WO2016086477A1 - Procédé permettant de faire directement croître une membrane de graphène sur un substrat en silicium - Google Patents

Procédé permettant de faire directement croître une membrane de graphène sur un substrat en silicium Download PDF

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WO2016086477A1
WO2016086477A1 PCT/CN2014/095114 CN2014095114W WO2016086477A1 WO 2016086477 A1 WO2016086477 A1 WO 2016086477A1 CN 2014095114 W CN2014095114 W CN 2014095114W WO 2016086477 A1 WO2016086477 A1 WO 2016086477A1
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silicon substrate
graphene film
gas
directly
directly growing
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PCT/CN2014/095114
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English (en)
Chinese (zh)
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连丽君
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连丽君
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite

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  • the invention relates to the field of preparing new graphene materials, in particular to a method for directly growing a graphene film material on a silicon substrate, which is suitable for the growth preparation of a large-area graphene film material without transfer, and is a silicon substrate-graphite.
  • the manufacture of olefinic devices provides materials.
  • Graphene refers to a single layer of carbon atoms that are closely packed into a two-dimensional honeycomb lattice structure. It is the basic unit for constructing other dimensional carbon materials (zero-dimensional fullerene, one-dimensional carbon nanotubes, three-dimensional graphite). . Graphene material is the lightest and thinnest material known at present. The single layer is only atomic in thickness, and it has extremely excellent physicochemical properties. For example, graphene is a zero-bandgap semiconductor in which electrons move at speeds up to 1 speed of light.
  • graphene has such excellent properties, there are still many key problems to be solved in the preparation of graphene.
  • the international mainstream is to prepare graphene materials by epitaxial growth method. This method is based on transition metal catalyzed CVD method. It needs to be filled with carbon source gas (methane, ethane, acetylene, etc.) at high temperature, and the gas is decomposed and on the substrate.
  • carbon source gas methane, ethane, acetylene, etc.
  • the formation of graphene requires a high temperature of 1000 degrees or more, and requires hydrogen as a reducing gas.
  • the production conditions are strict, the reaction time is long, the yield is low, and the use of a large amount of dangerous gas increases the production cost and limits the graphene. Further application.
  • Si is a wide bandgap material with good electrical and thermal properties and can be used to prepare power devices, frequency devices, and the like.
  • the critical dimensions of silicon (Si) groups have reached the theoretical and technical limits, and quantum effects have become the main limiting mechanism.
  • Si silicon
  • the quality of contact with the silicon substrate provides a monolithic material for the silicon-graphene structure device.
  • the whole material is directly used to manufacture various devices, which improves the optical characteristics, reliability, repeatability, operability, cost and complexity of device manufacturing, and directly grows graphene film on silicon substrate.
  • the method will have important industrial significance and scientific research value.
  • the object of the present invention is to overcome the above disadvantages and provide a super-large area with high operation area, high controllability, high transmittance and high light transmittance in a non-hydrogen environment.
  • a method of preparing a silicon-graphene thin film device is to overcome the above disadvantages and provide a super-large area with high operation area, high controllability, high transmittance and high light transmittance in a non-hydrogen environment.
  • the silicon substrate is used as a substrate. After reasonable pretreatment, the substrate is placed in a mixture of a metal phthalocyanine compound and an inorganic salt. Under a certain atmosphere and temperature, the metal phthalocyanine compound is thermally cracked, and finally on the silicon substrate. Direct growth yields a highly oriented graphene film.
  • the silicon substrate pretreatment method is as follows: firstly, the silicon substrate of a certain size obtained by cutting is sequentially placed in acetone, ethanol, deionized water for ultrasonic cleaning, each time for 10 to 20 minutes, and then from deionized water. The substrate is taken out and dried with high-purity nitrogen gas; then the silicon substrate is immediately intruded into a mixed solution of concentrated sulfuric acid and hydrogen peroxide, and boiled for 30 to 50 minutes, and the ratio of concentrated sulfuric acid to hydrogen peroxide is a volume ratio of 7:3 to 9:1. between. Finally, the silicon substrate was taken out and dried with high-purity nitrogen gas, and directly placed in a mixture of a metal phthalocyanine compound and an inorganic salt.
  • the treated silicon substrate is laid flat or side-mounted, and is buried in a mixture of a salt and a phthalocyanine.
  • the phthalocyanine-based substance includes a non-metal phthalocyanine substance, a metal phthalocyanine substance, a metal oxide phthalocyanine substance, a polymer containing a phthalocyanine ring structure, and a porphyrin group containing a phthalocyanine ring-like structure. polymer.
  • the inorganic salt reaction bed is filled with an inorganic salt for a high temperature resistant container;
  • the inorganic salt is a mixture of one or more of a sodium salt, a potassium salt, a sulfate salt, a hydrochloride salt, and a nitrate salt.
  • the mass ratio of the inorganic salt to the phthalocyanine-based substance is from 1 to 99%.
  • the inorganic salt and the reaction raw material are uniformly mixed by uniformly mixing the phthalocyanine substance and the inorganic salt before the temperature rise or after the inorganic salt is melted, and uniformly adding the phthalocyanine substance to the inorganic salt reaction bed.
