CN102154706A - Method for preparing one-dimension nano materials - Google Patents
Method for preparing one-dimension nano materials Download PDFInfo
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- CN102154706A CN102154706A CN2011100666292A CN201110066629A CN102154706A CN 102154706 A CN102154706 A CN 102154706A CN 2011100666292 A CN2011100666292 A CN 2011100666292A CN 201110066629 A CN201110066629 A CN 201110066629A CN 102154706 A CN102154706 A CN 102154706A
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Abstract
The invention provides a method preparing one-dimension nano materials. In the method, a macromolecular organic matter serving as a carbon source and silicon slices, of which a very thin layer of silicon oxide on the surface serves as the source of oxygen and silicon, are put in an environment of mixed gases of hydrogen and nitrogen or hydrogen and argon with a specific flow rate and heated according to a specific temperature rise curve to obtain various types of linear nano materials. In the method, the same equipment is used to prepare nano materials of various types and in various yields by regulating the temperature rise curve and the gas flow rate. Besides the characteristics of high temperature resistance, high strength, low density, low thermal expansion coefficient, stable chemical property and the like, the prepared nano materials also have the characteristics of special fluorescent property and piezoelectricity and high reflectivity in the range of visible light and have a very bright application prospect in fields of super capacitor industry and stealth materials for military equipment.
Description
Technical field
The invention belongs to the preparation field of nano material, be specifically related to for example Si-O-N, SiO
2, Si
3N
4Preparation method with monodimension nanometer materials such as SiC.
Background technology
Nano material receives much concern owing to having superior machinery, physics, chemical property and potential using value.Over nearly 20 years, the preparation research of nano material has been obtained significant progress, and the preparation and the Luminescence Study of Modified Porous that contain the Si nano material have also become one of focus of research.
Since 1991 find the one-dimensional material CNT (carbon nano-tube), monodimension nanometer materials such as carbon nanotube, as silicon nanowires, SiC nano fiber, silicon nitride nano fiber and monox nanometer fiber etc., receive much concern owing to having superior machinery, physics, chemical property and potential application foreground.Monodimension nanometer material is again that the size and the dimensionality effect of physical propertiess such as the behavior of research electric transmission, optical characteristics and mechanical property gets idealized system, serving as very important role in constructing integrated circuits such as nanoelectronic and opto-electronic device and functional element, is the research focus of current field of nanometer material technology.Monodimension nanometer material is significant at aspects such as photoluminescence, low-dimensional waveguide and the connections of optics nanometer buried regions, is expected to be applied in being connected of Near-field Optical Microscope and integrated optical device.
In recent years, people use diverse ways, as chemical vapour deposition, laser ablation and carbon auxiliary law etc., prepared silica white nano-wire, beta-silicon nitride nanowire and the silicon carbide nanometer line etc. of multiple pattern, high orientation arrangement respectively, and luminescent properties, the piezoelectric property of these monodimension nanometer materials have been studied.Wei Ge people such as (Karine Saulig-Wenger) is at its paper " Direct synthesis of amorphous silicon dioxide nanowires and helical self-assembled nanostructures derived therefrom " (Journal of Materials Chemistry, 2003,13,3058-3061), utilize the auxiliary principle of carbon, it is 500 microns that monox nanometer powder and graphite Hybrid Heating are prepared length, and diameter is the monox nanometer fiber of 100-300nm.The quickest people such as (Z.Jiang) of Jiang is at its paper " Catalytic synthesis and photoluminescence of silicon oxide nanowires and nanotubes " (Applied Physics A, 2005,81, adopting the Fe-Co-Ni alloy to go out length as Preparation of Catalyst in 477-479) is that 100 micron diameters are the monox nanometer fiber of 100 nanometers.Wang Feng people such as (Feng Wang) is at paper " Temperature-controlled synthesis of Si
3N
4Nanomaterials via direct nitridation of Si powders " (Physica E, 2010,42,2033-2035) the middle synthetic Si of Si powder high temperature in nitrogen atmosphere that uses
3N
4Nanofiber has the method characteristic of simple.Haake people such as (S.K.Hark) is at paper " Fabrication and Optical Properties of Erbium-Doped Silicon-Rich Silicon Oxide Nanofibers " (Journal of Physics and Chemistry C, 2007,111, use the method for meteorological electroless plating 4083-4086), utilization sputters at Au on the silicon base of having cleaned as catalyzer, adopt the speed of 40 ℃/min to be rapidly heated 900 ℃, feed the ammonia of certain flow, continue to be heated to 1150 ℃, keep the certain hour naturally cooling can obtain the Si-O-N nanofiber.Zhang Yafei people such as (Ya-Fei Zhang) is at paper " SiC Nanowires Synthesized by Rapidly Heating a Mixture of SiO and Arc-Discharge Plasma Pretreated Carbon Black " (Nanoscale Research Letters, 2009,4,153-156), use pretreated SiO of ion arc discharge and sooty powder as starting raw material, feed argon gas and be heated to specific range of temperatures and keep certain hour, can obtain the SiC nanofiber of sapphirine.
