CN101812730A - 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 ultralong monocrystal beta-SiC nanowire metal-free Preparation of catalysts method.
Technical background
Silicon carbide nanometer line has 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 nano photoelectronic devices such as preparation blue light-emitting diode, laser diode and high power transistor, also be the desirable wild phase material of 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, large-area preparation overlength silicon carbide nanometer line is the matter of utmost importance that realizes its suitability for industrialized production and practical application.The gong-yi Li of the National University of Defense technology in 2009 etc. have reported employing CVD method, are parent material with the mixture of ferrocene, L-Ps and gac, and 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 (a few cm long SiC nano wires of CVD pyrolytic decomposition polymer precursor large-area preparation) .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, impurity such as containing metal catalyzer is more in the product, can pollute silicon carbide nanometer line, the intrinsic structure and the performance study of silicon carbide nanometer line have been influenced, 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 2 H-SiC nano wire); Chemical Physics Letters 2003; 381,628-633 " discloses a kind of to be starting raw material with methane and SiO, to prepare the method for 2H-SiC nano whisker under the reaction pressure condition of 300Torr.It is starting raw material that document " J.Z.Guo; Y.Zuo; Z.J.Li, W.D.Gao, J.L.Zhang; Preparation of SiCnanowires with fins by chemical vapor deposition (the chemical Vapor deposition process preparation contains the fin silicon carbide nanometer line); Physica E, 2007,39; 262-266 " discloses a kind of mixture with methane, silicon oxide and silicon, 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 length-to-diameter ratio of preparation is less, 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 exist temperature too high; Complex process needs multistep synthetic; Output is on the low side, length-to-diameter ratio is less, is difficult to large-scale production; Some generates a large amount of silicon-carbide particles inevitably, has more difficult isolating problem, and particularly, many methods need be added metal catalyst, and the existence of metal catalyst has influenced 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, this 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, growing single-crystal beta-SiC nano-wire on a large scale.
Technical solution of the present invention is as follows:
A kind of ultralong monocrystal beta-SiC nanowire metal-free Preparation of catalysts method is characterized in that, in vacuum tube furnace or chemical vapor deposition stove, is carbon source with the carbonaceous gas, and 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 ℃ earlier, insulation 1h, and the speed with 6-8 ℃/min cools to 600 ℃ again, and powered-down naturally cools to room temperature then.
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 insulation for the second time is a 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) when being the silicon source wherein as with SiO, (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 following 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), make the growth velocity of silicon carbide nanometer line reduce like this, output reduces, 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 to control or directly in stove, flow making that the stove inner and outer air pressure all is a normal atmosphere, make a large amount of SiO, C, CO and CO by carrier gas by vacuum pump
2Gas runs off with the discharge of carrier gas.Low and reaction pressure is no more than and will reaches just difficulty relatively of supersaturated condition under the atmospheric condition in temperature like this, thereby the silicon carbide nanometer line of growth yields poorly, and length is shorter, and is the longest in millimeter level scope.There are some researches show that 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 the loss of SiO gas on the one hand, can make C and CO on the other hand
2Following reaction: C fully takes place
(gas)+ CO
2 (gas)=2CO
(gas)Even, under the less situation of temperature, also can make SiO and CO gas reach hypersaturated state very soon like this, thereby reaction (4) is carried out smoothly, this point was not considered in the prior art.But consider the 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 develops skill greatly (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 (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 produced 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 the pollution of metal catalyst to product; (2). owing to be gasiform carbon source and the reaction of gasiform silicon source in the process of growth, sufficient reacting, and resultant is to separate with starting material 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 soaking time (as shown in Figure 1) for the second time 1200 ℃ of temperature control curves, the silicon carbide nanometer line (as 2H-SiC etc.) that helps other types has time enough to be converted into beta-SiC nano-wire, has avoided SiO that disproportionation decomposition reaction (SiO (g) → Si (g)+SiO takes place simultaneously
2(g)) material that is produced 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, does 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 for preparing one all be subjected to metal catalyst and the raw-material completely 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 enough silicon source gases for a long time because increase the amount of silicon source material, suitably the raising temperature of reaction can (3) and (4) are easier carries out so that react, thereby improve the transformation efficiency of silicon carbide nanometer line, improve output, time expand, can make the carrying out time lengthening of reaction (3) and (4), thereby make silicon carbide nanometer line can continue growth, thereby can guarantee the synthetic of extensive centimetre-sized monocrystalline beta-SiC nano-wire.These advantages make this method have the ability of large-scale industrial production.
