CN105129803A - Method for precisely controlling SiC one-dimensional nanomaterial - Google Patents
Method for precisely controlling SiC one-dimensional nanomaterial Download PDFInfo
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- CN105129803A CN105129803A CN201510511060.4A CN201510511060A CN105129803A CN 105129803 A CN105129803 A CN 105129803A CN 201510511060 A CN201510511060 A CN 201510511060A CN 105129803 A CN105129803 A CN 105129803A
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Abstract
The invention discloses a method for precisely controlling a SiC one-dimensional nanomaterial. The method comprises the steps of precursor preparation, matrix pretreatment, nanowire growth and cooling, the matrix pretreatment step comprises introducing a catalyst into the matrix, the nanowire growth step comprises sintering the matrix and the precursor in a protective atmosphere, and heating to a pyrolysis temperature to pyrolyze the precursor and further to form the SiC one-dimensional nanomaterial on the matrix surface. The SiC one-dimensional nanomaterial comprises a main body and a head part formed at the main body end. The method realizes the cylindrical structure of multiple cross section shapes, and also the SiC one-dimensional nanomaterial possesses good structure stability and semiconductor performances, and also processing preparation is convenient and easy to realize.
Description
Technical field
The present invention relates to a kind of preparation method of 1-dimention nano semiconductor material, particularly a kind of method of accurate control SiC monodimension nanometer material.
The involved cross section of the present invention program is that trilateral includes, without being limited to conventional trilateral that border is straight line and border is the nearly trilateral etc. of curve; Spherical or elliposoidal comprises general globosity and approximate construction thereof or elliposoidal structure and approximate construction thereof; Smooth except specific restriction, all refer to the visual effect under the general condition of corresponding environment of observation, the visual effect of rough finger under corresponding environment of observation has fluctuating or concavo-convex or hole slot structure for being observed thing surface; When it should be noted that in the technical program the technical scheme relating to complete processing, word restriction successively is not equal to the restriction before and after processing step simultaneously.
Background technology
Since Japan Science family expenses high-resolution electron microscope in 1991 has found carbon nanotube, the preparation science of One, Dimensional Semiconductor Nano Materials and device application thereof are research emphasis in nanosecond science and technology and focus always, become the effective Study system of one of the electricity of research material, calorifics and mechanical property and dimension and quantum limitation effect dependency, to play an increasingly important role in micro-nano device as connection and functional unit, and be expected to provide opportunity for novel, efficient photoelectric device obtains important breakthrough.Nearly ten years, researchist constantly explores new synthesis technique, prepares the various one-dimensional nanometer semiconductor structure such as nanotube, nanometer rod, nano wire, quantum wire semiconductor, nano belt, nano-wire array with excellent properties.
SiC is the third generation semiconductor material grown up after the first-generation (Si) and the s-generation (GaAs) semiconductor material.Compared with its conventional bulk, one dimension SiC nanostructure has excellent process based prediction model, the characteristics such as such as high energy gap, high thermal conductivity and the saturated mobility of electronics, little specific inductivity and good mechanical property, huge application prospect is had in fields such as field-transmitting cathode, field-effect transistor, photodetector and pressure transmitters, quite concerned in recent years.The research such as Zhang shows: the SiC nanowire through Al doping has very low threshold electric field (E
to=0.55 ~ 1.54V μm
-1), be the filed emission cathode material of excellent performance.The longitudinal piezoresistance coefficient of p-type SiC nanowire under 43.8 ~ 140.2nN pressure reaches 51.2 ~ 159.5 × 10
-11pa
-1, represent huge applications potentiality in high sensibility pressure transducer field.High hole (~ 1.7 × 10 is shown with the p-type field-effect transistor that 3C-SiC nano wire builds
17cm
-3), low mobility (~ 6.4cm
2/ (Vs)) and more weak threshold effect.
The pattern of one dimension SiC nanostructure has a direct impact its application, realizes being of great importance to its potential application to the accurate control of SiC one dimension pattern.
Summary of the invention
For solving the problem, the invention discloses a kind of method of accurate control SiC monodimension nanometer material, by in production technique to the control of the processing parameters such as pyrolysis temperature, achieve the column construction of multiple section form, achieve the cylindrical and triangular prism shaped structural form of nano material, there is good structural stability and semiconducting behavior simultaneously, process easy to prepare simultaneously, be easy to realize.
SiC monodimension nanometer material disclosed by the invention, wherein SiC monodimension nanometer material comprises the body of column and is formed at the head of body end, the radial section of described body is circular or trilateral, and described main body comprises the SiC crystal existed in crystalline form, and described head includes element cobalt.
