CN103346073B - A kind of preparation method of beta-silicon carbide thin film - Google Patents
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- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 84
- 239000010409 thin film Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000000758 substrate Substances 0.000 claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000010439 graphite Substances 0.000 claims abstract description 39
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000007789 gas Substances 0.000 claims abstract description 33
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 28
- 239000010703 silicon Substances 0.000 claims abstract description 28
- 238000004050 hot filament vapor deposition Methods 0.000 claims abstract description 26
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910000077 silane Inorganic materials 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 239000012159 carrier gas Substances 0.000 claims abstract description 5
- 238000007865 diluting Methods 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000000137 annealing Methods 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 239000010408 film Substances 0.000 abstract description 30
- 239000000463 material Substances 0.000 abstract description 17
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 abstract description 15
- 239000013078 crystal Substances 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 6
- 230000007423 decrease Effects 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052721 tungsten Inorganic materials 0.000 description 8
- 239000010937 tungsten Substances 0.000 description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007770 graphite material Substances 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Abstract
The present invention relates to technical field of semiconductor, disclose a kind of preparation method of beta-silicon carbide thin film, using silane as silicon source, hydrogen is as silicon source diluting gas and carrier gas, using graphite as substrate and carbon source, adopt hot filament CVD to prepare beta-silicon carbide thin film in graphite substrate, the beta-silicon carbide thin film prepared carries out subsequent anneal process under an inert gas, peels off obtain beta-silicon carbide thin film further by micromechanics.The invention provides a kind of new method preparing carborundum films in graphite substrate, namely in the graphite substrate of electric-conductivity heat-conductivity high, beta-silicon carbide thin film is prepared, decrease the lattice defect of film inside, substantially increase film crystal quality, thus improve heat dispersion and the useful life of silicon carbide-based electronics (photoelectron) high-power component further, be very easy to by means such as micromechanics strippings the stripping realizing carborundum films material and graphite substrate, and present invention process is simple, with low cost.
Description
Technical field
The present invention relates to technical field of semiconductor, particularly a kind of preparation method of the beta-silicon carbide thin film in graphite substrate.
Background technology
Carborundum (SiC) film has the characteristic of the uniquenesses such as the chemical stability that energy gap is large, breakdown electric field is high, thermal conductivity is large, electronics saturation drift velocity is high, dielectric constant is little, capability of resistance to radiation is strong, good, make it gain great popularity in high frequency, high power, high-temperature electronic device and photoelectric device etc., be described as one of third generation semi-conducting material most with prospects.But carbofrax material crystalline form is numerous and preparation is very difficult, as: silicon B-carbide has cubic crystal structure, similar to diamond, needs could generate under lower than 2000 ° of C conditions.
In silicon carbidebased devices application, the quality of high-power component heat dispersion directly affects its performance and used life, and the preparation of the quality of film quality and device, performance have very large dependence to substrate, therefore, in practical operation, problem the most important and the most key is exactly the selection of device substrate material.Up to now, domestic and international scientist has successfully prepared carborundum films material by various preparation method on monocrystalline silicon (Si) substrate.But, because silicon (Si) exists the factors such as larger lattice mismatch and thermal expansion mismatch between backing material and carborundum, seriously limit the performance and used life of silicon (Si) substrate silicon carbide silicon-based electronic (photoelectron) device.In addition, in the device application field that some are special, as: large area can fold out display and high-power component etc., need the silicon carbide nano material prepared to transfer in flexible substrate or metal substrate and carry out follow-up processing process and device preparation.But, owing to there is very strong adhesive force between carborundum films material and silicon (Si) substrate, be difficult to strip down from substrate, therefore cause carbofrax material being applied in order to a great problem in this field.
Graphite substrate has very particular advantages relative to conventional substrate, if: low cost, excellent mechanical performance and chemical stability and its conduction and heat dispersion are considerably beyond metallic copper, has broad application prospects in high-power component field; Simultaneously because graphite material has layer structure, combine with very weak Van der Waals force between each layer, can be very easy to realize graphite substrate by means such as micromechanics strippings peel off, silicon carbide-based opto-electronic device prepared by graphite substrate can be transferred on other substrate.