Description of drawings
The programed temperature curve of Fig. 1 for being provided with;
Fig. 2 is the 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, with the vacuum tube furnace is experimental installation, with the carbonaceous gas is 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), in temperature is 1350-1600 ℃, 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 substrates such as porcelain boat, can see at substrate surface covering the light blue or absinthe-green product of one deck in a large number that length can reach several centimetres.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, the about 40-50nm of mean diameter.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 increase slightly.Simultaneously, when increasing to 80sccm with the carbon-source gas flow, the more coarse carbon of silicon carbide nanometer line surface attachment layer of surface, purity descends, but products therefrom can obtain the silicon carbide nanometer line of purified pale blue through after burning in the 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, charge into high-purity argon gas (99.999%) to 1atm and after cleaning 20 minutes by mass flowmeter in the mode of cleaning again, with flow control at 80sccm, treat to begin to be warming up to 1400 ℃ behind the stability of flow, charge into high-purity CH of 20sccm by temperature curve shown in Figure 1
4Adjust the furnace chamber internal gas pressure to 1.1-1.5atm, be incubated 3 hours, the temperature curve of follow procedure setting is cooled to 1200 ℃ then, be incubated 1 hour, reduce 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, charge into high-purity argon gas (99.999%) to 1atm and after cleaning 20 minutes by mass flowmeter in the mode of cleaning again, with flow control at 80sccm, treat to begin to be warming up to 1400 ℃ behind the stability of flow, charge into high-purity CH of 40sccm by temperature curve shown in Figure 1
4Adjust the furnace chamber internal gas pressure to 1.1-1.5atm, be incubated 3 hours, the temperature curve of follow procedure setting is cooled to 1200 ℃ then, be incubated 1 hour, reduce 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, charge into high-purity argon gas (99.999%) to 1atm and after cleaning 20 minutes by mass flowmeter in the mode of cleaning again, with flow control at 80sccm, treat to begin to be warming up to 1400 ℃ behind the stability of flow, charge into high-purity CH of 80sccm by temperature curve shown in Figure 1
4Adjust the furnace chamber internal gas pressure to 1.1-1.5atm, be incubated 3 hours, the temperature curve of follow procedure setting is cooled to 1200 ℃ then, be incubated 1 hour, reduce 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, after the long product of surface black burnt in air, obtain light blue product, 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, charge into high-purity argon gas (99.999%) to 1atm and after cleaning 20 minutes by mass flowmeter in the mode of cleaning again, with flow control at 20sccm, treat to begin to be warming up to 1500 ℃ behind the stability of flow, charge into high-purity CH of 40sccm by temperature curve shown in Figure 1
4Adjust the furnace chamber internal gas pressure to 1.1-1.5atm, be incubated 3 hours, the temperature curve of follow procedure setting is cooled to 1200 ℃ then, be incubated 1 hour, reduce to 600 ℃ by temperature curve again, powered-down, naturally be cooled to room temperature, having deposited mean sizes in a large number 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, charge into high-purity argon gas (99.999%) to 1atm and after cleaning 20 minutes by mass flowmeter in the mode of cleaning again, with flow control at 80sccm, treat to begin to be warming up to 1250 ℃ behind the stability of flow, charge into high-purity CH of 20sccm by temperature curve shown in Figure 1
4, adjust the furnace chamber internal gas pressure to 1.1-1.5atm, be incubated 3 hours, the temperature curve of follow procedure setting is cooled to 1200 ℃ then, is incubated 1 hour, reduces 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, charge into high-purity argon gas (99.999%) to 1atm and after cleaning 20 minutes by mass flowmeter in the mode of cleaning again, with flow control at 80sccm, treat to begin to be warming up to 1300 ℃ behind the stability of flow, charge into high-purity CH of 20sccm by temperature curve shown in Figure 1
4Adjust the furnace chamber internal gas pressure to 1.1-1.5atm, be incubated 3 hours, the temperature curve of follow procedure setting is cooled to 1200 ℃ then, be incubated 1 hour, reduce 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, charge into high-purity argon gas (99.999%) to 1atm and after cleaning 20 minutes by mass flowmeter in the mode of cleaning again, with flow control at 80sccm, treat to begin to be warming up to 1350 ℃ behind the stability of flow, charge into high-purity CH of 20sccm by temperature curve shown in Figure 1
4Adjust the furnace chamber internal gas pressure to 1.1-1.5atm, be incubated 1 hour, the temperature curve of follow procedure setting is cooled to 1200 ℃ then, be incubated 1 hour, reduce 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, charge into high-purity argon gas (99.999%) to 1atm and after cleaning 20 minutes by mass flowmeter in the mode of cleaning again, with flow control at 80sccm, treat to begin to be warming up to 1400 ℃ behind the stability of flow, charge into high-purity C of 40sccm by temperature curve shown in Figure 1
