CN101381887B - Single crystal boron nanotaper, method for preparing same and applications in electricity and field emission device - Google Patents
Single crystal boron nanotaper, method for preparing same and applications in electricity and field emission device Download PDFInfo
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- CN101381887B CN101381887B CN200710121358XA CN200710121358A CN101381887B CN 101381887 B CN101381887 B CN 101381887B CN 200710121358X A CN200710121358X A CN 200710121358XA CN 200710121358 A CN200710121358 A CN 200710121358A CN 101381887 B CN101381887 B CN 101381887B
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Abstract
The invention provides a monocrystalline boron nano-cone, which consists of pure boron, and has a monocrystalline structure. The invention also provides a method for preparing the boron nano-cone, which is to use the mixture of boride and boron powder as raw materials and the mixture of Fe3O4 catalyst nano-particles and trace boron powder as a co-catalyst to synthesize the boron nano-cone by a chemical vapor deposition CVD method. The boron nano-cone prepared by the method has excellent electrical property and field emission performance.
Description
Technical field
The present invention relates to a kind of monodimension nanometer material of boron, in particular to a kind of single crystal boron nanocone, its preparation method and in the application of electricity and feds.
Background technology
(S.Jijima after Iijima in 1992 is found carbon nanotube; Nature; 354 (1991); 56), the preparation and the application of metal, semi-conductor, oxide compound and mixture nanometer one-dimensional material have caused the great interest of people, and especially they are in the potential application in fields such as electronics, information, biomedicine, national defence, the energy.
Boron is unique in an IIIA family semiconductor element.Because boron has the electronic structure and the distinctive icosahedral structure of virus of unique " three centers, two electronics ", can form with the icosahedron is the boron monodimension nanometer material (nanotube, nano wire, nano belt and nanocone etc.) of structural unit.And pure boron is one density is low, fusing point is high, difficult evaporable solid, and its hardness is a few element that can be used for nuclear reaction, airship strongthener and fields such as resist, high temperature semiconductors only time and diamond.Simultaneously, Theoretical Calculation shows that boron can form unusual directrix plane type, cage shape and tubular structure.And the boron nanotube is compared with carbon nanotube; It has shown metallic density of states(DOS); Therefore; The boron monodimension nanometer material is an extraordinary conductor, therefore, and the emission on the scene of boron one-dimensional nano structure material, Chu Qing, storage lithium and have the potential using value at high temperature light material, high temperature memory device.
Yet the research of boron monodimension nanometer material at present also is confined to boron nanowire and nano belt, does not see that with the boron nanocone of an emission characteristic any document and patent report are arranged for having peculiar electricity as yet.
Summary of the invention
The object of the present invention is to provide a kind of single crystal boron nanocone, a kind of preparation method of simple single crystal boron nanocone, and the single crystal boron nanocone is in the application at electricity and feds.
First aspect of the present invention relates to a kind of boron nanocone, and it is made up of pure boron, has single crystal structure.The base diameter of this boron nanocone is the 300-500 nanometer, and top end diameter is the 50-100 nanometer, and length is 3-10 μ m.
Second aspect of the present invention relates to a kind of method for preparing the boron nanocone, its with the mixture of boride and boron powder as source material, Fe
3O
4The mixture of catalyst nanoparticles and trace B powder utilizes chemical vapour deposition CVD method to synthesize the boron nanocone as co-catalyst, and this method may further comprise the steps:
(a) Fe that tensio-active agent is coated
3O
4Catalyst nanoparticles solution mixes the formation co-catalyst with the trace B powder;
(b) co-catalyst that obtains in the step (a) is deposited on the silicon chip substrate;
(c) under the atmosphere of shielding gas, 200-500 ℃ temperature heated substrate to remove solvent and the tensio-active agent in the co-catalyst;
(d) under the atmosphere of shielding gas; To heat together with the substrate that deposits the co-catalyst of having removed solvent as the boride of source material and the mixture of boron powder 1000-1300 ℃ temperature; The source material evaporation is diffused on the co-catalyst molten melt drop on the substrate surface, thereby forms the boron nanocone through gas-liquid-solid growth pattern.
In aforesaid method, surfactant package oil scraper amine and oleic acid in the step (a), the Fe in the co-catalyst
3O
4The particle dia of catalyst nanoparticles is 8-14nm, and the particle dia of boron powder is 500nm-20 μ m, and trace B powder and Fe
3O
4The weight of catalyst nanoparticles solution is 0.0001-0.001.Wherein, at Fe
3O
4The effect of the boron of doping trace is to form ferro-boron in the nano particle, becomes the mix source material evaporation back deposition active site of boride and boron powder, helps the formation of nanocone.
