阅读说明：本技术 一种石墨烯半导体制备装置及方法 (Graphene semiconductor preparation device and method ) 是由 吕尊华 李继森 司崇殿 于 2020-05-07 设计创作，主要内容包括：本发明公开了一种石墨烯半导体制备装置及方法,一种石墨烯半导体制备方法,包括以下步骤：I、提供SiC衬底,利用氢气刻蚀；II、在氩气氛围下对SiC衬底片进行升温；III、在超高真空的环境下,形成六方蜂窝状的石墨烯薄膜；IV：形成石墨烯半导体复合材料。一种石墨烯半导体制备装置,包括：氢气刻蚀模块；C原子自组装模块；同质外延成长模块；反应合成模块。本发明不仅可以获得大面积、高质量的石墨烯,而且所获得的石墨烯具有较好的均一性,且与当前的集成电路技术有很好的兼容性；同时利用了半导体材料的优点与石墨烯的特性,实现了石墨烯的制备及其与半导体材料复合同时进行,具有广泛的适用性。(The invention discloses a graphene semiconductor preparation device and method, and a graphene semiconductor preparation method comprises the following steps: I. providing a SiC substrate, and etching by using hydrogen; II. Heating the SiC substrate slice in an argon atmosphere; III, forming a hexagonal honeycomb graphene film in an ultrahigh vacuum environment; IV: and forming the graphene semiconductor composite material. A graphene semiconductor manufacturing apparatus includes: a hydrogen etching module; a C atom self-assembly module; a homoepitaxial growth module; and (3) a reaction synthesis module. The method can obtain large-area high-quality graphene, and the obtained graphene has good uniformity and good compatibility with the current integrated circuit technology; meanwhile, the advantages of the semiconductor material and the characteristics of the graphene are utilized, the preparation of the graphene and the compounding with the semiconductor material are simultaneously carried out, and the method has wide applicability.)

1. A graphene semiconductor preparation method is characterized by comprising the following steps: the method comprises the following steps:

I. providing a SiC substrate, and carrying out planarization treatment on the surface of the SiC substrate by utilizing the etching effect of hydrogen to the substrate at 1450-1600 ℃, and etching for 25-35min to form a surface with atomic-level flatness and step array morphology;

II. Heating the SiC substrate slice to 1000-1100 ℃ in the argon atmosphere of 1.5L/min to ensure that the self-assembly process of the C atoms is more fully carried out, and preparing a large-area and uniform graphene film;

III, continuously heating the surface of the SiC substrate to 1400-1500 ℃ in an ultrahigh vacuum environment to break carbon-silicon bonds on the surface of the SiC substrate, wherein Si atoms are sublimated earlier than C atoms to be desorbed from the surface, and the C atoms enriched on the surface are reconstructed to form a hexagonal honeycomb graphene film;

IV: and (3) depositing semiconductor material particles on the surface of the graphene film prepared in the step III to form the graphene semiconductor composite material.

2. The method for producing a graphene semiconductor according to claim 1, wherein: the SiC substrate is one of 4H-SiC, 6H-SiC and 3C-SiC single crystals.

3. The method for preparing a graphene semiconductor according to claim 2, wherein in the step II, the pressure of argon gas is controlled to be 2 × 10³Pa or less.

4. The method for preparing a graphene semiconductor according to claim 3, wherein in the step III, the pressure of the ultra-high vacuum is 1-2 × 10³Pa。

5. The method for producing a graphene semiconductor according to claim 4, wherein: the specific steps of the step IV are as follows: dispersing the graphene film into an aqueous solution, and then adding semiconductor material particles serving as a complex; the grain diameter of the semiconductor material grains is 0.05-8 mu m, and the semiconductor material grains are stirred for 12-18 hours; in the stirring process, the graphene is uniformly dispersed, so that the semiconductor material is uniformly compounded on the surface of the graphene; and after the reaction is finished, performing suction filtration, washing with an organic solvent, drying, and sintering at 550-650 ℃ for 35-40min to obtain the graphene semiconductor composite material.

6. The method for producing a graphene semiconductor according to claim 5, wherein: the semiconductor particle material is one of silicon carbide, gallium nitride, zinc oxide and aluminum nitride; the organic solvent is one or more of pyrrolidone, imidazolidinone and amide.

7. A production apparatus used in the graphene semiconductor production method according to claim 1, characterized in that: the device comprises:

the hydrogen etching module is used for carrying out planarization treatment on the SiC substrate by using hydrogen;

the C atom self-assembly module is used for heating the SiC substrate by utilizing argon gas;

a homoepitaxy growth module, wherein a graphene film is prepared under ultrahigh vacuum;

and the reaction synthesis module is used for forming the graphene semiconductor composite material.

8. The graphene semiconductor manufacturing apparatus according to claim 7, wherein: the C atom self-assembly module further comprises: and the control unit is used for controlling the flow, the temperature and the air pressure of the argon.

9. The graphene semiconductor manufacturing apparatus according to claim 8, wherein: the control unit comprises an access enabling valve used for controlling access time through switch action.

