CN101434406B - Copper germinate nano-wire and preparation thereof - Google Patents
Copper germinate nano-wire and preparation thereof Download PDFInfo
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- CN101434406B CN101434406B CN2008102357639A CN200810235763A CN101434406B CN 101434406 B CN101434406 B CN 101434406B CN 2008102357639 A CN2008102357639 A CN 2008102357639A CN 200810235763 A CN200810235763 A CN 200810235763A CN 101434406 B CN101434406 B CN 101434406B
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Abstract
The invention discloses a copper germanic acid nano wire and a preparation method thereof, belonging to the technical field of nano material preparation. The copper germanic acid nano wire consists of single-crystal copper germanic acid core and a very thin amorphous copper germanic acid casing covered on the external layer. The preparation method takes germanium dioxide and sheet copper as raw material and water as a solvent, wherein, the sheet copper is also used as a deposition substrate. The preparation method comprises the steps of: ultrasonically cleaning the sheet copper in distilled water for 10 minutes, fixing the sheet copper in a reaction kettle vessel, uniformly stirring the sheet copper, insulating heat for 0-24 hours under the temperature of 200-500 DEG C and the pressure of 1-15MPa, and finally obtaining the copper germanic acid nano wire on the sheet copper. The preparation method has the advantages of free growth template addition, simple preparation process, easy operation and control, low growth temperature and lower preparation cost. In addition, as the method adopts the processes of innocuous germanium oxide and hydro-deposition, the raw material and the preparation process are harmless to the environment, therefore, the requirement of environmental protection is met. The preparation method can realize the mass preparation of the copper germanic acid nano wire.
Description
Technical field:
The invention belongs to the nano material preparation technical field, be specifically related to a kind of germanic acid copper (CuGeO
3) nano wire and preparation method thereof.
Background technology:
Germanic acid copper (CuGeO
3) have the mineral crystal of spin-Pei Ersi (Spin-Peierls) attitude phase transformation as first that find, it is a kind of spin-electronic material, caused people's research interest, utilize its electron spinning characteristic to make microelectronic device, carry out information storage and transmission, have good application prospects as hard disc playback head, magnetic RAM (MRAM) and device aspects such as magneto-dependent sensor, spin transistor, field-effect transistor, spinning LED and logitron.Monodimension nanometer material is following nano electron device, the important tectonic element of photoelectric device, fundamental research and application and development field in nano material have good development prospect, by the block spin-electronic material is prepared into monodimension nanometer material, the novel characteristics that block materials does not possess can appear, as quantum limitation effect, giant magnetoresistance effect etc., widen its use range, so can estimate that one dimension germanic acid copper nano materials such as copper germinate nano-wire are at information storage and transmission apparatus, magneto-dependent sensor, aspect such as spin transistor and spinning LED has good application prospects, can become a kind of novel material that application potential is arranged very much in nanometer field.Block germanic acid copper single crystal mainly prepares by float zone growth method (float zone method) at present.Yet, up to now, copper germinate nano-wire shape structure and preparation method's bibliographical information is not arranged as yet.
Summary of the invention:
The purpose of this invention is to provide a kind of copper germinate nano-wire and preparation method thereof.
Copper germinate nano-wire provided by the present invention, by the monocrystalline attitude germanic acid copper of the about 100nm of mean diameter nuclear and be wrapped in the amorphous germanic acid copper shell that outer layer thickness is lower than 2nm and formed, described monocrystalline attitude germanic acid copper is oblique square structure.
The preparation method of copper germinate nano-wire provided by the present invention is that employing germanium dioxide, copper sheet are starting material, prepares copper germinate nano-wire by the hydro-thermal deposition process, and the preparation method is specific as follows:
With germanium dioxide and copper sheet is starting material, wherein copper sheet is simultaneously as deposition substrate, water is solvent, at first with copper sheet ultrasonic cleaning ten minutes in distilled water, be fixed in then on the stainless steel stent in the sealed reactor container, then a certain proportion of germanium dioxide is mixed with distilled water and be placed in the sealed reactor, evenly stir, in temperature 200-500 ℃, pressure 1-15MPa is incubated 0-24 hour down, the amount of described germanium dioxide is not more than 10% of water solvent weight, the compactedness that germanium dioxide and solvent total amount account for the reactor container is not more than 10%, adopt magnetic stirrer, the final velvet-like light blue settling that has obtained surperficial uniform deposition on copper sheet is copper germinate nano-wire.
