CN102936009B - Method for manufacturing low layer number graphene film on silicon carbide substrate - Google Patents
Method for manufacturing low layer number graphene film on silicon carbide substrate Download PDFInfo
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- CN102936009B CN102936009B CN201210383666.0A CN201210383666A CN102936009B CN 102936009 B CN102936009 B CN 102936009B CN 201210383666 A CN201210383666 A CN 201210383666A CN 102936009 B CN102936009 B CN 102936009B
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Abstract
The present invention relates to a method for manufacturing a low layer number graphene film on a silicon carbide substrate. The method comprises the following process steps: 1) selecting a silicon surface silicon carbide substrate, and placing on a graphite base having a tantalum carbide coating; 2) carrying out system heating; 3) reducing a reaction chamber temperature to less than 1200 DEG C; 4) increasing argon flow; 5) carrying out system heating; 6) reducing argon flow, and reducing reaction chamber pressure to 0-1 mbar; 7) continuously adopting a mechanical pump to control a reaction chamber vacuum degree; 8) adopting a molecular pump to control the reaction chamber vacuum degree, and starting a carbonization process; 9) closing heating, and introducing argon; 10) reducing the reaction chamber temperature to 1000 DEG C, and closing argon; and 11) reducing the reaction chamber temperature, introducing argon to the reaction chamber to achieve atmospheric pressure, opening the chamber, and taking the sheet. The method has the following advantages that: graphene film formation can be promoted, sublimation of silicon atoms in the SiC substrate during heating and cooling processes can be effectively inhibited, and the carbonization process is easily controlled so as to achieve low layer number graphene film preparation.
Description
Technical field
What the present invention proposed is a kind of method of making low number of plies graphene film in silicon carbide substrates, and the graphene film number of plies of preparing by the method is low, and reproducible, stablizes controlled.Belong to technical field of semiconductor.
Background technology
Graphene is the monoatomic layer graphite crystal film that Geim seminar of Univ Manchester UK found in 2004, it is the bi-dimensional cellular shape material being formed by the carbon atom of sp2 hydridization, it is the elementary cell that builds other dimension carbon material, can wrap up the soccerballene that forms zero dimension, roll the carbon nanotube that forms one dimension, pile up layer by layer and form three-dimensional graphite.Graphene C-C bond distance is about 0.142nm, and perfectly Graphene is two-dimentional, only includes hexagonal cellular (isogonism hexagon), is the two dimensional crystal that the mankind find first.
Graphene film has many excellent specific properties, for example: under room temperature up to 200000 cm
2the intrinsic electronic mobility of/Vs (silicon 140 times); The mean free path of micron order electronics; Than the current density (108A/cm of high two orders of magnitude of copper
2); Good thermal conductivity [5000W/ (mK)], (adamantine 5 times); Specific surface area (the 2630m of high strength (1060GPa) and super large
2/ g).
Electronics can not be scattered and transmit in Graphene, and the transistor size prepared with it is less, speed is faster, and energy consumption is lower.Simultaneously graphene device technique also with traditional CMOS process compatible, can utilize planar light lithography to prepare graphene device and circuit, Graphene is the first-selection of the update of device critical material.The achievement in research of scholarly forecast Graphene will produce surging force difficult to the appraisal to the innovation and development of high-end military systems, comprises supercomputer, the accurate imaging system of millimeter wave, millimeter wave ultra-wideband communication system, radar and electronic warfare system etc.At present, the working speed of silicon device can reach GHz scope, and the operating frequency of graphene device can reach THz.If can further develop, its meaning is self-evident.
The preparation of grapheme material at present mainly contains following several: mechanically peel method, SiC thermal decomposition method, CVD (Chemical Vapor Deposition) method, molecular beam epitaxy and chemical dispersion method.SiC thermal decomposition method is more suitable in other graphene film preparation of wafer level.The reasons are as follows: first from the angle of element manufacturing, can directly prepare graphene/carbon SiClx structure by SiC thermal decomposition method, without the operation that adds graphene film to shift to device substrate, simplification of flowsheet, reduce the disadvantageous effect of the course of processing to film performance, therefore more believable quality and interface can be provided, thereby there is good producibility and repeatability.
The performance of graphene film and the number of plies have very large relation.SiC thermal decomposition method, by the Siliciumatom in distillation SiC substrate, makes the carbonization of SiC substrate, and carbon atom remaining after Siliciumatom distillation forms Graphene in substrate surface absorption nucleation.Different with epitaxy, time and flow that SiC thermal decomposition method cannot pass into source by adjusting are realized the control of the graphene film number of plies.How to control effective carbonization time of SiC substrate, how suppressing to reach before carbonization temperature and completing in carbonization technique temperature-fall period the distillation of Siliciumatom in SiC substrate is to realize the key issue that the preparation of low number of plies graphene film need to solve.
