Two-dimensional covalent polymer carbon skeleton polymer film and preparation method and application thereof
阅读说明：本技术 二维共价聚合物碳骨架聚合物薄膜及其制备方法与应用 (Two-dimensional covalent polymer carbon skeleton polymer film and preparation method and application thereof ) 是由 胡文平 张紫超 董焕丽 甄永刚 于 2019-04-02 设计创作，主要内容包括：本发明公开了一种二维共价碳骨架聚合物薄膜及其制备方法与应用。本发明主要是将二炔基有机化合物作为单体,在金属基底上加热并光照,得到全碳聚合物薄膜。将金属基底刻蚀,聚合物薄膜清洗,转移到器件测试的基底上,测得材料的电子学性质。本发明制备的全碳聚合物薄膜厚度在30～500nm之间,迁移率相较其他炔类二维聚合物提高两到三个数量级。且制备过程不需要真空度,反应温度在200～300℃之间。(The invention discloses a two-dimensional covalent carbon skeleton polymer film and a preparation method and application thereof. The invention mainly uses a dialkynyl organic compound as a monomer, and the full carbon polymer film is obtained by heating and illuminating on a metal substrate. And etching the metal substrate, cleaning the polymer film, transferring the polymer film onto a substrate for device testing, and measuring the electronic property of the material. The thickness of the all-carbon polymer film prepared by the method is 30-500nm, and the mobility is improved by two to three orders of magnitude compared with other alkyne two-dimensional polymers. The preparation process does not need vacuum degree, and the reaction temperature is 200-300 ℃.)
1. A method of making a two-dimensional covalent carbon backbone polymer, comprising:
activating a substrate, and then adding a compound shown in a formula II to perform a polymerization reaction, so as to obtain the two-dimensional covalent carbon skeleton polymer on the substrate;
in the formula II, R1Is halogen, H, -Si (CH)3)3、
R2Is composed of-Si(CH3)3、H、
R3Is halogen, -CCH, -O (CH)2)3CH3or-O (CH)2)5CH3；
R4Is H or-CCH;
R5is H or-CCH;
R6is H or-CCH.
2. The method of claim 1, wherein: the substrate is a metal substrate; specifically, any one selected from copper, silver and gold;
in the activation step, the activation temperature is 900-1200 ℃; in particular 1050 ℃; the time is 0.5 to 3 hours; in particular 1 h; the activating atmosphere is hydrogen and argon mixed gas; the volume percentage concentration of the hydrogen is 5-20%; more specifically 10%;
before the activating step, the method also comprises the steps of cleaning the substrate and drying; in the cleaning step, the cleaning agent consists of water, ethanol and acetic acid; the volume ratio of the water to the ethanol to the acetic acid is specifically 1: 1: 1;
in the blow-drying step, the used gas is argon.
3. The method according to claim 1 or 2, characterized in that: in the step of polymerization reaction, the temperature is 200-300 ℃; in particular 220 ℃; the time is 1-10 hours; in particular 7 h; the polymerization atmosphere is inert atmosphere; specifically argon atmosphere; the illumination condition is full spectrum illumination;
the method further comprises the following steps: cooling the system after the polymerization step;
in the cooling step, the cooling mode is natural cooling.
4. A method according to any one of claims 1-3, characterized in that: the compound shown in the formula II is any one of the following compounds:
5. a two-dimensional covalent carbon skeleton polymer or a two-dimensional covalent carbon skeleton polymer film produced by the method according to any one of claims 1 to 4.
6. The film of claim 5, wherein: the thickness of the film is 30-500 nm.
7. Use of a two-dimensional covalent carbon-backbone polymer or a two-dimensional covalent carbon-backbone polymer thin film according to claim 5 in the preparation of an organic field effect transistor;
an organic field effect transistor comprising the two-dimensional covalent carbon skeleton polymer or the two-dimensional covalent carbon skeleton polymer thin film according to claim 5 as an organic semiconductor layer.
8. A compound of the formula IIa, wherein,
in the formula IIa, RaIs Cl, Br or I.
9. A process for preparing a compound of formula IIa as claimed in claim 8, comprising:
carrying out substitution reaction on a compound shown as a formula III, a chlorine-containing compound, a bromine-containing compound or an iodine-containing compound and a catalyst in an organic solvent to obtain the compound;
10. the method of claim 9, wherein: the bromine-containing compound is NBS;
the chlorine-containing compound is NCS;
the iodine containing compound is NIS;
the catalyst is DBU or AgNO3And TBAF;
the feeding molar ratio of the chlorine-containing compound, the bromine-containing compound or the iodine-containing compound to the formula III is 1.0-3.2: 1; specifically 2.0: 1;
the feeding molar ratio of the catalyst to the formula III is 1.0-3.2; specifically 2.0: 1;
the organic solvent is acetonitrile;
in the step of substitution reaction, the temperature is 20-40 ℃; in particular 25 ℃; the time is 0.5 to 3 hours; specifically 1 hour; the quenching agent is water;
the method further comprises the following steps: extracting the reaction system after the substitution reaction, collecting an organic phase, and performing column chromatography;
in particular, the method comprises the following steps of,
in the extraction step, the used extracting agent is dichloromethane, trichloromethane or ethyl acetate;
in the step of column chromatography, a solvent is n-hexane or n-pentane; the mesh number of the silica gel is 200 meshes and 400 meshes.
