CN110228811A - A kind of low-dimensional rare-earth boride nano material and its method for preparing solid phase - Google Patents
A kind of low-dimensional rare-earth boride nano material and its method for preparing solid phase Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- C01B35/00—Boron; Compounds thereof
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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Abstract
The invention discloses a kind of low-dimensional rare-earth boride nano material and its method for preparing solid phase, and the preparation method comprises the following steps: S1 catalyst film synthesis: will be on catalyst deposit to substrate；S2 solid phase source thermal evaporation deposition: under the protection of carrier gas; it is 700~1200 DEG C that boron source, anhydrous rare earth halide and substrate, which are placed in growth temperature; growing air pressure is under 0.1~100kPa, and evaporation, 0.5~4h of growth obtain low-dimensional rare-earth boride nano material on substrate.The controllable preparation that different catalysts realize large area, high density, single crystal rare earth boride nanostructure on various substrates can be used.
Description
Technical field
The present invention relates to preparation method of nano material, more particularly, to a kind of low-dimensional rare-earth boride nano material and
Its method for preparing solid phase.
Background technique
In the prior art, there are three types of methods to prepare low-dimensional rare-earth boride nano material.
Using chemical vapour deposition technique, BCl is used3Gas has synthesized PrB as boron source6Nano wire and PrB6Nanotube
(The synthesis of PrB6Nanowires and nanotubes by the self~catalyzed method,
Ceram.Int.).Required BCl3Gas is hazardous chemical, and sucking takes orally or absorbs through skin to body nocuousness, can be drawn
Play chemical burn.Inevitably there are hidden danger in terms of the pollution of the safety of people and environment for this, and will increase original
The cost of material.
Using the method for hydrothermal synthesis, respectively with Sm, H3BO3, Mg and I2Solid mixture, by multistep reaction and processing
Step obtains SmB6Nano wire (Low temperature synthesis and electronic transport of
topological insulator SmB6nanowires.).But the density of the product of this method is not high, process flow compared with
More, this not only adds manufacturing cycles, and to regulate and control the pattern of product and crystallinity more difficult.And used Sm
Cost it is excessively high, while Mg mealiness matter is very active, and there are some potential safety problemss.
Utilize ultraviolet photolithographic, electron beam deposition combination electrochemical etching or plasma etching LaB6The method of single crystalline substrate
To obtain LaB6Nanometer monocrystalline bores array (Field emission characteristics of single crystal
LaB6field emitters fabricated by electrochemical etching method.).This method one
Aspect has used LaB6For monocrystalline as substrate, the cost of raw material is higher；And on the other hand, there is substrate special in electrochemical corrosion
Fixed requirement and selectivity, and plasma etch rate is slower, and ultraviolet lithographic system, electron beam evaporation system and wait from
The production equipment of daughter etching system is expensive, is not suitable for promoting the use of on a large scale, therefore during use all
There are no small limitations.
So the preparation process of low-dimensional rare-earth boride nano material has largely fettered it in micro-nano electricity at present
The further development of sub- devices field.
Summary of the invention
The present invention is to overcome defect described in the above-mentioned prior art, provides a kind of low-dimensional rare-earth boride nano material and its solid
Phase preparation method, raw material required for this method are solid phase, and chemical activity is weak, at low cost and non-toxic, environmentally friendly,
Process flow is few, and the low-dimensional rare-earth boride nano material speed of growth is fast.Large area, high density, list can be prepared in this method
Brilliant nano material, and Effective Regulation its growth morphology.
Another object of the present invention is to provide a kind of low-dimensional rare-earth boride nano materials.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A kind of low-dimensional rare-earth boride nano material and its method for preparing solid phase, comprising the following steps:
S1 catalyst film synthesis: will be on catalyst deposit to substrate；
S2 solid phase source thermal evaporation deposition: under the protection of carrier gas, boron source, anhydrous rare earth halide and substrate are placed in growth
Temperature is 700~1200 DEG C, growth air pressure is under 0.1~100kPa, and it is dilute to obtain low-dimensional on substrate for evaporation, 0.5~4h of growth
Native boride nano material.