Summary of the invention
What the present invention proposed is a kind of method of making low number of plies graphene film in silicon carbide substrates, and its object is intended to control effective carbonization time that SiC thermal decomposition method is prepared graphene film, realizes the preparation of low number of plies graphene film.The present invention, after SiC substrate completes hydrogen etching, reduces reaction chamber temperature, passes into hydrogen remaining in argon replaces reaction chamber, and improve chamber pressure to reaction chamber, suppresses the distillation of Siliciumatom in SiC substrate in temperature-rise period.Complete carbonization technique, in temperature-fall period, passing into equally argon gas and improve chamber pressure, suppressing the distillation of Siliciumatom in SiC substrate in temperature-fall period.
Technical solution of the present invention, the method comprises following processing step:
One, choose silicon face silicon carbide substrates (1), substrate is placed on the graphite base of tantalum carbide coating;
Two, system is warming up to 1570 ℃, it is 100mbar that chamber pressure is set, and under hydrogen flowing quantity 80L/min, argon flow amount 3L/min atmosphere, online substrate surface is processed, and removes surperficial damage, and forming micro-step at substrate surface, the treatment time approximately needs 30 minutes;
Three, reduce reaction chamber temperature to 1200 ℃, and hydrogen flowing quantity is reduced to 0L/min by gradual mode from 80L/min, argon flow amount keeps 3L/min constant, and it is 100mbar that chamber pressure is set, and the treatment time approximately needs 20 minutes;
Four, argon flow amount is increased to 15L/min by gradual mode from 3L/min, the treatment time approximately needs 5 minutes, and chamber pressure is climbed gradually to more than 200mbar;
Five, system is warming up to 1580 ~ 1650 ℃ of carbonization temperatures, and it is 200mbar that chamber pressure is set, argon flow amount 15L/min;
Six, reduce argon flow amount to 0L/min by gradual method, chamber pressure is reduced to 0 ~ 1mbar, and the treatment time approximately needs 10 minutes;
Seven, continue to adopt mechanical pump control reaction chamber vacuum tightness, the treatment time approximately needs 15 minutes;
Eight, close mechanical pump, adopt molecular pump control reaction chamber vacuum tightness, reaction chamber vacuum tightness 10
-4~ 10
-1mbar, starts carbonization technique, and the treatment time approximately needs 15 ~ 60 minutes;
Seven, close heating, pass into argon gas to reaction chamber, argon flow amount is gradual to 10L/min by 0L/min, and chamber pressure is gradual to 200mbar by 0mbar, and the treatment time approximately needs 5 minutes;
Eight, reaction chamber temperature is reduced to after 1000 ℃, closes argon gas input;
Nine, after reaction chamber temperature is reduced to room temperature, pass into argon gas to normal atmosphere to reaction chamber, begin to speak to get sheet.
Advantage of the present invention: after completing hydrogen etching technics, pass into the hydrogen in argon replaces reaction chamber, can effectively reduce the amount of remaining hydrogen in reaction chamber, the hydrogen adsorbing while avoiding high temperature discharges and causes the carbon atom producing after Siliciumatom distillation to form gaseous hydrocarbon but not Graphene.In intensification and temperature-fall period, in conjunction with the method that improves chamber pressure, can effectively suppress the distillation of Siliciumatom in intensification and temperature-fall period by argon atmospher in addition, stablize controlled thereby realize the effective carbonization time of SiC substrate.
Accompanying drawing explanation
In accompanying drawing 1 carbonization process, reaction chamber vacuum tightness schematic diagram over time, has good repeatability.
Accompanying drawing 2 adopts the Raman collection of illustrative plates of single-layer graphene on SiC substrate prepared by present method, and the 2D peak of Graphene can be by the peak matching of single Lorentz, halfwidth 36cm
-1.
Accompanying drawing 3 adopts the Raman collection of illustrative plates of double-layer graphite alkene on SiC substrate prepared by present method, and the 2D peak of Graphene can be by 4 Lorentz peak matchings.
Embodiment
Embodiment
What provide comprises the following steps in the grow method of low number of plies graphene film of positive crystal orientation (0001) silicon face high-purity semi-insulating silicon carbide substrate:
1) choose positive crystal orientation (0001) silicon face high-purity semi-insulating silicon carbide substrate, substrate is placed on the graphite base of tantalum carbide coating;
2) system is warming up to 1570 ℃, it is 100mbar that chamber pressure is set, and under hydrogen flowing quantity 80L/min, argon flow amount 3L/min atmosphere, online substrate surface is processed, and removes surperficial damage, and forming micro-step at substrate surface, the treatment time is 30 minutes;
3) reduce reaction chamber temperature to 1200 ℃, and hydrogen flowing quantity is reduced to 0L/min gradually from 80L/min, argon flow amount keeps 3L/min constant, and it is 100mbar that chamber pressure is set, and the treatment time is 20 minutes;
4) argon flow amount is increased to 15L/min gradually from 3L/min, chamber pressure is increased to 200mbar gradually by 100mbar, and the treatment time is 5 minutes;
5) system is warming up to 1600 ℃, and chamber pressure is set 200mbar, argon flow amount 15L/min, and the heating-up time is 30 minutes;
6) argon flow amount is reduced to 0L/min gradually by 15 L/min, chamber pressure is reduced to 0 ~ 1mbar, and the treatment time is 10 minutes;
7) continue to adopt mechanical pump control reaction chamber vacuum tightness, 15 minutes treatment times;
8) close mechanical pump, open molecular pump control reaction chamber vacuum tightness, start carbonization technique, reaction chamber vacuum tightness 10
-4~ 10
-1mbar, 30 minutes treatment times;
9) close heating, pass into argon gas to reaction chamber, argon flow amount is enlarged to 10L/min gradually by 0L/min, and chamber pressure is increased to 200mbar gradually by 0mbar, and the treatment time is 5 minutes;
10) reaction chamber temperature is reduced to after 1000 ℃, closes argon gas input;
11) after reaction chamber temperature is reduced to room temperature, pass into argon gas to normal atmosphere to reaction chamber, begin to speak to get sheet.
