WO2018176995A1 - Method for preparing composite field-effect transistor - Google Patents

Method for preparing composite field-effect transistor Download PDF

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Publication number
WO2018176995A1
WO2018176995A1 PCT/CN2018/072964 CN2018072964W WO2018176995A1 WO 2018176995 A1 WO2018176995 A1 WO 2018176995A1 CN 2018072964 W CN2018072964 W CN 2018072964W WO 2018176995 A1 WO2018176995 A1 WO 2018176995A1
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polymer
graphene
composite
dispersion
effect transistor
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PCT/CN2018/072964
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French (fr)
Chinese (zh)
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吴雨辰
刘芸
江雷
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北京赛特超润界面科技有限公司
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Publication of WO2018176995A1 publication Critical patent/WO2018176995A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass

Definitions

  • the invention belongs to the field of microelectronic devices. Specifically, a non-covalent adsorption between graphene and a polymer provides a simple and efficient method for preparing a high performance composite field effect transistor.
  • the organic-effect transistor based on conjugated polymer molecules has attracted wide attention in low-cost, flexible, large-area electrical devices such as integrated circuits, pressure sensors, organic memory components, etc.
  • the molecular chain of polymers is relatively Large, highly imaged liberalization and irregular interchain entanglement reduce their mobility and thus the electrical performance of the device.
  • the performance of polymer field effect transistors can be improved by optimizing their molecular structure, the effect is not significant.
  • molecules with high electric field mobility such as graphene, carbon nanotubes, and the like may be added thereto.
  • the valence band and the conduction band are symmetrically distributed above and below the Fermi level, and the intersection of the Dirac points coincides.
  • the transmission of electrons in the graphene follows the Dirac equation and the whole graphite.
  • Each ⁇ bond in the molecular structure of the olefin is conjugated to each other to form a large conjugated large ⁇ bond.
  • the electron or hole can move at a high electron Fermi rate in such a large conjugate system, exhibiting zero mass behavior.
  • the carrier mobility can reach 2 ⁇ 10 5 cm 2 V -1 s -1 , and it has electron conduction phenomena such as room temperature quantum echo effect and quantum tunneling effect.
  • the molecular chain of the polymer is large, the height of the conformation is liberalized, and the irregular interchain entanglement reduces the mobility, which in turn affects the electrical properties of the device.
  • the polymer molecules are adsorbed on the surface of the graphene molecules to form a polymer-graphene composite structure, and then
  • the silicon structure of the column structure can prepare a polymer-graphene composite structure nanowire with a large-area direction controllable and accurate positioning, and can be transferred to a specific substrate for device application.
  • the composite dispersion is added to a silicon wafer having a microcolumn structure and covered with a flat substrate, so that the polymer-graphene composite self-assembles into a regular one-dimensional array at the top of the microcolumn to form a polymerization.
  • Field effect transistor
  • step 2) after suction filtration, the filter residue is rinsed using the same organic solvent as in step 1), and then filtered again, and repeatedly filtered and rinsed to remove excess polymerization.
  • Object molecule the filter residue is rinsed using the same organic solvent as in step 1), and then filtered again, and repeatedly filtered and rinsed to remove excess polymerization.
  • the concentration of the polymer solution in step 1) is 0.01-0.05 Mg/mL; the mass ratio of graphene to polymer in the mixed dispersion is about 1:0.05 to 1:1.
  • the present invention is applicable to various polythiophene p-type conjugated polymers such as, but not limited to, polyalkylthiophene (P3AT); or polyacene compounds such as naphthalene and anthracene. , tetracene, pentacene, hexacene; or a conjugated system containing a hetero atom.
  • P3AT polyalkylthiophene
  • polyacene compounds such as naphthalene and anthracene.
  • tetracene pentacene, hexacene
  • conjugated system containing a hetero atom such as, but not limited to, polyalkylthiophene (P3AT)
  • P3AT polyalkylthiophene
  • acene compounds such as naphthalene and anthracene.
  • tetracene pentacene, hexacene
  • conjugated system containing a hetero atom
  • the organic solvent of the step 1) is one or more of o-dichlorobenzene, tetrahydrofuran, dichloromethane, N,N-dimethylformamide and chlorobenzene.
  • the organic solvent of the step 1) is one or more of o-dichlorobenzene, tetrahydrofuran, dichloromethane, N,N-dimethylformamide and chlorobenzene.
  • the filtration membrane of step 2) may be a cellulose acetate membrane having a pore diameter of preferably 0.2 to 0.45. Mm.
  • an alumina filter may be used, and its pore diameter is preferably 0.02 to 0.2 ⁇ m.
  • step 2) drying is to remove residual organic solvent.
  • the drying method can be in a manner well known in the art. For example, the filter residue is placed in an oven at 80-120 ° C for thorough drying.
  • the organic solvent of the step 3) is one or more of DMF, tetrahydrofuran, dichloromethane, o-dichlorobenzene, chlorobenzene and the like.
  • Step 3) The added concentration of the polymer (complex dispersion concentration) 0.01 -0.1 mg/mL.
  • the spacing between the microcolumns in step 4) is 5-20 ⁇ m
  • the width of the microcolumn (width and length of the rectangular section) is 2-10 ⁇ m.
  • step 4) is to apply a dispersion of the polymer-graphene composite to a silicon wafer having a micro-pillar structure, and to cover a layer of the substrate to form a "sandwich" assembly structure.
  • the solution forms a continuous liquid film on the surface of the microcolumn.
  • the liquid film first ruptures at the microcolumn groove, thereby forming a parallel liquid bridge between the top of the microcolumn and the substrate, and the liquid bridge Gradually shrinking, after the solvent is completely volatilized, it will be observed that the polymer-graphene compound self-assembles at the top of the silicon column to form a large-area micron-scale one-dimensional array of micrometer-scale nano-scale, realizing the polymer-graphene Patterned assembly of composite materials.
  • the flat substrate of the step 4) may use a glass substrate, ITO or a conductive silicon wafer.
  • the invention utilizes a conjugate interaction force between a polymer molecule having a benzene ring structure and a two-dimensional crystal having a large ⁇ -conjugated system such as graphene to obtain a composite structure in which a polymer molecule is adsorbed on the surface of the graphene, and then the graphite is washed away. Excess polymer molecules on the surface of the olefin ensure that there are only a few polymer molecules on the surface of the graphene.
  • Graphene molecules encapsulated by polymer molecules can be uniformly dispersed in an organic solvent, dropped on a silicon wafer with micropillars and covered with a substrate to form a "sandwich" assembly structure in a silicon column (microcolumn)
  • Auxiliary, liquid bridge induction allows the molecules to self-assemble at the top of the column, ultimately forming a regular array of nanowires that can be transferred to the desired substrate.
  • the performance of the polymer-graphene composite structure field effect transistor prepared by the invention is significantly improved compared with the simple polymer field effect transistor, and the method is simple and convenient, and the cost is low.
  • the invention saves the amount of organic matter, thereby reducing the cost, and at the same time, the directional assembly of the material improves the performance of the device. Moreover, there is a significant increase in switching ratio and electron/hole mobility.
  • FIG. 1 is a schematic view showing a method of preparing a composite field effect transistor according to the present invention
  • a is a schematic diagram of fully adsorbing the graphene powder in a dilute solution of the polymer
  • b is an optical photograph of the polymer-graphene composite after filtration on the filter
  • c is a schematic diagram of preparing a polymer-graphene composite dispersion after dispersing the composite in an organic solvent
  • d is a schematic diagram of an assembly structure in which a uniformly dispersed droplet of a polymer-graphene composite structure is applied to a silicon wafer having a microcolumn structure and covered with a layer of a substrate to form a "sandwich";
  • e is a schematic diagram of forming a continuous liquid film between the template silicon wafer and the substrate;
  • f is a schematic diagram of a liquid bridge formed at the top of the silicon column
  • g is a schematic representation of a regular nanowire array formed by self-assembly at the top of a silicon column, wherein the enlarged portion shows a layered stack configuration of the polymer-graphene composite.