The one of SiC monodimension nanometer material disclosed by the invention is improved, and in the body of SiC monodimension nanometer material, the crystal habit of SiC is the one in 3C, 2H, 4H, 6H, 15R.
The one of SiC monodimension nanometer material disclosed by the invention is improved, and head is the cobalt-base alloy containing carbon and element silicon.
The one of SiC monodimension nanometer material disclosed by the invention is improved, and body surface is smooth surface or uneven surface; When body surface is uneven surface, body surface has rib male structure or concaveconvex structure or pore structure, and the convex bearing of trend of rib is consistent or inconsistent.
The one of SiC monodimension nanometer material disclosed by the invention is improved, and head sizes is 0.5-1 micron (maximum diameter).
The one of SiC monodimension nanometer material disclosed by the invention is improved, and the maximum diameter of body is 0.3-2 micron.
The one of SiC monodimension nanometer material disclosed by the invention is improved, and head is spherical or elliposoidal, and the surface of head is smooth surface or rough surface (as surface has concaveconvex structure or valvular structure).
SiC monodimension nanometer material disclosed by the invention is in the opto-electronic device as the application of semiconductor material.
The method of accurate control SiC monodimension nanometer material disclosed by the invention, comprises the steps,
Precursor prepares;
Substrate pretreated, comprises and catalyzer is introduced matrix (matrix can be carbon cloth);
Nanowire growth, for matrix and precursor being sintered protecting under atmosphere, is warming up to pyrolysis temperature, pyrolysis precursor thus form SiC monodimension nanometer material at matrix surface, and wherein SiC monodimension nanometer material comprises body and is formed at the head of body end;
Cooling.
The one of the method for accurate control SiC monodimension nanometer material disclosed by the invention is improved, and when sintering in nanowire growth, the pyrolysis temperature of precursor is 1550 ~ 1650 DEG C, and pyrolysis time is 5-30min.Temperature is too low to be unfavorable for the complete pyrolysis of carbon element silicon in precursor raw material and to form carbon silicon key, is easy to introduce impurity element; Too high, have and burn gelatinization, also can be unfavorable for carbon element silicon Cheng Jian because energy is too high equally, form the elementary cell of silicon carbide nano material.
The one of the method for accurate control SiC monodimension nanometer material disclosed by the invention is improved, and when sintering in nanowire growth, the heat-up rate being warming up to pyrolysis temperature is 20-40 DEG C/min.
The one of the method for accurate control SiC monodimension nanometer material disclosed by the invention is improved; protection atmosphere during precursor pyrolysis is nitrogen atmosphere or argon atmosphere or nitrogen argon gas gas mixture atmosphere (wherein during nitrogen argon gas gas mixture atmosphere, nitrogen accounts for 3-8 (v/v) % of gas mixture cumulative volume).
The one of the method for accurate control SiC monodimension nanometer material disclosed by the invention is improved, dry after the ethanolic soln impregnation matrix that during substrate pretreated, catalyzer is introduced as with catalyzer.
The one of the method for accurate control SiC monodimension nanometer material disclosed by the invention is improved, and catalyzer is cobalt salt (as Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES), and the concentration of cobalt ion in ethanolic soln is 0.02-0.15moL/L.
The one of the method for accurate control SiC monodimension nanometer material disclosed by the invention is improved, and also carries out ultrasonication 5-30S in the process that when catalyzer is introduced in described substrate pretreated, matrix floods with the ethanolic soln of catalyzer.Here ultrasonic wave is adopted to process, to utilize the generation of the supercavitation in ultrasonication and burying in oblivion formed energy impact, cobalt ion is made to be distributed to matrix surface fully, matrix and cobalt ion are activated simultaneously, improve the activity of matrix surface functional group and cobalt ion chelation structure, thus be conducive to the growth of nano material on matrix and the formation of promoting catalyst head, realize the specific material structure of the technical program and performance.
The one of the method for accurate control SiC monodimension nanometer material disclosed by the invention is improved, and when precursor prepares, the raw material of precursor is the organism at least containing Si and C element.
The one of the method for accurate control SiC monodimension nanometer material disclosed by the invention is improved, and precursor is prepared as raw material to pulverize after heat cross-linking solidification and obtains.