Reaction principle: at high temperature, boron source evaporates the steam to form boracic；Or redox occurs and generates B2O2Gas,
The steam or B of subsequent boracic2O2Gas is transported to above substrate by carrier gas；With the anhydrous rare earth halide being evaporated under high temperature
Gas molecule mixing, reaction generate rare-earth boride molecule.In step S2 temperature-rise period, the catalyst on substrate can melt
For catalyst droplets, rare-earth boride molecule generated, which constantly dissolves, to be entered among catalyst droplets, when in catalyst droplets
The solubility of rare-earth boride reaches hypersaturated state, will be precipitated to form low-dimensional rare-earth boride nano junction along energetic optimum direction
Structure.Obtained low-dimensional rare-earth boride nano material be large area, high density, single crystal rare earth boride nanostructure it is pure
Object.
With boron powder, boron oxide powder and SmCl3Synthesize SmB6For nano wire, in initial reaction stage, gaseous B, B2O3、
SmCl3The SmB that can be generated by catalysis reaction6It is added in catalyst droplets, B and Sm atom is analysed after supersaturation along low energy face
SmB is formed out6Particle.Since the active force of catalyst droplets and substrate is lower, thus can be by the following SmB that growth is precipitated6Particle
It jacks up.And with the continuous progress of reaction, SmB6Molecule, which will persistently dissolve in, not to be stopped to be precipitated in catalyst, is ultimately formed one-dimensional
Nanowire structure.With the raising of growth temperature and growth air pressure, more catalyst granules will be activated, and lead to nano wire
Density can be with increase.Also, the growth rate of nano wire can also be accelerated by improving growth temperature and growing air pressure, so as to cause phase
With longer nano wire under relatively low temperature available in growth time or air pressure.
Further, substrate is that silicon wafer, FTO glass, carbon fiber substrate, graphite paper substrates, metal substrate or high-melting-point have
Machine object substrate.
Wherein, silicon wafer and FTO glass are the common substrate material of microelectronic industry, carbon fiber, graphite paper, metal and Gao Rong
Point organic substrate is the flexible or rigid substrate material of function admirable.
The low-dimensional rare-earth boride nano material is LaB6、SmB6、CeB6、YbB6、GdB6Or EuB6One of or it is several
Kind.
The catalyst is magnetic Nano material or noble metal nanometer material.
Further, the catalyst is graininess or film-form.
Further, the catalyst is graininess.
It further, in step sl, is 500~700 DEG C in holding temperature by the above-mentioned substrate for being deposited with catalyst
Under, 0.5~1h of isothermal holding.
The present invention provides a kind of preparation method of pellet type catalyst herein: utilizing magnetron sputtering, ion beam sputtering or heat
The modes such as evaporation, will be on catalyst deposit to substrate.In the case where holding temperature is 500~700 DEG C, by the above-mentioned catalyst that is deposited with
0.5~1h of substrate isothermal holding.At being 500~700 DEG C in holding temperature or in the process for being warming up to required growth temperature
In, catalyst is dissolved into catalyst droplets, with a thickness of 0.1~1 μm.
Keeping the temperature to substrate can make catalyst sufficiently be melted into molten drop, and continuous film is cracked into nano particle
Film.
Further, the magnetic Nano is one or more of Fe, Co or Ni, noble metal nano Au, Ag, Pd or
One or more of Pt.
Under normal circumstances, when growing air pressure is 0.1kPa~2kPa, nanobelt is prepared, when growth air pressure is then
When 10kPa~100kPa, nano wire or nanocone is prepared, when air pressure is in 2k~10kPa, nanobelt is prepared and receives
Rice noodles or the simultaneous mixing pattern of nanocone.
Further, anhydrous rare earth halide are as follows: LaF3、LaCl3、LaBr3、LaI3、SmF3、SmCl3、SmBr3、SmI3、
CeF3、CeCl3、CeBr3、CeI3、YbF3、YbCl3、YbBr3、YbI3、GdF3、GdCl3、GdBr3、GdI3、EuF3、EuCl3、EuBr3
Or EuI3One or more of.
Further, the growth time is 1~1.5h.
By controlling growth time, the draw ratio and stand density for low-dimensional rare-earth boride nano material may be implemented
Effective Regulation.
Further, the boron source and the distance between anhydrous rare earth halide and substrate are respectively 1~6cm.
Under regular situation, boron source or the distance between anhydrous rare earth halide and substrate refer to the center of steam after evaporation
Distance arrives the centre distance of substrate.
