CN1850603A - Europium boride nano line, nano tube and its preparing method - Google Patents
Europium boride nano line, nano tube and its preparing method Download PDFInfo
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- CN1850603A CN1850603A CN 200610035611 CN200610035611A CN1850603A CN 1850603 A CN1850603 A CN 1850603A CN 200610035611 CN200610035611 CN 200610035611 CN 200610035611 A CN200610035611 A CN 200610035611A CN 1850603 A CN1850603 A CN 1850603A
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Abstract
The invention discloses an europium hexaborate nano line and nano tube and the preparing method thereof, firstly placing a monocrystalline silicon wafer substrate of europium source in the middle of quartz tube of a tubelike electric furnace, sealing the quartz tube and simultaneously prevacuumizing the quartz tube, then charging protective and reducing gases, heating the tube electric furnace to 930-1110 deg.C, charging boron source and simultaneously regulating the protective and reducing gases and keeping for 15-60 min; cooling to room temperature in the mixed gas atmosphere, where the boron source is BCl5 and the reducing gas is H2 and the protective gas is Ar gas. The test is simple in procedure and easy to operate, and convenient to industrial production. And the nano line can serve as cold cathode electron source, applied to field electron emission flat panel display, cold cathode light emitting tube, cold cathode light source, etc.
Description
Technical field
The present invention relates to field of nanometer material technology, be specifically related to nano wire, nanotube of europium boride and preparation method thereof.
Background technology
Lanthanum hexaborane is widely used in modern science and technology as a kind of field emmision material that the high-performance electronic source is provided.And europium boride is at RB
6Work function is relatively low in (R is a rare earth) series, and fusing point height, especially real high-temperature behavior are good, advantage such as rate of evaporation is little.And as field emmision material they to also have an advantage the most significant be exactly to export big emission, this point is extremely important when using on the field-causing electron ballistic device.
If one dimension europium boride nano material is used for scanning electron microscope as pistol, transmission electron microscope etc. need provide the device in high-performance electronic source.For similar bar-shaped field emission body, local electric field F (attracting the ability of electronics from radiator) can be expressed as the function of the distance (d) between institute's making alive (V), radiator tip radius (r), radiator length (h) the regulating YIN and YANG utmost point:
F＝1.2V(2.5+h/r)
0.9[1+0.013d/(d-h)-0.033(d-h)/d]/d
The above-mentioned relation table shows that the radiator radius is more little, and also h/r is just big more, and local electric field F will be strong more.That is to say, with the radiator of traditional same material comparatively speaking, it bigger transmitter current can occur under lower voltage.Concerning field emission, this just means and has reduced cut-in voltage, and these character are at other nanostructure SiC, W, CuS and MoO
3In be observed.The one-dimensional nano line of monodimension nanometer material minor diameter and big length-to-diameter ratio has improved the local electric field at radiator tip greatly.Therefore the europium boride of preparation and research nanostructure not only has scientific value, and has more realistic meaning.But, do not appear in the newspapers as yet about the europium boride nano wire of one-dimentional structure and the preparation of nanotube at present.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of europium boride nano wire and nanotube.
Another object of the present invention is to provide a kind of europium boride nano wire, nanotube of method for preparing.
A kind of nano wire of europium boride, the preparation method of nanotube comprise the steps and processing condition:
(1) the monocrystalline silicon piece substrate that will be placed with 0.1-0.5g europium source is put in the middle part of the silica tube of electric tube furnace, and sealed silica envelope simultaneously to silica tube forvacuum, feeds protection and reducing gas then, and its flow velocity is 10-100sccm;
(2) electric tube furnace with step (1) is heated to 930-1110 ℃, feeds the boron source then, and its flow velocity is 10-100sccm; Regulating protection and reducing gas flow velocity simultaneously is 20-200sccm; Kept 15-60 minute;
(3) warm in the gas mixture atmosphere decline of shielding gas and reducing gas, until being cooled to room temperature;
(4) take out the monocrystalline silicon piece substrate, in distilled water, soak, oven dry again, on the substrate material be nano wire, the nanotube of europium boride;
Described boron source is BCl
3Reducing gas in described step (1), (2) and (3) is H
2Gas, shielding gas are Ar gas, and reducing gas and shielding gas volume ratio are 0.1-10: 1.
Useful is, described europium source is metal Eu, and its granularity is 0.1-0.5mm.