The one of the method for accurate control SiC monodimension nanometer material disclosed by the invention is improved, and when precursor prepares, the grain size of the powder after crushed of the raw material after solidification is 0.3-5 μm.By controlling the size of raw material powder, the stability of crystal form be conducive to when growing in sintering process nano wire controls, when adopting less crystal grain, because pyrolysis rate is very fast, the speed of growth is higher, very easily there is the defects such as dislocation in cell configuration, the one-dimensional material of single crystal forms is made to be difficult to realize, the stacking cycle of atom can be extended equally simultaneously, no matter be all difficult to the cycle that obtains shorter crystalline structure when realizing C type, R type, H type structure, and due to fast growth, material directly can be comparatively slightly fat, to Properties Control not easily; And particle diameter is too thick, then sintering pyrolysis efficiency can be caused low, and inequality of being heated, even occurs that raw material has little time pyrolysis and becomes the phenomenon of impurity in material, slightly aobvious strict to the control overflow of sintering pyrolytic process.
Compared with prior art, the invention has the advantages that:
1, the present invention achieves the accurate control of SiC one dimension Nano structure pattern by simple regulation and control pyrolysis temperature, the accurate control of the monodimension nanometer material of the variform of cylindrical, triangular prism shaped and approximate form can be realized, specifically to sinter growth pattern, achieve under the state that technical scheme limits.
2, present invention achieves the accurate control of two kinds of triangular prism-shaped SiC one dimension Nano structures with uneven surface and smooth surface.
3, monodimension nanometer material of the present invention has good structural stability and the photoelectric properties of excellence, as semiconductor material performance give prominence to, simultaneously produce and easy to process, controllability is strong, be convenient to large-scale industrial production, body material has good orientation effect and stability.
4, the present invention program is by regulation and control pyrolysis temperature, can realize the accurate control to SiC one dimension Nano structure pattern, make it change ganoid triangular prism-shaped structure gradually into from cylinder shape.The SiC one dimension Nano structure of prepared different-shape has very large application potential in fields such as Field Emission Display, field-effect transistor, pressure transmitters.
Accompanying drawing explanation
X-ray diffraction (XRD) collection of illustrative plates of the SiC nanostructure of the growth of Fig. 1 obtained by the embodiment of the present invention one in carbon fiber substrate;
Low power scanning electron microscope (SEM) figure of the SiC one dimension Nano structure of Fig. 2 obtained by the embodiment of the present invention one;
High power scanning electron microscope (SEM) figure of the SiC one dimension Nano structure of Fig. 3 obtained by the embodiment of the present invention one;
Selected area electron diffraction (SAED) figure of the SiC one dimension Nano structure of Fig. 4 obtained by the embodiment of the present invention one;
Low power scanning electron microscope (SEM) figure of the SiC one dimension Nano structure of Fig. 5 obtained by the embodiment of the present invention two;
High power scanning electron microscope (SEM) figure of the SiC one dimension Nano structure of Fig. 6 obtained by the embodiment of the present invention two;
Low power scanning electron microscope (SEM) figure of the SiC flexible field emission cathode material of Fig. 7 obtained by the embodiment of the present invention three;
High power scanning electron microscope (SEM) figure of the SiC flexible field emission cathode material of Fig. 8 obtained by the embodiment of the present invention three.
Embodiment
Below in conjunction with the drawings and specific embodiments, illustrate the present invention further, following embodiment should be understood and be only not used in for illustration of the present invention and limit the scope of the invention.It should be noted that, the word "front", "rear" of use is described below, "left", "right", "up" and "down" refer to direction in accompanying drawing, word " interior " and " outward " refer to the direction towards or away from particular elements geometric centre respectively.
Constructive embodiment one
In the present embodiment, SiC monodimension nanometer material comprises the body of column and is formed at the head of body end, and the radial section of body is circular, and main body comprises the 3C-SiC crystal existed in crystalline form, and head includes element cobalt.
Constructive embodiment two
In the present embodiment, SiC monodimension nanometer material comprises the body of column and is formed at the head of body end, and the radial section of body is, main body comprises the 3C-SiC crystal existed in crystalline form, and head includes element cobalt.
Constructive embodiment three
In the present embodiment, SiC monodimension nanometer material comprises the body of column and is formed at the head of body end, and the radial section of body is circular, and main body comprises the 3C-SiC crystal existed in crystalline form, and head includes element cobalt.
With unique difference of constructive embodiment one to three, constructive embodiment four to six is only that the cylinder of body is smooth surface.
With unique difference of constructive embodiment one to three, constructive embodiment seven to nine is only that the cylinder of body is uneven surface.