  • Example 2 is a schematic view of a polymer solution according to Example 1 of the present invention; wherein a is a polymer solution, and b is a mixed dispersion obtained by adding graphene to a polymer solution.
  • Figure 3 is a polymer-graphene composite dispersion of Example 1 of the present invention.
  • FIG. 4 is a schematic view of a microcolumn according to Embodiment 1 of the present invention.
  • Example 5 is an infrared characterization diagram of a polymer molecule, a graphene, and a polymer-graphene composite according to Example 2 of the present invention.
  • Figure 6 is an optical photograph of a filtered polymer-graphene composite on a filter membrane according to Example 2 of the present invention.
  • Example 7 is a performance test curve of a polymer-graphene composite dispersion according to Example 2 of the present invention; wherein a is a transfer characteristic curve and b is an output curve.
  • Example 8 is an infrared characterization diagram of a polymer molecule, a graphene, and a polymer-graphene composite according to Example 3 of the present invention.
  • Example 9 is a performance test curve of the polymer-graphene composite dispersion of Example 3 of the present invention; wherein a is a transfer characteristic curve and b is an output curve.
  • Figure 10 is an infrared characterization diagram of a polymer molecule, graphene, polymer-graphene composite of Example 4 of the present invention.
  • Figure 11 is a performance test curve of the polymer-graphene composite dispersion of Example 4 of the present invention; wherein a is a transfer characteristic curve and b is an output curve.
  • the method controls the re-wetting of the liquid film by forming a liquid bridge between the top end of the micro-column structure of the template silicon wafer and the substrate, thereby forming a one-dimensional structure of regular arrangement.
  • the template wafer needs to be selectively modified to obtain a template wafer with asymmetric wettability: the liquid at the top of the silicon column, the side wall of the silicon column and the liquid in the trench.
  • a uniformly dispersed droplet of the polymer-graphene composite structure was applied to a silicon wafer having a microcolumn structure, and a flat substrate was covered to form a "sandwich" assembly structure (Fig. 1d). Since the top of the silicon column is liquid, the liquid first forms a continuous liquid film between the template wafer and the substrate (Fig. 1e). As the solvent gradually evaporates, the amount of liquid also decreases, and finally the liquid film ruptures and forms a plurality of regular liquid strip regions. Because of the asymmetric wetting characteristics of the template wafer, a uniform dispersion of the polymer-graphene composite structure is adhered to the top of the lyophilic portion of the silicon column and forms a regular liquid bridge at the top of the silicon column (Fig.
  • the method controls the re-wetting of the liquid film by forming a liquid bridge between the top end of the micro-column structure of the template silicon wafer and the substrate, thereby forming a one-dimensional structure of regular arrangement.
  • the template wafer needs to be selectively modified to obtain a template wafer with asymmetric wettability: the liquid at the top of the silicon column, the side wall of the silicon column and the liquid in the trench.
  • a uniformly dispersed droplet of the polymer-graphene composite structure was applied to a silicon wafer having a microcolumn structure, and a flat substrate was covered to form a "sandwich" assembly structure (Fig. 1d). Since the top of the silicon column is liquid, the liquid first forms a continuous liquid film between the template wafer and the substrate (Fig. 1e). As the solvent gradually evaporates, the amount of liquid also decreases, and finally the liquid film ruptures and forms a plurality of regular liquid strip regions. Because of the asymmetric wetting characteristics of the template wafer, a uniform dispersion of the polymer-graphene composite structure is adhered to the top of the lyophilic portion of the silicon column and forms a regular liquid bridge at the top of the silicon column (Fig.
  • the cellulose acetate membrane (pore size 0.2) ⁇ m) is subjected to suction filtration, and is repeatedly rinsed with o-dichlorobenzene and filtered to remove excess polymer molecules on the surface of graphene, ensuring that only a small number of polymer molecules are adsorbed on the surface of graphene (infrared is used to characterize the presence of polymer molecules) .
  • the obtained composite powder was sufficiently dried in an oven at 80 ° C to remove residual o-dichlorobenzene solvent, and uniformly dispersed in DMF after drying to prepare a polymer-graphene composite structure uniform dispersion (0.08 mg/mL). (Fig. 3) for the preparation of subsequent molecular devices.
  • FIG. 7 An optical photograph of the polymer-graphene complex on the filter after suction filtration is shown in FIG.
  • the obtained composite powder was sufficiently dried in an oven at 80 ° C to remove residual o-dichlorobenzene solvent, and uniformly dispersed in DMF after drying to prepare a polymer-graphene composite structure uniform dispersion (0.08 mg/mL). In order to prepare the subsequent molecular device.
  • the performance test curve is shown in Figure 7.
  • FIG. 5 illustrates that the polymer molecule CDTBTZ of the present embodiment is successfully adsorbed on the surface of graphene.
  • a is a transfer characteristic curve of a device constructed based on a polymer-graphene composite
  • Fig. 7b is an output curve.
  • Figure 7 illustrates that the polymer-graphene composite has excellent electrical properties.
  • the obtained composite powder is sufficiently dried in an oven at 120 ° C to remove the residual chlorobenzene solvent, and after drying, it can be uniformly dispersed in tetrahydrofuran to prepare a polymer-graphene composite structure uniform dispersion (0.01 mg/mL), so that Preparation of subsequent molecular devices.
  • the performance test curve is shown in Figure 9.
  • FIG. 8 illustrates that the polymer molecule P3HT is successfully adsorbed on the graphene surface.
  • Figure 9a is a transfer characteristic curve of a device constructed based on a polymer-graphene composite
  • Figure 9b is an output curve.
  • Figure 9 illustrates that the polymer-graphene composite has excellent electrical properties.
  • the obtained composite powder was sufficiently dried in an oven at 100 ° C to remove residual o-dichlorobenzene solvent, and uniformly dispersed in tetrahydrofuran after drying to prepare a polymer/graphene composite structure uniform dispersion (0.1 mg/mL). In order to prepare the subsequent molecular device.
  • the performance test curve is shown in Figure 11.
  • FIG. 10 illustrates that the polymer molecule P3HT is successfully adsorbed on the graphene surface.
  • Figure 11a is a transfer characteristic curve of a device constructed based on a polymer-graphene composite, and Figure 11b is an output curve.
  • Figure 11 illustrates that the polymer-graphene composite has excellent electrical properties.
  • the performance of the polymer-graphene composite structure field effect transistor prepared by the invention is significantly improved compared with the simple polymer field effect transistor, and the method is simple and convenient, and the cost is low.
  • the invention saves the amount of organic matter, thereby reducing the cost, and at the same time, the directional assembly of the material improves the performance of the device. Moreover, there is a significant increase in switching ratio and electron/hole mobility.

Abstract

Disclosed is a method for preparing a composite field-effect transistor, comprising the following steps: 1) dissolving polymer molecules in an organic solvent to obtain a polymer solution, and immersing graphene in the polymer solution to obtain a mixed dispersion; 2) suction-filtering the mixed dispersion and cleaning same to obtain a graphene composite, wherein the polymer is adsorbed on the surface of same; 3) re-dispersing the graphene composite in the organic solvent to obtain a composite dispersion; and 4) dropwise adding the composite dispersion onto a silicon wafer having a microcolumn structure and covering same with a plate substrate, such that the polymer-graphene composite self-assembles into a regular one-dimensional array at the microcolumn position on the surface of the plate, so as to form a composite field-effect transistor. The performance of the prepared field-effect transistor of the polymer-graphene composite structure is significantly improved compared with that of the field-effect transistor with only a polymer. The method is simple and convenient, and the cost is low.

Description

一种制备复合物场效应晶体管的方法Method for preparing composite field effect transistor 技术领域Technical field
本发明属于微电子器件领域，具体地，通过石墨烯与聚合物之间的非共价吸附，提供了一种简单高效制备高性能复合物场效应晶体管的方法。The invention belongs to the field of microelectronic devices. Specifically, a non-covalent adsorption between graphene and a polymer provides a simple and efficient method for preparing a high performance composite field effect transistor.