Technical Field

The present invention relates to a manufacturing apparatus and method, and in particular, to a graphene semiconductor manufacturing apparatus and method.

Background

Semiconductors are the mainstay of the modern electronics industry, which is the core material for transistors, integrated circuits, and various types of electronic components. With the development of semiconductor technology, the performance of conventional elemental semiconductors such as silicon and germanium has been improved in a smaller and smaller space. Graphene receives more and more attention in the technical field of semiconductors with excellent conductivity and wide development prospect. At present, the chemical vapor deposition method is the most important way to prepare high-quality large-area graphene. However, there are the following drawbacks: the morphology and the performance of the prepared graphene are greatly influenced by a substrate material, the graphene is difficult to transfer and is difficult to be compatible with the current mature large-scale integrated circuit process, and the popularization and the application of the graphene-based device are influenced.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention provides a graphene semiconductor preparation device and a graphene semiconductor preparation method.

In order to solve the technical problems, the invention adopts the technical scheme that: a graphene semiconductor preparation method comprises the following steps:

I. providing a SiC substrate, and carrying out planarization treatment on the surface of the SiC substrate by utilizing the etching effect of hydrogen to the substrate at 1450-1600 ℃, and etching for 25-35min to form a surface with atomic-level flatness and step array morphology;

II. Heating the SiC substrate slice to 1000-1100 ℃ in the argon atmosphere of 1.5L/min to ensure that the self-assembly process of the C atoms is more fully carried out, and preparing a large-area and uniform graphene film;

III, continuously heating the surface of the SiC substrate to 1400-1500 ℃ in an ultrahigh vacuum environment to break carbon-silicon bonds on the surface of the SiC substrate, wherein Si atoms are sublimated earlier than C atoms to be desorbed from the surface, and the C atoms enriched on the surface are reconstructed to form a hexagonal honeycomb graphene film;

IV: and (3) depositing semiconductor material particles on the surface of the graphene film prepared in the step III to form the graphene semiconductor composite material.

Further, the SiC substrate is one of 4H-SiC, 6H-SiC and 3C-SiC single crystals.

Further, in step II, the pressure of argon gas was controlled to 2 × 10³Pa or less.

Further, in step III, the pressure of the ultrahigh vacuum is 1-2 × 10³Pa。

Further, the specific steps of step IV are: dispersing the graphene film into an aqueous solution, and then adding semiconductor material particles serving as a complex; the grain diameter of the semiconductor material grains is 0.05-8 μm, and the mixture is stirred for 12-18 hours; in the stirring process, the graphene is uniformly dispersed, so that the semiconductor material is uniformly compounded on the surface of the graphene; and after the reaction is finished, performing suction filtration, washing with an organic solvent, drying, and sintering at 550-650 ℃ for 35-40min to obtain the graphene semiconductor composite material.

Further, the semiconductor particle material is one of silicon carbide, gallium nitride, zinc oxide and aluminum nitride; the organic solvent is one or more of pyrrolidone, imidazolidinone and amide.

A graphene semiconductor manufacturing apparatus includes:

the hydrogen etching module is used for carrying out planarization treatment on the SiC substrate by using hydrogen;

the C atom self-assembly module is used for heating the SiC substrate by utilizing argon gas;

a homoepitaxy growth module, wherein a graphene film is prepared under ultrahigh vacuum;

and the reaction synthesis module is used for forming the graphene semiconductor composite material.

Further, the C atom self-assembly module further comprises: and the control unit is used for controlling the flow, the temperature and the air pressure of the argon.

Further, the control unit comprises an access enabling valve for controlling access time through switching action.

The method can obtain large-area high-quality graphene, and the obtained graphene has good uniformity, is slightly influenced by the substrate material, and has good compatibility with the current integrated circuit technology; meanwhile, the semiconductor material is deposited on the surface of the graphene to form the graphene semiconductor composite material, so that the advantages of the semiconductor material are utilized, the semiconductor material has sensitivity to photoelectricity, and the characteristics of the graphene are utilized, and the graphene semiconductor composite material plays a role in controlling the electron transmission property of the material, improving the photoelectric conversion efficiency of the material, increasing the stability of the semiconductor, enhancing the mechanical property of the material and the like. In addition, the design process is simple, the preparation of the graphene and the compounding with the semiconductor material are simultaneously carried out, and the method has wide applicability.

Drawings

Fig. 1 is a connection block diagram of a graphene semiconductor manufacturing apparatus according to a first embodiment of the present invention.

Detailed Description

The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.

A graphene semiconductor preparation method comprises the following steps:

I. providing a SiC substrate, and carrying out planarization treatment on the surface of the SiC substrate by utilizing the etching effect of hydrogen to the substrate at 1450-1600 ℃, and etching for 25-35min to form a surface with atomic-level flatness and step array morphology; the SiC substrate is one of 4H-SiC, 6H-SiC and 3C-SiC single crystals. The SiC substrate material can provide a C source required by graphene preparation. Since the SiC crystal is selected, the graphene must be carried out under high temperature conditions.