Germanium dioxide of the present invention accounts for 8% of weight of solvent, and germanium dioxide and solvent total amount account for the compactedness 5% of container.
Germanium dioxide of the present invention accounts for 5% of weight of solvent, and germanium dioxide and solvent total amount account for the compactedness 8% of container.
The present invention can be incubated 1-24 hour and evenly stir under 200-400 ℃ of temperature, 1-10MPa pressure.
The preferable preparation condition of the present invention is 200-350 ℃ of temperature, 1-8MPa pressure insulation 1-18 hour and evenly stirring down.
Another preferable preparation condition of the present invention is 250-300 ℃, insulation 1-12 hour and the evenly stirring down of 2-6MPa pressure.
The growth mechanism that the inventive method prepares copper germinate nano-wire is summarized as follows:
Explained the formation and the growth of copper germinate nano-wire Gu adopt solid-liquid-(SLS) growth mechanism.See accompanying drawing 1, the fusing point height of germanium dioxide be difficult to gasification under the temperature of hundreds of degree centigrade and normal pressure atmosphere, but hydrothermal condition of the present invention need carry out under certain pressure, hydro-thermal pressure has reduced the temperature of reaction of material, has promoted the reaction between material.In addition, germanium dioxide used in the present invention is the nanometer powder less than 100nm, and when the size of material is dwindled greatly, when especially narrowing down to nano-grade size, and the temperature of reaction between other materials also can reduce greatly.The copper sheet surface is except existing the cupric oxide that forms because of atmospheric oxidation under the atmospheric pressure environment, and the oxygen that also absorbs in the atmosphere under the hydrothermal condition of copper under certain temperature, pressure has quickened the oxidation of copper in addition.Therefore, under hydrothermal condition, germanium dioxide is deposited on the copper sheet that is positioned in advance in the container, react with the cupric oxide on copper sheet surface and to have generated germanic acid copper, germanic acid copper combines with germanium dioxide and has formed germanic acid copper, germanium dioxide liquid nano cluster (Fig. 1 (a)), this liquid nano cluster constantly absorbs the germanium dioxide that is deposited in the atmosphere on the copper sheet, wherein germanium dioxide constantly with cupric oxide reaction generation germanic acid copper, germanic acid copper reaches hypersaturated state in nanocluster, from nanocluster, separate out and formed monocrystalline germanic acid copper nuclear, and nanocluster has also limited the diameter of copper germinate nano-wire simultaneously, has caused the one dimension of copper germinate nano-wire to continue growth (Fig. 1 (b)).In addition, a spot of germanium dioxide is adsorbed in the surface of nano wire, and has formed thin germanic acid copper skin with the cupric oxide reaction, has further limited the growth of germanic acid copper crystal on diametric(al).Therefore, finally obtained reaching the copper germinate nano-wire (Fig. 1 (c)) that very thin amorphous germanic acid copper shell constitutes by germanic acid copper single crystal nuclear.
The present invention adopts above-mentioned hydro-thermal depositing operation method, utilize the oxygen reaction in copper, cupric oxide and the atmosphere on germanium dioxide and the copper sheet to generate germanic acid copper, a large amount of highly purified copper germinate nano-wires have been prepared, this method preparation temperature is lower, need not to add growth templates, preparation process is simple, easy handling control, growth temperature are low, so preparation cost is lower, for the practical application of copper germinate nano-wire provides condition.The present invention has developed the new purposes of hydrothermal technique, the novel method of a large amount of deposition copper germinate nano-wires under a kind of hydrothermal condition is provided, utilize similar approach probably to obtain monodimension nanometer material more, unique properties, for new approaches have been opened up in the research of monodimension nanometer material, help obtaining the higher monodimension nanometer material product of purity, and significant for the growth mechanism of research monodimension nanometer material.What the present invention adopted is nontoxic germanium oxide compound and hydro-thermal deposition process, the equal environmentally safe of raw material and preparation process, and the development of modern industry direction of compliance with environmental protection requirements can realize the mass preparation of copper germinate nano-wire.
Description of drawings:
Fig. 1 is the growth mechanism synoptic diagram that is deposited on the copper germinate nano-wire on the copper sheet.
