WO2016086477A1 - Method for directly growing graphene membrane on silicon substrate - Google Patents
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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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- 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
Disclosed is a method for directly growing a graphene membrane on a silicon substrate. A semiconductor silicon substrate is used as a substrate, after a reasonable pretreatment is carried out on the silicon substrate, a phthalocyanine compound is used as a solid carbon source, the graphene membrane is directly grown on the silicon substrate by a solid phase thermal cracking technique, under a certain atmosphere condition, by adjusting the reaction temperature, the kind of atmospheres, the flowing speed and the like, wherein a silicon substrate device sample deposited with the graphene membrane is as shown in the figure in the abstract. Furthermore, since the surface of the silicon substrate is covered with the graphene membrane, the sheet resistance of the silicon substrate is up to 1 Ω·□-1, which is equivalent to the conductivity of copper. The present invention is obtained in a non-hydrogen environment, with no metal as a catalyst, and the method is safe, environmentally friendly and simple; the resulting graphene membrane is easy to control in thickness, structure and size and has high plane orientation; the grown graphene can be directly used for manufacturing various devices without the need of a transferring process, which improves the electrochemical property and reliability of the devices, reduces the manufacturing complexity of the devices, and can achieve the industrial production.
Description
本发明涉及石墨烯新材料制备领域，特别涉及一种在硅基片上直接生长得到石墨烯膜材料的方法，适用于无需转移的大面积石墨烯膜材料的生长制备，并为硅基片-石墨烯器件的制造提供材料。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.
石墨烯(graphene)是指紧密堆积成二维蜂窝状晶格结构的单层碳原子，他是构建其他维数炭材料(零维富勒烯、一维纳米碳管、三维石墨)的基本单元。石墨烯材料是目前已知最轻最薄的材料，单层仅原子厚度，它具有极其优异的物理化学性质，比如石墨烯是一种零带隙半导体，电子在其中运动速度可达光速的1/300；石墨烯载流子迁移速率高达2×105cm2·V-1·S-1，是Si的数百倍；超强的机械性能，杨氏模量约1000GPa；极高的比表面积和极好的气敏性；极高的透明性和柔韧性，而且它与衬底不存在失配问题，可以与Si基器件工艺完全兼容，具有突出的产业优势。因此石墨烯的出现为产业界和科学界带来曙光，它是最被看好的替代Si成为下一代基础半导体材料的新材料。同时由于石墨烯独特的结构及优异的电学、热学和力学性能，可望在高功能纳电子器件、复合材料、催化材料、电池材料、场发射
材料、气体传感器及气体存储等领域获得广泛应用。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. /300; graphene carrier mobility rate of up to 2 × 10 5 cm 2 · V -1 · S -1 , is hundreds of times of Si; superior mechanical properties, Young's modulus of about 1000GPa; very high ratio Surface area and excellent gas sensitivity; extremely high transparency and flexibility, and it has no mismatch with the substrate, can be fully compatible with the Si-based device process, and has outstanding industrial advantages. Therefore, the emergence of graphene has brought dawn to the industry and the scientific community. It is the most promising new material to replace Si as the next generation of basic semiconductor materials. At the same time, due to the unique structure of graphene and excellent electrical, thermal and mechanical properties, it is expected to be widely used in high-function nanoelectronic devices, composite materials, catalytic materials, battery materials, field emission materials, gas sensors and gas storage.
尽管石墨烯具有如此优异的性质，但是目前在石墨烯的制备方面仍然存在很多亟待解决的关键问题。目前国际主流是以外延生长法制备石墨烯材料，这种方法是基于过渡金属催化的CVD法，需要在高温下，充入碳源气体(甲烷、乙烷、乙炔等)，气体分解并在基底形成石墨烯，该方法需要1000度以上的高温，且需要氢气作为还原性气体，对生产条件要求严格，反应时间长，产率低下，且大量危险气体的使用增加了生产成本也限制了石墨烯的进一步应用。且石墨烯从基底(如铜、镍、碳化硅等衬底)上剥离也十分困难，往往采用强酸腐蚀、高温气化等极端方法，不仅成本高、环境污染大、也损伤了石墨烯成品。如发明专利CN102903616、CN102891074、CN101285175A等。因此必须突破现有技术的限制，从工艺上探索新的合成石墨烯器件方法，实现无转移的大面积洁净石墨烯薄膜的生长方法。Although graphene has such excellent properties, there are still many key problems to be solved in the preparation of graphene. At present, 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. 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. Moreover, it is very difficult to peel off graphene from a substrate (such as copper, nickel, silicon carbide, etc.), and extreme methods such as strong acid corrosion and high temperature gasification are often used, which not only has high cost, large environmental pollution, but also damages the finished graphene. Such as invention patents CN102903616, CN102891074, CN101285175A and so on. Therefore, it is necessary to break through the limitations of the prior art, explore a new method of synthesizing graphene devices from the process, and realize a growth method of a large-area clean graphene film without transfer.