In aforesaid method, shielding gas is the mixed gas of rare gas element and 0-10% hydrogen, and rare gas element comprises nitrogen and argon gas.And chemical vapour deposition CVD can carry out under vacuum or a normal atmosphere.
In aforesaid method, boride comprises B
2O
3, and the part by weight of boride and boron powder is 1: 5～5: 1.
In aforesaid method, the shield gas flow rate in the step (d) is less than 100sccm.
The third aspect of the invention relates to the application of boron nanocone at feds.
Fourth aspect of the present invention relates to the application of boron nanocone at electricity device.
The present invention has obtained high-quality single crystal boron nanocone first, and it has good shapes.And the method for preparing the boron nanocone of the present invention is a kind of simple method, adopts this method can prepare big area, high-quality single crystal boron nanocone, prepared go out the boron nanocone have good electrical properties and field emission performance.
Description of drawings
Fig. 1 is monodispersed Fe
3O
4The TEM figure of nanoparticle.
Fig. 2 is the SEM figure of single crystal boron nanocone; A) being big area figure, b) is partial enlarged drawing.
Fig. 3 is the TEM figure and the SEAD figure (SAED) of single crystal boron nanocone.
Fig. 4 is electron energy loss spectroscopy (EELS) (EELS) figure of single crystal boron nanocone.
Fig. 5 shows the flow of carrier gas and the figure of corresponding B nanocone pattern.
Fig. 6 is the SEM picture of the boron nanocone under the different growth times.
Fig. 7 is the field launching curve of B nanocone.
Fig. 8 is the SEM photo of the B nanocone device electrode of three different sizes.
Fig. 9 is that three B nanocone electrodes are-20 to 20V current curve at input voltage.
Embodiment
Embodiment one, monodisperse magnetic nanoparticle Fe
3O
4Preparation
Adopt grandson to keep the synthetic Fe of identical high-temperature liquid-phase reduction method
3O
4Nanoparticle (Sun, S.H. etc., J.Am.Chem.Soc.2004,126,273), but reaction conditions has been carried out improving to obtain the 8-14 nanometer Fe
3O
4Particle.Concrete preparation method is following:
With 0.5mmol ferric acetyl acetonade, 20ml phenylate, 2.5mmol 1,2-dodecanediol, 0.75mmol oleic acid and 0.75mmol oleyl amine join in the three-necked bottle successively.Rate of heating with 5 ℃/min is heated to 200 ℃ with mixing solutions, reacts half a hour, continues heating then and raises the temperature to 270 ℃, and reaction is one hour under this temperature, removes heating source, makes reaction soln naturally cool to room temperature.Add the 40ml absolute ethyl alcohol then and stirred ten minutes, leave standstill 3-4 hour, centrifugal under 7000rpm, with the gained sample in being distributed to ethanol, little ultrasonic and recentrifuge, the black product that obtains at last is distributed in the heptane to be preserved.If 270 ℃ of reactions 2 hours, can obtain the Fe of 8nm
3O
4Particle; If improve the concentration of ferric acetyl acetonade, can obtain the Fe of 14nm
3O
4Particle.
The Fe of 8 nanometers that prepare in this way
3O
4Particulate TEM (transmission electron microscope) image is as shown in Figure 1.
Embodiment two: the preparation of single crystal boron nanocone:
At first with 2ml Fe
3O
4The nanoparticle n-heptane solution mixes with the boron powder of 0.1-1.0 milligram, then mixed solution is dropped on the silicon substrate, dries naturally.
Secondly with B
2O
3(99.99%) and B (99.9%) mix by 1: 5 mass ratio, grind evenly, put into Al
2O
3In the reaction boat.The substrate silicon chip is placed on Al
2O
3Reaction boat vertical upper, the reaction boat is placed in the silica tube of level, and the reaction boat places outside the cryogenic reaction zone before the heating.
Take two step heating steps to carry out chemical vapour deposition afterwards, specific as follows:
The first step is at H
2/ Ar gas mixture (5%H
2) protect down, reaction zone being heated to 300-400 ℃ with the heat-up rate of 5-50 ℃/min earlier, will react boat to push high temperature reaction zone rapidly, be incubated 30～60 minutes, keep H
2/ Ar gas mixture (5%H
2) airshed is 200～300sccm (standard cubic centimeters per minute), is coated on Fe to remove
3O
4Organic molecule on the nano particle will react boat then and shift out high temperature reaction zone.