Wherein: (a) CuGeO
3And GeO
2The formation of nanocluster, (b) Cu sheet surface absorbs the O in the atmosphere
2Reaction generates CuO, and nanocluster absorbs the GeO in the atmosphere
2, generate CuGeO with the CuO reaction
3Gu nano wire continues growth by solid-liquid-(SLS) growth mechanism, (c) the final copper germinate nano-wire that forms.
Fig. 2 is scanning electronic microscope (SEM) image of the copper germinate nano-wire of the present invention's preparation.
Deposited the copper germinate nano-wire of lot of pure as can be seen from Figure on the copper sheet, do not have other mixing up of structure in together, this copper germinate nano-wire diameter is more even, and length is above 10 microns, even reach tens of microns, illustrate that this method can obtain even, the purified copper germinate nano-wire of diameter Distribution.
Fig. 3 is energy-dispersive spectroscopy (power spectrum, EDS) figure of the copper germinate nano-wire of the present invention's preparation.
Copper germinate nano-wire mainly is made of germanium, oxygen and three kinds of elements of copper as we can see from the figure.
Fig. 4 is the TEM image of the copper germinate nano-wire of the present invention's preparation.
The copper germinate nano-wire diameter Distribution is more even as can be seen from Figure, the about 100nm of mean diameter, and minimum diameter can be as small as 10nm, the smooth surface of nano wire, length is greater than 10 microns.The head of copper germinate nano-wire is a fault structure, this be preparation during sample for use in transmitted electron microscope from the copper sheet machinery scrape scrape along has caused nano wire when ultrasonic dispersing is vibrated fracture.
Fig. 5 is high resolution transmission electron microscopy (HRTEM) image of the copper germinate nano-wire of the present invention's preparation.
This is the HRTEM image on single copper germinate nano-wire border, as can be seen from the figure the gained nano wire is the intact single crystal structure of crystal formation, there is the very thin amorphous shell of one deck in outermost layer, its thickness is lower than 2nm, Gu germanium dioxide has played certain effect in the solid-liquid-process of growth of copper germinate nano-wire, the skin that a spot of germanium dioxide is coated on nano wire has played the effect that restriction copper germinate nano-wire diametric(al) is grown, and formed unbodied germanic acid copper shell, so the amorphous outer layer of the nano wire amorphous germanic acid copper that is amorphous with cupric oxide reaction.
Fig. 6 is the XRD diffracting spectrum of the copper germinate nano-wire of the present invention's preparation.
XRD diffracting spectrum and JCPDS PDF card (JCPDS PDF # 32-0333) according to copper germinate nano-wire, can retrieve the gained copper germinate nano-wire is oblique square structure, the characteristic peak of nano wire (2 θ=21.2 °, 28.1 °, 30.3 °, 35.8 °, 37.2 °, 39.0 °, 42.7 °, 50.2 °, 53.8 °, 56.9 °, 59.4 °, 61.9 °, 66.4 °, 70.5 °, 74.5 °) correspond respectively to (110) of germanic acid copper, (120), (001), (101), (021), (210), (040), (211), (221), (141), (231), (320), (301), (122), (061) crystal face.
Fig. 7 is the Raman spectrum of the copper germinate nano-wire of the present invention's preparation.
According to the Raman spectrum of gained copper germinate nano-wire as can be seen, at 217.5cm
-1, 592.5cm
-1, 852.9cm
-1There are three stronger Raman characteristic peaks the position, and at 317.5cm
-1, 413.8cm
-1, 706.9cm
-1There are three more weak Raman characteristic peaks the position, the Raman characteristic peak (220cm of this and germanic acid copper powder
-1, 330cm
-1, 430cm
-1, 592cm
-1, 710cm
-1, 856cm
-1) be consistent, further confirmed the XRD result of copper germinate nano-wire simultaneously.
Embodiment:
Embodiment 1: with the ultrasonic cleaning ten minutes in distilled water of the copper sheet of the about 6 * 2cm of size, be fixed in then on the interior intermediary stainless steel stent of reactor, the germanium dioxide that will account for weight of solvent 1% then mixes with distilled water and is placed in the sealed reactor, germanium dioxide and solvent total amount account for 5% of reactor container, under the even stirring of magnetic stirring apparatus, in 200 ℃ of temperature, 1-2MPa pressure is incubated 24 hours down, on copper sheet, prepared the velvet-like light blue settling of surperficial uniform deposition, obtained length greater than 10 μ m, diameter Distribution is more even, the copper germinate nano-wire of the about 100nm of mean diameter.