Technical Field
The invention belongs to the field of organic two-dimensional semiconductor materials, and particularly relates to a two-dimensional covalent carbon skeleton polymer film, and a preparation method and application thereof.
Background
Graphene was first discovered in 1962 (H.P.Boehm, A.Clauss, G.O.Fischer, U.S. Hofmann, Zeitschrift Fur Anorganische Und Allgemeine Chemie,316(1962) 119-), and was re-exfoliated and characterized in 2004 (K.S.Novoselov, A.K.Geim, S.V.Morozov, D.Jiang, Y.Zhang, S.V.Dubonos, I.V.Grigaoveva, A.A.Firsov, science.306(2004): 666- -669), scientists found graphene to have extraordinary mechanical properties (C.Lee, X.D.Weii, J.W.Kysiar, J.Hone, Science 321, 385), optical properties (R.R.Blaker, J.Blaker, J.2008, J.S.O.J.R.J.S.S.W.J.S.D. K. 2008, S.S.D. 12, N.S.S.S.O.D. 12-, (R.S.S.S.S.S.S.S.S.S.O.S.S. Bazov.. 12), and (R.S.S.S.S.S.S.S.J.S.S.S.S.S.S. Pat. 7. No. (Navoseo.320), S.D. 7. 10, S.S.S.J.S.S.J.S.S.S. 14), and (S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S.S. 14. 10. As.S.S.S.S.S.S.. Graphene is therefore also considered to be a very potential two-dimensional electronic device material of The next generation and has acquired The Nobel Prize of Physics 2010 ("The Nobel Prize in Physics 2010".
However, in the actual synthesis process of graphene by using the chemical vapor deposition method, the interior of graphene is composed of small crystal grains, so that many crystal boundaries exist, and therefore, the synthesis of graphene in a large area becomes a challenge in the current scientific community. In addition to trying to find ways to reduce grain boundary formation, scientists have conducted extensive research to explore two-dimensional conjugated polymers other than graphene, such as graphyne. However, the mobility of the graphite alkyne reported at present is up to 6.25cm2V-1s-1(j, Zhou, z.xie, r.liu, x.gao, j.li, y.xiong, l.tong, j.zhang, z.liu, ACS appl.mater. Interfaces,11(2019), 2632). The other type of conjugated polymer formed by organic small molecule coupling through Ullmann reaction on the metal surface has the reaction temperature of over 400 ℃ generally, and the formation of a more ordered film requires reaction in an ultrahigh vacuum environment, so that the cost of industrial production is high. In either of the above methods, the large-area production of two-dimensional covalent polymer films is a great challenge.
Disclosure of Invention
The invention aims to provide a two-dimensional covalent carbon skeleton polymer film and a preparation method and application thereof.
The invention provides a method for preparing a two-dimensional covalent carbon skeleton polymer, which comprises the following steps:
activating a substrate, and then adding a compound shown in a formula II to perform a polymerization reaction, so as to obtain the two-dimensional covalent carbon skeleton polymer on the substrate;
in the formula II, R1Is halogen, H, -Si (CH)3)3、
R2Is composed of-Si(CH3)3、H、
R3Is halogen, -CCH, -O (CH)2)3CH3or-O (CH)2)5CH3；
R4Is H or-CCH;
R5is H or-CCH;
R6is H or-CCH.
In the above method, the substrate is a metal substrate; specifically, any one selected from copper, silver and gold;
in the activation step, the activation temperature is 900-1200 ℃; in particular 1050 ℃; the time is 0.5 to 3 hours; specifically 1 h; the activating atmosphere is hydrogen and argon mixed gas; the volume percentage concentration of the hydrogen is 5-20%; more specifically 10%;
before the activating step, the method also comprises the steps of cleaning the substrate and drying; in the cleaning step, the cleaning agent consists of water, ethanol and acetic acid; the volume ratio of the water to the ethanol to the acetic acid is specifically 1: 1: 1;
in the blow-drying step, the used gas is argon.
In the step of polymerization reaction, the temperature is 200-300 ℃; in particular 220 ℃; the time is 1-10 hours; the specific time is 7 h; the polymerization atmosphere is inert atmosphere; specifically argon atmosphere; the illumination condition is full spectrum illumination;
specifically, the polymerization reaction comprises two steps of coupling reaction (scientific name: Click coupling reaction and Ullmann coupling reaction) and topological polymerization reaction which occur in sequence; the coupling reaction time can be specifically 1.5 h; the time of the topological coupling polymerization reaction can be specifically 5.5 h;
the method further comprises the following steps: cooling the system after the polymerization step;
in the cooling step, the cooling mode is natural cooling.