The etching using hydrogen can remove mechanical damage, scratches and the like brought by the SiC surface grinding and polishing process, so that the SiC surface presents a regular step shape, H2 reacts with SiC at high temperature to generate gaseous hydrocarbons such as C2H2 and the like, and in addition, some basic Si-based by-products and other impurities are generated, however, as the vapor pressure of CH4 and C2H2 is higher than that of silicon, the silicon at the earliest stage of the reaction cannot form vapor, but condenses on the SiC surface in a liquid state, Si droplets are preferentially formed at the edges of defects or steps along with the increase of the number of Si atoms, as the reaction progresses, the C atoms on the surface layer are gradually exhausted, and the Si droplets begin to react with hydrogen to form gaseous SiH4, which is carried away from the SiC surface by the hydrogen flow, so that the etching effect is achieved, the SiC surface is roughened by the excessively high etching speed, so that in order to slow down the etching speed and improve the etching quality, the high hydrogen pressure is kept in the etching process, and is controlled at 2 × 10³Pa or so.

II. Heating the SiC substrate slice to 1000-1100 ℃ in the argon atmosphere of 1.5L/min to ensure that the self-assembly process of the C atoms is more fully carried out, and preparing a large-area and uniform graphene film;

heating the SiC substrate slice in an argon atmosphere, wherein at a given temperature, the dense molecular cloud of argon can cause Si atoms and Ar atoms evaporated from the surface of the SiC substrate to collide with each other with a certain probability and be reflected back to the surface of the SiC substrate, so that the evaporation of the Si atoms is limited, the conversion rate of the SiC surface is reduced, and the growth speed of a Z axis of graphene is slowed down. Meanwhile, the temperature in the reaction crucible is correspondingly increased by the atmosphere, the graphitization temperature of the surface of the SiC substrate is increased by hundreds of degrees, and the heating temperature and the heating time are increased, so that the activity of C atoms is improved, the radial growth rate of graphene is further improved, the self-assembly process of the C atoms is more sufficient, and a large-area and uniform graphene film can be prepared.

Through the convection effect of the argon, the temperature distribution can be more uniform, and the uniformity and consistency of the generated graphene are greatly improved, however, the pressure of the argon cannot be too high, and the pressure of the argon is controlled to be 2 × 10³And the Pa is lower than the Pa, so that the phenomenon that Si atoms cannot be evaporated from the SiC wafer due to overhigh argon pressure is avoided, and the self-assembly process of the C atoms is influenced.

III, continuously heating the surface of the SiC substrate to 1400-1500 ℃ in an ultrahigh vacuum environment to break carbon-silicon bonds on the surface of the SiC substrate, leading Si atoms to be sublimated earlier than C atoms and be desorbed from the surface, leading the C atoms enriched on the surface to be reconstructed to form a hexagonal honeycomb-shaped graphene film, wherein the air pressure of the ultrahigh vacuum is 1-2 × 10³Pa。

And (3) raising the temperature again after vacuumizing, wherein oxides on the surface of the SiC sample can be heated and decomposed into SiO gas to be evaporated from the surface, the residual C atoms are gathered together on the surface of the SiC substrate, particularly near defects or at step edges to carry out self-assembly, and then the residual C atoms gradually extend to the whole surface of the SiC step to be uniformly distributed to form a continuous graphene sheet layer.

IV: and (3) depositing semiconductor material particles on the surface of the graphene film prepared in the step III to form the graphene semiconductor composite material.

The specific steps of the step IV are as follows: dispersing the graphene film into an aqueous solution, and then adding semiconductor material particles serving as a complex; the grain diameter of the semiconductor material grains is 0.05-8 μm, and the mixture is stirred for 12-18 hours; in the stirring process, the graphene is uniformly dispersed, so that the semiconductor material is uniformly compounded on the surface of the graphene; and after the reaction is finished, performing suction filtration, washing with an organic solvent, drying, and sintering at 550-650 ℃ for 35-40min to obtain the graphene semiconductor composite material.

The semiconductor particle material is one of silicon carbide, gallium nitride, zinc oxide and aluminum nitride; the organic solvent is one or more of pyrrolidone, imidazolidinone and amide.

The graphene semiconductor manufacturing apparatus shown in fig. 1 includes:

the hydrogen etching module is used for carrying out planarization treatment on the SiC substrate by using hydrogen;

the C atom self-assembly module is used for heating the SiC substrate by utilizing argon gas;

a homoepitaxy growth module, wherein a graphene film is prepared under ultrahigh vacuum; comprises a vacuum system and an induction heating and heat preservation system;

and the reaction synthesis module is used for forming the graphene semiconductor composite material.

The C atom self-assembly module further comprises: and the control unit is used for controlling the flow, the temperature and the air pressure of the argon. The control unit comprises an access enabling valve used for controlling access time through switch action. The control unit also comprises a temperature detection system and a gas flowmeter partial pressure system.