Embodiment 2: with the ultrasonic cleaning ten minutes in distilled water of the copper sheet of the about 6 * 2cm of size, be fixed in then on the interior intermediary stainless steel stent of reactor, the germanium dioxide that will account for weight of solvent 5% then mixes with distilled water and is placed in the sealed reactor, germanium dioxide and solvent total amount account for 5% of reactor container, under the even stirring of magnetic stirring apparatus, in 200 ℃ of temperature, 1-2MPa pressure is incubated 12 hours down, on copper sheet, prepared the velvet-like light blue settling of surperficial uniform deposition, obtained length greater than 10 μ m, diameter Distribution is more even, the copper germinate nano-wire of the about 100nm of mean diameter.
Embodiment 3, with the ultrasonic cleaning ten minutes in distilled water of the copper sheet of the about 6 * 2cm of size, be fixed in then on the interior intermediary stainless steel stent of reactor, the germanium dioxide that will account for weight of solvent 5% then mixes with distilled water and is placed in the sealed reactor, germanium dioxide and solvent total amount account for 8% of reactor container, under the even stirring of magnetic stirring apparatus, in 250 ℃ of temperature, 2-4MPa pressure is incubated 24 hours down, on copper sheet, prepared the velvet-like light blue settling of surperficial uniform deposition, obtained length greater than 10 μ m, diameter Distribution is more even, the copper germinate nano-wire of the about 100nm of mean diameter.
Embodiment 4: with the ultrasonic cleaning ten minutes in distilled water of the copper sheet of the about 6 * 2cm of size, be fixed in then on the interior intermediary stainless steel stent of reactor, the germanium dioxide that will account for weight of solvent 10% then mixes with distilled water and is placed in the sealed reactor, germanium dioxide and solvent total amount account for 5% of reactor container, under the even stirring of magnetic stirring apparatus, in 250 ℃ of temperature, 2-4MPa pressure is incubated 12 hours down, on copper sheet, prepared the velvet-like light blue settling of surperficial uniform deposition, obtained length greater than 10 μ m, diameter Distribution is more even, the copper germinate nano-wire of the about 100nm of mean diameter.
Embodiment 5: with the ultrasonic cleaning ten minutes in distilled water of the copper sheet of the about 6 * 2cm of size, be fixed in then on the interior intermediary stainless steel stent of reactor, the germanium dioxide that will account for weight of solvent 10% then mixes with distilled water and is placed in the sealed reactor, germanium dioxide and solvent total amount account for 10% of reactor container, under the even stirring of magnetic stirring apparatus, in 350 ℃ of temperature, 4-7MPa pressure is incubated 24 hours down, on copper sheet, prepared the velvet-like light blue settling of surperficial uniform deposition, obtained length greater than 10 μ m, diameter Distribution is more even, the copper germinate nano-wire of the about 100nm of mean diameter.
Embodiment 6: with the ultrasonic cleaning ten minutes in distilled water of the copper sheet of the about 6 * 2cm of size, be fixed in then on the interior intermediary stainless steel stent of reactor, the germanium dioxide that will account for weight of solvent 6% then mixes with distilled water and is placed in the sealed reactor, germanium dioxide and solvent total amount account for 5% of reactor container, under the even stirring of magnetic stirring apparatus, in 400 ℃ of temperature, 5-8MPa pressure is incubated 12 hours down, on copper sheet, prepared the velvet-like light blue settling of surperficial uniform deposition, obtained length greater than 10 μ m, diameter Distribution is more even, the copper germinate nano-wire of the about 100nm of mean diameter.
Embodiment 7: with the ultrasonic cleaning ten minutes in distilled water of the copper sheet of the about 6 * 2cm of size, be fixed in then on the interior intermediary stainless steel stent of reactor, the germanium dioxide that will account for weight of solvent 4% then mixes with distilled water and is placed in the sealed reactor, germanium dioxide and solvent total amount account for 8% of reactor container, under the even stirring of magnetic stirring apparatus, in 450 ℃ of temperature, 8-10MPa pressure is incubated 12 hours down, on copper sheet, prepared the velvet-like light blue settling of surperficial uniform deposition, obtained length greater than 10 μ m, diameter Distribution is more even, the copper germinate nano-wire of the about 100nm of mean diameter.