背景技术Background technique
基于共轭聚合物分子的有机场效应晶体管在低成本、柔性、大面积电学器件如集成电路、压力传感器、有机存储元件等方面具有广泛的应用而受到人们的关注，然而聚合物的分子链较大，构像高度自由化以及不规则的链间缠绕现象会降低其迁移率，进而影响器件的电学性能。虽然目前已有报道通过优化其分子结构可以提高聚合物场效应晶体管的性能，但效果并不显著。为了进一步提高共轭聚合物场效应晶体管的性能，可以向其中加入高电场迁移率的分子，比如石墨烯、碳纳米管等。特别是石墨烯，这是一个零带隙的半导体，价带与导带对称地分布在费米能级上下，在狄拉克点交叉重合，电子在石墨烯中的传输遵循狄拉克方程，整个石墨烯分子结构中的每个π键相互共轭形成了巨大的共轭大π键，电子或空穴在如此巨大的共轭体系中可以以很高的电子费米速率移动，表现出零质量行为。载流子迁移率可达2 × 10 5 cm 2 V -1s -1，并具有室温量子霍夫效应、量子隧穿效应等电子传导现象。并且，为了进一步实现器件化，大规模制备并且排列组装成有序定向的结构是很有必要的。 The organic-effect transistor based on conjugated polymer molecules has attracted wide attention in low-cost, flexible, large-area electrical devices such as integrated circuits, pressure sensors, organic memory components, etc. However, the molecular chain of polymers is relatively Large, highly imaged liberalization and irregular interchain entanglement reduce their mobility and thus the electrical performance of the device. Although it has been reported that the performance of polymer field effect transistors can be improved by optimizing their molecular structure, the effect is not significant. In order to further improve the performance of the conjugated polymer field effect transistor, molecules with high electric field mobility such as graphene, carbon nanotubes, and the like may be added thereto. Especially graphene, which is a zero-bandgap semiconductor, the valence band and the conduction band are symmetrically distributed above and below the Fermi level, and the intersection of the Dirac points coincides. The transmission of electrons in the graphene follows the Dirac equation and the whole graphite. Each π bond in the molecular structure of the olefin is conjugated to each other to form a large conjugated large π bond. The electron or hole can move at a high electron Fermi rate in such a large conjugate system, exhibiting zero mass behavior. . The carrier mobility can reach 2 × 10 5 cm 2 V -1 s -1 , and it has electron conduction phenomena such as room temperature quantum echo effect and quantum tunneling effect. Moreover, in order to further implement the deviceization, it is necessary to prepare and arrange the assembled structures in an orderly orientation on a large scale.
技术问题technical problem
聚合物的分子链较大，构像高度自由化以及不规则的链间缠绕现象会降低其迁移率，进而影响器件的电学性能The molecular chain of the polymer is large, the height of the conformation is liberalized, and the irregular interchain entanglement reduces the mobility, which in turn affects the electrical properties of the device.
技术解决方案Technical solution
本发明目的在于：提供一种低成本、简单方便的提高共轭聚合物场效应晶体管性能的方法。利用石墨烯的大π共轭体系，与共轭聚合物分子之间的π-π相互作用力，使聚合物分子吸附在石墨烯分子表面形成聚合物-石墨烯的复合结构，再利用带有微柱结构的硅片制备出大面积方向可控、定位准确的直径为微米级的聚合物-石墨烯复合结构纳米线，同时可转移到特定的基底上，实现器件化应用。It is an object of the present invention to provide a low cost, simple and convenient method of improving the performance of a conjugated polymer field effect transistor. Using the large π-conjugated system of graphene and the π-π interaction force between the conjugated polymer molecules, the polymer molecules are adsorbed on the surface of the graphene molecules to form a polymer-graphene composite structure, and then The silicon structure of the column structure can prepare a polymer-graphene composite structure nanowire with a large-area direction controllable and accurate positioning, and can be transferred to a specific substrate for device application.
本发明技术方案如下：The technical scheme of the present invention is as follows:
本发明的制备复合物场效应晶体管的方法，包括以下步骤：The method for preparing a composite field effect transistor of the present invention comprises the following steps:
1）将聚合物分子溶解在有机溶剂中得到聚合物溶液，将石墨烯浸泡于聚合物溶液中，使石墨烯与聚合物分子相互吸附，得到混合分散液；1) dissolving the polymer molecules in an organic solvent to obtain a polymer solution, immersing the graphene in the polymer solution, and adsorbing the graphene and the polymer molecules to each other to obtain a mixed dispersion;
2）利用过滤膜对混合分散液进行抽滤，对抽滤后的滤渣烘干后得到表面吸附聚合物的石墨烯复合物；2) using a filtration membrane to filter the mixed dispersion, and drying the filtered residue to obtain a graphene composite of the surface adsorbed polymer;
3）将步骤2）得到的石墨烯复合物再次分散于有机溶剂中，制得复合物分散液；3) dispersing the graphene composite obtained in the step 2) in an organic solvent to obtain a composite dispersion;
4）将复合物分散液滴加在具有微柱结构的硅片上并盖上一层平板基底，使聚合物-石墨烯复合物在微柱顶端自组装成规整的一维阵列，制成聚合物场效应晶体管。4) The composite dispersion is added to a silicon wafer having a microcolumn structure and covered with a flat substrate, so that the polymer-graphene composite self-assembles into a regular one-dimensional array at the top of the microcolumn to form a polymerization. Field effect transistor.
根据本发明所述的方法，其中，步骤2）抽滤后使用与步骤1）相同的有机溶剂对滤渣进行淋洗，然后再抽滤，反复多次进行抽滤淋洗用以除去多余的聚合物分子。According to the method of the present invention, in step 2) after suction filtration, the filter residue is rinsed using the same organic solvent as in step 1), and then filtered again, and repeatedly filtered and rinsed to remove excess polymerization. Object molecule.
根据本发明所述的方法，其中，步骤1）所述聚合物溶液的浓度为0.01-0.05 mg/mL；所述混合分散液中石墨烯和聚合物的质量比约为1:0.05～1:1。The method according to the present invention, wherein the concentration of the polymer solution in step 1) is 0.01-0.05 Mg/mL; the mass ratio of graphene to polymer in the mixed dispersion is about 1:0.05 to 1:1.
根据本发明所述的方法，本发明适用于适用于多种聚噻吩类p型共轭高分子，例如但不限于聚烷基噻吩（P3AT）；或者，多并苯类化合物，如萘、蒽、并四苯、并五苯、并六苯；或者，含有杂原子的共轭体系。According to the method of the present invention, the present invention is applicable to various polythiophene p-type conjugated polymers such as, but not limited to, polyalkylthiophene (P3AT); or polyacene compounds such as naphthalene and anthracene. , tetracene, pentacene, hexacene; or a conjugated system containing a hetero atom.
根据本发明所述的方法，其中优选地，步骤1）所述有机溶剂为邻二氯苯、四氢呋喃、二氯甲烷、N，N-二甲基甲酰胺和氯苯等中的一种或几种。According to the method of the present invention, preferably, the organic solvent of the step 1) is one or more of o-dichlorobenzene, tetrahydrofuran, dichloromethane, N,N-dimethylformamide and chlorobenzene. Kind.
根据本发明所述的方法，其中优选地，步骤2）所述过滤膜可以是醋酸纤维素膜，其孔径优选为0.2-0.45 µm。或者，可以选用氧化铝滤膜，其孔径优选为0.02-0.2 µm。According to the method of the present invention, wherein preferably, the filtration membrane of step 2) may be a cellulose acetate membrane having a pore diameter of preferably 0.2 to 0.45. Mm. Alternatively, an alumina filter may be used, and its pore diameter is preferably 0.02 to 0.2 μm.
