CN101812730B - Preparation method of ultralong monocrystal beta-SiC nanowire metal-free catalyst - Google Patents
Preparation method of ultralong monocrystal beta-SiC nanowire metal-free catalyst Download PDFInfo
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Abstract
The invention provides a preparation method of an ultralong monocrystal beta-SiC nanowire metal-free catalyst, comprising the following steps of: carrying out heat preservation for 1-6h by adopting a chemical vapor deposition method by taking a carbonaceous gas as a carbon source, a mixture of silicon monoxide or monox and silicon as a silicon source and Ar or N2 as a carrier gas in a vacuum tube type furnace or a chemical vapor deposition furnace under the conditions that the temperature is 1350-1600 DEG C, the flow of the gas of the carbon source is 10-80sccm, the flow of the carrier gas is 20-80sccm and the air pressure is 1.1-1.5atm, and depositing and growing on a porcelain boat, a corundum sheet or a silicon wafer to obtain a monocrystal beta-SiC nanowire, the length of which reaches the centimetre grade. The invention synthesizes the monocrystal beta-SiC nanowire completely without adding a metal catalyst and without a growing template by adopting a simple pollution-free process which is simple and easy to operate and control and low in cost, and the synthetized monocrystal beta-SiC nanowire has the characteristics of small diameter, even distribution, length reaching the centimetre grade, high yield and the like and is beneficial to industrial production.
Description
Technical field
The invention belongs to the preparation field of monocrystalline beta-SiC nano-wire, relate to a kind of preparation method of ultralong monocrystal beta-SiC nanowire metal-free catalyzer.
Technical background
Silicon carbide nanometer line has the performances such as excellent machinery, optics, electricity, characteristic of semiconductor, an emission, physical and chemical stability, high-temperature stability, it is the ideal material of the nano photoelectronic devices such as preparation blue light-emitting diode, laser diode and high power transistor, also be the desirable wild phase material of the matrix materials such as metal matrix, ceramic base and polymkeric substance simultaneously, thereby more and more receive the concern of vast researcher and enterprise.
On a large scale, big area prepares the matter of utmost importance that ultra-long silicon carbide nano-wires is its suitability for industrialized production of realization and practical application.The gong-yi Li of the National University of Defense technology in 2009 etc. have reported employing CVD method, and take the mixture of ferrocene, L-Ps and gac as parent material, preparation length reaches the beta-SiC nano-wire of centimetre-sized.(Large Areasof Centimeters-Long SiC Nanowires Synthesized by Pyrolysis of a PolymerPrecursor by a CVD Route (CVD pyrolytic decomposition polymer precursor big area prepares a few cm long SiC nano wires) .J.Phys.Chem.C 2009,113,17655-17660), above-mentioned preparation method adopts metal catalyst to pass through gas-liquid-solid growth mechanism growing silicon carbide nano wire, the impurity such as containing metal catalyzer is more in the product, can pollute silicon carbide nanometer line, intrinsic structure and the performance study of silicon carbide nanometer line have been affected, for subsequent disposal and practical application have brought difficulty and improved technical requirements.
Document " Y.Yao; S.T.Lee; F.H.Li; Direct synthesis of 2H-SiC nanowhiskers (directly synthetic 2H-SiC nano wire); Chemical Physics Letters 2003; 381,628-633 " discloses a kind of take methane and SiO as starting raw material, prepares the method for 2H-SiC nano whisker under the reaction pressure condition of 300Torr.Document " J.Z.Guo; Y.Zuo; Z.J.Li, W.D.Gao, J.L.Zhang; Preparation of SiCnanowires with fins by chemical vapor deposition (chemical Vapor deposition process preparation contain fin silicon carbide nanometer line); Physica E, 2007,39; 262-266 " discloses a kind of mixture take methane, silicon oxide and silicon as starting raw material, prepares the method for beta-SiC nano-wire under the reaction pressure condition of 200Torr.But above preparation method's output is lower, and the silicon carbide nanometer line major diameter of preparation is smaller, diameter Distribution is uneven, is difficult to realize its suitability for industrialized production and practical application.In recent years, the research of silicon carbide nanometer line has obtained certain achievement, yet, still there are many deficiencies.As there is an excess Temperature; Complex process needs multistep synthetic; Output is on the low side, major diameter is smaller, is difficult to large-scale production; Some generates a large amount of silicon-carbide particles inevitably, has difficult problem of separating, and particularly, many methods need to be added metal catalyst, and the existence of metal catalyst has affected the performance of silicon carbide nano material greatly.