The heat-up rate of second step with 20-30 ℃/min is heated to 1000～1300 ℃ with reaction zone fast, will react boat then and push high temperature reaction zone once more rapidly, under this temperature, reacts 1～4 hour, at this moment H
2/ Ar gas mixture (5%H
2) airshed be 20～40sccm (standard cubic centimeters per minute).After reaction finished, product was at H
2/ Ar gas mixture (95%Ar and 5%H
2) the following cool to room temperature of protection.Can observe dim black of one deck or brownish black film at silicon chip surface.Silicon chip is directly carried out scanning electronic microscope observation obtain the SEM image.In addition, it is ultrasonic that silicon chip is put into absolute ethyl alcohol, and the drips of solution that obtains is carried out the TEM test on little grid.
Shown in the electron photomicrograph of boron nanocone such as Fig. 2 (SEM, sem) and Fig. 3 (TEM, transmission electron microscope).The base diameter of nanocone is between the 300-500 nanometer, and top end diameter is between the 50-100 nanometer, and length is about 3-10 μ m.SEAD figure (SAED) shows that the boron nanocone has single crystal structure.The electron energy loss spectroscopy (EELS) of nanocone (Electron Energy Loss Spectrum) test result is as shown in Figure 4; Occurring at 188eV in the EELS spectrum is the K shell peak value of B element; EELS spectrum detected result is not found the characteristic peak of other element yet, shows that the composition for preparing nanocone is pure boron.
Instance three, B
2O
3Influence with the B mass ratio
Work as B
2O
3(99.99%) and B (99.9%) mass ratio at 1: 5,1: 4,1: 3,1: 2,1: 1,2: 1,3: 1,4: 1 and 5: 1 o'clock, temperature of reaction reaction times 1-4 hour, can obtain the boron nanocone at 1000-1300 ℃.Under these ratios, can obtain the boron nanocone of consistent appearance.
The influence of instance four, shield gas flow rate
1200 ℃ of temperature of reaction, reaction times 1-4 hour, Ar and H
2Gas mixture (5%H
2) airshed be respectively 20,30,40,50,60,70, during 80sccm, can obtain highly purified boron nanocone, its pattern and size basically identical surface.The electron photomicrograph of boron nanocone is as shown in Figure 5.When airshed surpasses 100sccm, do not find the formation of B nanocone.
The influence in instance five, reaction times
Work as B
2O
3(99.99%) and B (99.9%) mass ratio at 1: 5, temperature of reaction is at 1000-1300 ℃, the reaction times was respectively 1 hour; 2 hours; 3 hours and 4 hours, can obtain high purity, highdensity boron nanocone, the electron photomicrograph of boron nanocone is as shown in Figure 6.Reaction times is little to its pattern influence, and just when increasing the reaction times, the diameter of nanocone and length increase thereupon gradually.
The influence of instance six, temperature of reaction
At B
2O
3(99.99%) and B (99.9%) mass ratio be 1: 5, the reaction times is 2 hours, temperature of reaction is under 1000,1100,1200 and 1300 ℃ the condition, all can obtain high purity, highdensity boron nanocone, and is as shown in Figure 2.Therefore, temperature of reaction is little to the surface topography influence of boron nanocone.
Instance seven, the test of boron nanocone field emission performance:
As field-transmitting cathode, the Mo needle point is as anode with the boron nanocone that grows in silicon face, two interelectrode distances, 200 μ m.Slowly increase by two interpolar voltages, write down transmitter current simultaneously.Fig. 7 is the field launching curve of boron nanocone, when voltage reaches 10 μ A/cm
2The time, opening field intensity is 3.5V/ μ m.As the minimum emission that reaches the flat-panel monitor requirement, i.e. 1mA/cm
2The time, threshold field strength is 5.3V/ μ m.Field emission performance test shows, single crystal boron nanocone have low unlatching field intensity and threshold field strength, are very ideal field emmision materials.
The electrical properties test of instance eight, boron nanocone device:
3 boron nanocone electrodes have been prepared through EBL (electron beam exposure) technology.Fig. 8 has provided the SEM photo of the boron nanocone electrode of three different sizes respectively.The size of these three electrodes is respectively: (a) electrode 1 (long: 3.1 μ m, diameter: 110nm and 90nm), and (b) electrode 2 (long: 3.8 μ m, diameter: 240nm and 280nm), (c) electrode 3 is (long: 2.5 μ m, diameter: 450nm).