在本发明所述方法中，步骤2）烘干的目的是为了除去残留的有机溶剂。烘干方式可以本领域公知的方式。例如，将滤渣置于80-120℃烘箱中充分干燥。In the process of the present invention, the purpose of step 2) drying is to remove residual organic solvent. The drying method can be in a manner well known in the art. For example, the filter residue is placed in an oven at 80-120 ° C for thorough drying.
根据本发明所述的方法，其中优选地，步骤3）所述有机溶剂为DMF、四氢呋喃、二氯甲烷、邻二氯苯和氯苯等中的一种或几种。步骤3）所述聚合物的添加浓度（复合物分散液浓度）0.01 -0.1 mg/mL。According to the method of the present invention, preferably, the organic solvent of the step 3) is one or more of DMF, tetrahydrofuran, dichloromethane, o-dichlorobenzene, chlorobenzene and the like. Step 3) The added concentration of the polymer (complex dispersion concentration) 0.01 -0.1 mg/mL.
根据本发明所述的方法，其中，步骤4）所述微柱之间的间距为5-20 µm，所述微柱宽度（长方形截面的宽长）为2-10 µm。The method according to the present invention, wherein the spacing between the microcolumns in step 4) is 5-20 Μm, the width of the microcolumn (width and length of the rectangular section) is 2-10 μm.
在本发明中，步骤4）将聚合物-石墨烯复合物的分散液滴加在具有微柱结构的硅片上，盖上一层平板基底构成“三明治”的组装结构。溶液在微柱表面形成一层连续的液膜，随着溶剂的挥发，液膜在微柱沟槽处首先破裂，从而在微柱顶端与基底之间形成一个个相互平行的液桥，液桥逐渐收缩，最终待溶剂完全挥发后会观察到聚合物-石墨烯复合物在硅柱顶端自组装形成大面积的尺度为微米级的规整的纳米线一维阵列，实现了对于聚合物-石墨烯复合材料的图案化组装。In the present invention, step 4) is to apply a dispersion of the polymer-graphene composite to a silicon wafer having a micro-pillar structure, and to cover a layer of the substrate to form a "sandwich" assembly structure. The solution forms a continuous liquid film on the surface of the microcolumn. As the solvent evaporates, the liquid film first ruptures at the microcolumn groove, thereby forming a parallel liquid bridge between the top of the microcolumn and the substrate, and the liquid bridge Gradually shrinking, after the solvent is completely volatilized, it will be observed that the polymer-graphene compound self-assembles at the top of the silicon column to form a large-area micron-scale one-dimensional array of micrometer-scale nano-scale, realizing the polymer-graphene Patterned assembly of composite materials.
在本发明中，步骤4）所述平板基底可以使用玻璃基底、ITO或导电硅片。In the present invention, the flat substrate of the step 4) may use a glass substrate, ITO or a conductive silicon wafer.
有益效果Beneficial effect
本发明利用带苯环结构的聚合物分子与石墨烯这样具有大π共轭体系的二维晶体之间的共轭相互作用力得到石墨烯表面吸附有聚合物分子的复合结构，再洗去石墨烯表面多余的聚合物分子，保证在石墨烯表面只有少层聚合物分子。被聚合物分子包裹的石墨烯分子可以均匀分散于有机溶剂中，将其滴加在带有微柱的硅片上并覆盖一层基底构成“三明治”的组装结构，在硅柱（微柱）辅助、液桥诱导作用下分子在柱子的顶端实现自组装，最终形成规整的纳米线阵列，并且可以转移到所需基底上。本发明所制备的聚合物-石墨烯复合结构场效应晶体管的性能较之于单纯聚合物场效应晶体管有了显著的提高，方法简单方便，成本低廉。The invention utilizes a conjugate interaction force between a polymer molecule having a benzene ring structure and a two-dimensional crystal having a large π-conjugated system such as graphene to obtain a composite structure in which a polymer molecule is adsorbed on the surface of the graphene, and then the graphite is washed away. Excess polymer molecules on the surface of the olefin ensure that there are only a few polymer molecules on the surface of the graphene. Graphene molecules encapsulated by polymer molecules can be uniformly dispersed in an organic solvent, dropped on a silicon wafer with micropillars and covered with a substrate to form a "sandwich" assembly structure in a silicon column (microcolumn) Auxiliary, liquid bridge induction allows the molecules to self-assemble at the top of the column, ultimately forming a regular array of nanowires that can be transferred to the desired substrate. The performance of the polymer-graphene composite structure field effect transistor prepared by the invention is significantly improved compared with the simple polymer field effect transistor, and the method is simple and convenient, and the cost is low.
本发明节省有机物用量，从而降低成本，同时对于材料的定向组装使得器件性能得到提高。并且，在开关比和电子/空穴迁移率上有显著提高。The invention saves the amount of organic matter, thereby reducing the cost, and at the same time, the directional assembly of the material improves the performance of the device. Moreover, there is a significant increase in switching ratio and electron/hole mobility.
附图说明DRAWINGS
图1为本发明制备复合物场效应晶体管的方法示意图；其中，1 is a schematic view showing a method of preparing a composite field effect transistor according to the present invention;
a为将石墨烯粉末浸泡于聚合物稀溶液中达到充分吸附示意图；a is a schematic diagram of fully adsorbing the graphene powder in a dilute solution of the polymer;
b为将聚合物-石墨烯复合物经过抽滤后的在滤膜上的光学照片；b is an optical photograph of the polymer-graphene composite after filtration on the filter;
c为将复合物分散于有机溶剂后制备得到聚合物-石墨烯复合分散液示意图；c is a schematic diagram of preparing a polymer-graphene composite dispersion after dispersing the composite in an organic solvent;
d为将聚合物-石墨烯复合结构的均匀分散液滴加在具有微柱结构的硅片上，盖上一层基底构成“三明治”的组装结构示意图；d is a schematic diagram of an assembly structure in which a uniformly dispersed droplet of a polymer-graphene composite structure is applied to a silicon wafer having a microcolumn structure and covered with a layer of a substrate to form a "sandwich";
e为在模板硅片和基底之间形成一层连续的液膜示意图；e is a schematic diagram of forming a continuous liquid film between the template silicon wafer and the substrate;
f为在硅柱顶端形成的液桥示意图；f is a schematic diagram of a liquid bridge formed at the top of the silicon column;
g为在硅柱顶端自组装形成的规整的纳米线阵列示意图，其中，放大部分显示的聚合物-石墨烯复合物的层层堆叠构型。g is a schematic representation of a regular nanowire array formed by self-assembly at the top of a silicon column, wherein the enlarged portion shows a layered stack configuration of the polymer-graphene composite.
图2为本发明实施例1的聚合物溶液示意图；其中，a为聚合物溶液，b为向聚合物溶液中添加石墨烯后的混合分散液。2 is a schematic view of a polymer solution according to Example 1 of the present invention; wherein a is a polymer solution, and b is a mixed dispersion obtained by adding graphene to a polymer solution.
图3为本发明实施例1的聚合物-石墨烯复合分散液。Figure 3 is a polymer-graphene composite dispersion of Example 1 of the present invention.
图4为本发明实施例1的微柱示意图。4 is a schematic view of a microcolumn according to Embodiment 1 of the present invention.
图5为本发明实施例2的聚合物分子、石墨烯、聚合物-石墨烯复合物的红外表征图。5 is an infrared characterization diagram of a polymer molecule, a graphene, and a polymer-graphene composite according to Example 2 of the present invention.
图6为本发明实施例2的经过抽滤后聚合物-石墨烯复合物在滤膜上的光学照片。Figure 6 is an optical photograph of a filtered polymer-graphene composite on a filter membrane according to Example 2 of the present invention.
图7为本发明实施例2的聚合物-石墨烯复合分散液的性能测试曲线；其中，a为转移特性曲线，b为输出曲线。7 is a performance test curve of a polymer-graphene composite dispersion according to Example 2 of the present invention; wherein a is a transfer characteristic curve and b is an output curve.
