CN116514112B - Preparation method of large-area graphene on silicon surface - Google Patents
Preparation method of large-area graphene on silicon surface Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 71
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 60
- 239000010703 silicon Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000005530 etching Methods 0.000 claims abstract description 50
- 239000000758 substrate Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000000137 annealing Methods 0.000 claims abstract description 23
- 239000013078 crystal Substances 0.000 claims abstract description 21
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 14
- 230000008719 thickening Effects 0.000 claims abstract description 13
- 238000004518 low pressure chemical vapour deposition Methods 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 60
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- 238000000197 pyrolysis Methods 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 238000001657 homoepitaxy Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 81
- 239000000463 material Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 5
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- 230000007547 defect Effects 0.000 description 3
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- 238000001704 evaporation Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009103 reabsorption Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
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Classifications
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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
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/186—Epitaxial-layer growth characterised by the substrate being specially pre-treated by, e.g. chemical or physical means
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/36—Carbides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/08—Etching
- C30B33/12—Etching in gas atmosphere or plasma
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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
- C01B2204/00—Structure or properties of graphene
- C01B2204/02—Single layer graphene
Abstract
The invention provides a preparation method of large-area graphene on a silicon surface, which comprises the following steps: mounting the cleaned silicon substrate in equipment with a rapid annealing function, and forming a 3C-SiC single crystal seed layer on the silicon substrate; growing a 3C-SiC thickening layer on the 3C-SiC single crystal seed layer based on an LPCVD method on the 3C-SiC single crystal seed layer; etching the 3C-SiC thickened layer to obtain a step-shaped 3C-SiC etched layer; and carrying out high-temperature thermal decomposition on the step-shaped 3C-SiC etching layer, and growing a layer of graphene on the surface of the 3C-SiC etching layer. Because the silicon substrate has various specifications, a compact 3C-SiC monocrystalline seed layer can be firstly grown on a large-size silicon substrate, and then a 3C-SiC thickening layer is continuously grown on the compact 3C-SiC monocrystalline seed layer in a homoepitaxy manner, so that the subsequent preparation of large-area and high-quality graphene is facilitated.
Description
Technical Field
The invention relates to the technical field of semiconductor film materials, in particular to a preparation method of large-area graphene on a silicon surface.
Background
With the rapid development of microelectronics technologies, traditional silicon-based semiconductor electronic devices have significantly lagged behind the footsteps of the late moore's law era. Graphene can exist stably in nature as a two-dimensional material formed by carbon atom arrangement, and has huge application potential in the fields of next-generation photoelectric devices, transparent conductive films, sensors and the like due to unique properties such as thinnest, firmest, high thermal conductivity, high strength, high electron mobility, zero effective mass, high thermal conductivity and the like. In particular, it has high electron mobility at normal temperature, and is expected to be used as a substitute for silicon for developing new-generation electronic components or optoelectronic devices which are thinner and have a faster conduction speed.
Because of the growth mechanism of Si-surface epitaxial graphene, the growth condition of the Si-surface epitaxial graphene is mainly single-layer, double-layer or three-layer graphene alternately distributed, and thus the crystal domain size of the graphene is limited by the width of a platform to be in the order of tens of micrometers, so that the prior art does not have a scheme for growing large-crystal-domain semiconductor graphene on the Si surface. However, the small domain area of the Si-plane single-layer graphene is often unfavorable for the integration level of the device, thereby limiting the application of the single-layer graphene in industrial production.
Therefore, a method that can grow large-area semiconducting graphene is needed.
Disclosure of Invention
The embodiment of the invention provides a preparation method of large-area graphene on a silicon surface, which aims to solve the problem that large-area graphene cannot be grown at present.
In a first aspect, an embodiment of the present invention provides a method for preparing large-area graphene on a silicon surface, including the following steps:
mounting the cleaned silicon substrate in equipment with a rapid annealing function, and forming a 3C-SiC single crystal seed layer on the silicon substrate;
growing a 3C-SiC thickening layer on the 3C-SiC single crystal seed layer based on an LPCVD method on the 3C-SiC single crystal seed layer;
etching the 3C-SiC thickened layer to obtain a step-shaped 3C-SiC etched layer;
and carrying out high-temperature thermal decomposition on the step-shaped 3C-SiC etching layer, and growing a layer of graphene on the surface of the 3C-SiC etching layer.
In one possible implementation, the step-shaped 3C-SiC etch layer is obtained by etching the 3C-SiC thickened layer, including:
and (3) introducing grinding gas into the surface of the 3C-SiC thickened layer, and etching the 3C-SiC thickened layer to obtain the step-shaped 3C-SiC etched layer.