2H
2Adjust the furnace chamber internal gas pressure to 1.1-1.5atm, be incubated 6 hours, the temperature curve of follow procedure setting is cooled to 1200 ℃ then, be incubated 1 hour, reduce 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, charge into high pure nitrogen (99.999%) to 1atm and after cleaning 20 minutes by mass flowmeter in the mode of cleaning again, with flow control at 40sccm, treat to begin to be warming up to 1500 ℃ behind the stability of flow, charge into high-purity CH of 40sccm by temperature curve shown in Figure 1
4Adjust the furnace chamber internal gas pressure to 1.1-1.5atm, be incubated 3 hours, the temperature curve of follow procedure setting is cooled to 1200 ℃ then, be incubated 1 hour, reduce 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, charge into high-purity argon gas (99.999%) to 1atm and after cleaning 20 minutes by mass flowmeter in the mode of cleaning again, with flow control at 80sccm, treat to begin to be warming up to 1400 ℃ behind the stability of flow, charge into high-purity CH of 40sccm by temperature curve shown in Figure 1
4Adjust the furnace chamber internal gas pressure to 1.1-1.5atm, be incubated 3 hours, the temperature curve of follow procedure setting is cooled to 1200 ℃ then, be incubated 1 hour, reduce 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 diameter slightly length 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, charge into high-purity argon gas (99.999%) to 1atm and after cleaning 20 minutes by mass flowmeter in the mode of cleaning again, with flow control at 20sccm, treat to begin to be warming up to 1600 ℃ behind the stability of flow, charge into high-purity CH of 40sccm by temperature curve shown in Figure 1
4Adjust the furnace chamber internal gas pressure to 1.1-1.5atm, be incubated 3 hours, the temperature curve of follow procedure setting is cooled to 1200 ℃ then, be incubated 1 hour, reduce to 600 ℃ by temperature curve again, powered-down, naturally be cooled to room temperature, having deposited mean sizes in a large number 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. a ultralong monocrystal beta-SiC nanowire metal-free Preparation of catalysts method is characterized in that, in vacuum tube furnace or chemical vapor deposition stove, is carbon source with the carbonaceous gas, and 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 silicon carbide nanometer line non-metal catalyst according to claim 1 is characterized in that, described carbonaceous gas is methane, acetylene or ethene.
3. the preparation method of ultralong monocrystal silicon carbide nanometer line non-metal catalyst 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 ℃ earlier, insulation 1h, and the speed with 6-8 ℃/min cools to 600 ℃ again, and powered-down naturally cools to room temperature then.
4. the preparation method of ultralong monocrystal silicon carbide nanometer line non-metal catalyst 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 silicon carbide nanometer line non-metal catalyst according to claim 1 is characterized in that, described soaking time is 1-6h.
6. the preparation method of ultralong monocrystal silicon carbide nanometer line non-metal catalyst according to claim 1 is characterized in that, described super-atmospheric pressure is 1.1-1.5atm.
7. according to the preparation method of each described ultralong monocrystal silicon carbide nanometer line non-metal catalyst of claim 1～6, it is characterized in that substrate is porcelain boat, corundum sheet or silicon chip.
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| CN102351182A (en) * | 2011-07-06 | 2012-02-15 | 西安建筑科技大学 | Preparation method of ultra-long silicon carbide nano-wires |
| 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 |
| CN105632585A (en) * | 2015-12-31 | 2016-06-01 | 哈尔滨工业大学 | SiC@SiO2 coaxial nanocable 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 |
| CN111115634A (en) * | 2020-01-17 | 2020-05-08 | 江苏大学 | Method for preparing SiC fibers by using silicon wafer cutting waste |
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| 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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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102154706A (en) * | 2011-03-18 | 2011-08-17 | 华中科技大学 | Method for preparing one-dimension nano materials |
| CN102351182A (en) * | 2011-07-06 | 2012-02-15 | 西安建筑科技大学 | Preparation method of ultra-long silicon carbide nano-wires |
| 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 |
| CN105632585A (en) * | 2015-12-31 | 2016-06-01 | 哈尔滨工业大学 | SiC@SiO2 coaxial nanocable 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 |
| CN111115634A (en) * | 2020-01-17 | 2020-05-08 | 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 |
| CN111115634B (en) * | 2020-01-17 | 2022-11-18 | 江苏大学 | Method for preparing SiC fibers by using silicon wafer cutting 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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