CN102891074A - SiC substrate-based graphene CVD (Chemical Vapor Deposition) direct epitaxial growth method and manufactured device - Google Patents
SiC substrate-based graphene CVD (Chemical Vapor Deposition) direct epitaxial growth method and manufactured device Download PDFInfo
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- CN102891074A CN102891074A CN201210408187XA CN201210408187A CN102891074A CN 102891074 A CN102891074 A CN 102891074A CN 201210408187X A CN201210408187X A CN 201210408187XA CN 201210408187 A CN201210408187 A CN 201210408187A CN 102891074 A CN102891074 A CN 102891074A
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Abstract
The invention discloses a SiC substrate-based graphene CVD (Chemical Vapor Deposition) direct epitaxial growth method. By using a semiconductor SiC as a substrate and reasonably preprocessing the SiC substrate, the growth pressure, the flow and the temperature are regulated, graphene directly grows on the SiC substrate without using metal as a catalyst, the growing graphene does not need to be transferred and can be directly used for manufacturing various kinds of devices, so that electrical properties and the reliability of the devices are improved, and the complexity of device manufacture is lowered. According to the SiC substrate-based graphene CVD direct epitaxial growth method, a large-area graphene material with semiconductor cleanness can grow, the growth preparation of the large-area graphene material without transfer can be used, and a material is provided for the manufacture of a silicon carbide-graphene device.
Description
Technical field
The invention belongs to semiconductor materials and devices manufacturing technology field, the growing method that relates to semi-conducting material, a kind of Graphene CVD epitaxial growth method of semiconductor silicon carbide substrate particularly, can be used for the growth preparation of the large tracts of land grapheme material that need not to shift, and provide material for the manufacturing of carborundum-graphene device.
Background technology
Graphene is a kind of two dimensional crystal that is comprised of carbon atom, is present known the thinnest the lightest material, has very peculiar physicochemical properties, has outstanding industrial advantage, is expected to substitute the new material that Si becomes base semiconductor material of future generation.
Magnesium-yttrium-transition metal catalytic chemistry vapor phase deposition (CVD) extension is the method for the large tracts of land Graphene preparation of in the world extensive employing, and it is not subjected to the restriction of substrate dimension, and equipment is simple, can produce in enormous quantities.But, the metal substrate conductivity of the primary Graphene below of CVD extension preparation so that its can't directly use, must rely on substrate transfer technology, then the metal substrate removal is transferred on the suitable substrate, pollute and damage and in transfer process, can produce graphene film inevitably, affect grapheme material and performance of devices.
Carborundum (SiC) has good electricity and thermal property as a kind of wide-band gap material, becomes the popular research topic of electronics research field.Can be used for preparing power device, frequency device etc.After particularly Graphene was found, carborundum-graphene device structure had become study hotspot.Therefore, on silicon carbide substrates, directly utilize CVD method extending and growing graphene, can reduce lattice mismatch, avoid the performance degradation that cull causes in the transfer process, improve Graphene and silicon carbide substrates contact quality, have great importance.
Summary of the invention
The object of the invention is to overcome the deficiency in the existing large tracts of land Graphene growing technology, propose a kind of large-area high-quality Graphene growing method that need not to shift based on the SiC substrate, to improve the electrology characteristic of Graphene and device.
Realize that key problem in technology of the present invention is: adopt semiconductor SiC as substrate, by the SiC substrate being carried out rational preliminary treatment, growth regulation pressure, flow and temperature, direct growth graphene film on SiC, need not metal as catalyst, the Graphene of growth need not transfer process, for carborundum-graphene-structured device provides material, can be directly used in and make various devices, improved the electrology characteristic of device, reliability has reduced the complexity that device is made.Its growing method performing step comprises as follows:
(1) the SiC substrate is successively put into acetone, clean in ethanol and the deionized water, each time 5～10min takes out substrate from deionized water, dry up with high pure nitrogen (99.9999%).
(2) the SiC substrate is put into chemical vapor deposition CVD reative cell, extracting vacuum to 10
-5～10
-6Torr is to remove the residual gas in the reative cell;
(3) pass into high-purity Ar in reative cell, 150～250 ℃ of temperature keep 10～30min, then are evacuated to 10
-5～10
-6Torr discharges substrate surface adsorbed gas.