In one possible implementation, the grinding gas is hydrogen, the working temperature of the grinding gas is 1000-1150 ℃, and the charging time of the grinding gas is 10-60s.
In one possible implementation, the introduction of the abrasive gas at the surface of the 3C-SiC thickening layer is performed in a high temperature annealing furnace or a microwave plasma chemical vapor deposition apparatus.
In one possible implementation, mounting the cleaned silicon substrate in an apparatus having a rapid annealing function, forming a 3C-SiC single crystal seed layer on the silicon substrate, comprising:
continuously introducing a first preset gas into the equipment, heating the equipment, continuously introducing a second preset gas into the equipment when the temperature reaches the first preset temperature, stopping heating and keeping the second preset temperature unchanged after the temperature is increased to the second preset temperature, and performing rapid annealing on the silicon substrate, wherein the first preset gas is a protective gas, and the second preset gas contains at least one gas of methane or acetylene; and stopping introducing the first preset gas and the second preset gas after the rapid annealing reaches the preset time, introducing the third preset gas, and cooling to form the 3C-SiC monocrystalline seed layer on the silicon substrate.
In one possible implementation, the first preset gas is H 2 、Ar+H 2 、N 2 +H 2 Or one or more of inert gases, wherein the second preset gas is mixed gas of methane and acetylene, and the preset time is 1s-180s.
In one possible implementation, the second preset temperature is 800-1400 ℃, the first preset temperature is 550-650 ℃, and the temperature gradient of the device when the device is raised from the first preset temperature to the second preset temperature is greater than 25 ℃/s.
In one possible implementation, the step-shaped 3C-SiC etching layer is subjected to high-temperature pyrolysis at a temperature of 1000-1250 ℃, the duration of the high-temperature pyrolysis is 30-60s, and the pressure of the high-temperature pyrolysis is less than 10 -3 torr。
In one possible implementation, the step-shaped 3C-SiC etching layer is subjected to thermal decomposition, and a layer of graphene is grown on the surface of the 3C-SiC etching layer, including:
argon is introduced at high temperature as protective gas, the stepped 3C-SiC etching layer is subjected to high-temperature pyrolysis, and graphene grows on the surface of the 3C-SiC etching layer.
In one possible implementation, the step-shaped 3C-SiC etching layer is subjected to thermal decomposition, and a layer of graphene is grown on the surface of the 3C-SiC etching layer, including:
disilane is introduced at high temperature as a protective gas, the stepped 3C-SiC etching layer is subjected to high-temperature thermal decomposition, and graphene grows on the surface of the 3C-SiC etching layer.
The embodiment of the invention provides a preparation method of large-area graphene on a silicon surface, which comprises the steps of firstly, mounting a cleaned silicon substrate in equipment with a rapid annealing function, and forming a 3C-SiC single crystal seed layer on the silicon substrate. Then, a 3C-SiC thickening layer is grown on the 3C-SiC single crystal seed layer based on the LPCVD method. And then, etching the 3C-SiC thickened layer to obtain a step-shaped 3C-SiC etched layer. And finally, carrying out high-temperature thermal decomposition on the step-shaped 3C-SiC etching layer, and growing a layer of graphene on the surface of the 3C-SiC etching layer. Because the silicon substrate has various specifications, a compact 3C-SiC monocrystalline seed layer can be firstly grown on a large-size silicon substrate, and then a 3C-SiC thickening layer is continuously grown on the compact 3C-SiC monocrystalline seed layer in a homoepitaxy manner, so that the subsequent preparation of large-area and high-quality graphene is facilitated.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments or the description of the prior art will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a flowchart of a preparation method of large-area graphene on a silicon surface according to an embodiment of the present invention.
Detailed Description
In the following description, for purposes of explanation and not limitation, specific details are set forth such as the particular system architecture, techniques, etc., in order to provide a thorough understanding of the embodiments of the present invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced in other embodiments that depart from these specific details. In other instances, detailed descriptions of well-known systems, devices, circuits, and methods are omitted so as not to obscure the description of the present invention with unnecessary detail.
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the following description will be made by way of specific embodiments with reference to the accompanying drawings.