But these methods that prepare monodimension nanometer material exist defective: can't utilize identical simple equipments to switch efficiently, carry out the preparation fast in enormous quantities of multiple class nanofiber.
Summary of the invention
For solving complex process among the existing preparation method, little, the different product technology difference of the preparation problem huge, with high costs of output, the invention provides the preparation method of monodimension nanometer material, only use same set of equipment, by changing the purpose that processing parameter reaches preparation different sorts nanofiber in enormous quantities simply, and can under specific processing parameter condition, prepare multiple nanofiber simultaneously.
A kind of preparation method of monodimension nanometer material is specially: macromolecule organic is patterned on the silicon chip, places hydrogen to mix with nitrogen then or hydrogen and argon gas blended atmosphere surrounding, to the atmosphere surrounding heating, generate monodimension nanometer material.
Further, the volume ratio 1: 1～10 of the volume ratio of described hydrogen and nitrogen 1: 5～20 or hydrogen and argon gas.
Further, be heated to 1000～1300 ℃, be incubated 1～4 hour with 5～20 ℃/min of temperature rise rate.
Further, described monodimension nanometer material is Si-O-N nano-fiber material or SiO
2Nano-fiber material or Si
3N
4Nano-fiber material or SiC nano-fiber material.
Technique effect of the present invention is embodied in:
The present invention only need use same set of equipment, comprise annealing furnace, gas mixer, vacuum pump etc., utilize identical be simple and easy to raw material, comprise: macromolecule organic is as carbon source, common silicon chip surface inherent one deck silicon oxide film is as the source of silicon and oxygen, adopt composition to comprise the atmosphere of hydrogen, argon gas, nitrogen,, can obtain the nanofiber of multiple class by the ratio heating curve different of regulating various atmosphere with employing.
Main among the present invention what utilize is the principle of meteorological electroless plating: under hot conditions, macromolecule organic can decompose and discharges multiple organic gas; Under hot conditions, the oxide thin layer silicon of silicon chip surface can be evaporated to SiO
2Steam with SiO; And in the atmosphere all gases also play crucial effects; argon gas and hydrogen are mainly as shielding gas; prevent that oxygen element and other compositions that the macromolecule organic pyrolysis discharges from reacting, hydrogen can be preferentially and oxygen element produce reaction with its consumption, hydrogen can also quicken SiO
2With the formation of SiO steam, increase speed of reaction, organic gas and SiO that nitrogen can discharge with pyrolysis
2, SiO steam produces the reaction of meteorological electroless plating, generates required nano material.
In sum, preparation method among the present invention compares with prior preparation method has following advantage: technology is simple, output is improved, when preparing different nanofiber the technology adjustment simple, do not need more exchange device, even in needs, can prepare the nanofiber of multiple different ratios simultaneously, and cost is comparatively cheap, is suitable for scale operation.The characteristics such as the nano material of preparing is high temperature resistant except that having, high strength, low density, low thermal coefficient of expansion, chemically stable, also have special fluorescent characteristic and piezoelectric property, in visible-range, have high-reflectivity, in the stealth material field of super capacitor industry and military equipment, be with a wide range of applications.