图8为本发明实施例3的聚合物分子、石墨烯、聚合物-石墨烯复合物的红外表征图。8 is an infrared characterization diagram of a polymer molecule, a graphene, and a polymer-graphene composite according to Example 3 of the present invention.
图9为本发明实施例3的聚合物-石墨烯复合分散液的性能测试曲线；其中，a为转移特性曲线，b为输出曲线。9 is a performance test curve of the polymer-graphene composite dispersion of Example 3 of the present invention; wherein a is a transfer characteristic curve and b is an output curve.
图10为本发明实施例4的聚合物分子、石墨烯、聚合物-石墨烯复合物的红外表征图。Figure 10 is an infrared characterization diagram of a polymer molecule, graphene, polymer-graphene composite of Example 4 of the present invention.
图11为本发明实施例4的聚合物-石墨烯复合分散液的性能测试曲线；其中，a为转移特性曲线，b为输出曲线。Figure 11 is a performance test curve of the polymer-graphene composite dispersion of Example 4 of the present invention; wherein a is a transfer characteristic curve and b is an output curve.
本发明的最佳实施方式BEST MODE FOR CARRYING OUT THE INVENTION
本发明制备复合物场效应晶体管的方法，具体步骤如下：The method for preparing a composite field effect transistor of the invention has the following specific steps:
（1）将聚合物分子溶解在有机溶剂中得到均匀分散的溶液，稀释使得聚合物溶液浓度在0.01-0.05 mg/mL，将石墨烯粉末浸泡于聚合物稀溶液中已达到充分吸附（图1a），再利用过滤膜进行抽滤，以同种溶剂反复淋洗以除去石墨烯表面多余的聚合物分子，保证只有少层聚合物分子吸附在石墨烯表面（用红外表征聚合物分子的存在）。图1b中展示了聚合物-石墨烯复合物经过抽滤后的在滤膜上的光学照片。得到的复合物粉末充分干燥后可均匀分散于有机溶剂中，制备得到聚合物-石墨烯复合结构均匀分散液，如图1c所示，以便后续分子器件的制备。(1) Dissolving the polymer molecules in an organic solvent to obtain a uniformly dispersed solution, and diluting the polymer solution at a concentration of 0.01-0.05 Mg/mL, the graphene powder is immersed in the dilute solution of the polymer to achieve sufficient adsorption (Fig. 1a), and then filtered by a filtration membrane, and repeatedly washed with the same solvent to remove excess polymer molecules on the surface of the graphene. It is ensured that only a small number of polymer molecules are adsorbed on the graphene surface (the presence of polymer molecules is characterized by infrared). An optical photograph of the polymer-graphene composite on the filter after suction filtration is shown in Figure 1b. After the obtained composite powder is sufficiently dried, it can be uniformly dispersed in an organic solvent to prepare a polymer-graphene composite structure uniform dispersion, as shown in FIG. 1c, for subsequent preparation of the molecular device.
（2）利用带有微柱结构的硅片对分子进行自组装。微柱的直径为微米级尺度，两个微柱之间的间距为5-20 µm。该方法是通过在模板硅片的微柱结构顶端与基底之间形成液桥来调控液膜的退浸润，从而形成规整排列的一维结构。首先模板硅片需要先经过选择性修饰，得到具有不对称浸润性的模板硅片：硅柱顶端输液体，硅柱侧壁及沟槽亲液体。将聚合物-石墨烯复合结构的均匀分散液滴加在具有微柱结构的硅片上，盖上一层平板基底构成“三明治”的组装结构（图1d）。由于硅柱顶端亲液体，所以液体首先会在模板硅片和基底之间形成一层连续的液膜（图1e）。随着溶剂的逐渐挥发，液体量也随之减少，最后液膜破裂并形成多个规整的液体条带区域。因为模板硅片具有不对称浸润性特征，聚合物-石墨烯复合结构的均匀分散液被粘附在硅柱亲液的顶端，并在硅柱顶端形成一条条规整的液桥（图1f）。随着液桥的退浸润，三相接触线后退，液桥尺寸逐渐减小。最终待溶剂完全挥发后会观察到聚合物-石墨烯复合物在硅柱顶端自组装形成大面积的尺度为微米级的规整的纳米线阵列（图1g）。图1g下边的图展示了聚合物-石墨烯复合物的层层堆叠构型。(2) Self-assembly of molecules using a silicon wafer with a microcolumn structure. The diameter of the microcolumns is on the order of micrometers, and the spacing between the two microcolumns is 5-20. Mm. The method controls the re-wetting of the liquid film by forming a liquid bridge between the top end of the micro-column structure of the template silicon wafer and the substrate, thereby forming a one-dimensional structure of regular arrangement. First, the template wafer needs to be selectively modified to obtain a template wafer with asymmetric wettability: the liquid at the top of the silicon column, the side wall of the silicon column and the liquid in the trench. A uniformly dispersed droplet of the polymer-graphene composite structure was applied to a silicon wafer having a microcolumn structure, and a flat substrate was covered to form a "sandwich" assembly structure (Fig. 1d). Since the top of the silicon column is liquid, the liquid first forms a continuous liquid film between the template wafer and the substrate (Fig. 1e). As the solvent gradually evaporates, the amount of liquid also decreases, and finally the liquid film ruptures and forms a plurality of regular liquid strip regions. Because of the asymmetric wetting characteristics of the template wafer, a uniform dispersion of the polymer-graphene composite structure is adhered to the top of the lyophilic portion of the silicon column and forms a regular liquid bridge at the top of the silicon column (Fig. 1f). As the liquid bridge retreats, the three-phase contact line recedes and the size of the liquid bridge gradually decreases. Finally, after the solvent is completely volatilized, it is observed that the polymer-graphene composite self-assembles at the top of the silicon column to form a large-area regular nanowire array of a micron scale (Fig. 1g). The lower panel of Figure 1g shows the layer stack configuration of the polymer-graphene composite.
本发明的实施方式Embodiments of the invention
本发明制备复合物场效应晶体管的方法，具体步骤如下：The method for preparing a composite field effect transistor of the invention has the following specific steps:
（1）将聚合物分子溶解在有机溶剂中得到均匀分散的溶液，稀释使得聚合物溶液浓度在0.01-0.05 mg/mL，将石墨烯粉末浸泡于聚合物稀溶液中已达到充分吸附（图1a），再利用过滤膜进行抽滤，以同种溶剂反复淋洗以除去石墨烯表面多余的聚合物分子，保证只有少层聚合物分子吸附在石墨烯表面（用红外表征聚合物分子的存在）。图1b中展示了聚合物-石墨烯复合物经过抽滤后的在滤膜上的光学照片。得到的复合物粉末充分干燥后可均匀分散于有机溶剂中，制备得到聚合物-石墨烯复合结构均匀分散液，如图1c所示，以便后续分子器件的制备。(1) Dissolving the polymer molecules in an organic solvent to obtain a uniformly dispersed solution, and diluting the polymer solution at a concentration of 0.01-0.05 Mg/mL, the graphene powder is immersed in the dilute solution of the polymer to achieve sufficient adsorption (Fig. 1a), and then filtered by a filtration membrane, and repeatedly washed with the same solvent to remove excess polymer molecules on the surface of the graphene. It is ensured that only a small number of polymer molecules are adsorbed on the graphene surface (the presence of polymer molecules is characterized by infrared). An optical photograph of the polymer-graphene composite on the filter after suction filtration is shown in Figure 1b. After the obtained composite powder is sufficiently dried, it can be uniformly dispersed in an organic solvent to prepare a polymer-graphene composite structure uniform dispersion, as shown in FIG. 1c, for subsequent preparation of the molecular device.