In sum, we turn to the preparation of carborundum films in graphite substrate sight, and graphite material both can as substrate, simultaneously can also as the carbon source of carborundum films.Experimental result confirms: by optimizing the experiment parameters such as silane concentration, Chamber vacuum degree, underlayer temperature and subsequent annealing process, successfully can prepare beta-silicon carbide thin film.Therefore, this preparation method has major application potentiality in the preparation of carborundum films and silicon carbide-based large power long life-span and transferable field of electronic devices.
Summary of the invention
The object of the invention is: affect silicon (Si) substrate silicon carbide silicon-based electronic (photoelectron) device performance and the heat dissipation problem in useful life to solve, and carborundum films material is difficult to the technical problem peeled off from silicon (Si) substrate, provide a kind of preparation method of beta-silicon carbide thin film, using have high connductivity, heat conductivility graphite as substrate and carbon source, with silane (SiH
4) as silicon source, hydrogen, as silicon source diluting gas and carrier gas, on graphite substrate material surface, adopts hot-wire chemical gas-phase deposition (HotFilamentChemicalVaporDeposition, HFCVD) method, prepares beta-silicon carbide thin film; Meanwhile, the high-quality growth of graphite substrate beta-silicon carbide thin film facilitates the application of silicon carbide-based large power long life-span and transferable (electronics) opto-electronic device greatly.
For achieving the above object, the technical solution used in the present invention is: the preparation method providing a kind of beta-silicon carbide thin film, with silane (SiH
4) as silicon source, hydrogen, as silicon source diluting gas and carrier gas, using graphite as substrate and carbon source, adopts hot filament CVD to prepare beta-silicon carbide thin film in graphite substrate, then it is carried out subsequent anneal process under an inert gas, complete the preparation of beta-silicon carbide thin film.
Wherein, described inert gas is argon gas or nitrogen.
Wherein, described beta-silicon carbide thin film after subsequent anneal process is peeled off from substrate by micromechanics stripping method.
Wherein, namely described hot filament CVD utilizes the high temperature of hot tungsten filament to decompose source of the gas and silane and hydrogen, and then utilize the atom decomposing and produce and atomic group to grow at the deposited on substrates of lower temperature, hot tungsten filament temperature is 2000-2300 DEG C.
Wherein, describedly to prepare in graphite substrate in beta-silicon carbide thin film process, need to control silicon source concentration, reaction system vacuum degree and underlayer temperature, the effective control to obtained beta-silicon carbide thin film crystal mass can be realized.
Wherein, described silicon source is the diluted in hydrogen silane of concentration 5%-10%, and silane gas flow is 0.5-1sccm.
Wherein, described silicon source optimization value is the diluted in hydrogen silane of concentration 10%, and silane gas flow optimization value is 0.5sccm.
Wherein, in the reaction system of described hot filament CVD, gas pressure intensity is 30-40Pa.
Wherein, in the reaction system of described hot filament CVD, gas pressure intensity optimal value is 40Pa.
Wherein, in the reaction system of described hot filament CVD, graphite substrate temperature is 250-300 DEG C.
Wherein, in the reaction system of described hot filament CVD, graphite substrate temperature optimization value is 300 DEG C.
Wherein, the annealing temperature of described subsequent anneal process is 500-800 DEG C, and annealing time is 30-60 minute.
The invention has the beneficial effects as follows: the invention provides a kind of new method preparing carborundum films in graphite substrate, namely in the graphite substrate of electric-conductivity heat-conductivity high, beta-silicon carbide thin film is prepared, decrease the lattice defect of film inside, substantially increase film crystal quality, thus improve heat dispersion and the useful life of silicon carbide-based electronics (photoelectron) high-power component further, be very easy to by means such as micromechanics strippings the stripping realizing carborundum films material and graphite substrate, and present invention process is simple, with low cost.