Summary of the invention
Technical problem to be solved of the present invention is, mostly need to adopt metal catalyst and template in order to overcome prior art, length-to-diameter ratio is little, and output is little, be difficult to realize the deficiency of its suitability for industrialized production, the present invention proposes a kind of preparation method of ultralong monocrystal silicon carbide nanometer line non-metal catalyst, the method need not to add metal catalyst, need not growth templates, and technological process is simple, easy handling control, cost is low, pollution-free, diameter is little, be evenly distributed, length reaches centimetre-sized, extensive growing single-crystal beta-SiC nano-wire.
Technical solution of the present invention is as follows:
A kind of preparation method of ultralong monocrystal beta-SiC nanowire metal-free catalyzer is characterized in that, in vacuum tube furnace or chemical vapor deposition stove, take carbonaceous gas as carbon source, silicon monoxide, silicon and aktivton are the silicon source, Ar or N
2Being carrier gas, is that 1350-1600 ℃, carbon-source gas flow are that 10-80sccm, carrier gas flux are 20-80sccm, are incubated a few hours under condition of super atmospheric pressure in temperature, and deposition growing obtains the monocrystalline beta-SiC nano-wire that length reaches centimetre-sized on substrate.
Temperature-rise period is: adopt the speed of 5-10 ℃/min to be warmed up to 300 ℃, be incubated 10 minutes, the speed with 5-10 ℃/min is warmed up to 1350-1600 ℃ again, is incubated 1-6h again; Temperature-fall period was divided into for two stages, and the speed with 10-15 ℃/min cools to 1200 ℃ first, insulation 1h, and the speed with 6-8 ℃/min cools to 600 ℃ again, and then powered-down naturally cools to room temperature.
The blending ratio of silicon and aktivton is 1: 1-1: 3.
Described soaking time is 1-6h.
Total reaction air pressure is 1.1-1.5atm.
Substrate is porcelain boat, corundum sheet or silicon chip.
In these parameters, the setting of total reaction air pressure, temperature, carbonaceous gas flow and for the second time insulation is key parameter.The growth of silicon carbide nanometer line is grown with vapor-solid growth mechanism among the present invention.Concrete reaction process of growth is to be undertaken by following reaction equation, only need carry out (2) during wherein as take SiO as the silicon source, (3) and (4) react:
Si
(solid)+SiO
2(solid)＝2SiO
(gas) (1)
CH
4(gas)＝C
(gas)+2H
2(gas) (2)
SiO
(gas)+2C
(gas)＝SiC
(solid)+CO
(gas) (3)
SiO
(gas)+3CO
(gas)＝SiC
(solid)+CO
2(gas) (4)
Because the temperature of reaction (1) or SiO gasification is more than 1250 ℃, so the lower of temperature of reaction is limited to 1250, simultaneously when temperature of reaction is no more than 1400 ℃, reaction (4) can not be carried out, the growth of silicon carbide nanometer line can only be undertaken by reaction (3), so that the growth velocity of silicon carbide nanometer line reduces, output reduces like this, and length is shorter.In addition, existing technology is all carried out being no more than under the atmospheric pressure, create such environment and mainly be by vacuum pump and control or directly flow so that the stove inner and outer air pressure all is a normal atmosphere, so that a large amount of SiO, C, CO and CO in stove by carrier gas
2Gas runs off with the discharge of carrier gas.Low in temperature like this and reaction pressure is no more than and will reaches just difficulty relatively of supersaturated condition under the atmospheric condition, thereby the silicon carbide nanometer line of growth yields poorly, and length is shorter, and is the longest in the grade scope.There are some researches show when the pressure of CO gas in the stove reaches supersaturated condition, reaction (4) just can be carried out (Y.H.Gao, Y.Bando, K.Kurashima, T.Sato, J.Mater.Sci.37,2023 (2002); J.Wei, K.Z.Li, H.J.Li, Q.G.Fu, L.Zhang, Mater.Chem.Phys.95,140 (2006)).Therefore, in order to address this problem, we adopt suitably higher temperature and total reaction pressure to realize.Wherein improving reaction pressure is to realize by reducing free air delivery, can reduce on the one hand the loss of SiO gas, can make C and CO on the other hand
2Following reaction: C fully occurs
(gas)+ CO
2 (gas)=2CO