Under normal circumstances, it when boron source or the distance between anhydrous rare earth halide and substrate are 4~6cm, is prepared
Nanobelt or nanocone；When the distance between mixture and substrate are 1~3cm, nano wire is prepared；When last mixture with
The distance between substrate is 3~4cm, and nanobelt and nano wire or the simultaneous mixing pattern of nanocone is prepared.
Further, the carrier gas is inert gas or H2One or more of.
Further, the carrier gas is inert gas and H2Gaseous mixture, H in the gaseous mixture2Volume fraction be 1
~10%.H under high temperature2Processing effect for catalyst film, is exactly cracked into nanometer particle film, energy for continuous film
Catalyst film is preferably handled, uniform catalyst granules is made.Meanwhile hydrogen facilitates the reduction of boron oxide.
Further, the growth temperature is 1100 DEG C.
Large area, high density and equally distributed nanobelt film, and the table of nano material can be obtained at this temperature
Face is very smooth.
Further, the mass ratio of boron source and anhydrous rare earth halide powder is 2~4:1~4.
Further, the boron source is boron and boron oxide.
Further, the mass ratio of boron, boron oxide and anhydrous rare earth halide is 2:2:3.It is low over the entire substrate
The density for tieing up rare-earth boride nano material is very high, and its surface is very smooth.
The present invention also provides one kind to be prepared low-dimensional rare-earth boride nano material by the preparation method.
The pattern of the low-dimensional rare-earth boride nano material is one or more of nanobelt, nano wire or nanocone.
Compared with prior art, the beneficial effects of the present invention are:
The solid phase source thermal evaporation deposition technology of low-dimensional rare-earth boride nanostructure of the invention is able to achieve large area, highly dense
The controllable preparation of degree, single crystal rare earth boride nanostructure；
It, can by adjusting the distance between boron source, anhydrous rare earth halide powder and substrate, growth air pressure, growth temperature
To use different catalysts in various flexible and rigid substrates, regulate and control the pattern of product, it is easy to operate；
The chemical vapor depsotition equipment of used nano material grown and sputtering or the thermal evaporation apparatus for preparing catalyst
Cost it is low, and the preparation of nano material can be fast implemented using step chemical reaction, being suitable for promoting on a large scale makes
With；
The raw material of the use of this programme is boron source, anhydrous rare earth halide, is not inflammable and explosive compound, and raw material are equal
For solid phase, while rare earth halide chemical activity is not strong, safer, to more environment-friendly, simultaneously because chemical activity is weak, no
Need to be excessively added reactant, it also can save the cost.
This programme only needs two steps, is synthesis catalytic agent film first, secondly by the thermal evaporation of solid phase source, is deposited on catalysis
On agent film, process flow is few, it is very high that stand density is made, and pattern is single.
This programme can grow low-dimensional rare-earth boride nano material in 0.5~4h, and growth rate is fast.
Detailed description of the invention
Fig. 1 is LaB prepared on carbon cloth6The scanning electron microscope diagram of nano wire film low power and high power；
Fig. 2 is typical case LaB6The low resolution and high-resolution transmission electron microscope figure of nano wire；
Fig. 3 is SmB prepared in graphite paper substrates6The scanning electron microscope diagram of nanobelt low power and high power；
Fig. 4 is typical case SmB6The low resolution and high-resolution transmission electron microscope figure of nanobelt；
Fig. 5 is CeB prepared on silicon substrate6The scanning electron microscope diagram of nano wire film low power and high power；
Fig. 6 is typical case CeB6The low resolution and high-resolution transmission electron microscope figure of nano wire；
Fig. 7 is YbB prepared on silicon substrate6Nanobelt low power and high power scanning electron microscope diagram；
Fig. 8 is typical case YbB6The low resolution and high-resolution transmission electron microscope figure of nanobelt；
Fig. 9 is the LaB in the present invention under different growth times6The scanning electron microscope diagram of nano wire；
Figure 10 is SmB prepared under different growth air pressures in the present invention6The typical pattern and corresponding X of nano material are penetrated
Line diffraction spectra and Raman spectrum；
Figure 11 is LaB under evaporation sources different in the present invention and substrate distance6The scanning electron microscope diagram of nano material and
X-ray diffraction spectrum and Raman spectrum corresponding to it；
Figure 12 is LaB prepared by the raw material under different quality ratio in the present invention6The typical pattern of nano material；
Figure 13 is SmB prepared under different growth temperatures in the present invention6The scanning electron microscope diagram of nanobelt.
