CN107161962B - A kind of preparation method and beta-silicon nitride nanowire of beta-silicon nitride nanowire - Google Patents
A kind of preparation method and beta-silicon nitride nanowire of beta-silicon nitride nanowire Download PDFInfo
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- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
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Abstract
The invention discloses a kind of preparation method of beta-silicon nitride nanowire and beta-silicon nitride nanowires, belong to technical field of nanometer material preparation.Wherein, preparation method includes the following steps: to contain the binary of one or more of Fe, Co, Ni, Cu and Mo, ternary or quaternary layer dihydroxy metal hydroxides (LDH) as catalyst precursor, is put into reactor after evenly mixing with silicon powder；Mixture is warming up to pretreatment temperature under the protection of carrier gas, is pre-processed with hydrogen；Pretreatment temperature is maintained, is passed through the gas containing nitrogen source in the reactor, carries out nitridation reaction, by chemical vapor deposition processes, the grown silicon nitride nano wire on LDH；The product obtained after chemical vapor deposition is purified, beta-silicon nitride nanowire is obtained.The present invention effectively controls diameter, length and the appearance of beta-silicon nitride nanowire, and yield is high.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, in particular to the preparation method and nitrogen of a kind of beta-silicon nitride nanowire
SiClx nano wire.
Background technique
Silicon nitride Si3N4It is a kind of high temperature resistant, oxidation resistant high performance structure ceramic, while is also that a kind of broad-band gap is partly led
Body has broad-band gap, high intensity, high rigidity, excellent thermal shock resistance and inoxidizability, can be in room temperature and high-temperature field conduct
Excellent semiconductor material application.Si3N4Nano wire is the one-dimensional nano structure form of silicon nitride material, has both had block material
Expect the various excellent properties possessed, while having many new characteristics as monodimension nanometer material.For example: Si3N4Nanometer
The bending strength (reaching 3.6GPa) of line is much higher than block materials with elastic model (reaching 570GPa), and has fabulous flexibility,
It is a kind of excellent composite material reinforcement body.
Currently, preparation Si3N4The method of nano wire is more: direct nitridation method, carbothermic method, chemical vapour deposition technique, combustion
Burn reaction method, organic precursor pyrolysismethod, solvent-thermal method, template etc..During the preparation process, metal is introduced into reaction system
Catalyst can not only increase reaction rate, improve feed stock conversion, reaction temperature, regulation nano wire can also be effectively reduced
Appearance structure, thus be all widely adopted in different preparation methods.For example: Huang etc. is using silicon powder as raw material, micron order Fe
Powder is catalyst, nitrogenizes the silicon nitride nano band for being prepared for d=300~1700nm at 1450 DEG C using chemical vapour deposition technique
With nano wire (Huang J et.al, Scientific reports, 2013,3:3504.).Gu etc. is deposited on Si powder surface
Co nano particle is as catalyst, and it is 80~320nm that 2h is nitrogenized at 1200-1400 DEG C and is prepared for diameter, about 10 μm of length
Si3N4Nano wire (Gu Y et al.Journal of the American Ceramic Society, 2015,98 (6):
1762-1768.)。
However, using Si prepared by metallic catalyst3N4Nano wire often exist diameter have a very wide distribution (50~
1000nm) and the problem of average diameter relatively thick (100~500nm), so that prepared Si3N4Relatively low (the < of nano wire major diameter
100).This is mainly due to common loaded catalyst, carrier is weaker with the interaction force between metallic catalyst,
And taken in preparation process dipping, ion exchange, the methods of co-precipitation, easily cause catalyst dispersion uneven.Therefore, exist
Si3N4In the preparation process of nano wire, easily migration occurs for the metallic catalyst on carrier simultaneously at high temperature (1100-1500 DEG C)
Gather and be further sintered, so that metal catalyst particles diameter significantly becomes larger and is unevenly distributed, so as to cause prepared Si3N4
There is also this problems for nano wire.