Accompanying drawing explanation
The apparatus structure schematic diagram that Fig. 1 uses for HFCVD method growth beta-silicon carbide thin film material.
Fig. 2 is graphite flake layer lattice structure schematic diagram.
Fig. 3 is the X-ray diffractogram of HFCVD method growth beta-silicon carbide thin film material under argon gas (500 °) condition after annealing in process.
Fig. 4 is the scanning electron microscope (SEM) photograph of HFCVD method growth beta-silicon carbide thin film material surface.
Fig. 5 is the FTIR spectrum of HFCVD method growth beta-silicon carbide thin film material.
Fig. 6 is the X-ray diffractogram of HFCVD method growth beta-silicon carbide thin film material under argon gas (700 °) condition after annealing in process.
Accompanying drawing identifies: 1-air inlet, 2-tungsten filament, 3-substrate, 4-heater, 5-exhaust outlet.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in detail.
With reference to Fig. 1-2, the preparation method of a kind of beta-silicon carbide thin film of the present invention, with silane (SiH
4) as silicon source, hydrogen, as silicon source diluting gas and carrier gas, using graphite as substrate and carbon source, adopts hot filament CVD to prepare beta-silicon carbide thin film in graphite substrate, then it is carried out subsequent anneal process under an inert gas, complete the preparation of beta-silicon carbide thin film.Described beta-silicon carbide thin film after subsequent anneal process is peeled off from substrate by micromechanics stripping method.
Material growth technique of the present invention adopts hot-wire chemical gas-phase deposition (HFCVD) method, namely utilizing the high temperature of hot tungsten filament to decompose source of the gas, then utilize the atom decomposing and produce and atomic group to grow at the deposited on substrates of lower temperature, is the effective ways solving low-temperature epitaxy.The method has that technique is simple, preparation cost is cheap, good stability, controllable parameter are more, the speed of growth is very fast, without the need to using the typical feature such as plasma, react without Ions Bombardment " soft ", the active deposit group of energy can be provided, impel thin film netowrk full relaxation, be conducive to low temperature crystallized, and the crystal structure defects formed is less.
Implementation procedure of the present invention comprises two parts;
Part I: optimize the experiment parameters such as silane concentration, reaction system gas pressure intensity and underlayer temperature, adopts HFCVD method at graphite substrate material surface growth beta-silicon carbide thin film; Described hot tungsten filament temperature is 2000-2300 DEG C, described silicon source is the diluted in hydrogen silane of concentration 5%-10%, and silane gas flow is 0.5-1sccm, in the reaction system of described hot filament CVD, gas pressure intensity is 30-40Pa, and graphite substrate temperature is 250-300 DEG C.Realize the effective control to obtained beta-silicon carbide thin film crystal mass.
Part II: carry out subsequent anneal process to the sample of preparation, the annealing temperature of described subsequent anneal process is 500-800 DEG C, and annealing time is 30-60 minute, improves beta-silicon carbide thin film crystal mass.
Embodiment 1:
The preparation method of a kind of beta-silicon carbide thin film of the present invention, comprises the following steps:
Step 1: by 0.5 × 0.5mm
2there is high connductivity, the graphite substrate of heat conductivility uses acetone, absolute ethyl alcohol and washed with de-ionized water 10 minutes successively, then with high pure nitrogen, substrate is dried up.
Step 2: optimize the experiment parameters such as silane concentration, reaction system gas pressure intensity and underlayer temperature; Silicon source is the silane of concentration 10%, and gas flow is 0.5sccm, and the gas pressure intensity of reaction system is 40Pa, and underlayer temperature is 300 DEG C.
Step 3: adopt HFCVD technology first to grow one deck carborundum (SiC) film (100nm) in graphite substrate cleaned in advance, wherein, hot tungsten filament temperature is 2000 DEG C.
Step 4: above-mentioned SiC film is carried out furnace annealing process 30 minutes under argon gas 500 DEG C of conditions, forms beta-silicon carbide thin film, decreases the lattice defect of film inside, improve film crystal quality.