Figure 14 is that comparative example 1 of the present invention synthesizes PrB by chemical deposition6The low power of nano wire and the scanning electron of high power
Microscope figure；
Specific embodiment
The present invention is further illustrated With reference to embodiment.
In following embodiment, holding temperature is 700 DEG C, and soaking time is 1h.
Embodiment 1
The present embodiment synthesizes LaB on carbon cloth substrate using solid phase technology of preparing6Nano wire film.Its preparation process
It is as follows.
Using magnetron sputtering technique, first in the environment of Ar gas, it is 10nm that a layer thickness is grown on fiber C cloth substrate
The Ni film of left and right is as catalyst.It will be loaded with the fiber C cloth substrate of Ni film, in Ar gas and H2(H2: Ar=30sccm:
700 DEG C are warming up under protection 300sccm, similarly hereinafter), isothermal holding 1h.Then, by B powder (99.99%), B2O3Powder
(99.99%) and anhydrous LaCl3Powder (99%) 2:2:3 in mass ratio mixing, is loaded in Al2O3It reacts in boat, by B powder, B2O3
Powder and anhydrous LaCl3The mixture of powder is placed on the place apart from substrate 1cm.Finally, by above-mentioned powder and substrate in Ar
Gas and H2It is brought rapidly up in the atmosphere of carrier gas to 700 DEG C, growth air pressure is 10kPa, after keeping the temperature 0.5h, then in fiber C cloth substrate
On grow the LaB of single shape6Nano wire film.
Fig. 1 a is LaB prepared on carbon cloth6Nano wire film low power scanning electron microscope diagram, Fig. 1 b are carbon fiber
The upper prepared LaB of Wei Bu6Nano wire film high power scanning electron microscope diagram.Such as Fig. 1 a, shown in Fig. 1 b, given birth at 1000 DEG C
The LaB grown6For the distribution of lengths of nano wire at 10~30 μm, average diameter is about 50nm, while Fig. 1 b and Figure 14 a is compared, whole
The stand density of nano wire on piece carbon cloth is very high, and in Figure 14 b material pattern it is not of uniform size, can from Fig. 1 a
Out, LaB6Nano wire film pattern is single.
As shown in Fig. 2, Fig. 2 a is typical case LaB6The low Resolution Transmission Electron microscope figure and SAED of nano wire compose (illustration),
Fig. 2 b is typical case LaB6The high resolution transmission electron microscopy and international standard X-ray powder diffraction data of nano wire
(JCPDS) 73~No. 1669 cards then provable prepared LaB6Nano wire is the cubic structure of monocrystalline, and the direction of growth is
[111]。
Embodiment 2
SmB is synthesized in graphite paper substrates using solid phase technology of preparing6Nanobelt film
Using ion sputtering, first in the environment of Ar gas, it is 15nm that a layer thickness is grown in graphite paper substrates
The Fe film of left and right is as catalyst.It will be loaded with the graphite paper cloth substrate of Fe film, in Ar gas and H2Protection under be warming up to 700
DEG C, isothermal holding 1h.Then, by B powder (99.99%), B2O3Powder (99.99%) and anhydrous SmCl3Powder (99%) presses quality
It is mixed than 1:1:1, is loaded in Al2O3It reacts in boat, by B powder, B2O3Powder and anhydrous SmCl3The mixture of powder is placed on distance
The place of substrate 4cm.Finally in Ar gas and H2It is brought rapidly up in the atmosphere of carrier gas to 700 DEG C, growth air pressure is 0.1kPa, heat preservation
The SmB of single shape is then grown after 4h in graphite paper substrates6Nanobelt film.
The SmB prepared by this solid reaction process6The surface topography of nanometer carry sample is as shown in Figure 3.Fig. 3 a is graphite
Prepared SmB in paper substrates6Nanobelt low power scanning electron microscope diagram, Fig. 3 b are SmB prepared in graphite paper substrates6
Nanobelt high power scanning electron microscope diagram, Cong Tuzhong is we can observe that the SmB grown at 1000 DEG C6Nanobelt
Distribution of lengths is being 50~100 μm, and thickness distribution is then distributed in 5~15 μm in 20~100nm, width.Meanwhile full wafer graphite paper
The smooth nanometer band structure in surface is all uniform-distribution on substrate.