Embodiment 8: with the ultrasonic cleaning ten minutes in distilled water of the copper sheet of the about 6 * 2cm of size, be fixed in then on the interior intermediary stainless steel stent of reactor, the germanium dioxide that will account for weight of solvent 3% then mixes with distilled water and is placed in the sealed reactor, germanium dioxide and solvent total amount account for 8% of reactor container, under the even stirring of magnetic stirring apparatus, in 450 ℃ of temperature, 9-11MPa pressure is incubated 24 hours down, on copper sheet, prepared the velvet-like light blue settling of surperficial uniform deposition, obtained length greater than 10 μ m, diameter Distribution is more even, the copper germinate nano-wire of the about 100nm of mean diameter.
Embodiment 9: with the ultrasonic cleaning ten minutes in distilled water of the copper sheet of the about 6 * 2cm of size, be fixed in then on the interior intermediary stainless steel stent of reactor, the germanium dioxide that will account for weight of solvent 4% then mixes with distilled water and is placed in the sealed reactor, germanium dioxide and solvent total amount account for 5% of reactor container, under the even stirring of magnetic stirring apparatus, in 400 ℃ of temperature, 6MPa pressure is incubated 0 hour down, on copper sheet, prepared the velvet-like light blue settling of surperficial uniform deposition, obtained length greater than 10 μ m, diameter Distribution is more even, the copper germinate nano-wire of the about 100nm of mean diameter.
Claims (8)
1. copper germinate nano-wire is characterized in that this copper germinate nano-wire by the monocrystalline attitude germanic acid copper nuclear of mean diameter 100nm and be wrapped in the amorphous germanic acid copper shell that outer layer thickness is lower than 2nm and formed, and described monocrystalline attitude germanic acid copper is oblique square structure.
2. preparation method of copper germinate nano-wire according to claim 1 is characterized in that this preparation method is as follows:
With germanium dioxide nanometer powder and copper sheet less than 100nm is starting material, wherein copper sheet is simultaneously as deposition substrate, water is solvent, at first with copper sheet ultrasonic cleaning ten minutes in distilled water, be fixed in then on the stainless steel stent in the sealed reactor container, then a certain proportion of germanium dioxide is mixed with distilled water and be placed in the sealed reactor container, evenly stir, in temperature 200-500 ℃, pressure 1-15MPa insulation down made described copper germinate nano-wire in 0-24 hour, the amount of described germanium dioxide is not more than 10% of water solvent weight, and the compactedness that germanium dioxide and solvent total amount account for the reactor container is not more than 10%.
3. preparation method according to claim 2 is characterized in that: described stirring is to adopt magnetic stirring apparatus to stir.
4. preparation method according to claim 2 is characterized in that: germanium dioxide accounts for 8% of weight of solvent, and germanium dioxide and solvent total amount account for the compactedness 5% of container.
5. preparation method according to claim 2 is characterized in that: germanium dioxide accounts for 5% of weight of solvent, and germanium dioxide and solvent total amount account for the compactedness 8% of container.
6. preparation method according to claim 2 is characterized in that: described temperature is that 200-400 ℃, pressure are 1-10MPa, soaking time 1-24 hour.
7. preparation method according to claim 2 is characterized in that: described temperature is that 200-350 ℃, pressure are 1-8MPa, soaking time 1-18 hour.
8. preparation method according to claim 2 is characterized in that: described temperature is that 250-300 ℃, pressure are 2-6MPa, soaking time 1-12 hour.
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| CN101434406B true CN101434406B (en) | 2011-11-09 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102225782B (en) * | 2011-04-14 | 2013-03-20 | 南京大学 | Preparation method for ultrafine In2Ge2O7(En) hybrid nano-wire, and nano-wire prepared by the same |
| CN103066262B (en) * | 2013-01-10 | 2015-02-25 | 西南大学 | Preparation method of anode material of Mn0.5-xCuxZn0.5 Fe2O4 lithium ion battery |
| CN103288125B (en) * | 2013-01-23 | 2015-09-02 | 西南大学 | CuGeO 3the preparation method of lithium ion battery anode material |
| CN103094543B (en) * | 2013-01-23 | 2015-01-07 | 西南大学 | Preparation method for CuGeO3/C compound anode material of lithium ion battery |
| CN103224250B (en) * | 2013-05-15 | 2014-07-23 | 东华大学 | Preparation method of copper germanate quantum dots |
| CN110510662A (en) * | 2019-10-11 | 2019-11-29 | 安徽工业大学 | A kind of germanic acid erbium nanorod electrodes material and preparation method thereof |
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