By nano wire, the nanotube of the europium boride of method for preparing, described nano wire and nanotube growth are on substrate, and the diameter of nano wire is about 50-500nm, and length is about 0.5-8 μ m; The about 1.3-1.6 μ of the diameter of nanotube m, the about 2-4 μ of length m, the about 50-60nm of wall thickness.Single LaB
6The effective emission of the nanometer field of line is up to 5 * 10
5Acm
-2, can be used as a kind of field emmision material that the high-performance electronic source is provided.Equally, as the EuB of rare earth metal hexaboride
6Material, work function is relatively low, and fusing point height, especially high-temperature behavior are good, and rate of evaporation is little, and more superior advantages such as field emission performance are arranged.Can be used as cold-cathode electron source, be applied to field electron emission flat panel display, cold cathode luminotron, cold cathode luminous source etc.
Advantage of the present invention: the present invention prepares europium boride nano wire and nanotube first, and process of the test is simple, and easy handling does not need complicated processing condition, is convenient to suitability for industrialized production.
Description of drawings
Fig. 1 is the SEM photo of europium boride nano wire among the embodiment 1.
Fig. 2 is the XRD spectrum of europium boride nanostructure among the embodiment 2.
Fig. 3 a is the SEM photo (nano wire oriented growth) of europium boride nano wire among the embodiment 2.
Fig. 3 b is the SEM photo (the crooked growth of nano wire) of europium boride nano wire among the embodiment 2.
Fig. 4 is the SEM photo of europium boride nanotube among the embodiment 2.
Fig. 5 a is single europium boride nano wire TEM photo and a corresponding electron diffraction photo among the embodiment 2.
Fig. 5 b is the high resolution TEM photo of europium boride nano wire among the embodiment 2.
Fig. 6 is the SEM photo of europium boride nano wire among the embodiment 3.
Fig. 7 is the SEM photo of europium boride nano wire among the embodiment 4.
Embodiment
The present invention is further illustrated below in conjunction with drawings and Examples, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1:
(1) the monocrystalline silicon piece substrate that will be placed with 0.5g Eu powder (the about 0.1-0.5mm of particle diameter) is put in the middle part of the silica tube of electric tube furnace, and sealed silica envelope simultaneously to silica tube forvacuum, feeds H then
2/ Ar gas, (H
2The volume ratio of gas and Ar gas is 0.1, below the step ratio with), its flow velocity is 10sccm;
(2) electric tube furnace is heated to 930 ℃, feeds BCl this moment
3, flow velocity is 100sccm; Regulating protection and reducing gas flow velocity simultaneously is 200sccm; Kept 60 minutes;
(3) after the reaction, cooling (air-flow velocity is not limit) under gas mixture (the flow velocity is not limit) atmosphere of shielding gas and reducing gas is until being cooled to room temperature.
(4) take out the monocrystalline silicon piece substrate, in distilled water, soaked 4 hours, in baking oven, dry then, on the substrate material be nano wire, the nanotube of europium boride.
Fig. 1 is the SEM photo of the prepared sample of present embodiment.As can be seen from the figure, this embodiment prepares the nano wire of europium boride, and most of nanowire diameter are about 50-300nm, the about 1-2 μ of length m.Examine with Electronic Speculum, can also find a spot of europium boride nanotube.
Embodiment 2:
(1) the monocrystalline silicon piece substrate that will be placed with 0.3g Eu powder (the about 0.1-0.5mm of particle diameter) is put in the middle part of the silica tube of electric tube furnace, and sealed silica envelope simultaneously to silica tube forvacuum, feeds H then
2/ Ar gas (H
2The volume ratio of gas and Ar gas is 1, below the step ratio with), its flow velocity is 60sccm;
(2) electric tube furnace is heated to 950 ℃, feeds BCl this moment
3, flow velocity is 60sccm; Regulating protection and reducing gas flow velocity simultaneously is 120sccm; Kept 30 minutes;
(3) after the reaction, cooling (air-flow velocity is not limit) under gas mixture (the flow velocity is not limit) atmosphere of shielding gas and reducing gas is until being cooled to room temperature.
(4) take out the monocrystalline silicon piece substrate, in distilled water, soaked 4 hours, in baking oven, dry then, on the substrate material be nano wire, the nanotube of europium boride.
Fig. 2 is X-ray diffraction (XRD) spectrum of the prepared sample of present embodiment, and all diffraction peaks are all corresponding to the EuB of simple cubic structure
6, corresponding lattice parameter a=4.161 is with EuB
6The lattice parameter of body material is coincide finely.Do not find other assorted peak.
Fig. 3 a is the SEM photo (nano wire) of prepared sample segment, and as can be seen from the figure, nano wire is grown perpendicular to substrate, and its diameter is about 60-300nm, is about 500nm-1.2 μ m.