With unique difference of constructive embodiment one to three, constructive embodiment ten to ten two is only that the cylinder of body is uneven surface, when body surface is uneven surface, it is convex that body surface has rib, the bearing of trend consistent (entirety as shown in figures 5-6, in " Z " type, becomes parallel or near parallel construction on each side) that rib is convex or inconsistent (intersecting or decussate texture).Here concaveconvex structure (groove structure or groove and protruding and the structure of depositing) can also be had when body surface is uneven surface, or can also for be formed with pore structure on surface.
Distinctively, in above embodiment, the radial section of body can also be trilateral; When radial section is trilateral, the side of cylindrical body can be evagination or indent or other type; The maximum diameter of body be 0.3 micron (can also be other arbitrary value in 0.36,0.4,0.45,0.5,0.54,0.6,0.68,0.7,0.72,0.8,0.85,0.9,0.93,1.0,1.05,1.1,1.14,1.2,1.22,1.3,1.36,1.4,1.45,1.5,1.54,1.6,1.68,1.7,1.72,1.8,1.85,1.9,1.93,2.0 micron and 0.3-2 micrometer range); The maximum diameter of head is close with the maximum diameter of body, it is ± 30% (other arbitrary value as in-30% ,-22% ,-20% ,-17% ,-15% ,-10% ,-8% ,-2%, 0%, 30%, 22%, 20%, 17%, 15%, 10%, 8%, 2% and-30%-30% scope) with the scope that differs of the maximum diameter of body, is equally applicable to the application of this section of aforementioned data here.
Embodiment one
Initial feed chooses polysilazane, at N
2heat cross-linking solidification is carried out in 260 DEG C of insulation 30min under atmosphere protection.Load solidifying the SiCN solid obtained in nylon resin ball grinder, ball mill pulverizing powdered, powder diameter 1 micron, takes 300mg and is placed in bottom plumbago crucible.Cut carbon cloth 5 × 5cm (long × wide), at 0.05mol/LCo (NO
3)
3dipping in ethanolic soln supersound process 10 second, take out to be placed in air ambient and naturally dries.The carbon cloth of dip treating is placed in plumbago crucible top, and is placed in the atmosphere sintering furnace of graphite resistance heating.Atmosphere furnace is first evacuated to 10
-4pa, then be filled with N
2: the nitrogen of Ar=5:95 is argon-mixed (volume ratio, purity is 99.99%, and purity refers to that gas mixture accounts for the percentage ratio of gas gross in atmosphere here), until pressure is a normal atmosphere (about 0.11Mpa), and after this constant pressure.Then be heated to 1550 DEG C with 30 DEG C/min from room temperature, cool to room temperature with the furnace afterwards.Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of the SiC nanostructure of growth on carbon cloth substrate of preparation, shows that the phase composition of the material prepared is 3C-SiC, and has higher crystallinity.Fig. 2 ~ 3 are high and low times of SEM figure of the SiC nanostructure at carbon cloth Grown, show that the SiC one dimension Nano structure prepared is evenly distributed in substrate surface, end is with granules of catalyst and head, its size (maximum diameter) be 0.5 micron (can also be other arbitrary value in 0.6,0.7,0.8,0.9,1.0 micron and 0.5-1 micrometer range), overall in cylinder shape, smooth surface.Fig. 4 is the SAED figure of SiC one dimension Nano structure, shows that the SiC prepared is single crystal structure.
Embodiment two
Initial feed chooses polysilazane, at N
2heat cross-linking solidification is carried out in 260 DEG C of insulation 30min under atmosphere protection.Load solidifying the SiCN solid obtained in nylon resin ball grinder, ball mill pulverizing powdered, powder diameter 1 micron, takes 300mg and is placed in bottom plumbago crucible.Cut carbon cloth 5 × 5cm (long × wide), at 0.05mol/LCo (NO
3)
3dipping in ethanolic soln supersound process 10 second, take out to be placed in air ambient and naturally dries.The carbon cloth of dip treating is placed in plumbago crucible top, and is placed in the atmosphere sintering furnace of graphite resistance heating.Atmosphere furnace is first evacuated to 10
-4pa, then be filled with N
2: the nitrogen of Ar=5:95 is argon-mixed (volume ratio, purity is 99.99%, and purity refers to that gas mixture accounts for the percentage ratio of gas gross in atmosphere here), until pressure is a normal atmosphere (about 0.11Mpa), and after this constant pressure.Then be heated to 1600 DEG C with 30 DEG C/min from room temperature, cool to room temperature with the furnace afterwards.Fig. 5 ~ 6 are scheme at the SEM of the SiC one dimension Nano structure of carbon cloth Grown, the SiC one dimension Nano structure entirety of display preparation is in triangular prism structure, surface has "the" shape to rise and fall, very coarse, end with granules of catalyst and head, its size (maximum diameter) be 0.5 micron (can also be other arbitrary value in 0.6,0.7,0.8,0.9,1.0 micron and 0.5-1 micrometer range).Show, by regulation and control pyrolysis temperature, the accurate control to SiC one dimension Nano structure pattern can be realized.