(4) in reative cell, pass into H
2Carry out the substrate surface preliminary treatment, gas flow 1～20sccm, reative cell vacuum degree 0.1～1Torr, 900～1000 ℃ of underlayer temperatures, processing time 1～10min;
(5) in reative cell, pass into H
2And CH
4, keep H
2And CH
4Flow-rate ratio be 10: 1～2: 1, H
2Flow 20～200sccm, CH
4Flow 1～20sccm, air pressure maintains 0.1～1atm, 1000～1300 ℃ of temperature, heating-up time 20～60min, retention time 30～60min;
(6) naturally cooling keeps the H in the operation (5)
2And CH
4Flow is constant, and air pressure 0.1～1atm finishes the growth of Graphene.
(7) temperature is down to below 100 ℃, closes CH
4, H
2, pass into Ar, open reative cell, take out sample.
The present invention has following advantage:
1. owing to adopt based on the normal pressure of the silicon carbide substrates Graphene CVD epitaxial growth method without catalytic metal, need not in subsequent step, Graphene to be shifted, avoided the destruction to grapheme material.
2. owing to be used in the Graphene CVD epitaxial growth method of silicon carbide substrates, can directly make graphene device in silicon carbide substrates, for carborundum-graphene device provides material foundation.
Description of drawings
Fig. 1 is the Graphene growth flow chart based on the SiC substrate of the present invention;
Fig. 2 is the Graphene growth course structural representation based on the SiC substrate of the present invention.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, the present invention is further described in detail.Should be appreciated that specific embodiment described herein only in order to explaining the present invention, and be not used in and limit invention.
Embodiment 1 prepares graphene film in silicon carbide substrates.
(1) the SiC substrate is successively put into acetone, clean in ethanol and the deionized water, each time 10min takes out substrate from deionized water, dry up with high pure nitrogen (99.9999%).
(2) the SiC substrate is put into chemical vapor deposition CVD reative cell, extracting vacuum to 10
-5Torr is to remove the residual gas in the reative cell;
(3) pass into high-purity Ar in reative cell, 150 ℃ of temperature keep 10min, then are evacuated to 10
-5Torr discharges substrate surface adsorbed gas.
(4) in reative cell, pass into H
2Carry out the substrate surface preliminary treatment, gas flow 1sccm, reative cell vacuum degree 0.1Torr, 1000 ℃ of underlayer temperatures, processing time 1min;
(5) in reative cell, pass into H
2And CH
4, keep H
2And CH
4Flow-rate ratio be 10: 1, H
2Flow 20sccm, CH
4Flow 2sccm, air pressure maintains 0.1atm, 1200 ℃ of temperature, heating-up time 20min, retention time 50min;
(6) naturally cooling keeps the H in the operation (5)
2And CH
4Flow is constant, and air pressure 0.1atm finishes the growth of Graphene.
(7) temperature is down to below 100 ℃, closes CH
4, H
2, pass into Ar, open reative cell, take out sample.
Embodiment 2 prepares graphene film in silicon carbide substrates.
(1) the SiC substrate is successively put into acetone, clean in ethanol and the deionized water, each time 8min takes out substrate from deionized water, dry up with high pure nitrogen (99.9999%).
(2) the SiC substrate is put into chemical vapor deposition CVD reative cell, extracting vacuum to 10
-6Torr is to remove the residual gas in the reative cell;
(3) pass into high-purity Ar in reative cell, 250 ℃ of temperature keep 30min, then are evacuated to 10
-6Torr discharges substrate surface adsorbed gas.
(4) in reative cell, pass into H
2Carry out the substrate surface preliminary treatment, gas flow 20sccm, reative cell vacuum degree 1Torr, 1100 ℃ of underlayer temperatures, processing time 10min;
(5) in reative cell, pass into H
2And CH
4, keep H
2And CH
4Flow-rate ratio be 2: 1, H
2Flow 200sccm, CH
4Flow 100sccm, air pressure maintains 1atm, 1200 ℃ of temperature, heating-up time 40min, retention time 40min;
(6) naturally cooling keeps the H in the operation (5)
2And CH
4Flow is constant, and air pressure 1atm finishes the growth of Graphene.
(7) temperature is down to below 100 ℃, closes CH
4, H
2, pass into Ar, open reative cell, take out sample.
Embodiment 3 prepares graphene film in silicon carbide substrates.
(1) the SiC substrate is successively put into acetone, clean in ethanol and the deionized water, each time 5min takes out substrate from deionized water, dry up with high pure nitrogen (99.9999%).
(2) the SiC substrate is put into chemical vapor deposition CVD reative cell, extracting vacuum to 10
-6Torr is to remove the residual gas in the reative cell;
(3) pass into high-purity Ar in reative cell, 100 ℃ of temperature keep 20min, then are evacuated to 10
-6Torr discharges substrate surface adsorbed gas.