Fig. 3 b is the SEM photo (nano wire) of prepared another part sample, and these nano wires are compared with the nano wire shown in Fig. 3 a, have different patterns.The crooked growth of most of nano wires, its diameter is about 180nm, is about 5-8 μ m.Substrate is uneven be since the Si surface by BCL
3Due to the corrosion.
Fig. 4 is the SEM photo (nanotube) of prepared sample segment, as can be seen from the figure, and the about 1.3-1.6 μ of the diameter of nanotube m, the about 2-4 μ of length m, the about 50-60nm of wall thickness.
Fig. 5 is the TEM pattern picture and the corresponding selected area electron diffraction (Fig. 5 a upper right corner) of a nano wire.From the pattern picture about 190nm of diameter of this root nano wire as can be known, surface ratio is more coarse.The selected area electron diffraction in Fig. 5 a upper right corner can be according to the EuB of simple cubic structure
6Indexing, resulting result is consistent for this X-ray powder diffraction with Fig. 2.
Fig. 5 b is the high resolution lattice fringe picture of nano wire.Fringe spacing 0.422nm among the figure and 0.243nm correspond respectively to simple cubic structure EuB
6(001) and (11-1) crystal face, the angle of two crystal faces is 125 ° in survey sheet, this and 125.3 ° of meet fine of theoretical value.The direction of growth [001] of the long arrow points nano wire among the figure.
Fig. 2～Fig. 5 explanation, the method for present embodiment can prepare the nano wire and the nanotube of europium boride simultaneously.Learn that from the observation of scanning electron microscope what occupy the majority is nano wire, nanotube is less relatively.In addition, X-ray diffraction, scanning electron microscope and transmission electron microscope characterize the nano wire and the nanotube of preparation.The XRD spectrum, high resolution lattice fringe picture and selected area electron diffraction have shown that all prepared nano wire is a monocrystal material.
Embodiment 3:
(1) the monocrystalline silicon piece substrate that will be placed with 0.2g Eu powder (the about 0.1-0.5mm of particle diameter) is put in the middle part of the silica tube of electric tube furnace, and sealed silica envelope simultaneously to silica tube forvacuum, feeds H then
2/ Ar gas (H
2The volume ratio of gas and Ar gas is 5, below the step ratio with), its flow velocity is 50sccm;
(2) electric tube furnace is heated to 1050 ℃, feeds BCl this moment
3, flow velocity is 50sccm; Regulating protection and reducing gas flow velocity simultaneously is 100sccm; Kept 30 minutes;
(3) after the reaction, cooling (air-flow velocity is not limit) under gas mixture (the flow velocity is not limit) atmosphere of shielding gas and reducing gas is until being cooled to room temperature.
(4) take out the monocrystalline silicon piece substrate, in distilled water, soaked 4 hours, in baking oven, dry then, on the substrate material be nano wire, the nanotube of europium boride.
Fig. 6 is this embodiment sample EuB
6The SEM photo of nano wire, as shown in Figure 6, this embodiment prepares the nano wire of europium boride, and most of nanowire diameter are about 50-100nm, the about 2-5 μ of length m.Examine with Electronic Speculum, also can find a spot of nanotube.
Embodiment 4:
(1) the monocrystalline silicon piece substrate that will be placed with 0.1g Eu powder (the about 0.1-0.5mm of particle diameter) is put in the middle part of the silica tube of electric tube furnace, and sealed silica envelope simultaneously to silica tube forvacuum, feeds H then
2/ Ar gas (H
2With the volume ratio of Ar be 10, below the step ratio with), its flow velocity is 100sccm;
(2) electric tube furnace is heated to 1100 ℃, feeds BCl this moment
3, flow velocity is that 10sccm regulates protection simultaneously and the reducing gas flow velocity is 20sccm; Kept 15 minutes;
(3) after the reaction, cooling (air-flow velocity is not limit) under gas mixture (the flow velocity is not limit) atmosphere of shielding gas and reducing gas is until being cooled to room temperature.
(4) take out the monocrystalline silicon piece substrate, in distilled water, soaked 4 hours, in baking oven, dry then, on the substrate material be nano wire, the nanotube of europium boride.
Fig. 7 is the higher sample EuB of present embodiment
6The SEM photo of nano wire, from this figure as can be known, present embodiment is prepared the nano wire of europium boride, and most of nanowire diameter are about 50-500nm, and length is 1-7 μ m.Examine sample with Electronic Speculum, can also find a spot of nanotube.
The detection of prepared europium boride nano material sample in the above example is to observe and analyze with spread out XRD (DRIC-Y2000), scanning electron microscope sem (JSM-6330F), transmission electron microscope TEM (JEM-2010HR) etc. of X ray.