As shown in figure 4, Fig. 4 a is typical case SmB6The low Resolution Transmission Electron microscope figure of nanobelt, Fig. 4 b are typical case SmB6
High resolution transmission electron microscopy and the SAED spectrum (illustration) and international standard X-ray powder diffraction data of nanobelt
(JCPDS) 73~No. 1669 cards then provable prepared SmB6Nanobelt is the cubic structure of monocrystalline, and the direction of growth is
[110]。
Embodiment 3
CeB is synthesized on a si substrate using solid phase technology of preparing6Nano wire film
Using thermal evaporation techniques, first in the environment of Ar gas, growing a layer thickness on a si substrate is 10nm's or so
Au film is as catalyst.It will be loaded with the Si substrate of Au film, in Ar gas and H2Protection under be warming up to 700 DEG C, isothermal holding
1h.Then, by B powder (99.99%), B2O3Powder (99.99%) and anhydrous CeCl3Powder (99%) 1:1:2 in mass ratio is mixed
It closes, is loaded in Al2O3It reacts in boat, by B powder, B2O3Powder and anhydrous CeCl3The mixture of powder is placed on apart from substrate 3cm's
Place.Finally in Ar gas and H2It is brought rapidly up in the atmosphere of carrier gas to 1200 DEG C, growth air pressure is 100kPa, is kept the temperature after 2.5h then
The smooth CeB in single shape, surface is grown on a si substrate6Nano wire film.
The CeB prepared by this solid reaction process6The surface topography of nano wire sample is as shown in Figure 5.Fig. 5 a is Si lining
Prepared CeB on bottom6Nano wire film low power scanning electron microscope diagram, Fig. 5 b are CeB prepared on Si substrate6Nanometer
The scanning electron microscope diagram of line film high power, Cong Tuzhong is we can observe that the CeB grown at 1100 DEG C6Nano wire
For the distribution of lengths of sample at 30~50 μm, average diameter is about 50nm.Meanwhile table is all uniform-distribution in full wafer graphite paper substrates
The smooth nanometer band structure in face.
As shown in fig. 6, Fig. 6 a is typical case CeB6The low Resolution Transmission Electron microscope figure and SAED of nano wire compose (illustration),
Fig. 6 b is high resolution transmission electron microscope figure and international standard X-ray powder diffraction data (JCPDS) 73~1669
Card then provable prepared CeB6Nano wire sample is the cubic structure of monocrystalline, and the direction of growth is [110].
Embodiment 4
YbB is synthesized on a si substrate using solid phase technology of preparing6Nanobelt film
Using magnetron sputtering technique, first in the environment of Ar gas, growing a layer thickness on a si substrate is 10nm or so
Ni film as catalyst.It will be loaded with the Si substrate of Ni film, in Ar gas and H2Protection under be warming up to 700 DEG C, at heat preservation
Manage 1h.Then, by B powder (99.99%), B2O3Powder (99.99%) and anhydrous YbCl3Powder (99%) 1:1:2 in mass ratio is mixed
It closes, is loaded in Al2O3It reacts in boat, by B powder, B2O3Powder and anhydrous YbCl3The mixture of powder is placed on apart from substrate 6cm's
Place.Finally in Ar gas and H2It is brought rapidly up in the atmosphere of carrier gas to 1200 DEG C, growth air pressure is 2kPa, is kept the temperature after 1h then in stone
The YbB of single shape is grown in black paper substrates6Nanobelt film.
The YbB prepared by this solid reaction process6The surface topography of nanometer carry sample is as shown in Figure 7.Fig. 7 a is Si lining
Prepared YbB on bottom6Nanobelt low power scanning electron microscope diagram, Fig. 7 b are YbB prepared on Si substrate6Nanobelt is high
Times scanning electron microscope diagram；We can observe that the YbB grown at 1100 DEG C from figure6The average length of nanobelt
About 80 μm, thickness distribution is in 30~100nm, and width is then distributed in 5~10 μm, and surface is smooth.Meanwhile Fig. 7 a and figure
14a is compared, and is all uniform-distribution with highdensity nanometer band structure on full wafer Si substrate in Fig. 7 a.