Specifically, the compound shown in the formula II is any one of the following compounds:
the above compounds are commercially available from a variety of publicly available sources.
In addition, the two-dimensional covalent carbon skeleton polymer or the two-dimensional covalent carbon skeleton polymer film prepared by the method also belongs to the protection scope of the invention.
Specifically, the thickness of the film is 30-500 nm.
The application of the two-dimensional covalent carbon skeleton polymer or the two-dimensional covalent carbon skeleton polymer film provided by the invention in preparing an organic field effect transistor and the organic field effect transistor using the two-dimensional covalent carbon skeleton polymer or the two-dimensional covalent carbon skeleton polymer film as an organic semiconductor layer also belong to the protection scope of the invention.
The invention also claims compounds of intermediate formula IIa,
in the formula IIa, RaIs Cl, Br or I.
The invention provides a method for preparing the compound shown in the formula IIa, which comprises the following steps:
carrying out substitution reaction on a compound shown as a formula III, a chlorine-containing compound, a bromine-containing compound or an iodine-containing compound and a catalyst in an organic solvent to obtain the compound;
in the above method, the bromine-containing compound is NBS;
the chlorine-containing compound is NCS;
the iodine containing compound is NIS;
the catalyst is DBU or AgNO3And TBAF; wherein, when a bromine-containing compound or a chlorine-containing compound is used, the catalyst is DBU; when iodine-containing compounds are used, the corresponding catalyst is AgNO3And TBAF;
the feeding molar ratio of the chlorine-containing compound, the bromine-containing compound or the iodine-containing compound to the formula III is 1.0-3.2: 1; specifically 2.0: 1;
the feeding molar ratio of the catalyst to the formula III is 1.0-3.2; specifically 2.0: 1;
the organic solvent is acetonitrile;
in the step of substitution reaction, the temperature is 20-40 ℃; in particular 25 ℃; the time is 0.5 to 3 hours; specifically 1 hour; the quenching agent is water;
the method further comprises the following steps: extracting the reaction system after the substitution reaction, collecting an organic phase, and performing column chromatography;
in particular, the method comprises the following steps of,
in the extraction step, the used extracting agent is dichloromethane, trichloromethane or ethyl acetate;
in the step of column chromatography, a solvent is n-hexane or n-pentane; the mesh number of the silica gel is 200 meshes and 400 meshes.
The invention provides a simple and feasible molecular improvement method for synthesizing a large-area two-dimensional organic all-carbon covalent structure film with semiconductor properties at a lower temperature. The invention mainly uses a dialkynyl organic compound as a monomer, and the full carbon polymer film is obtained by heating and illuminating on a metal substrate. And etching the metal substrate, cleaning the polymer film, transferring the polymer film to a substrate for device testing, and measuring the electronic property of the material. The thickness of the all-carbon polymer film prepared by the method is 30-500nm, and the mobility is improved by two to three orders of magnitude compared with other alkyne two-dimensional polymers. The preparation process does not need vacuum degree, and the reaction temperature is 200-300 ℃. The method has a great guiding effect on the development of novel graphene-like materials, the reduction of reaction cost and other practical applications.
Drawings
FIG. 1 shows the NMR spectrum of monomeric BEEB.
FIG. 2 is a nuclear magnetic resonance carbon spectrum of monomeric BEEB.
FIG. 3 is a crystal structure of a mono-substituted bromine monomer in three directions.
FIG. 4 shows (a) the surface topography and the corresponding height map of the polymer pBEEB film and (b) the atomic force microscope photograph of the polymer pBBEB film after transfer to a silicon wafer.
FIG. 5 is a photograph of a pBEEB film under a scanning electron microscope.
FIG. 6 (a) is a comparison of the IR spectra before and after the reaction between the monomer BEEB and the polymer pBEEB; (b) the infrared spectrograms before and after the reaction of the monomer BBEB and the polymer pBBEB are compared.
FIG. 7 is a graph of (a) XPS surfey on copper foil after reaction of polymer pBEEB; (b) XPS profile for C1 s; (c) XPS surfey curve on copper foil after reaction of polymer pBBEB; (d) XPS curve for C1 s.
FIG. 8 is an XPS survey plot of the polymer pBEEB after transfer to a silicon wafer to make a device.
FIG. 9 shows the reaction scheme for the synthesis of the monomers BEEB and BBEB.
FIG. 10 is a schematic diagram of the polymerization reaction process between BEEB and BBEB.
Fig. 11 is (a) a schematic diagram of an OFET device structure; (b) an optimal performance OFET transfer curve; (c) an OFET output curve with optimal performance; (d) statistical plot of the performance of 20 OFET devices.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
- 上一篇：一种医用注射器针头装配设备
- 下一篇：一种液体丁基橡胶及其制备方法