Embodiment three
Initial feed chooses polysilazane, at N
2heat cross-linking solidification is carried out in 260 DEG C of insulation 30min under atmosphere protection.Load solidifying the SiCN solid obtained in nylon resin ball grinder, ball mill pulverizing powdered, powder diameter 1 micron, takes 300mg and is placed in bottom plumbago crucible.Cut carbon cloth 5 × 5cm (long × wide), at 0.05mol/LCo (NO
3)
3dipping in ethanolic soln supersound process 10 second, take out to be placed in air ambient and naturally dries.The carbon cloth of dip treating is placed in plumbago crucible top, and is placed in the atmosphere sintering furnace of graphite resistance heating.Atmosphere furnace is first evacuated to 10
-4pa, then be filled with N
2: the nitrogen of Ar=5:95 is argon-mixed (volume ratio, purity is 99.99%, and purity refers to that gas mixture accounts for the percentage ratio of gas gross in atmosphere here), until pressure is a normal atmosphere (about 0.11Mpa), and after this constant pressure.Then be heated to 1650 DEG C with 30 DEG C/min from room temperature, cool to room temperature with the furnace afterwards.Fig. 7 ~ 8 are scheme at the SEM of the SiC one dimension Nano structure of carbon cloth Grown, the SiC one dimension Nano structure entirety of display preparation is in triangular prism structure, surface is more smooth, end with granules of catalyst and head, its size (maximum diameter) be 0.5 micron (can also be other arbitrary value in 0.6,0.7,0.8,0.9,1.0 micron and 0.5-1 micrometer range).Show, by regulation and control pyrolysis temperature, the accurate control to SiC one dimension Nano structure pattern can be realized.
Embodiment four
Initial feed chooses polysilazane, at N
2heat cross-linking solidification is carried out in 260 DEG C of insulation 30min under atmosphere protection.Load solidifying the SiCN solid obtained in nylon resin ball grinder, ball mill pulverizing powdered, powder diameter 1 micron, takes 300mg and is placed in bottom plumbago crucible.Cut carbon cloth 5 × 5cm (long × wide), at 0.05mol/LCo (NO
3)
3dipping in ethanolic soln supersound process 10 second, take out to be placed in air ambient and naturally dries.The carbon cloth of dip treating is placed in plumbago crucible top, and is placed in the atmosphere sintering furnace of graphite resistance heating.Atmosphere furnace is first evacuated to 10
-4pa, then be filled with N
2, purity is 99.99%, until pressure is a normal atmosphere (about 0.11Mpa), and after this constant pressure.Then be heated to 1550 DEG C with 30 DEG C/min from room temperature, cool to room temperature with the furnace afterwards.The phase composition detecting testimonial material is 3C-SiC, and has higher crystallinity, has single crystal structure.SiC one dimension Nano structure is evenly distributed in substrate surface, end is with granules of catalyst, overall in cylinder shape, smooth surface, end with granules of catalyst and head, its size (maximum diameter) be 0.5 micron (can also be other arbitrary value in 0.6,0.7,0.8,0.9,1.0 micron and 0.5-1 micrometer range).
Embodiment five
Initial feed chooses polysilazane, at N
2heat cross-linking solidification is carried out in 260 DEG C of insulation 30min under atmosphere protection.Load solidifying the SiCN solid obtained in nylon resin ball grinder, ball mill pulverizing powdered, powder diameter 1 micron, takes 300mg and is placed in bottom plumbago crucible.Cut carbon cloth 5 × 5cm (long × wide), at 0.05mol/LCo (NO
3)
3dipping in ethanolic soln supersound process 10 second, take out to be placed in air ambient and naturally dries.The carbon cloth of dip treating is placed in plumbago crucible top, and is placed in the atmosphere sintering furnace of graphite resistance heating.Atmosphere furnace is first evacuated to 10
-4pa, then be filled with N
2, purity is 99.99%, until pressure is 1.5 normal atmosphere (about 0.17Mpa), and after this constant pressure.Then be heated to 1600 DEG C with 30 DEG C/min from room temperature, cool to room temperature with the furnace afterwards.The phase composition detecting testimonial material is 3C-SiC, and has higher crystallinity, has single crystal structure.SiC one dimension Nano structure is evenly distributed in substrate surface, end is with granules of catalyst, structure entirety is in triangular prism structure, surface has "the" shape to rise and fall, very coarse, end with granules of catalyst and head, its size (maximum diameter) be 0.5 micron (can also be other arbitrary value in 0.6,0.7,0.8,0.9,1.0 micron and 0.5-1 micrometer range).