(gas)Even, like this in the situation that less SiO and the CO gas of also making of temperature reaches hypersaturated state very soon, thereby reaction (4) is carried out smoothly, this point was not considered in the prior art.But consider cost and the security of experiment, be that temperature will prolong the reaction times when too low, and temperature and air pressure may exceed the safe handling scope of equipment or require equipment to have higher performance when too high, thereby the cost that greatly develops skill (regular service condition of domestic conventional CVD depositing device be temperature be lower than 1800 ℃, total gas pressure be no more than 0.5MPa), therefore the scope that we select to total reaction air pressure and two key parameters of temperature is respectively: total reaction air pressure is between 1.1-1.5atm, and temperature is between 1350-1600 ℃.On the other hand, when if the carbonaceous gas flow surpasses 80sccm, under the total reaction air pressure conditions of 1350-1600 ℃ temperature and 1.1-1.5atm, carbon source is with excessive, therefore remaining carbon will be deposited on the silicon carbide nanometer line surface and become pollutent, so we choose the carbonaceous gas flow between 10-80sccm.We are provided with at 1200 ℃ and locate to carry out the insulation second time in the present invention, its objective is silicon carbide nanometer line for other types (such as 2H-SiC etc.) have time enough be converted into may be unnecessary in beta-SiC nano-wire and the cleaning reaction process carbon source, simultaneously for fear of at insulating process SiO gas generation disproportionation decomposition reaction (SiO (g) → Si (g)+SiO
2(g), decomposition temperature is greater than 1250 ℃) material that produces pollutes silicon carbide nanometer line.Our mode that adopts rate of temperature fall faster to be cooled to 1200 ℃ solves for this reason.
Beneficial effect:
The invention has the beneficial effects as follows: (1). synthetic process is simple, controlled, need not to add metal catalyst, need not growth templates, avoids metal catalyst to the pollution of product; (2). owing to being the carbon source of gaseous state and the silicon source reaction of gaseous state in the process of growth, sufficient reacting, and resultant is to separate with starting material such as the silicon source, thereby synthetic monocrystalline beta-SiC nano-wire is not subjected to the pollution of solid silicon source, and locate to be provided with for the second time soaking time (as shown in Figure 1) 1200 ℃ of temperature control curves, the silicon carbide nanometer line (such as 2H-SiC etc.) that is conducive to other types has time enough to be converted into beta-SiC nano-wire, has avoided simultaneously SiO that disproportionation decomposition reaction (SiO (g) → Si (g)+SiO occurs
2(g)) material that produces pollutes silicon carbide nanometer line, thereby the purity that has guaranteed the monocrystalline beta-SiC nano-wire reaches more than 95%.Can see that from Fig. 2 and Fig. 3 product is very clean, not have other materials to exist.EDS (Fig. 4), XRD (Fig. 5), Raman (Fig. 6) and FTIR (Fig. 7) analyze has also proved do not have metal catalyst and unreacted starting material to exist in the product.And the silicon carbide nanometer line of prior art preparation one all be subject to metal catalyst and completely raw-material pollution of unreacted, one is lower than 90% its purity; (3). also have outstanding characteristics be can be by increasing the initial silicon source material amount, suitably improve temperature of reaction and prolong length and the output that soaking time is effectively controlled the monocrystalline beta-SiC nano-wire.Can provide for a long time enough silicon source gases because increase the amount of silicon source material, suitably improving temperature of reaction can more easily carry out so that react (3) and (4), thereby improve the transformation efficiency of silicon carbide nanometer line, improve output, time expand, can make the carrying out time of reaction (3) and (4) lengthen, thereby so that silicon carbide nanometer line can continue growth, thereby can guarantee the synthetic of extensive centimetre-sized monocrystalline beta-SiC nano-wire.These advantages make the method have the ability of large-scale industrial production.