As shown in figure 8, Fig. 8 a is typical case YbB6Transmission electron microscope figure and the SAED spectrum of the low resolution of nanobelt (are inserted
Figure), Fig. 8 b is typical case YbB6The high-resolution transmission electron microscope figure and international standard X-ray powder diffraction of nanobelt
73~No. 1669 cards of data (JCPDS) then provable prepared YbB6Nanobelt is the cubic structure of monocrystalline, growth side
To for [110].
Embodiment 5
Using the similar solid phase technology of preparing in embodiment 1, under different growth times, Si substrate prepares LaB6It receives
Rice material.
In growth air pressure be 55kPa and growth temperature is 1100 DEG C, and distance is the constant reality of 2cm between mixture and substrate
Under the conditions of testing, change growth time, prepares LaB6Nano wire.
It is as shown in Figure 9:
(1) when growth time is 0.5h, the LaB of short length can be prepared in Si substrate6Nano wire, and
The pattern of nano wire is almost the same on entire Si substrate, and density is higher, and length is substantially distributed in 7~12 μm, as Fig. 9 a,
Shown in 9b, 9c.
(2) when growth time is 1h, the LaB of greater depth can be prepared in Si substrate6Nano wire, Er Qiena
Rice noodles are uniform in Si substrate surface topography, and density is very high, and length is substantially distributed in 12~18 μm, such as Fig. 9 d, 9e, 9f institute
Show.
(3) when growth time extends to 1.5h, the LaB of very long length can be prepared in Si substrate6Nano wire,
And nano wire is uniform in Si substrate surface topography, and density is very high, and average length reaches 40 μm, such as Fig. 9 g, 9h, 9i institute
Show.
By controlling growth time, may be implemented for LaB6The draw ratio of nano wire and the Effective Regulation of stand density,
Optimal growth time is 1~1.5h.
Embodiment 6
Using the similar solid phase technology of preparing in embodiment 1, under different growth air pressures, Si substrate prepares SmB6It receives
Rice material.
At B powder (99.99%): B2O3Powder (99.99%): anhydrous SmB6Powder (99%)=2:2:3, growth time are
Under 1100 DEG C of constant experiment conditions of 1h and growth temperature, change growth air pressure, to control SmB6The growth morphology of nanostructure.
SmB prepared under different growth air pressures in Figure 10 present invention6The typical pattern of nano material and corresponding X-ray
Diffraction spectra (XRD) and Raman (Raman) spectrum, as shown in Figure 10:
(1) when growing air pressure is 55kPa, distance is 2cm between mixture and substrate, can be prepared into Si substrate
To large area, highdensity SmB6Nano wire.Meanwhile the pattern of nano wire is almost the same on entire Si substrate, surface ten
Light splitting is slided, and the diameter (about 50nm) of nano wire from bottom to top is basically unchanged, as shown in Figure 10 a, 10b.
(2) when growing air pressure is 1kPa, distance is 5cm between mixture and substrate, can be prepared into Si substrate
The SmB single to high density, pattern6Nanobelt, and nanobelt is very smooth in Si substrate surface, and density is very high, Er Qiecong
The width at bottom to top is essentially identical (about 8 μm), as shown in Figure 10 c, 10d.
As shown in Figure 10 e, 10f, X-ray diffraction spectrum and Raman spectrum show to change nanobelt prepared by growth air pressure and receive
Nanowire structure is still SmB6Cubic monocrystalline structure.Air pressure is grown by control, may be implemented for SmB6Nano material growth
The Effective Regulation of pattern.
Embodiment 7
Using the similar solid phase technology of preparing in embodiment 1, LaB is prepared under different evaporation sources and substrate distance6
Nano material.
At B powder (99.99%): B2O3Powder (99.99%): anhydrous LaB6Powder (99%)=2:2:3, growth time are
1h and 1100 DEG C of reaction temperature, growth air pressure are to change distance between mixture and substrate under the constant experiment condition of 60kPa,
To control LaB6The growth morphology of nanostructure.It is as shown in figure 11:
By B powder (99.99%), B2O3Powder (99.99%) and anhydrous LaCl3(99%) mixture is placed on distance
When substrate is 5cm, large area, highdensity LaB can be prepared in Si substrate6Nanocone film.Meanwhile in entire Si
The pattern of nanocone is almost the same on substrate, and the average diameter of bottom end is about 500nm, and the average diameter on top is about 50nm,
Its surface is very smooth, as shown in Figure 11 a, 11b, 11c.