The preparation methods of graphene are mainly two main types, one is a SiC pyrolysis method and the other is a CVD method. The SiC pyrolysis method can release silicon atoms on the surface of SiC through high-temperature treatment above 1300 ℃, the carbon atoms are structurally formed into graphene, and when the substrate is semi-insulating SiC, the prepared graphene can be directly used for device preparation. However, due to the limitation of a growth mechanism, graphene obtained by a SiC pyrolysis method is not high in uniformity, and the quality of a sample is highly dependent on the quality of crystals of a substrate.
However, the high mismatch of Si and SiC lattice constants and thermal expansion coefficients can lead to a large number of defects in the 3C-SiC epitaxial layer, with a large lattice mismatch between Si and SiC, and more crystal defects in the heteroepitaxial 3C-SiC layer. In addition, the thermal expansion coefficients of Si and SiC are different, and the defect of the difference of the thermal expansion coefficients of epitaxial layers in the cooling process after growth is overcome. Therefore, it is difficult to form high quality 3C-SiC on Si. The existing method for preparing the 3C-SiC material on the silicon substrate generally adopts a CVD method, and the 3C-SiC material is deposited on the silicon substrate, so that the quality of the 3C-SiC material is ensured, the thickness of the material which is generally prepared is thicker than 500nm or more, the surface roughness of the material is larger, island-shaped protrusions exist, and the quality of the subsequent epitaxial material and the performance of a device are not improved. Thus, if high quality graphene is to be grown on a 3C-SiC layer, it is necessary to first grow a high quality 3C-SiC layer on a silicon substrate.
The CVD method for preparing graphene is simple and low in cost, but generally needs to use metals such as copper, nickel, platinum and the like as a substrate, and in order to apply graphene to the field of semiconductor devices, the graphene needs to be placed on a non-conductive substrate, so that after growth, the graphene needs to be peeled off from the metal substrate and further transferred to an insulating substrate. The process is easy to damage or pollute the graphene, and the performance of the device is reduced. For this reason, the preparation method of graphene needs to be further optimized to improve the quality of graphene.
In order to solve the problems in the prior art, the embodiment of the invention provides a preparation method of large-area graphene on a silicon surface, and the preparation method of large-area graphene provided by the embodiment of the invention is first described below.
As shown in fig. 1, the invention also provides a preparation method of large-area graphene on a silicon surface, comprising the following steps:
and step S110, mounting the cleaned silicon substrate in equipment with a rapid annealing function, and forming a 3C-SiC single crystal seed layer on the silicon substrate.
In some embodiments, the 3C-SiC monocrystalline seed layer is prepared as follows:
step S1101, mounting the cleaned silicon substrate into an apparatus having a rapid annealing function.
In this embodiment, any device having a rapid annealing function may be used.
The silicon substrate may be any crystal face and size, or may be a silicon epitaxial wafer.
The silicon substrate needs to be cleaned before being installed in the rapid annealing apparatus.
The rapid annealing means that various heat radiation sources are directly irradiated on the surface of the sample, and the sample is rapidly heated to a preset temperature for a period of several seconds to several tens of seconds to complete the annealing.
Step 1102, continuously introducing a first preset gas into the equipment, heating the equipment, continuously introducing a second preset gas into the equipment when the temperature reaches the first preset temperature, stopping heating and keeping the second preset temperature unchanged after the temperature rises to the second preset temperature, and performing rapid annealing on the silicon substrate.
The first preset gas is a protective gas, and the second preset gas contains at least one gas of methane or acetylene.
In some embodiments, the first predetermined gas is H 2 、Ar+H 2 、N 2 +H 2 Or one or more of inert gases. Wherein H is 2 The concentration of (2) is required to be controlled to 4% or less.
The second preset gas is a mixed gas of methane and acetylene.
In some embodiments, the first preset temperature is 550 ℃ to 650 ℃, the second preset temperature is 800 ℃ to 1400 ℃, and the temperature rise gradient of the device when the device is raised from the first preset temperature to the second preset temperature is greater than 25 ℃/s, so that rapid temperature rise, rapid annealing, reaction speed acceleration and whole growth reduction are realized. The first preset temperature may be 600 c, for example.
The preset temperature may be, for example, 800-1000 deg.c, with a temperature gradient of greater than 25 deg.c/s when the device is raised from ambient temperature to the preset temperature.
At high temperature, silicon atoms in the silicon substrate can diffuse to the surface of the silicon substrate, the silicon atoms are separated from the original structure and diffuse to the surface, and react with carbon generated by methane decomposition on the surface to generate a very thin 3C-SiC thin layer, and the compactness is also very good.
And step S1103, stopping introducing the first preset gas and the second preset gas after the rapid annealing reaches the preset time, introducing the third preset gas, and cooling to form a 3C-SiC thin layer on the silicon substrate.