Description of drawings
The programed temperature curve of Fig. 1 for arranging;
Fig. 2 is low power and the high power SEM figure of monocrystalline beta-SiC nano-wire;
Fig. 3 is low power and high power TEM, HRTEM and the SAED figure of monocrystalline beta-SiC nano-wire;
Fig. 4 is the EDS figure of monocrystalline beta-SiC nano-wire;
Fig. 5 is the XRD figure of monocrystalline beta-SiC nano-wire;
Fig. 6 is the Ramam spectrogram of monocrystalline beta-SiC nano-wire;
Fig. 7 is the FTIR spectrogram of monocrystalline beta-SiC nano-wire.
Embodiment
The present invention adopts following proposal to realize: adopt chemical Vapor deposition process, take vacuum tube furnace as experimental installation, take carbonaceous gas as carbon source, the mixture of silicon monoxide or silicon oxide and silicon is the silicon source, rare gas element is carrier gas, the temperature curve of follow procedure setting is held lifting temperature (as shown in Figure 1), it is 1350-1600 ℃ in temperature, the carbon-source gas flow is 10-80sccm, carrier gas flux is 20-80sccm, the stove internal gas pressure is insulation 1-6 hour under the condition of 11-1.5atm, at porcelain boat, extensive deposition growing length reaches the monocrystalline beta-SiC nano-wire of centimetre-sized on the substrates such as corundum sheet and silicon chip.
Through above-mentioned preparation process, from tube furnace, take out the substrates such as porcelain boat, can see at substrate surface covering in a large number the light blue or absinthe-green product of one deck, length can reach several centimetres.The analyses such as SEM, TEM, HRTEM, SEAD, EDS, X-ray diffraction, Raman, FTIR show that prepare is a kind of monocrystalline beta-SiC nano-wire (shown in Fig. 2-7).The smooth surface of nano wire when the carbon-source gas flow is lower than 40sccm, diameter is even, and mean diameter is 40-50nm approximately.Along with the rising of temperature of reaction, the depositional area of silicon carbide nanometer line increases, output increases, length increases, the diameter of nano wire also has increased slightly.Simultaneously, when increasing to 80sccm with the carbon-source gas flow, the carbon that silicon carbide nanometer line surface attachment layer of surface is more coarse, purity descends, but products therefrom can obtain the silicon carbide nanometer line of pure pale blue through behind the combustion synthesis in air, and length also can reach centimetre-sized.
Below with reference to figure and specific implementation process the present invention is described in further details:
Embodiment 1. is divided into three parts of porcelain boats of packing into 4.0g SiO, after placing the center of horizontal vacuum tube type high-temperature furnace, adopt mechanical pump tube furnace to be evacuated to-0.1Mpa, be filled with high-purity argon gas (99.999%) to 1atm by mass flowmeter in the mode of cleaning again and after cleaning 20 minutes, with flow control at 80sccm, behind stability of flow, begin to be warming up to 1400 ℃ by temperature curve shown in Figure 1, be filled with high-purity CH of 20sccm
4Adjust the furnace chamber internal gas pressure to 1.1-1.5atm, be incubated 3 hours, then the temperature curve of follow procedure setting is cooled to 1200 ℃, be incubated 1 hour, be down to 600 ℃ by temperature curve again, powered-down, naturally be cooled to room temperature, porcelain boat surface and alundum tube surface deposition mean sizes be the monocrystalline beta-SiC nano-wire that 40-50nm, length reach centimetre-sized.
Embodiment 2. is divided into three parts of porcelain boats of packing into 4.0g SiO, after placing the center of horizontal vacuum tube type high-temperature furnace, adopt mechanical pump tube furnace to be evacuated to-0.1Mpa, be filled with high-purity argon gas (99.999%) to 1atm by mass flowmeter in the mode of cleaning again and after cleaning 20 minutes, with flow control at 80sccm, behind stability of flow, begin to be warming up to 1400 ℃ by temperature curve shown in Figure 1, be filled with high-purity CH of 40sccm
4Adjust the furnace chamber internal gas pressure to 1.1-1.5atm, be incubated 3 hours, then the temperature curve of follow procedure setting is cooled to 1200 ℃, be incubated 1 hour, be down to 600 ℃ by temperature curve again, powered-down, naturally be cooled to room temperature, porcelain boat surface and alundum tube surface deposition mean sizes be the monocrystalline beta-SiC nano-wire that 40-50nm, length reach centimetre-sized.