Adopt KEITHLEY 4200-SCS semi-conductor high precision measuring instrument respectively the device that three kinds of boron nanocone are formed to be carried out the test of electrical properties, Fig. 9 is that these three electrodes are-20 to 20V current curve at input voltage.(σ is a specific conductivity, and unit is Ω cm to adopt following formula to calculate its electric conductivity: σ=l/RS
-1L is a length, and unit is cm; R is a resistance, and unit is Ω; S is a sectional area, and unit is cm
2).For device one, positive and negative saturation currnet is respectively 20pA and 40pA, and the specific conductivity of calculating is respectively 3.7 * 10
-5(Ω cm)
-1With 7.3 * 10
-5(Ω cm)
-1For device two, positive and negative saturation currnet is respectively 32pA and 27pA, and the specific conductivity of calculating is respectively 2.1 * 10
-5(Ω cm)
-1With 1.8 * 10
-5(Ω cm)
-1For device three, positive and negative saturation currnet is respectively 60pA and 60pA, and the specific conductivity of calculating is 1.0 * 10
-5(Ω cm)
-1The I-V data of measuring show that the electron transport of B nanocone significant the variation do not occur with comparing of block boron simple substance.
Claims (11)
1. a boron nanocone is made up of pure boron, has single crystal structure, and the base diameter of said boron nanocone is the 300-500 nanometer, and top end diameter is the 50-100 nanometer, and length is 3-10 μ m.
2. method for preparing boron nanocone according to claim 1, this method with the mixture of boride and boron powder as source material, Fe
3O
4The mixture of catalyst nanoparticles and trace B powder utilizes chemical vapour deposition CVD method to synthesize the boron nanocone as co-catalyst, and this method may further comprise the steps:
(a) Fe that tensio-active agent is coated
3O
4Catalyst nanoparticles solution mixes the formation co-catalyst with the trace B powder;
(b) co-catalyst that obtains in the step (a) is deposited on the silicon chip substrate;
(c) under the atmosphere of shielding gas, 200-500 ℃ temperature heated substrate to remove solvent and the tensio-active agent in the co-catalyst;
(d) under the atmosphere of shielding gas; To heat together with the substrate that deposits the co-catalyst of having removed solvent as the boride of source material and the mixture of boron powder 1000-1300 ℃ temperature; The source material evaporation is diffused on the co-catalyst molten melt drop on the substrate surface; Thereby form the boron nanocone through gas-liquid-solid growth pattern
Wherein said tensio-active agent is oleyl amine and oleic acid, and trace B powder and Fe
3O
4The part by weight of catalyst nanoparticles solution is 0.0001-0.001.
3. method according to claim 2, wherein in step (a), Fe
3O
4The particle dia of catalyst nanoparticles is 8-14nm, and the particle dia of boron powder is 500nm-20 μ m.
4. method according to claim 2, wherein said shielding gas are the mixed gass of rare gas element and 0-10% hydrogen.
5. method according to claim 4, wherein said rare gas element comprises nitrogen and argon gas.
6. method according to claim 2, wherein chemical vapour deposition CVD can carry out under vacuum or a normal atmosphere.
7. method according to claim 2, wherein said boride comprises B
2O
3
8. method according to claim 7, wherein the part by weight of boride and boron powder is 1: 5～5: 1.
9. method according to claim 2, wherein the shield gas flow rate in the step (d) is less than 100sccm.
10. boron nanocone according to claim 1 is in the application of feds.
11. boron nanocone according to claim 1 is in the application of electricity device.
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| CN101381887B true CN101381887B (en) | 2012-02-15 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438176A (en) * | 2003-03-17 | 2003-08-27 | 郭水虎 | Method for preparing modified nano boron oxide |
| CN1594083A (en) * | 2004-06-22 | 2005-03-16 | 清华大学 | B6O nanowire and crystal whisker structure and its preparation method |
| CN1789115A (en) * | 2005-12-20 | 2006-06-21 | 山东大学 | Method for preparing boron nitride nanometer ring and tube |
-
2007
- 2007-09-05 CN CN200710121358XA patent/CN101381887B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438176A (en) * | 2003-03-17 | 2003-08-27 | 郭水虎 | Method for preparing modified nano boron oxide |
| CN1594083A (en) * | 2004-06-22 | 2005-03-16 | 清华大学 | B6O nanowire and crystal whisker structure and its preparation method |
| CN1789115A (en) * | 2005-12-20 | 2006-06-21 | 山东大学 | Method for preparing boron nitride nanometer ring and tube |
Non-Patent Citations (4)
| Title |
|---|
| Gao Yunpeng等.Crystalline boron nanowires grown by magnetron sputtering.《Materials Science and Engineering A》.2006,第434卷(第1-2期),53-57. * |
| Weiqiang Ding.Mechanics of crystalline boron nanowires.《Composites Science and Technology》.2006,第66卷1112–1124. * |
| 曹立民等.羽毛状硼纳米线并联结及其高定向列阵.《中国科学G辑》.2004,第34卷(第1期),76-86. * |
| 曹立民等.高取向硼纳米线列阵.《中国科学G辑》.2003,第33卷(第6期),551-560. * |
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