CN101457396A - Zinc oxide nano awl and preparation method thereof - Google Patents
Zinc oxide nano awl and preparation method thereof Download PDFInfo
- Publication number
- CN101457396A CN101457396A CNA2007101914077A CN200710191407A CN101457396A CN 101457396 A CN101457396 A CN 101457396A CN A2007101914077 A CNA2007101914077 A CN A2007101914077A CN 200710191407 A CN200710191407 A CN 200710191407A CN 101457396 A CN101457396 A CN 101457396A
- Authority
- CN
- China
- Prior art keywords
- zinc oxide
- substrate
- oxide nano
- awl
- zinc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 280
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 140
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000000758 substrate Substances 0.000 claims abstract description 125
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000002073 nanorod Substances 0.000 claims abstract description 48
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 36
- 239000002243 precursor Substances 0.000 claims abstract description 32
- 239000013078 crystal Substances 0.000 claims abstract description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000002110 nanocone Substances 0.000 claims abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 30
- 229910052725 zinc Inorganic materials 0.000 claims description 30
- 239000011701 zinc Substances 0.000 claims description 30
- 238000011010 flushing procedure Methods 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 28
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 238000005229 chemical vapour deposition Methods 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000013067 intermediate product Substances 0.000 claims description 8
- 239000004065 semiconductor Substances 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 abstract description 5
- 238000001514 detection method Methods 0.000 abstract description 2
- 238000004377 microelectronic Methods 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 2
- 238000005406 washing Methods 0.000 abstract 2
- 230000001699 photocatalysis Effects 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 150000003751 zinc Chemical class 0.000 abstract 1
- 229960001296 zinc oxide Drugs 0.000 description 111
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000011521 glass Substances 0.000 description 8
- 239000002086 nanomaterial Substances 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 229910052732 germanium Inorganic materials 0.000 description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000002127 nanobelt Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000004098 selected area electron diffraction Methods 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a zinc oxide nano awl and a preparation method thereof. The length of the zinc oxide nano awl is 2-2.5 mu m, the maximum diameter of the awl is 200-250 nm, and the taper is 3-15 degrees; the method comprises the steps of firstly placing a substrate and a zinc oxide nano rod/tower array on the substrate in an ammonia water solution with the mass fraction of 0.5-1.25%, placing for 1-5.5 h, taking out the substrate, washing with water, and separating to obtain the zinc oxide nano cone, wherein the step of preparing the zinc oxide nano rod/tower array by a hydrothermal method comprises the following steps: firstly, dropwise adding ammonia water with the mass fraction of 20-30% into a zinc salt solution with the concentration of 0.05-0.15M under stirring to obtain a precursor solution, and secondly, placing the precursor solution with a substrate with a zinc oxide seed crystal layer covered on the surface in a pressure of 2.5-5 multiplied by 105Pa and the temperature of 90-100 ℃ for 70-200 min, taking out and washing with water to obtain the zinc oxide nano rod/tower array arranged on the substrate. It can be widely used in the fields of optics, photocatalysis, biological detection, gas sensors, photoelectric devices and microelectronics.
Description
Technical field the present invention relates to a kind of nano awl and method for making, especially zinc oxide nano cone and preparation method thereof.
Background technology is since finding zinc oxide nano-belt, and the research of one-dimension zinc oxide nanostructure has caused the extensive concern of scientific research circle.Because unusual semi-conductor and the piezoelectric properties of zinc oxide, the one-dimension zinc oxide nanostructure has all demonstrated the potential application prospect as optics, electricity, piezoelectricity and catalysis etc. aspect a lot.In recent years, it is found that particularly have superior field emission performance and be regarded as place of carbon nanotubes and construct the best nano material of feds because the one-dimension zinc oxide nanostructure has high-melting-point, high heat/chemical stability.For this reason, people have done unremitting effort, and a large amount of preparation methods such as chemical Vapor deposition process, hydrothermal method, sonochemical method etc. all are applied in the preparation one-dimension zinc oxide nanostructure.As the method for growing oriented aligning zinc oxide nanometer rod array " a kind of on silicon base " who discloses among the disclosed Chinese invention patent ublic specification of application CN1769545A on May 10th, 2006, a kind of what mentioned among the disclosed Chinese invention patent ublic specification of application CN1557717A on December 29th, 2004
" preparation method of the nano zinc oxide material of nano tower oriented nano ".But these methods all exist weak point, at first, make or for nanometic zinc oxide rod array, or be zinc-oxide nano tower array, and fail to obtain Zinc oxide nano awl; Secondly, method both can not prepare Zinc oxide nano awl, technology when making zinc oxide nano rod/tower array is more numerous and diverse again, need during growing zinc oxide nanorod arrays magnetron sputtering zinc-oxide film in the substrate and in vacuum tube furnace heat, need more raw material during preparation zinc-oxide nano tower array, and need the vitriol oil to soak substrate for a long time and with the use ultrasonic device product is cleaned, these make that all production cost is difficult to reduce.