In some embodiments, the preset time is 1s-180s, and by adopting the method provided by the invention, the growth speed of the 3C-SiC can be greatly improved, and a thin layer of 3C-SiC is only grown on the surface of the silicon substrate, so that the compactness is also good.
In some embodiments, the third preset gas is N2 and/or an inert gas. After reaching the preset time, closing the first preset gas and the second preset gas, and then introducing N 2 And (5) protecting gas and cooling.
In some embodiments, the thickness of the 3C-SiC layer is on the order of nanometers.
The silicon substrate has various dimensions, and a large-size silicon substrate can be selected to grow a 3C-SiC single crystal seed layer.
And step S120, homoepitaxially growing a 3C-SiC thickening layer on the 3C-SiC single crystal seed layer based on the LPCVD method.
In some embodiments, the 3C-SiC thickening layer is prepared at a temperature of 800-1300 ℃.
And step S130, etching the 3C-SiC thickened layer to obtain a step-shaped 3C-SiC etched layer.
In some embodiments, in order to facilitate the growth of subsequent graphene, the 3C-SiC thickening layer may be etched before the growth of graphene, where the etching effect may planarize the substrate surface to form a surface with a step array morphology with atomic level flatness. Grinding gas can be introduced into the surface of the 3C-SiC thickened layer at high temperature, and the 3C-SiC thickened layer is etched, so that a stepped 3C-SiC etching layer is obtained.
In this embodiment, the polishing gas is hydrogen, the working temperature of the polishing gas is 1000-1150 ℃, and the introducing period of the polishing gas is 10-60s.
In this embodiment, the etching may be performed in a high temperature annealing furnace or in a microwave plasma chemical vapor deposition apparatus.
And step S140, performing high-temperature thermal decomposition on the step-shaped 3C-SiC etching layer, and growing a layer of graphene on the surface of the 3C-SiC etching layer.
And heating the surface of the 3C-SiC etching layer in a vacuum environment, so that carbon-silicon bonds on the surface of the 3C-SiC can be broken, silicon atoms can be desorbed from the surface before carbon atoms sublimate, and the carbon atoms enriched on the surface are reconstructed to form the hexagonal honeycomb graphene film.
In some embodiments, the step-shaped 3C-SiC etching layer is subjected to high temperature pyrolysis at 1000-1250 ℃ for 30-60s at a pressure of less than 10 -3 torr。
In some embodiments, graphene can grow at lower temperatures because silicon atoms are easily sublimated. And at lower growth temperatures and faster growth rates, the quality of graphene is reduced. Therefore, there is a need to control the growth rate of graphene.
In this embodiment, when the annealing temperature is gradually increased under high vacuum, the threshold value of silicon atom evaporation at the step of the 3C-SiC surface and the center of the platform is made close, resulting in an increase in the evaporation rate of silicon atoms and the growth rate of graphene, resulting in an increase in the surface roughness of graphene. At high temperature, the silicon atoms on the surface of the 3C-SiC are dispersed and diffused, and the process of reabsorption is accelerated, so that the uniformity and consistency of the grown graphene are not controlled.
The inventor finds in long-term experiments that if argon is introduced at high temperature as a protective gas to thermally decompose the stepped 3C-SiC etching layer, the argon dense molecular cloud can cause silicon atoms evaporated from the 3C-SiC surface to collide with argon atoms with a certain probability and be reflected back to the 3C-SiC surface, and the evaporation of the silicon atoms can be limited, so that the conversion rate of the 3C-SiC surface can be reduced, and the growth rate of graphene is slowed down. In addition, through the convection effect of argon, the temperature distribution can be more uniform, so that the uniformity and consistency of the graphene grown on the surface can be greatly improved.
In addition, disilane can be introduced at high temperature as a protective gas to thermally decompose the stepped 3C-SiC etching layer, and graphene is grown on the surface of the 3C-SiC etching layer.
According to the preparation method of graphene, firstly, a cleaned silicon substrate is installed in equipment with a rapid annealing function, and a 3C-SiC monocrystalline seed layer is formed on the silicon substrate. Then, a 3C-SiC thickening layer is grown on the 3C-SiC single crystal seed layer based on the LPCVD method. And then, etching the 3C-SiC thickened layer to obtain a step-shaped 3C-SiC etched layer. And finally, carrying out high-temperature thermal decomposition on the step-shaped 3C-SiC etching layer, and growing a layer of graphene on the surface of the 3C-SiC etching layer. Because the silicon substrate has various specifications, a compact 3C-SiC monocrystalline seed layer can be firstly grown on a large-size silicon substrate, and then a 3C-SiC thickening layer is continuously grown on the compact 3C-SiC monocrystalline seed layer in a homoepitaxy manner, so that the subsequent preparation of large-area and high-quality graphene is facilitated.