（2）利用带有微柱结构的硅片对分子进行自组装。微柱的直径为微米级尺度，两个微柱之间的间距为5-20 µm。该方法是通过在模板硅片的微柱结构顶端与基底之间形成液桥来调控液膜的退浸润，从而形成规整排列的一维结构。首先模板硅片需要先经过选择性修饰，得到具有不对称浸润性的模板硅片：硅柱顶端输液体，硅柱侧壁及沟槽亲液体。将聚合物-石墨烯复合结构的均匀分散液滴加在具有微柱结构的硅片上，盖上一层平板基底构成“三明治”的组装结构（图1d）。由于硅柱顶端亲液体，所以液体首先会在模板硅片和基底之间形成一层连续的液膜（图1e）。随着溶剂的逐渐挥发，液体量也随之减少，最后液膜破裂并形成多个规整的液体条带区域。因为模板硅片具有不对称浸润性特征，聚合物-石墨烯复合结构的均匀分散液被粘附在硅柱亲液的顶端，并在硅柱顶端形成一条条规整的液桥（图1f）。随着液桥的退浸润，三相接触线后退，液桥尺寸逐渐减小。最终待溶剂完全挥发后会观察到聚合物-石墨烯复合物在硅柱顶端自组装形成大面积的尺度为微米级的规整的纳米线阵列（图1g）。图1g下边的图展示了聚合物-石墨烯复合物的层层堆叠构型。(2) Self-assembly of molecules using a silicon wafer with a microcolumn structure. The diameter of the microcolumns is on the order of micrometers, and the spacing between the two microcolumns is 5-20. Mm. The method controls the re-wetting of the liquid film by forming a liquid bridge between the top end of the micro-column structure of the template silicon wafer and the substrate, thereby forming a one-dimensional structure of regular arrangement. First, the template wafer needs to be selectively modified to obtain a template wafer with asymmetric wettability: the liquid at the top of the silicon column, the side wall of the silicon column and the liquid in the trench. A uniformly dispersed droplet of the polymer-graphene composite structure was applied to a silicon wafer having a microcolumn structure, and a flat substrate was covered to form a "sandwich" assembly structure (Fig. 1d). Since the top of the silicon column is liquid, the liquid first forms a continuous liquid film between the template wafer and the substrate (Fig. 1e). As the solvent gradually evaporates, the amount of liquid also decreases, and finally the liquid film ruptures and forms a plurality of regular liquid strip regions. Because of the asymmetric wetting characteristics of the template wafer, a uniform dispersion of the polymer-graphene composite structure is adhered to the top of the lyophilic portion of the silicon column and forms a regular liquid bridge at the top of the silicon column (Fig. 1f). As the liquid bridge retreats, the three-phase contact line recedes and the size of the liquid bridge gradually decreases. Finally, after the solvent is completely volatilized, it is observed that the polymer-graphene composite self-assembles at the top of the silicon column to form a large-area regular nanowire array of a micron scale (Fig. 1g). The lower panel of Figure 1g shows the layer stack configuration of the polymer-graphene composite.
实施例Example 11
（1）将聚合物分子（PCDTPT）溶解在邻二氯苯中得到均匀分散的溶液，稀释使得聚合物溶液浓度在0.01mg/mL（图2a），将石墨烯粉末（100 mg）浸泡于聚合物稀溶液中已达到充分吸附（图2b），再利用醋酸纤维素膜（孔径0.2 µm）进行抽滤，以邻二氯苯反复淋洗并抽滤以除去石墨烯表面多余的聚合物分子，保证只有少层聚合物分子吸附在石墨烯表面（用红外表征聚合物分子的存在）。得到的复合物粉末置于80℃烘箱中充分干燥以除去残留的邻二氯苯溶剂，干燥后可均匀分散于DMF中，制备得到聚合物-石墨烯复合结构均匀分散液（0.08 mg/mL）（图3），以便后续分子器件的制备。(1) Dissolve the polymer molecule (PCDTPT) in o-dichlorobenzene to obtain a uniformly dispersed solution, dilute to a concentration of the polymer solution at 0.01 mg/mL (Fig. 2a), and immerse the graphene powder (100 mg) in the polymerization. Adequate adsorption has been achieved in the dilute solution (Fig. 2b), and then the cellulose acetate membrane (pore size 0.2) Μm) is subjected to suction filtration, and is repeatedly rinsed with o-dichlorobenzene and filtered to remove excess polymer molecules on the surface of graphene, ensuring that only a small number of polymer molecules are adsorbed on the surface of graphene (infrared is used to characterize the presence of polymer molecules) . The obtained composite powder was sufficiently dried in an oven at 80 ° C to remove residual o-dichlorobenzene solvent, and uniformly dispersed in DMF after drying to prepare a polymer-graphene composite structure uniform dispersion (0.08 mg/mL). (Fig. 3) for the preparation of subsequent molecular devices.
（2）利用带有微柱结构的硅片对分子进行自组装。微柱的直径为微米级尺度，两个微柱之间的间距为5 µm （图4）。将聚合物-石墨烯复合结构的均匀分散液（20 µL）滴加在具有微柱结构的硅片上，盖上一层修饰有OTS单分子层的SiO 2/Si基底（玻璃基底）构成“三明治”的组装结构。溶液在硅柱表面形成一层连续的液膜，随着溶剂的挥发，液膜在硅柱沟槽处首先破裂，从而在硅柱顶端与基底之间形成一个个相互平行的液桥，液桥逐渐收缩，最终待溶剂完全挥发后会观察到聚合物/石墨烯复合物在硅柱顶端自组装形成大面积的尺度为微米级的规整的纳米线一维阵列，制备所需的微电子器件以实现器件化应用。 (2) Self-assembly of molecules using a silicon wafer with a microcolumn structure. The diameter of the microcolumns is on the order of micrometers and the spacing between the two micropillars is 5 μm (Fig. 4). A uniform dispersion of polymer-graphene composite structure (20 μL) was dropped on a silicon wafer having a microcolumn structure, and covered with a SiO 2 /Si substrate (glass substrate) modified with an OTS monolayer. The assembly structure of the sandwich. The solution forms a continuous liquid film on the surface of the silicon column. As the solvent evaporates, the liquid film first breaks at the groove of the silicon column, thereby forming a parallel liquid bridge between the top of the silicon column and the substrate. Gradually shrinking, and finally, after the solvent is completely volatilized, it is observed that the polymer/graphene composite self-assembles at the top of the silicon column to form a large-area one-dimensional array of regular nanowires of a micrometer scale, and prepares the required microelectronic device. Implement deviceized applications.
实施例Example 22
（1）将聚合物分子（CDTBTZ）溶解在邻二氯苯中得到均匀分散的溶液，稀释使得聚合物溶液浓度在0.05mg/mL，将石墨烯粉末（500 mg）浸泡于聚合物稀溶液中已达到充分吸附，再利用醋酸纤维素膜（孔径0.2 µm）进行抽滤，以邻二氯苯反复淋洗并抽滤以除去石墨烯表面多余的聚合物分子，保证只有少层聚合物分子吸附在石墨烯表面（用红外表征聚合物分子的存在）（图5）。经过抽滤后聚合物-石墨烯复合物在滤膜上的光学照片如图6所示。得到的复合物粉末置于80℃烘箱中充分干燥以除去残留的邻二氯苯溶剂，干燥后可均匀分散于DMF中，制备得到聚合物-石墨烯复合结构均匀分散液（0.08 mg/mL），以便后续分子器件的制备。性能测试曲线如图7所示。(1) Dissolve the polymer molecule (CDTBTZ) in o-dichlorobenzene to obtain a uniformly dispersed solution, dilute to a concentration of the polymer solution at 0.05 mg/mL, and soak the graphene powder (500 mg) in a dilute polymer solution. Adequate adsorption has been achieved, and the cellulose acetate membrane is reused (pore size 0.2 Μm) is subjected to suction filtration, and is repeatedly rinsed with o-dichlorobenzene and filtered to remove excess polymer molecules on the surface of graphene, ensuring that only a small number of polymer molecules are adsorbed on the surface of graphene (infrared is used to characterize the presence of polymer molecules) (Figure 5). An optical photograph of the polymer-graphene complex on the filter after suction filtration is shown in FIG. The obtained composite powder was sufficiently dried in an oven at 80 ° C to remove residual o-dichlorobenzene solvent, and uniformly dispersed in DMF after drying to prepare a polymer-graphene composite structure uniform dispersion (0.08 mg/mL). In order to prepare the subsequent molecular device. The performance test curve is shown in Figure 7.
