and the reaction time is 1 ~ 60 minute.
In the present invention, " wet method " transfer is identical as graphene transfer technology, can refer to document Science,
2009 (5932), 324,1312-1314 (doi: 10.1126/science.1171245)。
The present invention is combined chemical vapour deposition technique with surface auxiliary Liv Ullmann coupling reaction, in chemical gas-phase deposition system
In by the way that reaction monomers are gasified, and metal substrate is made to be heated to certain temperature, the generation of catalytic surface chemical reaction, in substrate
On obtain large area polythiophene two-dimensional film.The preparation method of the present invention is simple for process, and reaction temperature is low, of low cost, is applicable in
In large-scale production；And due to the surface confinement effect of metal catalytic substrate, prepared polythiophene film has molecular level thick
Degree.
Description of the drawings
The surfaces Fig. 1 assistant chemical vapor deposition device schematic diagram.
Fig. 2 is the optical microscope photograph of gained in embodiment 1.
Fig. 3 is the atomic force microscopy of gained in embodiment 1.
Fig. 4 is the transmission electron microscope photo of gained, selected diffraction in embodiment 1.
Fig. 5 is the Raman spectrum result of gained in embodiment 1.
Fig. 6 is the x-ray photoelectron spectroscopy result of gained in embodiment 1.
Fig. 7 is the ultraviolet-visible absorption spectroscopy result of gained in embodiment 1.
Fig. 8 is the optical microscope photograph of gained in embodiment 2.
Fig. 9 is the optical microscope photograph of gained in embodiment 3.
Specific implementation mode
It is further illustrated the present invention below in conjunction with attached drawing and following embodiments, it is thus understood that, following embodiments are only used
In illustrating the present invention, it is not intended to limit the present invention.
Embodiment 1
The first step, by 2,5- dibromo thiophenes（Monomer 1）, 1,3,5- tribromo-benzenes（Monomer 2）With the copper foil by annealing（1×
2cm2）It is individually positioned in suitable position in quartz ampoule, quartz ampoule is put into electric furnace, is made in monomer alignment electric furnace heated upstream area
The heart, copper foil are directed at downstream and heat district center, as shown in Figure 1.It is continually fed into 150sccmH2With 30 sccmAr, and keep 20 min
It removes air in tube and atmosphere is made to stablize；
Second step first heats copper foil to 200 DEG C, then heats 2,5- dibromo thiophenes to 60 DEG C, heats 1,3,5- tribromo-benzenes to 100
DEG C, keep reaction 30min；
Third walks, and after the completion of reaction, holding is passed through gas, stops heating immediately and removes heating source fast cooling, waits near room
Wen Hou takes out copper foil, uses " wet method " that polythiophene two-dimensional film is transferred to SiO2On/Si substrates, it is observed that substrate table
There is thin film in face, which is polythiophene two-dimensional film, and optical microscope photograph is as shown in Fig. 2, atomic force microscopy
As shown in figure 3, the results are shown in Figure 4 for transmission electron microscope photo, selected diffraction, the results are shown in Figure 5 for Raman spectrum, and X is penetrated
The results are shown in Figure 6 for photoelectron spectra, and the results are shown in Figure 7 for ultraviolet-visible absorption spectroscopy, it was demonstrated that gained film is polythiophene
Two-dimensional film.
Embodiment 2
The first step, by 2,5- dibromo thiophenes, 2,3,5- tri- bromothiophenes and the copper foil by making annealing treatment（1×2cm2）It places respectively
The suitable position in quartz ampoule, quartz ampoule is put into electric furnace, so that monomer is directed at electric furnace heated upstream district center, under copper foil alignment
Trip heating district center, as shown in Figure 1.It is continually fed into 150sccmH2With 30 sccmAr, and keep 20 min remove air in tube
And atmosphere is made to stablize；
Second step first heats copper foil to 200 DEG C, then heats 2,5- dibromo thiophenes to 60 DEG C, 2,3,5- of heating, tri- bromothiophenes are extremely
70 DEG C, keep reaction 30min；
Third walks, and after the completion of reaction, holding is passed through gas, stops heating immediately and removes heating source fast cooling, waits near room
Wen Hou takes out copper foil, uses " wet method " that polythiophene two-dimensional film is transferred to SiO2On/Si substrates, it is observed that substrate table
There is thin film in face, which is polythiophene two-dimensional film, and optical microscope photograph is as shown in Figure 8.