It should be understood that the sequence number of each step in the foregoing embodiment does not mean that the execution sequence of each process should be determined by the function and the internal logic, and should not limit the implementation process of the embodiment of the present invention.
The above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention, and are intended to be included in the scope of the present invention.
Claims (8)
1. The preparation method of the large-area graphene on the silicon surface is characterized by comprising the following steps of:
mounting the cleaned silicon substrate in equipment with a rapid annealing function, and forming a 3C-SiC single crystal seed layer on the silicon substrate;
growing a 3C-SiC thickening layer on the 3C-SiC single crystal seed layer based on an LPCVD method on the 3C-SiC single crystal seed layer;
etching the 3C-SiC thickened layer to obtain a step-shaped 3C-SiC etched layer;
carrying out high-temperature pyrolysis on the step-shaped 3C-SiC etching layer, and growing a layer of graphene on the surface of the 3C-SiC etching layer;
forming a 3C-SiC single crystal seed layer on the silicon substrate, comprising:
continuously introducing a first preset gas into the equipment, heating the equipment, continuously introducing a second preset gas into the equipment when the temperature reaches the first preset temperature, stopping heating and keeping the second preset temperature unchanged after the temperature is increased to the second preset temperature, and carrying out rapid annealing on the silicon substrate, wherein the first preset gas is a protective gas, and the second preset gas contains at least one gas of methane or acetylene; stopping introducing the first preset gas and the second preset gas after the rapid annealing reaches the preset time, introducing the third preset gas, and cooling to form a 3C-SiC monocrystalline seed layer on the silicon substrate; the first preset gas is H 2 、Ar+H 2 、N 2 +H 2 Or one or more of inert gases, wherein the second preset gas is mixed gas of methane and acetylene, the second preset temperature is 800-1400 ℃, the first preset temperature is 550-650 ℃, and the temperature gradient of the equipment when the first preset temperature is increased to the second preset temperature is greater than 25 ℃/s.
2. The method for preparing large-area graphene on a silicon surface according to claim 1, wherein the step-shaped 3C-SiC etching layer is obtained by etching the 3C-SiC thickened layer, and comprises:
and (3) introducing grinding gas into the surface of the 3C-SiC thickened layer, and etching the 3C-SiC thickened layer to obtain a stepped 3C-SiC etching layer.
3. The method for preparing large-area graphene on a silicon surface according to claim 2, wherein the grinding gas is hydrogen, the working temperature of the grinding gas is 1000-1150 ℃, and the introducing time of the grinding gas is 10-60s.
4. The method for preparing large-area graphene on a silicon surface according to claim 2, wherein the step of introducing grinding gas into the surface of the 3C-SiC thickening layer is performed in a high-temperature annealing furnace or a microwave plasma chemical vapor deposition device.
5. The method for preparing large-area graphene on a silicon surface according to claim 1, wherein the preset time is 1s to 180s.
6. The method for preparing large-area graphene on a silicon surface according to claim 1, wherein the step-shaped 3C-SiC etching layer is subjected to high-temperature thermal decomposition at a temperature of 1000-1250 ℃, the duration of the high-temperature thermal decomposition is 30-60s, and the pressure of the high-temperature thermal decomposition is less than 10 -3 torr。
7. The method for preparing large-area graphene on a silicon surface according to any one of claims 1 to 6, wherein the step-shaped 3C-SiC etching layer is subjected to thermal decomposition at high temperature, and a layer of graphene is grown on the surface of the 3C-SiC etching layer, comprising:
argon is introduced as protective gas, the step-shaped 3C-SiC etching layer is subjected to high-temperature pyrolysis, and graphene grows on the surface of the 3C-SiC etching layer.
8. The method for preparing large-area graphene on a silicon surface according to any one of claims 1 to 6, wherein the step-shaped 3C-SiC etching layer is subjected to thermal decomposition at high temperature, and a layer of graphene is grown on the surface of the 3C-SiC etching layer, comprising:
and introducing disilane as a protective gas, performing high-temperature thermal decomposition on the step-shaped 3C-SiC etching layer, and growing graphene on the surface of the 3C-SiC etching layer.
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