As shown in Figure 3, test analysis shows X-ray diffraction (XRD) spectrum of the beta-silicon carbide thin film formed under above-mentioned condition, and graphite substrate successfully can prepare beta-silicon carbide thin film.
Embodiment 2:
The preparation method of a kind of beta-silicon carbide thin film of the present invention, comprises the following steps:
Step 1: by 0.5 × 0.5cm
2there is high connductivity, the graphite substrate of heat conductivility uses acetone, absolute ethyl alcohol and washed with de-ionized water 10 minutes successively, then with high pure nitrogen, substrate is dried up.
Step 2: optimize the experiment parameters such as silane concentration, reaction system gas pressure intensity and underlayer temperature; Silicon source is the silane of concentration 10%, and gas flow is 0.5sccm, and the gas pressure intensity of reaction system is 40Pa, and underlayer temperature is 300 DEG C.
Step 3: adopt hot-wire chemical gas-phase deposition (HFCVD) technology first to grow one deck carborundum (SiC) film (100nm) in graphite substrate cleaned in advance, wherein, hot tungsten filament temperature is 2000 DEG C.
Step 4: above-mentioned SiC film is carried out furnace annealing process 30 minutes under argon gas 600 DEG C of conditions, forms beta-silicon carbide thin film, decreases the lattice defect of film inside, improve film crystal quality.
As shown in Figure 4, test analysis shows scanning electron microscopy (SEM) picture of the carborundum films formed under above-mentioned condition, and graphite substrate successfully can prepare beta-silicon carbide thin film.
Embodiment 3:
The preparation method of a kind of beta-silicon carbide thin film of the present invention, comprises the following steps:
Step 1: by 0.5 × 0.5cm
2there is high connductivity, the graphite substrate of heat conductivility uses acetone, absolute ethyl alcohol and washed with de-ionized water 10 minutes successively, then with high pure nitrogen, substrate is dried up.
Step 2: optimize the experiment parameters such as silane concentration, reaction system gas pressure intensity and underlayer temperature; Silicon source is concentration 10% silane, and gas flow is 0.5sccm, and the gas pressure intensity of reaction system is 40Pa, and underlayer temperature is 300 DEG C.
Step 3: adopt hot-wire chemical gas-phase deposition (HFCVD) technology first to grow one deck carborundum (SiC) film (100nm) in graphite substrate cleaned in advance, wherein, hot tungsten filament temperature is 2000 DEG C.
Step 4: above-mentioned SiC film is carried out furnace annealing process 30 minutes under argon gas 700 DEG C of conditions, forms beta-silicon carbide thin film, decreases the lattice defect of film inside, improve film crystal quality.
As shown in Figure 5,6, test analysis shows, graphite substrate successfully can prepare beta-silicon carbide thin film for the FTIR spectrum (FTIR) of the carborundum films formed under above-mentioned condition and X-ray diffraction light (XRD) spectrum.
Above content is the further description done the present invention in conjunction with optimal technical scheme, can not assert that the concrete enforcement of invention is only limitted to these explanations.Concerning general technical staff of the technical field of the invention, under the prerequisite not departing from design of the present invention, simple deduction and replacement can also be made, all should be considered as protection scope of the present invention.
Claims (8)
1. the preparation method of a beta-silicon carbide thin film, it is characterized in that, using silane as silicon source, hydrogen is as silicon source diluting gas and carrier gas, using graphite as substrate and carbon source, adopt hot filament CVD to prepare beta-silicon carbide thin film in graphite substrate, then it is carried out subsequent anneal process under an inert gas, complete the preparation of beta-silicon carbide thin film; Described silicon source is the diluted in hydrogen silane of concentration 5%-10%, and silane gas flow is 0.5-1sccm.
2. the preparation method of a kind of beta-silicon carbide thin film according to claim 1, is characterized in that, described beta-silicon carbide thin film after subsequent anneal process is peeled off from substrate by micromechanics stripping method.