Description of drawings
Fig. 1 (a) is a Si-O-N nano-fiber material SEM picture;
Fig. 1 (b) is a Si-O-N nano-fiber material TEM picture;
Fig. 2 is SiO
2Nano-fiber material SEM picture;
Fig. 3 (a) is Si
3N
4Nano-fiber material SEM picture;
Fig. 3 (b) is Si
3N
4Nano-fiber material TEM picture;
Fig. 4 is a SiC nano-fiber material SEM picture.
Embodiment
The present invention is further described below in conjunction with embodiment.
Example 1
With the SU8 photoresist material by MEMS technology for example photoetching it is patterned on the silicon chip, be placed in the annealing furnace, adopt vacuum pump that its vacuum tightness is met the demands, adopt the nitrogen and the hydrogen gas mixture of different flow and ratio then, different temperature rise rates makes it be warmed up to 300 ℃, be incubated one hour to eliminate various thermal stresses, prevent that macromolecule organic from coming off, continue to be warmed up to different top temperatures, be incubated the different time, in the mixed airflow of nitrogen and hydrogen, be cooled to room temperature then, obtain the Si-O-N nanofiber of white amorphous, shown in Fig. 1 (a) and Fig. 1 (b).Corresponding processing parameter is as shown in table 1, and the result shows the adopting process parameter not simultaneously, and the output of Si-O-N nanofiber is also different, Temperature Influence maximum in each factor wherein, and when adopting 1200 ℃, products therefrom output is the highest.
Table 1
Example 2
Silicone oil is patterned in it on silicon chip by MEMS technology; be placed in the annealing furnace, adopt vacuum pump that its vacuum tightness is met the demands, feed the hydrogen and the argon gas of particular flow rate then; its purpose mainly is the shielding gas of argon gas as reaction, and hydrogen can quicken SiO
2Formation with SiO steam, adopt certain temperature rise rate to make it be warmed up to the temperature that needs, for example keep 1 hour to eliminate various thermal stresses at 400 ℃, prevent that macromolecule organic from coming off, continue to be warmed up to different top temperatures, be incubated the different time, in the mixed airflow of argon gas and hydrogen, be cooled to room temperature then, can obtain bright white powder at silicon chip, be SiO
2Nanofiber, as shown in Figure 2.Corresponding processing parameter is as shown in table 2, and the result shows the adopting process parameter not simultaneously, SiO
2The output of nanofiber is also different, the having the greatest impact of the flow of temperature and hydrogen in each factor wherein, and when adopting 1100 ℃ and 15L/hr, products therefrom output is the highest.
Table 2
Example 3
Resol is patterned in it on silicon chip by MEMS technology, is placed in the annealing furnace, adopt vacuum pump that its vacuum tightness is met the demands, feed the nitrogen and the hydrogen gas mixture of specified proportion and flow then, preparation Si
3N
4Ratio and the flow of hydrogen in mixed gas all adopts high value during nanofiber, adopt (for example 15 ℃/min) make it be warmed up to the temperature that needs of certain temperature rise rates, for example keep one hour to eliminate various thermal stresses at 300 ℃, prevent that macromolecule organic from coming off, continue to be warmed up to different top temperatures, be incubated the different time, in the mixed airflow of nitrogen and hydrogen, be cooled to room temperature then, preparation Si
3N
4The time top temperature generally need the hold-time comparatively permanent, cooling ends room temperature in the mixed airflow of nitrogen and hydrogen then, can obtain the Si of white crystals attitude
3N
4Nanofiber is shown in Fig. 3 (a) and Fig. 3 (b).Corresponding processing parameter is as shown in table 3, and the result shows the adopting process parameter not simultaneously, Si
3N
4The output of nanofiber is also different, the having the greatest impact of soaking time in each factor wherein, and when adopting the 4hr soaking time, products therefrom output is the highest.