Embodiment 3. is divided into three parts of porcelain boats of packing into 4.0g SiO, after placing the center of horizontal vacuum tube type high-temperature furnace, adopt mechanical pump tube furnace to be evacuated to-0.1Mpa, be filled with high-purity argon gas (99.999%) to 1atm by mass flowmeter in the mode of cleaning again and after cleaning 20 minutes, with flow control at 80sccm, behind stability of flow, begin to be warming up to 1400 ℃ by temperature curve shown in Figure 1, be filled with high-purity CH of 80sccm
4Adjust the furnace chamber internal gas pressure to 1.1-1.5atm, be incubated 3 hours, then the temperature curve of follow procedure setting is cooled to 1200 ℃, be incubated 1 hour, be down to 600 ℃ by temperature curve again, powered-down is cooled to room temperature naturally, porcelain boat surface and alundum tube surface deposition exhibiting high surface be black and a large amount of nattier blue product, the long product of surface black behind combustion synthesis in air, is obtained light blue product, and product is that mean sizes is the monocrystalline beta-SiC nano-wire that 50-70nm, length reach centimetre-sized.
Embodiment 4. is divided into two parts, 2.0gSi and 3.0gSiO with 4.0g SiO
2Mixture is divided into two parts of porcelain boats of packing into, after placing the center of horizontal vacuum tube type high-temperature furnace, adopt mechanical pump tube furnace to be evacuated to-0.1Mpa, be filled with high-purity argon gas (99.999%) to 1atm by mass flowmeter in the mode of cleaning again and after cleaning 20 minutes, with flow control at 20sccm, behind stability of flow, begin to be warming up to 1500 ℃ by temperature curve shown in Figure 1, be filled with high-purity CH of 40sccm
4Adjust the furnace chamber internal gas pressure to 1.1-1.5atm, be incubated 3 hours, then the temperature curve of follow procedure setting is cooled to 1200 ℃, be incubated 1 hour, be down to 600 ℃ by temperature curve again, powered-down, naturally be cooled to room temperature, having deposited in a large number mean sizes in porcelain boat surface and the alundum tube is the monocrystalline beta-SiC nano-wire that 40-50nm, length reach centimetre-sized.
Embodiment 5. is with 2.0gSi and 3.0gSiO
2Mixture is divided into two parts of porcelain boats of packing into, after placing the center of horizontal vacuum tube type high-temperature furnace, adopt mechanical pump tube furnace to be evacuated to-0.1Mpa, be filled with high-purity argon gas (99.999%) to 1atm by mass flowmeter in the mode of cleaning again and after cleaning 20 minutes, with flow control at 80sccm, behind stability of flow, begin to be warming up to 1250 ℃ by temperature curve shown in Figure 1, be filled with high-purity CH of 20sccm
4, adjust the furnace chamber internal gas pressure to 1.1-1.5atm, be incubated 3 hours, then the temperature curve of follow procedure setting is cooled to 1200 ℃, is incubated 1 hour, is down to 600 ℃ by temperature curve again, powered-down is cooled to room temperature naturally, and porcelain boat surface and alundum tube surface do not have the beta-SiC nano-wire deposition.
Embodiment 6. is with 2.0gSi and 3.0gSiO
2Mixture is divided into two parts of porcelain boats of packing into, after placing the center of horizontal vacuum tube type high-temperature furnace, adopt mechanical pump tube furnace to be evacuated to-0.1Mpa, be filled with high-purity argon gas (99.999%) to 1atm by mass flowmeter in the mode of cleaning again and after cleaning 20 minutes, with flow control at 80sccm, behind stability of flow, begin to be warming up to 1300 ℃ by temperature curve shown in Figure 1, be filled with high-purity CH of 20sccm
4Adjust the furnace chamber internal gas pressure to 1.1-1.5atm, be incubated 3 hours, then the temperature curve of follow procedure setting is cooled to 1200 ℃, be incubated 1 hour, be down to 600 ℃ by temperature curve again, powered-down, naturally be cooled to room temperature, porcelain boat surface and alundum tube surface deposition a small amount of mean sizes be that 40-50nm, length reach millimetre-sized monocrystalline beta-SiC nano-wire.