(4) in reative cell, pass into H
2Carry out the substrate surface preliminary treatment, gas flow 10sccm, reative cell vacuum degree 0.5Torr, 1200 ℃ of underlayer temperatures, processing time 50min;
(5) in reative cell, pass into H
2And CH
4, keep H
2And CH
4Flow-rate ratio be 5: 1, H
2Flow 100sccm, CH
4Flow 20sccm, air pressure maintains 0.5atm, 1300 ℃ of temperature, heating-up time 40min, retention time 50min;
(6) naturally cooling keeps the H in the operation (5)
2And CH
4Flow is constant, and air pressure 0.5atm finishes the growth of Graphene.
(7) temperature is down to below 100 ℃, closes CH
4, H
2, pass into Ar, open reative cell, take out sample.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. the direct epitaxial growth method of Graphene CVD based on the SiC substrate is characterized in that,
Adopt semiconductor SiC as substrate, by the SiC substrate is carried out rational preliminary treatment, growth regulation pressure, flow and temperature, direct growth Graphene on SiC need not metal as catalyst, and the Graphene of growth is directly used in makes various devices.
2. the direct epitaxial growth method of Graphene CVD as claimed in claim 1 is characterized in that, its growing method performing step comprises as follows:
(1) the SiC substrate is successively put into acetone, clean in ethanol and the deionized water, each time 5～10min takes out substrate from deionized water, dry up with high pure nitrogen;
(2) the SiC substrate is put into chemical vapor deposition CVD reative cell, extracting vacuum to 10
-5～10
-6Torr is to remove the residual gas in the reative cell;
(3) in reative cell, pass into high-purity Ar, discharge substrate surface adsorbed gas;
(4) in reative cell, pass into H
2Carry out the substrate surface preliminary treatment;
(5) in reative cell, pass into H
2And CH
4
(6) naturally cooling keeps the H in the operation (5)
2And CH
4Flow is constant, finishes the growth of Graphene.
(7) temperature is down to below 100 ℃, closes CH4, H2, passes into Ar, opens reative cell, takes out sample.
3. the direct epitaxial growth method of Graphene CVD as claimed in claim 2 is characterized in that, passes into high-purity Ar in reative cell, and when discharging substrate surface adsorbed gas, 150～250 ℃ of temperature keep 10～30min, then are evacuated to 10
-5～10
-6Torr.
4. the direct epitaxial growth method of Graphene CVD as claimed in claim 2 is characterized in that, passes into H in reative cell
2Carry out the substrate surface preliminary treatment, gas flow 1～20sccm, reative cell vacuum degree 0.1～1Torr, 900～1000 ℃ of underlayer temperatures, processing time 1～10min.
5. the direct epitaxial growth method of Graphene CVD as claimed in claim 2 is characterized in that, passes into H in reative cell
2And CH
4, keep H
2And CH
4Flow-rate ratio be 10: 1～2: 1, H
2Flow 20～200sccm, CH
4Flow 1～20sccm, air pressure maintains 0.1～1atm, 1000～1300 ℃ of temperature, heating-up time 20～60min, retention time 30～60min.
6. the direct epitaxial growth method of Graphene CVD as claimed in claim 2 is characterized in that, naturally cooling keeps the H in the operation (5)
2And CH
4Flow is constant, and air pressure 0.1～1atm finishes the growth of Graphene.
7. device that utilizes the direct epitaxial growth method of the Graphene CVD based on the SiC substrate claimed in claim 1 to make.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103556217A (en) * | 2013-09-27 | 2014-02-05 | 西安电子科技大学 | Preparation method for 1-5 layer single crystal graphene |
| 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 |
| WO2016149934A1 (en) * | 2015-03-26 | 2016-09-29 | 中国科学院上海微***与信息技术研究所 | Growing method for graphene |
| CN105990091A (en) * | 2015-01-29 | 2016-10-05 | 中国科学院微电子研究所 | Graphene growing method, graphene layer and semiconductor device |
| CN107611189A (en) * | 2017-09-08 | 2018-01-19 | 南通强生光电科技有限公司 | Thin film solar cell sheet and preparation method thereof |
| CN109399620A (en) * | 2018-12-05 | 2019-03-01 | 中国电子科技集团公司第十三研究所 | A method of preparing the silicon carbide-based grapheme material of high mobility |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN107611189A (en) * | 2017-09-08 | 2018-01-19 | 南通强生光电科技有限公司 | Thin film solar cell sheet and preparation method thereof |
| CN109399620A (en) * | 2018-12-05 | 2019-03-01 | 中国电子科技集团公司第十三研究所 | A method of preparing the silicon carbide-based grapheme material of high mobility |
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