Si是一种宽禁带材料，具有良好的电学和热学性能，可用于制备功率器件，频率器件等。目前硅(Si)基的关键尺寸已经达到理论和技术极限，量子效应已经成为主要限制机制。石墨烯发现之后，如果能够使其在硅基片上直接生长得到大面积，质量高的石墨烯膜，这必将减小晶格失配，避免转移过程中残胶引起的性能退化，提高石墨烯
和硅衬底接触质量，为硅-石墨烯结构器件提供整体材料。同时整体材料直接用于制造各种器件，提高了器件的光学特性、可靠性、可重复性、可操作性、降低了器件制造的成本和复杂性，硅基片上直接生长得到石墨烯膜的技术方法必将具有重要的产业意义和科学研究价值。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. At present, the critical dimensions of silicon (Si) groups have reached the theoretical and technical limits, and quantum effects have become the main limiting mechanism. After graphene is discovered, if it can be directly grown on a silicon substrate to obtain a large-area, high-quality graphene film, this will certainly reduce lattice mismatch, avoid performance degradation caused by residual glue during transfer, and improve graphene.
The quality of contact with the silicon substrate provides a monolithic material for the silicon-graphene structure device. At the same time, 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.
发明内容Summary of the invention
本发明的目的在于克服上述缺点，提供一种操作简单、易于控制、成本低、非氢环境下，在硅基片上直接生长得到面积大、导电率高、透光率高的超大面积高质量的硅-石墨烯薄膜器件的制备方法。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.
为实现上述目的，本发明采用的技术方案是：In order to achieve the above object, the technical solution adopted by the present invention is:
采用硅基片作为衬底，经过合理预处理后将基片放入金属酞菁化合物与无机盐的混合物中，在一定的气氛，温度条件下，金属酞菁化合物热裂解，最终在硅基片上直接生长得到具有高度取向的石墨烯膜。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.
进一步地，硅基片预处理方式为：首先将切割得到的一定尺寸大小的硅基片依次放入丙酮、乙醇、去离子水中进行超声清洗，每次时间10～20分钟，之后从去离子水中取出基片，用高纯氮气吹干；之后将硅基片立即侵入浓硫酸和双氧水的混合溶液中，煮沸30～50分钟，浓硫酸与双氧水的比例为体积比7:3～9:1之间。最后取出硅基片用高纯氮气吹干，直接放入金属酞菁化合物与无机盐的混合物中。
Further, 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.
进一步地，处理后的硅基片平放或者侧放，掩埋于盐类与酞菁类物质混合物中。Further, the treated silicon substrate is laid flat or side-mounted, and is buried in a mixture of a salt and a phthalocyanine.
进一步地，所述酞菁类物质包括非金属酞菁类物质、金属酞菁类物质、金属氧化物酞菁类物质、含有酞菁环结构的高分子和含类酞菁环结构的卟啉类聚合物。Further, 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.
进一步地，所述无机盐反应床为耐高温的容器装填无机盐；所述无机盐为钠盐、钾盐、硫酸盐、盐酸盐、硝酸盐的一种或几种的混合。Further, 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.
进一步地，无机盐与酞菁类物质的质量比为1-99％。Further, the mass ratio of the inorganic salt to the phthalocyanine-based substance is from 1 to 99%.
进一步地，所述将无机盐与反应原料混合均匀，方法为：酞菁类物质与无机盐在升温前混合均匀或在无机盐熔融后，将酞菁类物质均匀加入无机盐反应床中。Further, 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.
进一步地，所述保护气体为氮气、氩气、氩气/氢气混合气、氩气/氨气混合气、氮气/氢气混合气、氮气/氨气混合气之一，保护气体流速控制在10-50cm3·min-1之间。Further, 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.
进一步地，所述混合气体积比为0.1:9.9-1:9。Further, the mixed gas volume ratio is from 0.1:9.9 to 1:9.
进一步地，所述裂解温度为600-1000℃，裂解时间为4-24h。Further, the cleavage temperature is 600-1000 ° C, and the cleavage time is 4-24 h.
进一步地，裂解反应可在无催化剂或有金属催化剂条件下进行，所述金属催化剂为铜箔、铜网、镍箔、泡沫镍、铜合金或镍合金。Further, 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.