3. the preparation method of a kind of beta-silicon carbide thin film according to claim 1, is characterized in that, described silicon source is the diluted in hydrogen silane of concentration 10%, and silane gas flow is 0.5sccm.
4. the preparation method of a kind of beta-silicon carbide thin film according to claim 1, is characterized in that, in the reaction system of described hot filament CVD, gas pressure intensity is 30-40Pa.
5. the preparation method of a kind of beta-silicon carbide thin film according to claim 4, is characterized in that, in the reaction system of described hot filament CVD, gas pressure intensity is 40Pa.
6. the preparation method of a kind of beta-silicon carbide thin film according to claim 1, is characterized in that, in the reaction system of described hot filament CVD, graphite substrate temperature is 250-300 DEG C.
7. the preparation method of a kind of beta-silicon carbide thin film according to claim 1, is characterized in that, in the reaction system of described hot filament CVD, graphite substrate temperature is 300 DEG C.
8. the preparation method of a kind of beta-silicon carbide thin film according to claim 1, is characterized in that, the annealing temperature of described subsequent anneal process is 500-800 DEG C, and annealing time is 30-60 minute.
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| CN103911597B (en) * | 2014-04-22 | 2017-01-25 | 武汉理工大学 | Preparation method of silicon carbide film |
| CN104651789A (en) * | 2014-05-20 | 2015-05-27 | 鞠云 | Preparation process of novel C/Si film |
| CN111348821A (en) * | 2018-12-21 | 2020-06-30 | 财团法人工业技术研究院 | Graphite mold for glass shaping and manufacturing method thereof |
| CN112382699A (en) * | 2020-10-30 | 2021-02-19 | 重庆神华薄膜太阳能科技有限公司 | Flexible thin film device and preparation method thereof |
| CN113078047A (en) * | 2021-03-30 | 2021-07-06 | 芜湖启迪半导体有限公司 | Bonded Si substrate, preparation method thereof, and method for preparing Si/3C-SiC heterostructure and 3C-SiC film |
| CN115613139B (en) * | 2022-12-01 | 2023-04-14 | 浙江晶越半导体有限公司 | Chemical vapor deposition reactor and method for epitaxially growing silicon carbide film |
| CN116657114B (en) * | 2023-07-25 | 2023-10-27 | 青禾晶元(天津)半导体材料有限公司 | Low-resistance silicon carbide substrate and preparation method and application thereof |
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|---|---|---|---|---|
| US5879450A (en) * | 1997-08-13 | 1999-03-09 | City University Of Hong Kong | Method of heteroepitaxial growth of beta silicon carbide on silicon |
| US6221154B1 (en) * | 1999-02-18 | 2001-04-24 | City University Of Hong Kong | Method for growing beta-silicon carbide nanorods, and preparation of patterned field-emitters by chemical vapor depositon (CVD) |
| CN102850087A (en) * | 2012-09-29 | 2013-01-02 | 西安超码科技有限公司 | Method for preparing silicon carbide coating on graphite surface |
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| JP2000302576A (en) * | 1999-04-22 | 2000-10-31 | Tokai Carbon Co Ltd | Graphite material coated with silicon carbide |
| KR101224816B1 (en) * | 2008-02-28 | 2013-01-21 | 창원대학교 산학협력단 | Synthetic method for anti-oxidation ceramic coatings on graphite substrates |
| US9663374B2 (en) * | 2011-04-21 | 2017-05-30 | The United States Of America, As Represented By The Secretary Of The Navy | Situ grown SiC coatings on carbon materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5879450A (en) * | 1997-08-13 | 1999-03-09 | City University Of Hong Kong | Method of heteroepitaxial growth of beta silicon carbide on silicon |
| US6221154B1 (en) * | 1999-02-18 | 2001-04-24 | City University Of Hong Kong | Method for growing beta-silicon carbide nanorods, and preparation of patterned field-emitters by chemical vapor depositon (CVD) |
| CN102850087A (en) * | 2012-09-29 | 2013-01-02 | 西安超码科技有限公司 | Method for preparing silicon carbide coating on graphite surface |
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