Embodiment six
Initial feed chooses polysilazane, at N
2heat cross-linking solidification is carried out in 260 DEG C of insulation 30min under atmosphere protection.Load solidifying the SiCN solid obtained in nylon resin ball grinder, ball mill pulverizing powdered, powder diameter 1 micron, takes 300mg and is placed in bottom plumbago crucible.Cut carbon cloth 5 × 5cm (long × wide), at 0.05mol/LCo (NO
3)
3dipping in ethanolic soln supersound process 10 second, take out to be placed in air ambient and naturally dries.The carbon cloth of dip treating is placed in plumbago crucible top, and is placed in the atmosphere sintering furnace of graphite resistance heating.Atmosphere furnace is first evacuated to 10
-4pa, then be filled with Ar, purity is 99.99%, until pressure is 1.5 normal atmosphere (about 0.17Mpa), and after this constant pressure.Then be heated to 1650 DEG C with 30 DEG C/min from room temperature, cool to room temperature with the furnace afterwards.The phase composition detecting testimonial material is 3C-SiC, and has higher crystallinity, has single crystal structure.SiC one dimension Nano structure is evenly distributed in substrate surface, end is with granules of catalyst, SiC one dimension Nano structure entirety is in triangular prism structure, surface is more smooth, end with granules of catalyst and head, its size (maximum diameter) be 0.5 micron (can also be other arbitrary value in 0.6,0.7,0.8,0.9,1.0 micron and 0.5-1 micrometer range).
Embodiment seven
Initial feed chooses polysilazane, at N
2heat cross-linking solidification is carried out in 260 DEG C of insulation 30min under atmosphere protection.Load solidifying the SiCN solid obtained in nylon resin ball grinder, ball mill pulverizing powdered, powder diameter 1 micron, takes 300mg and is placed in bottom plumbago crucible.Cut carbon cloth 5 × 5cm (long × wide), at 0.05mol/LCo (NO
3)
3dipping in ethanolic soln supersound process 10 second, take out to be placed in air ambient and naturally dries.The carbon cloth of dip treating is placed in plumbago crucible top, and is placed in the atmosphere sintering furnace of graphite resistance heating.Atmosphere furnace is first evacuated to 10
-4pa, then be filled with Ar, purity is 99.99%, until pressure is a normal atmosphere (about 0.11Mpa), and after this constant pressure.Then be heated to 1550 DEG C with 30 DEG C/min from room temperature, cool to room temperature with the furnace afterwards.The phase composition detecting testimonial material is 3C-SiC, and has higher crystallinity, has single crystal structure.SiC one dimension Nano structure is evenly distributed in substrate surface, end is with granules of catalyst, overall in cylinder shape, smooth surface, end with granules of catalyst and head, its size (maximum diameter) be 0.5 micron (can also be other arbitrary value in 0.6,0.7,0.8,0.9,1.0 micron and 0.5-1 micrometer range).
Embodiment eight
Initial feed chooses polysilazane, at N
2heat cross-linking solidification is carried out in 260 DEG C of insulation 30min under atmosphere protection.Load solidifying the SiCN solid obtained in nylon resin ball grinder, ball mill pulverizing powdered, powder diameter 1 micron, takes 300mg and is placed in bottom plumbago crucible.Cut carbon cloth 5 × 5cm (long × wide), at 0.05mol/LCo (NO
3)
3dipping in ethanolic soln supersound process 10 second, take out to be placed in air ambient and naturally dries.The carbon cloth of dip treating is placed in plumbago crucible top, and is placed in the atmosphere sintering furnace of graphite resistance heating.Atmosphere furnace is first evacuated to 10
-4pa, then be filled with N
2: the nitrogen of Ar=3:97 is argon-mixed (volume ratio, purity is 99.99%), until pressure is a normal atmosphere (about 0.11Mpa), and after this constant pressure.Then be heated to 1600 DEG C with 30 DEG C/min from room temperature, cool to room temperature with the furnace afterwards.The phase composition detecting testimonial material is 3C-SiC, and has higher crystallinity, has single crystal structure.SiC one dimension Nano structure is evenly distributed in substrate surface, end is with granules of catalyst, structure entirety is in triangular prism structure, surface has "the" shape to rise and fall, very coarse, end with granules of catalyst and head, its size (maximum diameter) be 0.5 micron (can also be other arbitrary value in 0.6,0.7,0.8,0.9,1.0 micron and 0.5-1 micrometer range).