其中，图5说明本实施例的聚合物分子CDTBTZ成功吸附在石墨烯表面。图7中a为基于聚合物-石墨烯复合物所构筑的器件的转移特性曲线，图7b为输出曲线。图7说明聚合物-石墨烯复合物具有优异的电学性能。Here, FIG. 5 illustrates that the polymer molecule CDTBTZ of the present embodiment is successfully adsorbed on the surface of graphene. In Fig. 7, a is a transfer characteristic curve of a device constructed based on a polymer-graphene composite, and Fig. 7b is an output curve. Figure 7 illustrates that the polymer-graphene composite has excellent electrical properties.
（2）利用带有微柱结构的硅片对分子进行自组装。微柱的直径为微米级尺度，两个微柱之间的间距为20 µm。将聚合物-石墨烯复合结构的均匀分散液（20 µL）滴加在具有微柱结构的硅片上，盖上一层ITO基底构成“三明治”的组装结构。溶液在硅柱表面形成一层连续的液膜，随着溶剂的挥发，液膜在硅柱沟槽处首先破裂，从而在硅柱顶端与基底之间形成一个个相互平行的液桥，液桥逐渐收缩，最终待溶剂完全挥发后会观察到聚合物-石墨烯复合物在硅柱顶端自组装形成大面积的尺度为微米级的规整的纳米线一维阵列，制备所需的微电子器件以实现器件化应用。 (2) Self-assembly of molecules using a silicon wafer with a microcolumn structure. The diameter of the microcolumns is on the order of micrometers, and the spacing between the two microcolumns is 20 μm. A uniform dispersion of the polymer-graphene composite structure (20 μL) was dropped on a silicon wafer having a microcolumn structure, and an ITO substrate was covered to form a "sandwich" assembly structure. The solution forms a continuous liquid film on the surface of the silicon column. As the solvent evaporates, the liquid film first breaks at the groove of the silicon column, thereby forming a parallel liquid bridge between the top of the silicon column and the substrate. Gradually shrinking, and finally, after the solvent is completely volatilized, it is observed that the polymer-graphene composite self-assembles at the top of the silicon column to form a large-area one-dimensional array of regular nanowires of a micrometer scale, and prepares the required microelectronic device. Implement deviceized applications.
实施例Example 33
（1）将聚合物分子（P3HT）溶解在氯苯中得到均匀分散的溶液，稀释使得聚合物溶液浓度在0.03mg/mL，将石墨烯粉末（300 mg）浸泡于聚合物稀溶液中已达到充分吸附，再利用氧化铝滤膜（孔径0.02 µm）进行抽滤，以邻二氯苯反复淋洗并抽滤以除去石墨烯表面多余的聚合物分子，保证只有少层聚合物分子吸附在石墨烯表面（用红外表征聚合物分子的存在）（图8）。得到的复合物粉末置于120℃烘箱中充分干燥以除去残留的氯苯溶剂，干燥后可均匀分散于四氢呋喃中，制备得到聚合物-石墨烯复合结构均匀分散液（0.01mg/mL），以便后续分子器件的制备。性能测试曲线如图9所示。(1) Dissolving the polymer molecule (P3HT) in chlorobenzene to obtain a uniformly dispersed solution, diluting to a concentration of the polymer solution of 0.03 mg/mL, and immersing the graphene powder (300 mg) in the dilute polymer solution. Adequate adsorption, reuse of alumina filter (pore diameter 0.02 Μm) is subjected to suction filtration, and is repeatedly rinsed with o-dichlorobenzene and filtered to remove excess polymer molecules on the surface of graphene, ensuring that only a small number of polymer molecules are adsorbed on the surface of graphene (infrared is used to characterize the presence of polymer molecules) (Figure 8). The obtained composite powder is sufficiently dried in an oven at 120 ° C to remove the residual chlorobenzene solvent, and after drying, it can be uniformly dispersed in tetrahydrofuran to prepare a polymer-graphene composite structure uniform dispersion (0.01 mg/mL), so that Preparation of subsequent molecular devices. The performance test curve is shown in Figure 9.
其中，图8说明聚合物分子P3HT成功吸附在石墨烯表面。图9a为基于聚合物-石墨烯复合物所构筑的器件的转移特性曲线，图9b为输出曲线。图9说明聚合物-石墨烯复合物具有优异的电学性能。Among them, FIG. 8 illustrates that the polymer molecule P3HT is successfully adsorbed on the graphene surface. Figure 9a is a transfer characteristic curve of a device constructed based on a polymer-graphene composite, and Figure 9b is an output curve. Figure 9 illustrates that the polymer-graphene composite has excellent electrical properties.
（2）利用带有微柱结构的硅片对分子进行自组装。微柱的直径为微米级尺度，两个微柱之间的间距为10 µm。将聚合物-石墨烯复合结构的均匀分散液（20 µL）滴加在具有微柱结构的硅片上，盖上一层修饰有OTS单分子层的SiO 2/Si基底构成“三明治”的组装结构。溶液在硅柱表面形成一层连续的液膜，随着溶剂的挥发，液膜在硅柱沟槽处首先破裂，从而在硅柱顶端与基底之间形成一个个相互平行的液桥，液桥逐渐收缩，最终待溶剂完全挥发后会观察到聚合物-石墨烯复合物在硅柱顶端自组装形成大面积的尺度为微米级的规整的纳米线一维阵列，制备所需的微电子器件以实现器件化应用。 (2) Self-assembly of molecules using a silicon wafer with a microcolumn structure. The diameter of the microcolumns is on the order of micrometers, and the spacing between the two microcolumns is 10 μm. A uniform dispersion of polymer-graphene composite structure (20 μL) was dropped on a silicon wafer having a microcolumn structure, and a SiO 2 /Si substrate modified with an OTS monolayer was coated to form a "sandwich" assembly. structure. The solution forms a continuous liquid film on the surface of the silicon column. As the solvent evaporates, the liquid film first breaks at the groove of the silicon column, thereby forming a parallel liquid bridge between the top of the silicon column and the substrate. Gradually shrinking, and finally, after the solvent is completely volatilized, it is observed that the polymer-graphene composite self-assembles at the top of the silicon column to form a large-area one-dimensional array of regular nanowires of a micrometer scale, and prepares the required microelectronic device. Implement deviceized applications.
实施例Example 44
（1）将聚合物分子（PQT-12）溶解在邻二氯苯中得到均匀分散的溶液，稀释使得聚合物溶液浓度在0.02mg/mL，将石墨烯粉末（200 mg）浸泡于聚合物稀溶液中已达到充分吸附，再利用氧化铝滤膜（孔径0.2 µm）进行抽滤，以邻二氯苯反复淋洗并抽滤以除去石墨烯表面多余的聚合物分子，保证只有少层聚合物分子吸附在石墨烯表面（用红外表征聚合物分子的存在）（图10）。得到的复合物粉末置于100℃烘箱中充分干燥以除去残留的邻二氯苯溶剂，干燥后可均匀分散于四氢呋喃中，制备得到聚合物/石墨烯复合结构均匀分散液（0.1 mg/mL），以便后续分子器件的制备。性能测试曲线如图11所示。(1) Dissolve the polymer molecule (PQT-12) in o-dichlorobenzene to obtain a uniformly dispersed solution, dilute to a concentration of the polymer solution at 0.02 mg/mL, and soak the graphene powder (200 mg) in the polymer. Adequate adsorption has been achieved in the solution, and the alumina filter is used (pore size 0.2 Μm) is subjected to suction filtration, and is repeatedly rinsed with o-dichlorobenzene and filtered to remove excess polymer molecules on the surface of graphene, ensuring that only a small number of polymer molecules are adsorbed on the surface of graphene (infrared is used to characterize the presence of polymer molecules) (Figure 10). The obtained composite powder was sufficiently dried in an oven at 100 ° C to remove residual o-dichlorobenzene solvent, and uniformly dispersed in tetrahydrofuran after drying to prepare a polymer/graphene composite structure uniform dispersion (0.1 mg/mL). In order to prepare the subsequent molecular device. The performance test curve is shown in Figure 11.