Layer dihydroxy metal hydroxides (Layered Double Hydroxide, be abbreviated as LDH) is one kind by band
The laminate of positive charge with made of interlayer anion ordered fabrication have similar shepardite Mg (OH)2The two-dimensional nano material of structure
Material.The general expression of LDH are as follows: M2+ 1-xM3+ x(OH)2An- x/n·mH2O, wherein M2 +And M3 +Respectively represent divalent and trivalent metal
Cation；An -Represent interlayer anion；X is M3 +/(M2 ++M3 +) molar ratio, m be interlayer hydrone number.Section snow etc.
(patent publication No.: CN1718278) uses catalyst of the layer dihydroxy metal hydroxides as carbon nano tube growth, discovery
Can with growth diameter 20~50nm agglomerate shape multi-walled carbon nanotube.Wei Fei etc. (patent publication No.: CN101665248) etc. is adopted
It uses layer dihydroxy metal hydroxides as catalyst, is prepared for diameter in single double-walled carbon nano-tube of 3~5nm.Inventor
Early period, finding showed that at home and abroad there is no prepare one-dimensional Si based on LDH3N4The related patents and document report of nano material
Road.Based on this, the present invention is intended to provide a kind of prepare Si based on layer dihydroxy metal hydroxides3N4The method of nano wire, from
And abundant preparation Si3N4The catalyst type of nano wire promotes Si3N4The application study of nano wire.
Summary of the invention
The embodiment of the invention provides a kind of preparation method of beta-silicon nitride nanowire and beta-silicon nitride nanowires, existing to solve
There is a problem of that the silicon nitride nano linear diameter prepared has a very wide distribution and average diameter is thick in technology.In order to disclosure
The some aspects of embodiment have a basic understanding, and simple summary is shown below.The summarized section is not extensive overview,
Nor to determine key/critical component or describe the protection scope of these embodiments.Its sole purpose is with simple
Some concepts are presented in form, in this, as the preamble of following detailed description.
According to a first aspect of the embodiments of the present invention, a kind of preparation method of beta-silicon nitride nanowire is provided,
In some exemplary embodiments, the preparation method of beta-silicon nitride nanowire, includes the following steps:
1) by binary, ternary or quaternary layer dihydroxy metallic hydrogen containing one or more of Fe, Co, Ni, Cu and Mo
Oxide LDH is put into reactor as catalyst precursor with silicon Si powder after evenly mixing；
2) mixture is warming up to pretreatment temperature under the protection of carrier gas, is pre-processed with hydrogen；
3) pretreatment temperature is maintained, is passed through the gas containing nitrogen source in the reactor, nitridation reaction is carried out, passes through chemical gaseous phase
Deposition process, the grown silicon nitride Si on LDH3N4Nano wire；
4) product obtained after chemical vapor deposition is purified, obtains Si3N4Nano wire.
Above embodiments describe prepare Si using LDH3N4The process flow of nano wire, and indicate LDH should be containing Fe,
Binary, ternary or the quaternary LDH of one or more of Co, Ni and Mo.During the experiment, discovery contains above several metals
The catalytic effect of the LDH of element is good, the Si prepared3N4Nano wire is directly thin and distribution is uniform, is better than other common metal elements
Such as Ca, Mn and Cu.
Further, carrier gas is one or both of argon gas and helium mixture.
In some alternative embodiments,
The chemical composition general formula of LDH is M2+ 1-xM3+ x(OH)2An- x/n·mH2O；Wherein, M2+With M3+Molar ratio be 1~
4, x M3+With (M2++M3+) molar ratio；M is the number of interlayer hydrone；M2+For Mg2+、Fe2+、Co2+、Ni2+One in
Kind or several, M3+For Al3+、Co3+、Fe3+One or more of, An-For n valence anion, corresponding anion is Cl-、OH-、
NO3-、SO4 2-And CO3 2-One or more of, corresponding anion further includes isopolyacid or heteropolyacid anions containing Mo；
Fe, Co, Ni, Cu or Mo account for the 0.1~30% of LDH mass.
Preferably, Fe, Co, Ni, Cu or Mo account for 10%, 15% and the 25% of LDH mass.
In order to further optimize to LDH, above embodiments describe the selection details of LDH, including different prices gold
Belong to the information such as ratio, the range of choice of metallic element, the range of choice of anion of element.And disclose metallic element Fe, Co,
Ni, Cu or Mo account for the optimum valuing range of LDH mass.Further effectively implement the present invention for technical staff and the preferred side LDH is provided
Case.