  • the shielding gas is one of nitrogen gas, argon gas, argon/hydrogen gas mixture, argon gas/ammonia gas mixture gas, nitrogen/hydrogen gas mixture gas, nitrogen/ammonia gas mixture gas, and the shielding gas flow rate is controlled at 10- 50cm 3 ⁇ min -1 between.
  • the mixed gas volume ratio is from 0.1:9.9 to 1:9.
  • the cleavage temperature is 600-1000 ° C
  • the cleavage time is 4-24 h.
  • the cleavage reaction can be carried out in the absence of a catalyst or a metal catalyst, which is a copper foil, a copper mesh, a nickel foil, a nickel foam, a copper alloy or a nickel alloy.
  • a catalyst or a metal catalyst which is a copper foil, a copper mesh, a nickel foil, a nickel foam, a copper alloy or a nickel alloy.
  • the conductivity of the device is improved, and the square resistance test reaches 1 ⁇ -1 , which is equivalent to the conductivity of copper.
  • the invention is obtained in a non-hydrogen environment, does not require a metal as a catalyst, and the method is safe, environmentally friendly and simple; the thickness, structure and size of the obtained graphene film are easy to control and have high planar orientation; the grown graphene does not need a transfer process It can be directly used to manufacture various devices, improve the electrical characteristics, reliability, and reduce the complexity of device manufacturing, and is expected to achieve industrial production.
  • FIG. 1 is a sample of a silicon substrate device deposited with a graphene film according to an embodiment of the present invention
  • TEM 2 is a transmission electron microscope (TEM) spectrum of a graphene film on a silicon substrate according to an embodiment of the present invention (baking temperature: 800 ° C, raw material is copper phthalocyanine);
  • FIG 3 is a Raman diagram of a graphene film on a silicon substrate according to an embodiment of the present invention (a calcination temperature of 800 ° C, a raw material of copper phthalocyanine);
  • FIG. 4 is a Raman spectrum of a graphene film on a silicon substrate according to an embodiment of the present invention (a calcination temperature of 800 ° C, a raw material of nickel phthalocyanine);
  • FIG. 5 is a Raman spectrum of a graphene film on a silicon substrate according to an embodiment of the present invention (a calcination temperature of 800 ° C, and the raw material is a non-metal phthalocyanine).
  • a silicon substrate is used as a substrate, and after reasonable pretreatment, the substrate is placed in a mixture of a phthalocyanine compound and sodium chloride, wherein a mixing ratio of the phthalocyanine compound to sodium chloride is qualitative. The ratio is 1:99 to 10:90.
  • a temperature-programming technique it is calcined in an inert atmosphere at 600 to 1000 ° C for 4 to 10 hours, and finally grown directly on a silicon substrate to obtain a highly oriented graphene film.
  • the pretreatment method of the silicon substrate is as follows: firstly, the silicon substrate of a certain size obtained by cutting is sequentially placed in acetone, ethanol and deionized water for ultrasonic cleaning for 10 to 20 minutes each time, and then the substrate is taken out from the deionized water. After drying with high-purity nitrogen gas, the silicon substrate is immediately intruded into a mixed solution of concentrated sulfuric acid and hydrogen peroxide, and boiled for 30 to 50 minutes, and the ratio of concentrated sulfuric acid to hydrogen peroxide is between 7:3 and 9:1 by volume. Finally, the silicon substrate was taken out and dried with high-purity nitrogen gas, and directly placed in a mixture of a metal phthalocyanine compound and an inorganic salt.
  • Example 1 The embodiment is as follows. After the treatment, the silicon substrate is placed in a mixture of copper phthalocyanine and sodium chloride salt, and the mass ratio of the mixture is 1:99, and the mixture is baked at 800 ° C for 4 hours under an argon atmosphere, and finally Direct growth on a silicon substrate yields a highly oriented graphene film.
  • the appearance sample of the device is shown in Fig. 1 of the specification, and the transmission electron microscope pattern of the graphene film deposited on the silicon substrate is as shown in Fig. 1 of the specification.
  • the Raman spectrum of the device is shown in Fig. 3 of the accompanying drawings.
  • Embodiment 2 The embodiment is as follows. After the treatment, the silicon substrate is placed in a mixture of copper phthalocyanine and sodium chloride salt, and the mass ratio of the mixture is 1:99, and the mixture is baked at 600 ° C for 4 hours under an argon atmosphere, and finally Direct growth on a silicon substrate yields a highly oriented graphene film.
  • Embodiment 3 The embodiment is as follows. After the treatment, the silicon substrate is placed in a raw material of nickel phthalocyanine and chlorine. The mixture of sodium salts was mixed at a mass ratio of 1:99, and calcined at 800 ° C for 4 hours under an argon atmosphere, and finally grown directly on a silicon substrate to obtain a highly oriented graphene film. The Raman spectrum of this device is shown in Figure 4 of the specification.
  • Embodiments are as follows. After the treatment, the silicon substrate is placed in a mixture of nickel phthalocyanine and sodium chloride as a raw material, and the mass ratio of the mixture is 1:99, and calcined at 600 ° C for 4 hours under an argon atmosphere, and finally Direct growth on a silicon substrate yields a highly oriented graphene film.
  • Embodiments are as follows. After the treatment, the silicon substrate is placed in a mixture of a non-metal phthalocyanine and a sodium chloride salt, and the mass ratio of the mixture is 1:99, and calcined at 800 ° C for 4 hours under an argon atmosphere, and finally Direct growth on a silicon substrate yields a highly oriented graphene film.
  • the Raman spectrum of this device is shown in Figure 5 of the specification.
  • Embodiments are as follows. After the treatment, the silicon substrate is placed in a mixture of a non-metal phthalocyanine and a sodium chloride salt, and the mass ratio of the mixture is 1:99, and calcined at 600 ° C for 4 hours under an argon atmosphere, and finally Direct growth on a silicon substrate yields a highly oriented graphene film.