Adopt Raman spectrometer to characterize the graphene film of preparation.By can judge the number of plies of Graphene to the matching at Graphene 2D peak.Can judge the crystal mass of Graphene in conjunction with the contrast of Graphene D peak intensity and G peak intensity simultaneously.
Present method can effectively be prepared high quality low layer graphene film.Pass into the hydrogen in argon replaces reaction chamber, can effectively reduce the amount of remaining hydrogen in reaction chamber, in conjunction with the method that improves chamber pressure, can effectively suppress the distillation of Siliciumatom in intensification and temperature-fall period by argon atmospher, stablize controlled thereby realize effective carbonization time.Process repeatability and high conformity, be applicable to scale production.
Claims (2)
1. in silicon carbide substrates, make a method for low number of plies graphene film, it is characterized in that the method comprises following processing step:
One, choose silicon face silicon carbide substrates (1), silicon face silicon carbide substrates is placed on the graphite base of tantalum carbide coating;
Two, system is warming up to 1570 ℃, it is 100mbar that chamber pressure is set, under hydrogen flowing quantity 80L/min, argon flow amount 3L/min atmosphere, online silicon face silicon carbide substrates surface is processed, remove surperficial damage, and forming micro-step on silicon face silicon carbide substrates surface, the treatment time is 30 minutes;
Three, reduce below reaction chamber temperature to 1200 ℃, and hydrogen flowing quantity is reduced to 0L/min by gradual mode from 80L/min, argon flow amount keeps 3L/min constant, and it is 100mbar that chamber pressure is set, and the treatment time is 20 minutes;
Four, argon flow amount is increased to 15L/min by gradual mode from 3L/min, adopts mechanical pump control reaction chamber vacuum tightness, chamber pressure is climbed gradually to 200mbar, and the treatment time is 5 minutes;
Five, system is warming up to 1580 ~ 1650 ℃ of carbonization temperatures, more than chamber pressure 200mbar is set, and argon flow amount 15L/min, the heating-up time is 30 minutes;
Six, reduce argon flow amount to 0L/min by gradual method, the treatment time is 10 minutes;
Seven, continue to adopt mechanical pump control reaction chamber 0 ~ 1mbar, the treatment time is 15 minutes;
Eight, close mechanical pump, adopt molecular pump control reaction chamber vacuum tightness, chamber pressure 10
-4~ 10
-1mbar, starts carbonization technique, 15 ~ 60 minutes time;
Nine, close heating, pass into argon gas to reaction chamber, argon flow amount is gradual to 10L/min by 0L/min, and chamber pressure is gradual to 200mbar by 0mbar, and the treatment time is 5 minutes;
Ten, reaction chamber temperature is reduced to after 1000 ℃, closes argon gas input;
11, after reaction chamber temperature is reduced to room temperature, pass into argon gas to normal atmosphere to reaction chamber, begin to speak to get sheet.
2. a kind of method of making low number of plies graphene film in silicon carbide substrates as claimed in claim 1, is characterized in that described silicon face silicon carbide substrates (1) is selected from the many types of silicon carbide of 4H, 6H.
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| CN104409594A (en) * | 2014-11-20 | 2015-03-11 | 北京中科天顺信息技术有限公司 | SiC substrate-based nitride LED (Light Emitting Diode) film flip chip and preparation method thereof |
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| CN107954418A (en) * | 2017-12-29 | 2018-04-24 | 北京华进创威电子有限公司 | A kind of multi-disc carborundum pyrolytic graphite alkene preparation method |
| CN109411552A (en) * | 2018-10-11 | 2019-03-01 | 苏州大学 | A kind of miniature flexible ultraviolet detector and preparation method thereof based on gallium nitride film |
| CN111410191A (en) * | 2020-05-07 | 2020-07-14 | 山东华达新材料有限公司 | Graphene semiconductor preparation device and method |
| CN113735627B (en) * | 2021-09-06 | 2022-11-01 | 杭州幄肯新材料科技有限公司 | Graphite thermal field material with tantalum carbide coating coated on surface and preparation method thereof |
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