Wherein, in LDH, metal active constituent is evenly distributed in main layer board on atom level, can be by coprecipitated
Shallow lake method prepares the catalyst precursor.
In some alternative embodiments, in the mixture, the mass ratio of LDH and Si powder is 0.01~0.1.
Preferably, the mass ratio of LDH and Si powder is 0.01,0.05,0.1.
Further, the partial size of Si powder is 0.1~100 μm, and purity is 99.5~99.998%.
In some alternative embodiments, pretreatment temperature is 1000~1400 DEG C；The pretreated time be 10~
20min。
Preferably, pretreatment temperature is 1100 DEG C, 1150 DEG C, 1200 DEG C, 1250 DEG C and 1300 DEG C.
In some alternative embodiments, the gas containing nitrogen source also contains hydrogen；Wherein, hydrogen: the gas volume of nitrogen source
Than being less than or equal to 1.
In some alternative embodiments, during mixture is warming up to pretreatment temperature, heating rate control
In 1~20 DEG C/min.
In some alternative embodiments, nitrogen source is the mixture of one or both of nitrogen, ammonia.
In some alternative embodiments, reactor uses fixed bed, moving bed, fluidized bed or their combination.
According to a second aspect of the embodiments of the present invention, a kind of beta-silicon nitride nanowire is provided,
In some exemplary embodiments, Si3N4Nano wire is prepared according to the preparation method of any of the above-described embodiment
, using layer dihydroxy metal hydroxides LDH as catalyst precursor.
In some alternative embodiments, Si3N4The diameter of nano wire is 30~50nm；Si3N4Nano wire draw ratio is greater than
1000。
Although existing patent and document, which are disclosed, at present prepares carbon nanotube using LDH, application mechanism is not equivalent
It is not approximate.During preparing carbon nanotube, reaction temperature is generally less than 900 DEG C, and nano-metal particle thereon migrates group
It is poly- relatively light, therefore prepared carbon nanotube diameter is uniform, and growth mechanism is vapour-liquid-solid growth mechanism.And it is utilized in the present invention
LDH prepares Si3N4Temperature range at 1110-1300 DEG C, have been approached the fusing point of nano metal Fe, Ni etc., the migration of nano metal
Reunite and volatilize even more serious, and there are a degree of volatilizations, thus needed in reaction process strict control reaction temperature,
LDH composition could inhibit the migration of nano metal to reunite, Si3N4The growth mechanism of nano wire is gas-liquid-solid and gas-liquid mechanism coexistence.
Technical solution provided in an embodiment of the present invention can include the following benefits:
The present invention can effectively control Si by the component and size of control reaction condition and LDH3N4Nano wire it is straight
Diameter, length and appearance, and yield is higher.Wherein, Si3N4The controlled diameter system of nano wire is to 30~50nm, Si3N4Nanometer wire length
Diameter ratio is greater than 1000.The LDH that uses in technical solution, nitrogen source are cheap and easy to get, amplify convenient for engineering and produce in batches, are Si3N4
The mass production of nano wire is laid a good foundation.
It should be understood that above general description and following detailed description be only it is exemplary and explanatory, not
It can the limitation present invention.
Detailed description of the invention
The drawings herein are incorporated into the specification and forms part of this specification, and shows and meets implementation of the invention
Example, and be used to explain the principle of the present invention together with specification.
The stereoscan photograph of Fig. 1 Fe/Mg/Al LDH ternary hydrotalcite class intercalation material.
The X-ray diffraction (XRD, X-ray diffraction) of Fig. 2 Fe/Mg/Al LDH ternary hydrotalcite class intercalation material
Spectrogram.
Fig. 3 Fe/Mg/Al LDH is as catalyst precursor, with N2For nitrogen source, the Si prepared using method of the invention3N4
The typical low power stereoscan photograph at nanowire growth initial stage.
Fig. 4 Fe/Mg/Al LDH is as catalyst precursor, with N2For nitrogen source, the Si prepared using method of the invention3N4
Typical low power stereoscan photograph after nano wire is purified.