其中，图10说明聚合物分子P3HT成功吸附在石墨烯表面。图11a为基于聚合物-石墨烯复合物所构筑的器件的转移特性曲线，图11b为输出曲线。图11说明聚合物-石墨烯复合物具有优异的电学性能。Among them, FIG. 10 illustrates that the polymer molecule P3HT is successfully adsorbed on the graphene surface. Figure 11a is a transfer characteristic curve of a device constructed based on a polymer-graphene composite, and Figure 11b is an output curve. Figure 11 illustrates that the polymer-graphene composite has excellent electrical properties.
（2）利用带有微柱结构的硅片对分子进行自组装。微柱的直径为微米级尺度，两个微柱之间的间距为15 µm。将聚合物-石墨烯复合结构的均匀分散液（20 µL）滴加在具有微柱结构的硅片上，盖上一层导电硅片构成“三明治”的组装结构。溶液在硅柱表面形成一层连续的液膜，随着溶剂的挥发，液膜在硅柱沟槽处首先破裂，从而在硅柱顶端与基底之间形成一个个相互平行的液桥，液桥逐渐收缩，最终待溶剂完全挥发后会观察到聚合物-石墨烯复合物在硅柱顶端自组装形成大面积的尺度为微米级的规整的纳米线一维阵列，制备所需的微电子器件以实现器件化应用。 (2) Self-assembly of molecules using a silicon wafer with a microcolumn structure. The diameter of the microcolumns is on the order of micrometers, and the spacing between the two microcolumns is 15 μm. A uniform dispersion of the polymer-graphene composite structure (20 μL) was dropped on a silicon wafer having a microcolumn structure, and a layer of conductive silicon wafer was covered to form a "sandwich" assembly structure. The solution forms a continuous liquid film on the surface of the silicon column. As the solvent evaporates, the liquid film first breaks at the groove of the silicon column, thereby forming a parallel liquid bridge between the top of the silicon column and the substrate. Gradually shrinking, and finally, after the solvent is completely volatilized, it is observed that the polymer-graphene composite self-assembles at the top of the silicon column to form a large-area one-dimensional array of regular nanowires of a micrometer scale, and prepares the required microelectronic device. Implement deviceized applications.
工业实用性Industrial applicability
本发明所制备的聚合物-石墨烯复合结构场效应晶体管的性能较之于单纯聚合物场效应晶体管有了显著的提高，方法简单方便，成本低廉。本发明节省有机物用量，从而降低成本，同时对于材料的定向组装使得器件性能得到提高。并且，在开关比和电子/空穴迁移率上有显著提高。The performance of the polymer-graphene composite structure field effect transistor prepared by the invention is significantly improved compared with the simple polymer field effect transistor, and the method is simple and convenient, and the cost is low. The invention saves the amount of organic matter, thereby reducing the cost, and at the same time, the directional assembly of the material improves the performance of the device. Moreover, there is a significant increase in switching ratio and electron/hole mobility.

Claims (10)

  1. 一种制备复合物场效应晶体管的方法，包括以下步骤：A method of fabricating a composite field effect transistor includes the following steps:
    1）将聚合物分子溶解在有机溶剂中得到聚合物溶液，将石墨烯浸泡于聚合物溶液中，使石墨烯与聚合物分子相互吸附，得到混合分散液；1) dissolving the polymer molecules in an organic solvent to obtain a polymer solution, immersing the graphene in the polymer solution, and adsorbing the graphene and the polymer molecules to each other to obtain a mixed dispersion;
    2）利用过滤膜对混合分散液进行抽滤，将滤渣烘干后得到表面吸附聚合物的石墨烯复合物；2) using a filtration membrane to filter the mixed dispersion, and drying the filter residue to obtain a graphene composite having a surface adsorbed polymer;
    3）将步骤2）得到的石墨烯复合物再次分散于有机溶剂中，制得复合物分散液；3) dispersing the graphene composite obtained in the step 2) in an organic solvent to obtain a composite dispersion;
    4）将复合物分散液滴加在具有微柱结构的硅片上并盖上一层平板基底，使聚合物-石墨烯复合物在微柱顶端自组装成规整的一维阵列，制成复合物场效应晶体管。4) The composite dispersion is added to a silicon wafer having a microcolumn structure and covered with a flat substrate, so that the polymer-graphene composite self-assembles into a regular one-dimensional array at the top of the microcolumn to form a composite Field effect transistor.
  2. 根据权利要求1所述的方法，其特征在于，步骤2）抽滤后使用与步骤1）相同的有机溶剂对滤渣进行淋洗，然后再抽滤，除去多余的聚合物分子。The method according to claim 1, characterized in that in step 2), after filtering, the filter residue is rinsed using the same organic solvent as in step 1), and then filtered off to remove excess polymer molecules.
  3. 根据权利要求1或2所述的方法，其特征在于，步骤1）所述聚合物溶液的浓度为0.01-0.05 mg/mL；所述混合分散液中石墨烯和聚合物的质量比为1:0.05～1:1。The method according to claim 1 or 2, wherein the concentration of the polymer solution in step 1) is 0.01-0.05 Mg/mL; the mass ratio of graphene to polymer in the mixed dispersion is 1:0.05 to 1:1.
  4. 根据权利要求1或2所述的方法，其特征在于，步骤1）所述聚合物分子是聚噻吩类p型共轭高分子。The method according to claim 1 or 2, wherein the polymer molecule of the step 1) is a polythiophene p-type conjugated polymer.
  5. 根据权利要求1或2所述的方法，其特征在于，步骤1）所述有机溶剂为邻二氯苯、四氢呋喃、二氯甲烷、N，N-二甲基甲酰胺和氯苯等中的一种或几种。The method according to claim 1 or 2, wherein the organic solvent in step 1) is one of o-dichlorobenzene, tetrahydrofuran, dichloromethane, N,N-dimethylformamide and chlorobenzene. Kind or several.
  6. 根据权利要求1或2所述的方法，其特征在于，步骤2）所述过滤膜为醋酸纤维素膜，其孔径为0.2-0.45 µm；或者，所述过滤膜为氧化铝滤膜，其孔径为0.02-0.2 µm。The method according to claim 1 or 2, wherein the filter membrane is a cellulose acetate membrane having a pore diameter of 0.2 to 0.45 μm; or the filtration membrane is an alumina membrane having a pore diameter. It is 0.02-0.2 μm.
  7. 根据权利要求1或2所述的方法，其特征在于，步骤3）所述有机溶剂为DMF、四氢呋喃、二氯甲烷、邻二氯苯和氯苯等中的一种或几种。The method according to claim 1 or 2, wherein the organic solvent in the step 3) is one or more of DMF, tetrahydrofuran, dichloromethane, o-dichlorobenzene and chlorobenzene.
  8. 根据权利要求1、2或7所述的方法，其特征在于，步骤3）所述复合物分散液的浓度为0.01 -0.1 mg/mL。The method according to claim 1, 2 or 7, wherein the concentration of the complex dispersion in step 3) is from 0.01 to 0.1 mg/mL.
  9. 根据权利要求1所述的方法，其特征在于，步骤4）所述微柱之间的间距为5-20 µm，微柱的宽度为2-10 µm。The method according to claim 1, wherein the step 4) the spacing between the microcolumns is 5-20 μm, and the width of the microcolumns is 2-10 μm.
  10. 根据权利要求1、2或9所述的方法，其特征在于，步骤4）所述平板基底为玻璃基底、ITO或导电硅片。The method according to claim 1, 2 or 9, wherein the step substrate is a glass substrate, ITO or a conductive silicon wafer.
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