Embodiment nine
Initial feed chooses polysilazane, at N
2heat cross-linking solidification is carried out in 260 DEG C of insulation 30min under atmosphere protection.Load solidifying the SiCN solid obtained in nylon resin ball grinder, ball mill pulverizing powdered, powder diameter 1 micron, takes 300mg and is placed in bottom plumbago crucible.Cut carbon cloth 5 × 5cm (long × wide), at 0.05mol/LCo (NO
3)
3dipping in ethanolic soln supersound process 10 second, take out to be placed in air ambient and naturally dries.The carbon cloth of dip treating is placed in plumbago crucible top, and is placed in the atmosphere sintering furnace of graphite resistance heating.Atmosphere furnace is first evacuated to 10
-4pa, then be filled with N
2: the nitrogen of Ar=8:92 is argon-mixed (volume ratio, purity is 99.99%), until pressure is a normal atmosphere (about 0.11Mpa), and after this constant pressure.Then be heated to 1650 DEG C with 30 DEG C/min from room temperature, cool to room temperature with the furnace afterwards.The phase composition detecting testimonial material is 3C-SiC, and has higher crystallinity, has single crystal structure.SiC one dimension Nano structure is evenly distributed in substrate surface, end is with granules of catalyst, SiC one dimension Nano structure entirety is in triangular prism structure, surface is more smooth, end with granules of catalyst and head, its size (maximum diameter) be 0.5 micron (can also be other arbitrary value in 0.6,0.7,0.8,0.9,1.0 micron and 0.5-1 micrometer range).
Distinctively, in above embodiment, sintering atmosphere adopt nitrogen argon gas gas mixture time, nitrogen volume fraction in gas mixture can also be 3.3%, 3.5%, 3.7%, 3.8%, 3.9%, 4%, 4.3%, 4.5%, 4.7%, 4.8%, 4.9%, 5.3%, 5.5%, 5.7%, 5.8%, 5.9%, 6%, 6.3%, 6.5%, 6.7%, 6.8%, 6.9%, 7%, 7.3%, 7.5%, 7.7%, 7.8%, 7.9% and 3-8 (v/v) % within the scope of other arbitrary value, the heat-up rate being warming up to pyrolysis temperature can also be other arbitrary value within the scope of 20 DEG C/min, 22 DEG C/min, 23 DEG C/min, 24 DEG C/min, 25 DEG C/min, 26 DEG C/min, 27 DEG C/min, 28 DEG C/min, 29 DEG C/min, 21 DEG C/min, 32 DEG C/min, 33 DEG C/min, 34 DEG C/min, 35 DEG C/min, 36 DEG C/min, 37 DEG C/min, 38 DEG C/min, 39 DEG C/min, 31 DEG C/min, 40 DEG C/min and 20-40 DEG C/min, the concentration of cobalt ion in alcoholic solution can also be 0.02moL/L, 0.025moL/L, 0.03moL/L, 0.034moL/L, 0.04moL/L, 0.042moL/L, 0.055moL/L, 0.051moL/L, 0.06moL/L, 0.064moL/L, 0.07moL/L, 0.075moL/L, 0.08moL/L, 0.087moL/L, 0.09moL/L, 0.098moL/L, 0.100moL/L, 0.105moL/L, 0.110moL/L, 0.112moL/L, 0.120moL/L, 0.124moL/L, 0.130moL/L, 0.136moL/L, 0.140moL/L, 0.147moL/L, other arbitrary value within the scope of 0.15moL/L and 0.02-0.15moL/L, when catalyzer is introduced, the verse of ultrasonication can also be other arbitrary value within the scope of 5S, 6S, 7S, 8S, 9S, 10.5S, 11S, 12S, 13S, 14S, 15S, 16S, 17S, 18S, 19S, 20S, 21S, 22S, 23S, 24S, 25S, 26S, 27S, 28S, 29S, 30S and 5-30S, the grain size of raw material powder is after crushed 0.3 μm, 0.4 μm, 0.7 μm, 0.9 μm, 1.3 μm, 1.4 μm, 1.7 μm, 1.9 μm, 2 μm, 2.3 μm, 2.4 μm, 2.7 μm, 2.9 μm, 3 μm, 3.3 μm, 3.4 μm, 3.7 μm, 3.9 μm, 4 μm, 4.3 μm, 4.4 μm, 4.7 μm, 4.9 μm, (particle diameter exists other arbitrary value within the scope of 5 μm and 0.3-5 μm here, when being greater than 4 microns, in nano material, in the accumulation cycle, the solid matter number of plies of silicon carbide atom is less than or equal to 6, namely 3C can be realized in technical solution of the present invention, 2H, 4H, the nano material of 6H crystal habit, particle diameter is when 2-4 micron (comprising end points), and in the accumulation cycle, the solid matter number of plies of silicon carbide atom needs to be realized by the regulation and control of sintering temperature, and temperature is many compared with the high then solid matter number of plies, and be more than or equal to 6, the temperature lower then solid matter number of plies is lower, when particle diameter is less than 2 microns, in the accumulation cycle, the solid matter number of plies of silicon carbide atom is higher, can realize the nano material of 15R crystal habit).