半导体的硅基片由于表面均匀覆盖导电石墨烯膜后，器件导电性提高，方阻测试达到1Ω·□-1，与铜导电性相当。本发明是在非氢环
境中得到，无需金属作为催化剂，方法安全、环保、简单；所得到石墨烯膜的厚度、结构、尺寸容易控制，且具有高度平面取向性；生长的石墨烯无需转移过程，便可以直接用于制造各种器件，提高了器件的电学特性，可靠性，降低了器件制造复杂性，有望实现工业化生产。After the silicon substrate of the semiconductor uniformly covers the conductive graphene film, the conductivity of the device is improved, and the square resistance test reaches 1 Ω·□ -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.
图1为本发明实施例提供的沉积有石墨烯膜的硅基片器件样片；1 is a sample of a silicon substrate device deposited with a graphene film according to an embodiment of the present invention;
图2为本发明实施例提供的硅基片上石墨烯膜的透射电镜(TEM)图谱(焙烧温度800℃，原料为酞菁铜)；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);
图3为本发明实施例提供的硅基片上石墨烯膜的拉曼(Raman)图谱(焙烧温度800℃，原料为酞菁铜)；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);
图4为本发明实施例提供的硅基片上石墨烯膜的拉曼(Raman)图谱(焙烧温度800℃，原料为酞菁镍)；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);
图5为本发明实施例提供的硅基片上石墨烯膜的拉曼(Raman)图谱(焙烧温度800℃，原料为非金属酞菁)。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).
采用硅基片作为衬底，经过合理预处理后将基片放入酞菁类化合物与氯化钠的混合物中，其中酞菁类化合物与氯化钠的混合比例为质
量比1:99～10:90。采用程序升温技术，于600～1000℃惰性气氛下，焙烧4～10小时，最终在硅基片上直接生长得到具有高度取向的石墨烯膜。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. Using 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.
硅基片预处理方式为：首先将切割得到的一定尺寸大小的硅基片依次放入丙酮、乙醇、去离子水中进行超声清洗，每次时间10～20分钟，之后从去离子水中取出基片，用高纯氮气吹干；之后将硅基片立即侵入浓硫酸和双氧水的混合溶液中，煮沸30～50分钟，浓硫酸与双氧水的比例为体积比7:3～9:1之间。最后取出硅基片用高纯氮气吹干，直接放入金属酞菁化合物与无机盐的混合物中。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.
实施例一：实施方式如上，处理后硅基片放入原料为酞菁铜与氯化钠盐的混合物中，混合物质量比例为1:99，于800℃氩气气氛下焙烧4小时，最终在硅基片上直接生长得到具有高度取向的石墨烯膜。此器件的外观样片如说明书附图1所示，硅基片沉积石墨烯膜的透射电镜图谱如说明书附图1所示，此器件的拉曼图谱如说明书附图附图3所示。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.
实施例二：实施方式如上，处理后硅基片放入原料为酞菁铜与氯化钠盐的混合物中，混合物质量比例为1:99，于600℃氩气气氛下焙烧4小时，最终在硅基片上直接生长得到具有高度取向的石墨烯膜。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.
实施例三：实施方式如上，处理后硅基片放入原料为酞菁镍与氯
化钠盐的混合物中，混合物质量比例为1:99，于800℃氩气气氛下焙烧4小时，最终在硅基片上直接生长得到具有高度取向的石墨烯膜。此器件的拉曼图谱如说明书附图4所示。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.
实施例四：实施方式如上，处理后硅基片放入原料为酞菁镍与氯化钠盐的混合物中，混合物质量比例为1:99，于600℃氩气气氛下焙烧4小时，最终在硅基片上直接生长得到具有高度取向的石墨烯膜。Embodiment 4: 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.
实施例五：实施方式如上，处理后硅基片放入原料为非金属酞菁与氯化钠盐的混合物中，混合物质量比例为1:99，于800℃氩气气氛下焙烧4小时，最终在硅基片上直接生长得到具有高度取向的石墨烯膜。此器件的拉曼图谱如说明书附图5所示。Embodiment 5: 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.
实施例六：实施方式如上，处理后硅基片放入原料为非金属酞菁与氯化钠盐的混合物中，混合物质量比例为1:99，于600℃氩气气氛下焙烧4小时，最终在硅基片上直接生长得到具有高度取向的石墨烯膜。
Embodiment 6: 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.
Claims (9)
- 一种于硅基片上直接生长石墨烯膜的方法，其特征在于：采用硅基片作为衬底，经过合理预处理后将基片放入金属酞菁化合物与无机盐的混合物中，在一定的气氛，温度条件下，金属酞菁化合物热裂解，最终在硅基片上直接生长得到具有高度取向的石墨烯膜。A method for directly growing a graphene film on a silicon substrate, characterized in that a silicon substrate is used as a substrate, and after a reasonable pretreatment, the substrate is placed in a mixture of a metal phthalocyanine compound and an inorganic salt, at a certain Under the conditions of temperature and temperature, the metal phthalocyanine compound is thermally cracked, and finally grown directly on the silicon substrate to obtain a highly oriented graphene film.