Embodiment 3
The first step, by 2,5- dibromo thiophenes, tetrabromothiophene and the copper foil by making annealing treatment（1×2cm2）It is individually positioned in quartz
Suitable position in pipe, quartz ampoule is put into electric furnace, and monomer is made to be directed at electric furnace heated upstream district center, and copper foil is directed at downstream heating
District center, as shown in Figure 1.It is continually fed into 150sccmH2With 30 sccmAr, and keep 20 min to remove air in tube and making gas
Atmosphere is stablized；
Second step first heats copper foil to 200 DEG C, then heats 2,5- dibromo thiophenes to 60 DEG C, heating tetrabromothiophene to 100 DEG C,
Keep reaction 30min；
Third walks, and after the completion of reaction, holding is passed through gas, stops heating immediately and removes heating source fast cooling, waits near room
Wen Hou takes out copper foil, uses " wet method " that polythiophene two-dimensional film is transferred to SiO2On/Si substrates, it is observed that substrate table
There is thin film in face, which is polythiophene two-dimensional film, and optical microscope photograph is as shown in Figure 9.
Above are only the embodiment of the present invention, it will be apparent to those skilled in the art that the present invention there are many change and
Variation.It is all the present invention thought and principle in, make all any modification, equivalent and improvement etc., the present invention should all be included in
Protection domain within.
Claims (6)
1. a kind of preparation method of molecular level thickness polythiophene two-dimensional film, which is characterized in that be to assist Liv Ullmann using surface
The method that coupling reaction is combined with chemical vapor deposition, is as follows：
（1）It will be placed in chemical vapour deposition reaction system by the metal substrate of annealing, and be continually fed into specific gas
Stream, makes atmosphere stablize；
（2）Monomer and metal substrate are separately heated to required reaction temperature, reacted；
（3）Stop heating, after system is cooled to room temperature, takes out metal substrate, it is thin to obtain polythiophene two dimension on the metallic substrate
Film is transferred to required substrate by " wet method "；
Wherein, the monomer is dihalothiophene and polyhalo aromatic hydrocarbons, and the two dosage molar ratio is 100:1 to 1:10；
The air-flow being passed through is inert gas and reducibility gas, and gas flow is 1 ~ 1000 milliliter per minute；Inert gas and
The flow volume ratio of reducibility gas is 100:1 to 1:100.
2. preparation method according to claim 1, which is characterized in that the dihalothiophene be selected from 2,5- dibromo thiophenes,
2,3- dibromo thiophenes, the polyhalo aromatic hydrocarbons are selected from 1,3,5- tribromo-benzenes, 2,3,5- tri- bromothiophenes, 1,3,5- trichloropyridines, four
Bromothiophene.
3. preparation method according to claim 1, which is characterized in that the metal substrate be selected from gold, silver, copper or iron this
A little catalytic substrates.
4. preparation method according to claim 1, which is characterized in that the inert gas is selected from argon gas, nitrogen, described to go back
Originality gas is hydrogen.
5. the preparation method according to one of claim 1 ~ 4, which is characterized in that dihalothiophene heating temperature be 30 ~
100 DEG C, be 40 ~ 150 DEG C to polyhalo aromatic hydrocarbons heating temperature, is 150 ~ 400 DEG C to substrate heating temperature；Reaction time is 1 ~ 60
Minute.
6. the molecular level thickness polythiophene two-dimensional film being prepared by one of claim 1 ~ 5 preparation method.
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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 |
-
2018
- 2018-04-09 CN CN201810309284.0A patent/CN108794779B/en active Active
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 |
|---|
| J. A. LIPTON-DUFFIN ET AL: ""Step-by-step growth of epitaxially aligned polythiophene by surface-confined reaction"", 《PNAS》 * |
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