Fig. 5 Fe/Mg/Al LDH is as catalyst precursor, with N2For nitrogen source, the Si prepared using method of the invention3N4
XRD spectra after nano wire is purified
Fig. 6 Fe/Mg/Al LDH is as catalyst precursor, with N2For nitrogen source, the Si prepared using method of the invention3N4
The typical transmission electromicroscopic photograph of nano wire.
Fig. 7 is to use Fe/Mg/Al LDH as catalyst precursor, with N2For nitrogen source, prepared using method of the invention
Si3N4The typical high-resolution-ration transmission electric-lens photo of nano wire.
Specific embodiment
The following description and drawings fully show specific embodiments of the present invention, to enable those skilled in the art to
Practice them.
Embodiment 1: it is based on Fe/Mg/Al LDH, prepares Si in fixed bed3N4Nano wire.
Be 2.5% by Fe content, the Fe/Mg/Al LDH that Fe, Mg, Al atomic ratio are 0.1: 2: 1 as catalyst,
50mg and 1g silicon powder is taken to be placed in tubular fixed-bed reactor after evenly mixing.The catalyst morphology is referring to Fig. 1, it is known that it is main
Structure is uniform sheet hexagon.The XRD spectra of Fig. 2 shows that the catalyst is typical layer dihydroxy metal hydroxides
Structure, crystallinity are high.It the use of argon gas is carrier gas, flow 1000sccm.With the heating speed of 10 DEG C/min under the atmosphere
Temperature of reactor is raised to 1150 DEG C of pretreatment temperature by room temperature by rate, then passes to the H of 1sccm2Carry out pretreatment 10min；It
Reaction temperature is maintained 1150 DEG C afterwards, the gaseous mixture for being passed through nitrogen and hydrogen carries out nitridation reaction, wherein nitrogen: the body of hydrogen
Product carries out chemical vapor deposition processes than being 1000:1, total gas flow rate 1000sccm.Reaction gas is closed after 2h, in argon gas
Solid product is taken out after being cooled to room temperature under atmosphere.Fig. 3 is after nitrogenizing 20min with Si3N4The LDH pattern of nano wire, Fig. 4 are
Si3N4Product morphology after nano wire is purified, from nanowire diameter known to figure in 30-50nm, length is 20-100 μm.Fig. 5 is
Si after purification3N4The XRD spectrum of nano wire, the results showed that nano wire purity is higher, (is greater than 95%) based on а phase, containing few
Measure β phase.Fig. 6 and Fig. 7 is Si3N4The TEM photo and high resolution scanning electromicroscopic photograph of nano wire, it can be seen that prepared
Si3N4Unformed SiO on the outside of nano wire2Layer, crystallinity are good.
Embodiment 2: it is based on Fe/Mg/Al LDH, prepares Si in fluidized bed3N4Nano wire.
It is 10% by Fe content, the Fe/Mg/Al LDH that Fe, Mg, Al atomic ratio are 0.4: 2: 1 takes as catalyst
0.5g and 5g silicon powder are placed in after evenly mixing in corundum fluidized-bed reactor.It the use of argon gas is carrier gas, flow 2000sccm.
Temperature of reactor is raised to 1250 DEG C of pretreatment temperature by room temperature with the heating rate of 20 DEG C/min under the atmosphere, is then passed to
The H of 5sccm2Carry out pretreatment 10min；Reaction temperature is maintained 1250 DEG C later, nitrogen is passed through and carries out nitridation reaction, gas
Total flow is 2000sccm, carries out chemical vapor deposition processes.Nitrogen is closed after 1h, is taken after being cooled to room temperature under an argon atmosphere
Solid product out obtains the Si for being grown in flaky material surface3N4Nano wire.
Embodiment 3: based on Fe/Mg/Al-Mo LDH, Si is prepared in fixed bed3N4Nano wire.