When by B powder (99.99%), B2O3Powder (99.99%) and anhydrous LaCl3(99%) mixture is placed on distance
When substrate is 2cm, the single LaB of high density, pattern can be prepared in Si substrate6Nano wire film.And nano wire
Very smooth in Si substrate surface, density is very high, and diameter from bottom to top is basically unchanged, about 50nm, such as schemes
Shown in 11d, 11e, 11f.
X-ray diffraction spectrum and Raman spectrum show to change substrate and powder apart from prepared nanocone and nanowire structure still
It is so LaB6Cubic monocrystalline structure.By the distance between substrate and powder, may be implemented for LaB6Nano material grows shape
The Effective Regulation of looks, as shown in Figure 11 g, 11h.
Embodiment 8
Using the similar solid phase technology of preparing in embodiment 1, LaB is prepared under different proportion of raw material6Nanometer material
Material.
It is 1h and 1100 DEG C of reaction temperature in growth time, growth air pressure is 60kPa, and distance is between mixture and substrate
Under 4cm constant experiment condition, change raw material quality ratio to grow LaB6Nanocone film.It is as shown in figure 12:
(1) when B powder (99.99%): B2O3Powder (99.99%): anhydrous LaCl3It, can be with when powder (99%)=2:2:3
The LaB that large area is prepared in Si substrate, is evenly distributed6Nano wire film.Meanwhile the nano wire on entire Si substrate
Density is very high, and the average length of nano wire is about 15 μm, and average diameter is about 50nm, and its surface is very smooth, such as schemes
Shown in 12a, 12b, 12c.
(2) when B powder (99.99%): anhydrous LaCl3When powder (99%)=2:1, it can be prepared in Si substrate close
Spend lower LaB6Nano wire film, and nano wire being unevenly distributed in Si on piece.Meanwhile the average length of nano wire is about
It is 15 μm, average diameter is about 50nm, but its surface is very coarse, as shown in Figure 12 d, 12e, 12f.
(3) work as B2O3Powder (99.99%): anhydrous LaCl3When powder (99%)=2:1, it can be prepared into Si substrate
To the lower LaB of density6Nano wire film, and nano wire is very uneven in the distribution of Si on piece.Meanwhile nano wire is flat
Equal length is about 15 μm, and average diameter is about 50nm, but its surface is very coarse and apparent fold-type fluctuating occurs, such as schemes
Shown in 12g, 12h, 12i.
By controlling the ratio of raw material, may be implemented for LaB6Nanowire growth density, growth morphology and crystallinity
Effective Regulation.Optimal raw material quality ratio is B powder: B2O3Powder: anhydrous LaCl3Powder=2:2:3.
Embodiment 9
Using the similar solid phase technology of preparing in embodiment 1, SmB is prepared under different growth temperatures6Nanobelt.
At B powder (99.99%): B2O3Powder (99.99%): anhydrous SmCl3Powder (99%)=2:2:3, growth time are
1h, growth air pressure are 300Pa, and distance is to change growth temperature under the constant experiment condition of 6cm, come between mixture and substrate
Prepare SmB6Nanocone, as shown in figure 13:
(1) when growth temperature is 1000 DEG C, SmB can be prepared in Si substrate6Nanobelt film.But whole
Nano wire on a Si substrate, in nanobelt film or doped with part.The average length of nanobelt is about 20 μm simultaneously, average
Width is about 1 μm, and the edge of nanobelt is serrated pattern, as shown in Figure 13 a, 13b, 13c.
(2) when growth temperature is improved to 1100 DEG C, large area, high density and uniformly can be prepared in Si substrate
The SmB of distribution6Nanobelt film.Meanwhile the average length of nanobelt is about 60 μm, and mean breadth is about 3 μm, and nanometer
The surface of band is very smooth, as shown in Figure 13 d, 13e, 13f.
By controlling growth temperature, may be implemented for SmB6The Effective Regulation on nanowire growth surface.Optimum growh temperature
Degree is 1100 DEG C.