Embodiment 7. is with 2.0gSi and 3.0gSiO
2Mixture is divided into two parts of porcelain boats of packing into, after placing the center of horizontal vacuum tube type high-temperature furnace, adopt mechanical pump tube furnace to be evacuated to-0.1Mpa, be filled with high-purity argon gas (99.999%) to 1atm by mass flowmeter in the mode of cleaning again and after cleaning 20 minutes, with flow control at 80sccm, behind stability of flow, begin to be warming up to 1350 ℃ by temperature curve shown in Figure 1, be filled with high-purity CH of 20sccm
4Adjust the furnace chamber internal gas pressure to 1.1-1.5atm, be incubated 1 hour, then the temperature curve of follow procedure setting is cooled to 1200 ℃, be incubated 1 hour, be down to 600 ℃ by temperature curve again, powered-down, naturally be cooled to room temperature, porcelain boat surface and alundum tube surface deposition a large amount of mean sizess be the monocrystalline beta-SiC nano-wire that 40-50nm, length reach centimetre-sized.
Embodiment 8. is with 2.0gSi and 3.0gSiO
2Mixture is divided into two parts of porcelain boats of packing into, after placing the center of horizontal vacuum tube type high-temperature furnace, adopt mechanical pump tube furnace to be evacuated to-0.1Mpa, be filled with high-purity argon gas (99.999%) to 1atm by mass flowmeter in the mode of cleaning again and after cleaning 20 minutes, with flow control at 80sccm, behind stability of flow, begin to be warming up to 1400 ℃ by temperature curve shown in Figure 1, be filled with high-purity C of 40sccm
2H
2Adjust the furnace chamber internal gas pressure to 1.1-1.5atm, be incubated 6 hours, then the temperature curve of follow procedure setting is cooled to 1200 ℃, be incubated 1 hour, be down to 600 ℃ by temperature curve again, powered-down, naturally be cooled to room temperature, porcelain boat surface and alundum tube surface deposition a large amount of mean sizess be the monocrystalline beta-SiC nano-wire that 40-50nm, length reach centimetre-sized.
Embodiment 9. is divided into two parts, 2.0gSi and 3.0gSiO with 4.0g SiO
2Mixture is divided into two parts of porcelain boats of packing into, after placing the center of horizontal vacuum tube type high-temperature furnace, adopt mechanical pump tube furnace to be evacuated to-0.1Mpa, be filled with high pure nitrogen (99.999%) to 1atm by mass flowmeter in the mode of cleaning again and after cleaning 20 minutes, with flow control at 40sccm, behind stability of flow, begin to be warming up to 1500 ℃ by temperature curve shown in Figure 1, be filled with high-purity CH of 40sccm
4Adjust the furnace chamber internal gas pressure to 1.1-1.5atm, be incubated 3 hours, then the temperature curve of follow procedure setting is cooled to 1200 ℃, be incubated 1 hour, be down to 600 ℃ by temperature curve again, powered-down, naturally be cooled to room temperature, porcelain boat surface and alundum tube surface deposition mean sizes be the monocrystalline beta-SiC nano-wire that 50-60nm, length reach centimetre-sized.
Embodiment 11. is with 2.0g SiO
2Be divided into two parts of porcelain boats of packing into, after placing the center of horizontal vacuum tube type high-temperature furnace, adopt mechanical pump tube furnace to be evacuated to-0.1Mpa, be filled with high-purity argon gas (99.999%) to 1atm by mass flowmeter in the mode of cleaning again and after cleaning 20 minutes, with flow control at 80sccm, behind stability of flow, begin to be warming up to 1400 ℃ by temperature curve shown in Figure 1, be filled with high-purity CH of 40sccm
4Adjust the furnace chamber internal gas pressure to 1.1-1.5atm, be incubated 3 hours, then the temperature curve of follow procedure setting is cooled to 1200 ℃, be incubated 1 hour, be down to 600 ℃ by temperature curve again, powered-down, naturally be cooled to room temperature, porcelain boat surface and alundum tube surface deposition the thicker length of a small amount of diameter reach millimetre-sized monocrystalline beta-SiC nano-wire.