On the whole, through electron microscopic observation, method of the present invention can prepare europium boride nano wire and nanotube simultaneously, and the quantity of nanotube is less relatively.Wherein the diameter of nano wire is about 50-500nm, and length is about 0.5-8 μ m; The about 1.3-1.6 μ of the diameter of nanotube m, the about 2-4 μ of length m, the about 50-60nm of wall thickness.
Claims (3)
1, the preparation method of a kind of nano wire of europium boride, nanotube is characterized in that, comprises the steps and processing condition:
(1) the monocrystalline silicon piece substrate that will be placed with 0.1-0.5g europium source is put in the middle part of the silica tube of electric tube furnace, and sealed silica envelope simultaneously to silica tube forvacuum, feeds protection and reducing gas then, and its flow velocity is 10-100sccm;
(2) electric tube furnace with step (1) is heated to 930-1110 ℃, feeds the boron source then, and its flow velocity is 10-100sccm; Regulating protection and reducing gas flow velocity simultaneously is 20-200sccm; Kept 15-60 minute;
(3) warm in the gas mixture atmosphere decline of shielding gas and reducing gas, until being cooled to room temperature;
(4) take out the monocrystalline silicon piece substrate, in distilled water, soak, oven dry again, on the substrate material be nano wire, the nanotube of europium boride;
Described boron source is BCl
3Reducing gas in described step (1), (2) and (3) is H
2Gas, shielding gas are Ar gas, and reducing gas and shielding gas volume ratio are 0.1-10: 1.
2, the preparation method of europium boride nano wire according to claim 1 and nanotube is characterized in that: described europium source is metal Eu, and its granularity is 0.1-0.5mm.
3, a kind of europium boride nano wire, nanotube by the described method preparation of claim 1 is characterized in that described nano wire and nanotube growth are on substrate, and the diameter of nano wire is about 50-500nm, and length is about 0.5-8 μ m; The about 1.3-1.6 μ of the diameter of nanotube m, the about 2-4 μ of length m, the about 50-60nm of wall thickness.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583423A (en) * | 2012-03-19 | 2012-07-18 | 许军旗 | Praseodymium hexaboride nanowire and preparation method thereof |
| CN102616799A (en) * | 2012-03-19 | 2012-08-01 | 许军旗 | Lanthanum hexaboride nanowire and method for preparing same |
| CN108862299A (en) * | 2018-08-08 | 2018-11-23 | 成都理工大学 | A kind of amorphous state EuB6The preparation method of nano material |
| CN110228811A (en) * | 2019-05-16 | 2019-09-13 | 中山大学 | A kind of low-dimensional rare-earth boride nano material and its method for preparing solid phase |
| CN110642260A (en) * | 2019-11-13 | 2020-01-03 | 成都理工大学 | EuB6Method for preparing nanotubes |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1011247B (en) * | 1988-02-09 | 1991-01-16 | 南开大学 | Rare-earth hexaboronide synthesized by melted salt electrolysis technique |
| JP4250953B2 (en) * | 2002-01-18 | 2009-04-08 | 住友金属鉱山株式会社 | 6 boride particles, a dispersion in which the 6 boride particles are dispersed, and an article using the 6 boride particles or the dispersion |
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2006
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583423A (en) * | 2012-03-19 | 2012-07-18 | 许军旗 | Praseodymium hexaboride nanowire and preparation method thereof |
| CN102616799A (en) * | 2012-03-19 | 2012-08-01 | 许军旗 | Lanthanum hexaboride nanowire and method for preparing same |
| CN102583423B (en) * | 2012-03-19 | 2014-07-02 | 信阳师范学院 | Praseodymium hexaboride nanowire and preparation method thereof |
| CN108862299A (en) * | 2018-08-08 | 2018-11-23 | 成都理工大学 | A kind of amorphous state EuB6The preparation method of nano material |
| CN108862299B (en) * | 2018-08-08 | 2021-07-13 | 成都理工大学 | Amorphous EuB6Preparation method of nano material |
| CN110228811A (en) * | 2019-05-16 | 2019-09-13 | 中山大学 | A kind of low-dimensional rare-earth boride nano material and its method for preparing solid phase |
| CN110228811B (en) * | 2019-05-16 | 2023-03-28 | 中山大学 | Low-dimensional rare earth boride nano material and solid phase preparation method thereof |
| CN110642260A (en) * | 2019-11-13 | 2020-01-03 | 成都理工大学 | EuB6Method for preparing nanotubes |
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