Comparative example 1
Firstly, silicon wafer is cut into 1*1cm2, with a thickness of 1 millimeter of fritter as substrate.Secondly, metal Pr powder (purity
99.99%) covering on a si substrate, is then placed in quartz ampoule and reacts, temperature is risen to 1080 DEG C.In carrier gas (30%H2With
70%Ar) under the protection that flow is 80sccm, stablize BCl3Quartz ampoule is cooled to room temperature by gas flow after five minutes.Then
With dilute hydrochloric acid washed product distilled water for several times to eliminate impurity.Finally, finding one layer of ash after being dried in vacuo 4 hours at 80 DEG C
Color product deposition has obtained PrB on a si substrate6Nano wire.As shown in Figure 14 a and Figure 14 b, PrB6Nanowire diameter be 10~
100nm, length are 2~10 μm.
Comparative example 1 uses BCl3Gas has synthesized PrB as boron source6Nano wire.Required BCl3Gas is hazardous
Product, inevitably there are hidden danger in terms of the pollution of the safety of people and environment for this, and will increase raw material
Cost.
It is solid phase in conclusion raw material used by this programme is boron source, anhydrous rare earth halide, while rare earth oxyhalide
Compound chemical activity is not strong, safer, to more environment-friendly, simultaneously because chemical activity is weak, does not need that reaction is excessively added
Object, also can save the cost.This programme only needs two steps, is synthesis catalytic agent film first, secondly by the thermal evaporation of solid phase source, sinks
For product on catalyst film, process flow is few, it is very high that stand density is made, and pattern is single.This programme is in 0.5~4h
Low-dimensional rare-earth boride nano material is grown, growth rate is fast.To which large area, high density, the low-dimensional of monocrystalline be prepared
Rare-earth boride nano material.
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention.For those of ordinary skill in the art, may be used also on the basis of the above description
To make other variations or changes in different ways.There is no necessity and possibility to exhaust all the enbodiments.It is all this
Made any modifications, equivalent replacements, and improvements etc., should be included in the claims in the present invention within the spirit and principle of invention
Protection scope within.
Claims (10)
1. a kind of method for preparing solid phase of low-dimensional rare-earth boride nano material, which comprises the following steps:
S1 catalyst film synthesis: will be on catalyst deposit to substrate；
S2 solid phase source thermal evaporation deposition: under the protection of carrier gas, boron source, anhydrous rare earth halide and substrate are placed in growth temperature
It is under 0.1~100kPa for 700~1200 DEG C, growth air pressure, evaporation, 0.5~4h of growth obtain low-dimensional rare earth-boron on substrate
Compound nano material.
2. the method for preparing solid phase of low-dimensional rare-earth boride nano material according to claim 1, which is characterized in that described
Anhydrous rare earth halide are as follows: LaF3、LaCl3、LaBr3、LaI3、SmF3、SmCl3、SmBr3、SmI3、CeF3、CeCl3、CeBr3、
CeI3、YbF3、YbCl3、YbBr3、YbI3、GdF3、GdCl3、GdBr3、GdI3、EuF3、EuCl3、EuBr3Or EuI3One of or
It is several.
3. the method for preparing solid phase of low-dimensional rare-earth boride nano material according to claim 1, which is characterized in that in step
In rapid S1, by the above-mentioned substrate for being deposited with catalyst, in the case where holding temperature is 500~700 DEG C, 0.5~1h of isothermal holding.
4. the method for preparing solid phase of low-dimensional rare-earth boride nano material according to claim 1, which is characterized in that described
Growth time is 1~1.5h.
5. the method for preparing solid phase of low-dimensional rare-earth boride nano material according to claim 1, which is characterized in that described
Boron source and the distance between anhydrous rare earth halide and substrate are respectively 1~6cm.
6. the method for preparing solid phase of low-dimensional rare-earth boride nano material according to claim 1, which is characterized in that described
Carrier gas is inert gas, H2One or more of.
7. the method for preparing solid phase of low-dimensional rare-earth boride nano material according to claim 1, which is characterized in that described
Growth temperature is 1100 DEG C.
8. the method for preparing solid phase of low-dimensional rare-earth boride nano material according to claim 1, which is characterized in that boron source
Mass ratio with anhydrous rare earth halide powder is 1~4:2~4；Boron source is boron and boron oxide.
9. the method for preparing solid phase of low-dimensional rare-earth boride nano material according to claim 8, which is characterized in that boron,
The mass ratio of boron oxide and anhydrous rare earth halide is 2:2:3.
10. a kind of low-dimensional rare-earth boride nano material, which is characterized in that prepared by any the method for claim 1~9
It obtains.
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