It is 2.5% by Fe content, the Fe/Mg/Al LDH conduct that Mo, Fe, Mg, Al atomic ratio are 0.01:0.1: 2: 1
Catalyst takes 100mg and 1g silicon powder to be placed in tubular fixed-bed reactor after evenly mixing.It the use of helium is carrier gas, flow
For 500sccm.Temperature of reactor is raised to by room temperature by pretreatment temperature 1200 with the heating rate of 20 DEG C/min under the atmosphere
DEG C, then pass to the H of 1sccm2Carry out pretreatment 20min；Reaction temperature is maintained 1200 DEG C later, is passed through nitrogen and hydrogen
Gaseous mixture carry out nitridation reaction, wherein nitrogen: the volume ratio of hydrogen is 500:1, and total gas flow rate 1000sccm is changed
Learn vapor deposition processes.Reaction gas is closed after 3h, obtains the Si for being grown in flaky material surface3N4Nano wire.
Embodiment 4: it is based on Fe/Mg/Al LDH, prepares Si in fixed bed3N4Nano wire
It is 5% by Fe content, the Fe/Mg/Al LDH that Fe, Mg, Al atomic ratio are 0.2: 2: 1 takes as catalyst
10mg and 1g silicon powder are placed in tubular fixed-bed reactor after evenly mixing.It the use of argon gas is carrier gas, flow 600sccm.
Temperature of reactor is raised to 1150 DEG C of pretreatment temperature by room temperature with the heating rate of 15 DEG C/min under the atmosphere, is then passed to
The H of 2sccm2Carry out pretreatment 10min；Reaction temperature is maintained 1150 DEG C later, ammonia is passed through and carries out nitridation reaction, gas
Total flow is 1000sccm, carries out chemical vapor deposition processes.Reaction gas is closed after 4h, after being cooled to room temperature under an argon atmosphere
Solid product is taken out, the Si for being grown in flaky material surface is obtained3N4Nano wire.
Embodiment 5: based on Co/Mg/Al LDH, Si is prepared in fixed bed3N4Nano wire.
It is 2.5% by Co content, the Co/Mg/Al LDH conduct that Mo, Fe, Mg, Al atomic ratio are 0.01:0.1: 2: 1
Catalyst takes 100mg and 1g silicon powder to be placed in tubular fixed-bed reactor after evenly mixing.It the use of helium is carrier gas, flow
For 500sccm.Temperature of reactor is raised to by room temperature by pretreatment temperature 1300 with the heating rate of 20 DEG C/min under the atmosphere
DEG C, then pass to the H of 1sccm2Carry out pretreatment 20min；Reaction temperature is maintained 1300 DEG C later, is passed through nitrogen and hydrogen
Gaseous mixture carry out nitridation reaction, wherein nitrogen: the volume ratio of hydrogen is 500:1, and total gas flow rate 1000sccm is changed
Learn vapor deposition processes.Reaction gas is closed after 3h, obtains the Si for being grown in flaky material surface3N4Nano wire.
Embodiment 6: based on Ni/Mg/Al LDH, Si is prepared in fixed bed3N4Nano wire.
It is 10% by Ni content, the Ni/Mg/Al LDH that Ni, Mg, Al atomic ratio are 0.4: 2: 1 takes as catalyst
50mg and 1g silicon powder are placed in tubular fixed-bed reactor after evenly mixing.It the use of argon gas is carrier gas, flow 750sccm.
Temperature of reactor is raised to 1100 DEG C of pretreatment temperature by room temperature with the heating rate of 20 DEG C/min under the atmosphere, is then passed to
The H of 1sccm2Carry out pretreatment 20min；Reaction temperature is maintained 1100 DEG C later, be passed through the gaseous mixture of nitrogen and hydrogen into
Row nitridation reaction, wherein nitrogen: the volume ratio of hydrogen is 1000:1, total gas flow rate 1000sccm, carries out chemical vapor deposition
Product process.Reaction gas is closed after 3h, obtains the Si for being grown in flaky material surface3N4Nano wire.