4.0g SiO is divided into two parts, 2.0gSi to embodiment 12. and the 3.0gSiO2 mixture is divided into two parts of porcelain boats of packing into, after placing the center of horizontal vacuum tube type high-temperature furnace, adopt mechanical pump tube furnace to be evacuated to-0.1Mpa, be filled with high-purity argon gas (99.999%) to 1atm by mass flowmeter in the mode of cleaning again and after cleaning 20 minutes, with flow control at 20sccm, behind stability of flow, begin to be warming up to 1600 ℃ by temperature curve shown in Figure 1, be filled with high-purity CH of 40sccm
4Adjust the furnace chamber internal gas pressure to 1.1-1.5atm, be incubated 3 hours, then the temperature curve of follow procedure setting is cooled to 1200 ℃, be incubated 1 hour, be down to 600 ℃ by temperature curve again, powered-down, naturally be cooled to room temperature, having deposited in a large number mean sizes in porcelain boat surface and the alundum tube is the monocrystalline beta-SiC nano-wire that 60-80nm, length reach centimetre-sized.
Claims (7)
1. the preparation method of a ultralong monocrystal beta-SiC nanowire metal-free catalyzer is characterized in that, in vacuum tube furnace or chemical vapor deposition stove, take carbonaceous gas as carbon source, the mixture of silicon monoxide or silicon and silicon oxide is the silicon source, Ar or N
2Being carrier gas, is that 1350-1600 ℃, carbon-source gas flow are that 10-80sccm, carrier gas flux are 20-80sccm, are incubated a few hours under condition of super atmospheric pressure in temperature, and deposition growing obtains the single-crystal silicon carbide nanowires that length reaches centimetre-sized on substrate.
2. the preparation method of ultralong monocrystal beta-SiC nanowire metal-free catalyzer according to claim 1 is characterized in that, described carbonaceous gas is methane, acetylene or ethene.
3. the preparation method of ultralong monocrystal beta-SiC nanowire metal-free catalyzer according to claim 1, it is characterized in that, temperature-rise period is: adopt the speed of 5-10 ℃/min to be warmed up to 300 ℃, be incubated 10 minutes, speed with 5-10 ℃/min is warmed up to 1350-1600 ℃ again, is incubated 1-6h again; Temperature-fall period was divided into for two stages, and the speed with 10-15 ℃/min cools to 1200 ℃ first, insulation 1h, and the speed with 6-8 ℃/min cools to 600 ℃ again, and then powered-down naturally cools to room temperature.
4. the preparation method of ultralong monocrystal beta-SiC nanowire metal-free catalyzer according to claim 1 is characterized in that, the mixing quality ratio of silicon and silicon oxide is 1:1-1:3.
5. the preparation method of ultralong monocrystal beta-SiC nanowire metal-free catalyzer according to claim 1 is characterized in that, described soaking time is 1-6h.
6. the preparation method of ultralong monocrystal beta-SiC nanowire metal-free catalyzer according to claim 1 is characterized in that, described super-atmospheric pressure is 1.1-1.5atm.
7. the preparation method of each described ultralong monocrystal beta-SiC nanowire metal-free catalyzer is characterized in that according to claim 1～6, and substrate is porcelain boat, corundum sheet or silicon chip.
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| CN104787765A (en) * | 2015-04-15 | 2015-07-22 | 哈尔滨工业大学 | Method for preparing super-long SiC nanowire from inorganic powder |
| CN105632585B (en) * | 2015-12-31 | 2017-12-29 | 哈尔滨工业大学 | A kind of SiC@SiO2Coaxial nano cable and preparation method thereof |
| CN111087245A (en) * | 2020-01-17 | 2020-05-01 | 泰州市海创新能源研究院有限公司 | Method for synthesizing low-oxygen low-carbon-content SiC fibers by gas phase method |
| CN111115634B (en) * | 2020-01-17 | 2022-11-18 | 江苏大学 | Method for preparing SiC fibers by using silicon wafer cutting waste |
| CN111118667A (en) * | 2020-01-17 | 2020-05-08 | 泰州市海创新能源研究院有限公司 | Method for preparing SiC fibers by using highly oxidized silicon waste |
| CN111591994A (en) * | 2020-06-03 | 2020-08-28 | 璨隆科技发展有限公司 | Preparation method of high-purity silicon carbide powder for silicon carbide single crystal growth |
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| Jun Li等.The synthesis of twinned silicon carbide nanowires by a catalyst-free pyrolytic deposition technique.《Nanotechnology》.2009,第20卷145602. |
| The synthesis of twinned silicon carbide nanowires by a catalyst-free pyrolytic deposition technique;Jun Li等;《Nanotechnology》;20090318;第20卷;145602 * |
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