Abstract

Cette invention concerne un procédé permettant de faire directement croître une membrane de graphène sur un substrat en silicium. Un substrat en silicium semi-conducteur est utilisé à titre de substrat, après qu'un prétraitement raisonnable est mis en œuvre sur le substrat en silicium, un composé de phtalocyanine est utilisé à titre de source de carbone solide, et on fait directement croître la membrane de graphène sur le substrat en silicium par une technique de craquage thermique en phase solide, dans une certaine condition d'atmosphère, par ajustement de la température de réaction, du type d'atmosphères, de la vitesse d'écoulement et autre, pour obtenir ainsi un échantillon de dispositif à substrat en silicium sur lequel la membrane de graphène est déposée comme illustré sur la figure de l'abrégé. De plus, comme la surface du substrat en silicium est recouverte avec la membrane de graphène, la résistance surfacique du substrat en silicium va jusqu'à 1 Ω·□-1, ce qui équivaut à la conductivité du cuivre. La présente invention s'obtient dans un environnement non-hydrogène, sans métal à titre de catalyseur, et le procédé est sans danger, respectueux de l'environnement et simple; la membrane de graphène obtenue est facile à contrôler en termes d'épaisseur, de structure et de taille et présente une forte orientation de plan; après croissance, le graphène peut être directement utilisé pour la fabrication de divers dispositifs sans besoin de processus de transfert, ce qui améliore la propriété électrochimique et la fiabilité des dispositifs, réduit la complexité de fabrication de ces dispositifs, et permet une production à l'échelle industrielle.
PCT/CN2014/095114 2014-12-03 2014-12-26 Procédé permettant de faire directement croître une membrane de graphène sur un substrat en silicium WO2016086477A1 (fr)

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CN109136842B (zh) * 2018-08-22 2021-07-27 中国科学院宁波材料技术与工程研究所 石墨烯薄膜及其制备方法
CN113651356A (zh) * 2021-08-16 2021-11-16 电子科技大学 核壳空腔结构二氧化钛石墨烯复合体制备方法及其应用
CN114774856A (zh) * 2022-04-28 2022-07-22 常州二维碳素科技股份有限公司 石墨烯导热膜制备方法

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CN113651356A (zh) * 2021-08-16 2021-11-16 电子科技大学 核壳空腔结构二氧化钛石墨烯复合体制备方法及其应用
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