- 如权利要求1所述的于硅基片上直接生长石墨烯膜的方法，其特征在于：所述酞菁类物质包括非金属酞菁类化合物、金属酞菁类化合物、金属氧化物酞菁类化合物、含有酞菁环结构的高分子和含类酞菁环结构的卟啉类聚合物。The method for directly growing a graphene film on a silicon substrate according to claim 1, wherein the phthalocyanine compound comprises a non-metal phthalocyanine compound, a metal phthalocyanine compound, and a metal oxide phthalocyanine compound. A polymer containing a phthalocyanine ring structure and a porphyrin polymer containing a phthalocyanine ring-like structure.
- 如权利要求1所述的于硅基片上直接生长石墨烯膜的方法，其特征在于：所述无机盐为为钠盐、钾盐、硫酸盐、盐酸盐、硝酸盐的一种或几种的混合。The method for directly growing a graphene film on a silicon substrate according to claim 1, wherein the inorganic salt is one or more of a sodium salt, a potassium salt, a sulfate salt, a hydrochloride salt, and a nitrate salt. the mix of.
- 如权利要求1所述的于硅基片上直接生长石墨烯膜的方法，其特征在于：硅基片预处理方式为：首先将切割得到的一定尺寸大小的硅基片依次放入丙酮、乙醇、去离子水中进行超声清洗，每次时间10～20分钟，之后从去离子水中取出基片，用高纯氮气吹干；之后将硅基片立即侵入浓硫酸和双氧水的混合溶液中，煮沸30～50分钟，浓硫酸与双氧水的比例为体积比7:3，最后取出硅基片用高纯氮气吹干，直接放入金属酞菁化合物与无机盐的混合物中。The method for directly growing a graphene film on a silicon substrate according to claim 1, wherein the silicon substrate is pretreated by first cutting the silicon substrate of a certain size into acetone, ethanol, and the like. Ultrasonic cleaning in deionized water for 10-20 minutes each time, after which the substrate is taken out from the deionized water and dried with high-purity nitrogen; then the silicon substrate is immediately intruded into the mixed solution of concentrated sulfuric acid and hydrogen peroxide, and boiled for 30~ At 50 minutes, the ratio of concentrated sulfuric acid to hydrogen peroxide was 7:3 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.
- 如权利要求1所述的于硅基片上直接生长石墨烯膜的方法，其特征在于：所述保护气体为氮气、氩气、氩气/氢气混合气、氩气/氨气混合气、氮气/氢气混合气、氮气/氨气混合气之一，保护气体流速控制在10～50cm3·min-1之间。 The method for directly growing a graphene film on a silicon substrate according to claim 1, wherein the shielding gas is nitrogen gas, argon gas, argon/hydrogen gas mixture, argon gas/ammonia gas mixture gas, nitrogen gas/ One of a mixture of hydrogen gas and nitrogen/ammonia gas, and the flow rate of the shielding gas is controlled between 10 and 50 cm 3 ·min -1 .
- 如权利要求1所述的于硅基片上直接生长石墨烯膜的方法，其特征在于：所述混合气体积比为0.1:9.9～1:9。The method of directly growing a graphene film on a silicon substrate according to claim 1, wherein the mixed gas volume ratio is from 0.1:9.9 to 1:9.
- 如权利要求1所述的于硅基片上直接生长石墨烯膜的方法，其特征在于：所述裂解温度为600～1000℃。A method of directly growing a graphene film on a silicon substrate according to claim 1, wherein the cracking temperature is 600 to 1000 °C.
- 如权利要求1所述的于硅基片上直接生长石墨烯膜的方法，其特征在于：所述裂解时间为4～24小时。A method of directly growing a graphene film on a silicon substrate according to claim 1, wherein the cracking time is 4 to 24 hours.
- 如权利要求1所述的于硅基片上直接生长石墨烯膜的方法，其特征在于：裂解反应可在无催化剂或有金属催化剂条件下进行，所述金属催化剂为铜箔、铜网、镍箔、泡沫镍、铜合金或镍合金。 The method for directly growing a graphene film on a silicon substrate according to claim 1, wherein the cracking reaction is carried out without a catalyst or a metal catalyst, and the metal catalyst is copper foil, copper mesh, and nickel foil. , foamed nickel, copper alloy or nickel alloy.
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