Table 3
Example 4
The polyethylene silazane is patterned in it on silicon chip by MEMS technology, be placed in the annealing furnace, adopt vacuum pump that its vacuum tightness is met the demands, feed the hydrogen of specified proportion and flow and the mixed gas of argon gas then, the main effect of hydrogen is reduction SiO during preparation SiC nanofiber
2With the oxygen element in the SiO steam, in order to arrive the SiC nanofiber purity higher requirement of generation, need in mixed gas, suitably improve the ratio and the flow of hydrogen, adopt certain temperature rise rate to make it be warmed up to the temperature that needs, for example keep one hour to eliminate various thermal stresses at 360 ℃, prevent that macromolecule organic from coming off, fully discharge simultaneously carbon containing organic gas, continue to be warming up to optimal reaction temperature and keep the enough time, cooling ends room temperature in the mixed airflow of argon gas and hydrogen then, can obtain the bright green powder, be the SiC nanofiber, as shown in Figure 4.Corresponding processing parameter is as shown in table 4, and the result shows the adopting process parameter not simultaneously, and the output of SiC nanofiber is also different, and when the parameter of adopting process scheme 2, products therefrom output is the highest.
Table 4
Claims (4)
1. the preparation method of a monodimension nanometer material is specially: macromolecule organic is patterned on the silicon chip, places hydrogen to mix with nitrogen then or hydrogen and argon gas blended atmosphere surrounding, to the atmosphere surrounding heating, generate monodimension nanometer material.
2. the preparation method of monodimension nanometer material according to claim 1 is characterized in that, the volume ratio 1:1 of the volume ratio 1:5 of described hydrogen and nitrogen～20 or hydrogen and argon gas～10.
3. the preparation method of monodimension nanometer material according to claim 1 is characterized in that, is heated to 1000～1300 ℃ with 5～20 ℃/min of temperature rise rate, is incubated 1～4 hour.
4. the preparation method of monodimension nanometer material according to claim 1 is characterized in that, described monodimension nanometer material is Si-O-N nano-fiber material or SiO
2Nano-fiber material or Si
3N
4Nano-fiber material or SiC nano-fiber material.
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Cited By (7)
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| CN103065956A (en) * | 2012-12-27 | 2013-04-24 | 南京大学 | Method and device for achieving smoothness of silicon surface structure |
| CN103578908A (en) * | 2013-10-10 | 2014-02-12 | 浙江大学 | Discrete carbon nano-tube array discharge ionization source |
| CN104499053A (en) * | 2014-12-17 | 2015-04-08 | 青岛桥海陶瓷新材料科技有限公司 | Method for preparing silicon nitride crystal whisker |
| CN105133021A (en) * | 2015-08-19 | 2015-12-09 | 宁波工程学院 | SiC one-dimensional nanomaterial and application 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 |
| CN112341207A (en) * | 2020-11-20 | 2021-02-09 | 哈尔滨工业大学 | Silicon nitride-silicon oxynitride column-hole composite ceramic material and preparation method thereof |
| CN112607715A (en) * | 2020-12-29 | 2021-04-06 | 黑龙江冠瓷科技有限公司 | Preparation method of high-purity alpha-phase silicon nitride nanowire |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103065956A (en) * | 2012-12-27 | 2013-04-24 | 南京大学 | Method and device for achieving smoothness of silicon surface structure |
| CN103065956B (en) * | 2012-12-27 | 2015-02-25 | 南京大学 | Method and device for achieving smoothness of silicon surface structure |
| CN103578908A (en) * | 2013-10-10 | 2014-02-12 | 浙江大学 | Discrete carbon nano-tube array discharge ionization source |
| CN104499053A (en) * | 2014-12-17 | 2015-04-08 | 青岛桥海陶瓷新材料科技有限公司 | Method for preparing silicon nitride crystal whisker |
| CN105133021A (en) * | 2015-08-19 | 2015-12-09 | 宁波工程学院 | SiC one-dimensional nanomaterial and application 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 |
| CN112341207A (en) * | 2020-11-20 | 2021-02-09 | 哈尔滨工业大学 | Silicon nitride-silicon oxynitride column-hole composite ceramic material and preparation method thereof |
| CN112607715A (en) * | 2020-12-29 | 2021-04-06 | 黑龙江冠瓷科技有限公司 | Preparation method of high-purity alpha-phase silicon nitride nanowire |
| 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 |
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Application publication date: 20110817 |