Prepared Si in the different embodiments of table 13N4The quality of nano wire
| Diameter (nm) | Length (μm) | Draw ratio | |
| Embodiment 1 | 30-50 | 20-100 | 1000-5000 |
| Embodiment 2 | 30-50 | 30-80 | 1000-1500 |
| Embodiment 3 | 20-40 | 10-100 | 2000-8000 |
| Embodiment 4 | 15-30 | 50-100 | 5000-10000 |
| Embodiment 5 | 20-40 | 40-150 | 2000-5000 |
| Embodiment 6 | 30-60 | 30-80 | 1000-2000 |
As known from Table 1, Si prepared in all embodiments3N4Wire diameter distribution is uniform, and draw ratio is greater than 1000.
The present invention can effectively control Si by the component and size of control reaction condition and LDH3N4The diameter of nano wire, length with
Appearance, and yield is higher.Wherein, Si3N4The controlled diameter system of nano wire is to 30~50nm, Si3N4Nano wire draw ratio is greater than
1000.The LDH that uses in technical solution, nitrogen source are cheap and easy to get, amplify convenient for engineering and produce in batches, are Si3N4Nano wire
Mass production is laid a good foundation.
It should be understood that the invention is not limited to the process and structure that are described above and are shown in the accompanying drawings,
And various modifications and changes may be made without departing from the scope thereof.The scope of the present invention is only limited by the attached claims
System.
Claims (8)
1. a kind of preparation method of beta-silicon nitride nanowire, which comprises the steps of:
1) by binary, ternary or quaternary layer dihydroxy metal hydrogen-oxygen containing one or more of Fe, Co, Ni, Cu and Mo
Compound LDH is put into reactor as catalyst precursor with silicon Si powder after evenly mixing；
2) mixture is warming up to pretreatment temperature under the protection of carrier gas, is pre-processed with hydrogen；
3) pretreatment temperature is maintained, is passed through the gas containing nitrogen source in the reactor, nitridation reaction is carried out, passes through chemical vapor deposition
Process, the grown silicon nitride Si on LDH3N4Nano wire；
4) product obtained after chemical vapor deposition is purified, obtains Si3N4Nano wire.
2. preparation method as claimed in claim 1, which is characterized in that
The chemical composition general formula of LDH is M2+ 1-xM3+ x(OH)2An- x/n·mH2O；Wherein, M2+With M3+Molar ratio be 1 ~ 4, x be
M3+With (M2++M3+) molar ratio；M is the number of interlayer hydrone；M2+For Mg2+、Fe2+、Co2+、Ni2+One of or
It is several, M3+For Al3+、Co3+、Fe3+One or more of, An-For n valence anion, corresponding anion is Cl-、OH-、NO3-、
SO4 2-And CO3 2-One or more of, corresponding anion further includes isopolyacid or heteropolyacid anions containing Mo；
Fe, Co, Ni or Mo account for the 0.1~30% of LDH mass.
3. preparation method as claimed in claim 1, which is characterized in that in the mixture, the mass ratio of LDH and Si powder is 0.01 ~ 1.
4. preparation method as claimed in claim 1, which is characterized in that pretreatment temperature is 1000 ~ 1400 DEG C；The pretreated time is
10~20min。
5. preparation method as claimed in claim 1, characteristic are, the gas containing nitrogen source also contains hydrogen；Wherein, hydrogen: nitrogen source
Gas volume ratio be less than or equal to 1.
6. preparation method as claimed in claim 1, which is characterized in that during mixture is warming up to pretreatment temperature, rise
Warm rate control is in 1 ~ 20 DEG C/min.
7. preparation method as claimed in claim 1, which is characterized in that nitrogen source is the mixture of one or both of nitrogen, ammonia.
8. such as the preparation method of any one of claim 1-7, which is characterized in that reactor uses fixed bed, moving bed, fluidisation
Bed or their combination.
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| CN110436934B (en) * | 2019-07-09 | 2022-02-11 | 南昌大学 | Preparation method of high alpha-phase silicon nitride powder and ultra-long silicon nitride nanowire |
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| CN112607715B (en) * | 2020-12-29 | 2021-12-10 | 哈尔滨工业大学 | Preparation method of high-purity alpha-phase silicon nitride nanowire |
| CN116535238A (en) * | 2023-04-27 | 2023-08-04 | 西北工业大学 | Radial SiC nanowire grown on surface of one-dimensional micro-nano silicon-based ceramic substrate in situ and preparation method |
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