The technical scope mid point value non-limit part that this place embodiment is protected application claims and in embodiment technical scheme to the new technical scheme that the equal replacement of single or multiple technical characteristic is formed, equally all in the scope of protection of present invention; Simultaneously in all embodiments enumerated or do not enumerate of the present invention program, parameters in the same embodiment only represents an example (i.e. a kind of feasible scheme) of its technical scheme, and between parameters, there is not strict cooperation and qualified relation, wherein each parameter can be replaced, except special declaration mutually when stating ask without prejudice to axiom and the present invention.
Technique means disclosed in the present invention program is not limited only to the technique means disclosed in above-mentioned technique means, also comprises the technical scheme be made up of above technical characteristic arbitrary combination.The above is the specific embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. a method for accurate control SiC monodimension nanometer material, is characterized in that: comprise the steps,
Precursor prepares;
Substrate pretreated, comprises and catalyzer is introduced matrix;
Nanowire growth, for matrix and precursor being sintered protecting under atmosphere, is warming up to pyrolysis temperature, pyrolysis precursor thus form SiC monodimension nanometer material at matrix surface, and wherein SiC monodimension nanometer material comprises body and is formed at the head of body end;
Cooling.
2. the method for accurate control SiC monodimension nanometer material according to claim 1, is characterized in that: when sintering in described nanowire growth, and the pyrolysis temperature of precursor is 1550 ~ 1650 DEG C, and pyrolysis time is 5-30min.
3. the method for accurate control SiC monodimension nanometer material according to claim 1 and 2, is characterized in that: when sintering in described nanowire growth, and the heat-up rate being warming up to pyrolysis temperature is 20-40 DEG C/min.
4. the method for accurate control SiC monodimension nanometer material according to claim 1 and 2, is characterized in that: protection atmosphere during described precursor pyrolysis is nitrogen atmosphere or argon atmosphere or nitrogen argon gas gas mixture atmosphere.
5. the method for accurate control SiC monodimension nanometer material according to claim 1, is characterized in that: dry after the ethanolic soln impregnation matrix that during described substrate pretreated, catalyzer is introduced as with catalyzer.
6. the method for accurate control SiC monodimension nanometer material according to claim 5, it is characterized in that: described catalyzer is cobalt salt, the concentration of cobalt ion in ethanolic soln is 0.02-0.15moL/L.
7. the method for accurate control SiC monodimension nanometer material according to claim 5, is characterized in that: also carry out ultrasonication 5-30S in the process that when catalyzer is introduced in described substrate pretreated, matrix floods with the ethanolic soln of catalyzer.
8. the method for accurate control SiC monodimension nanometer material according to claim 1, is characterized in that: when described precursor prepares, and the raw material of precursor is the organism at least containing Si and C element.
9. the method for the accurate control SiC monodimension nanometer material according to claim 1 or 8, is characterized in that: described precursor is prepared as to be pulverized by raw material and obtain after heat cross-linking solidification.
10. the method for accurate control SiC monodimension nanometer material according to claim 9, is characterized in that: when described precursor prepares, the grain size of the powder after crushed of the raw material after solidification is 0.3-5 μm.
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| CN101649491A (en) * | 2009-07-17 | 2010-02-17 | 宁波工程学院 | Method for directionally growing SiC monocrystal nanowire array |
| CN103311068A (en) * | 2013-06-08 | 2013-09-18 | 宁波工程学院 | Sic flexible field emission cathode material |
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| CN101649491A (en) * | 2009-07-17 | 2010-02-17 | 宁波工程学院 | Method for directionally growing SiC monocrystal nanowire array |
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