The summary of the invention the technical problem to be solved in the present invention is the limitation that overcomes above-mentioned various technical schemes, provides a kind of end to be the Zinc oxide nano awl of taper.
Another technical problem that the present invention will solve is for providing the preparation method of a zinc oxide nano cone.
For solving technical problem of the present invention, the technical scheme that is adopted is: Zinc oxide nano awl comprises zinc oxide, particularly said zinc oxide is the nano awl shape, and the awl length of said nano awl shape is that 2～2.5 μ m, auger directly are that 200～250nm, tapering are 3～15 degree.
As the further improvement of Zinc oxide nano awl, the awl of described nano awl point diameter is 6～15nm; Described Zinc oxide nano awl is positioned on the substrate.
For solving another technical problem of the present invention, another technical scheme that is adopted is: the preparation method of Zinc oxide nano awl comprises that use hydrothermal method or chemical Vapor deposition process obtain to place the zinc oxide nano rod/tower array on the substrate, particularly it is finished according to the following steps: earlier substrate and the zinc oxide nano rod/tower array on it being placed massfraction is that 0.5～1.25% ammonia soln is placed 1～5.5h, again substrate and the intermediate product on it are taken out also water flushing, then, separate substrate and the product on it make Zinc oxide nano awl.
Further improvement as the preparation method of Zinc oxide nano awl, described hydrothermal method is made and is placed the step of the zinc oxide nano rod/tower array on the substrate to be: the first step, with massfraction is that 20～30% ammoniacal liquor is added dropwise in the zinc solution that concentration under stirring is 0.05～0.15M and obtains precursor solution, wherein, volume ratio between ammoniacal liquor and zinc solution is 1:800～1000, second step, the substrate that earlier its surface is covered with the young crystal layer of zinc oxide places precursor solution, and will wherein being equipped with precursor solution that the surface is covered with the young crystal layer substrate of zinc oxide again, to place pressure be 2.5～5 * 10
5Pa, temperature are 90～100 ℃ of heating 70～200min down, then, take out substrate down in normal temperature, and the resultant on the water flushing substrate, obtain to place the zinc oxide nano rod/tower array on the substrate; Described zinc solution is liquor zinci chloridi or zinc acetate solution or zinc nitrate solution; The drop rate of described ammoniacal liquor is 0.6～0.8ml/min, and ammoniacal liquor drips the back and continues to stir 10～30min; The thickness of the young crystal layer of the zinc oxide that described substrate surface is covered with is 50～200nm; Described substrate is metal or semi-conductor or isolator; Described metal is zinc or titanium or aluminium, and semi-conductor is silicon or germanium or conductive glass, and isolator is glass or ceramic plate or vitrified pipe; Described water is deionized water or distilled water, and the number of times of flushing is 3～6 times; Described separate substrate and the product on it are peeled off for using blade.
Beneficial effect with respect to prior art is, one, use field emission scanning electron microscope, transmission electron microscope and x-ray diffractometer to characterize respectively to the product that makes, from the stereoscan photograph, transmission electron microscope photo and the X-ray diffraction spectrogram that obtain as can be known, product is the nano awl shape, its awl length is that 2～2.5 μ m, auger directly are that 200～250nm, tapering are 3～15 degree, and the sharp diameter of the awl of nano awl is 6～15nm.Nano awl is that the zinc oxide by the wurtzite hexagonal structure constitutes, and has the preferred orientation of very high [0001] and good monocrystalline; They are two years old, the product that makes, be that Zinc oxide nano awl is taper because of its end, so can be widely used in fields such as optics, photochemical catalysis, biological detection, gas sensor, photoelectric device and microelectronics, particularly when cone was sharp, emission on the scene improves most advanced and sophisticated local electric field, and the electron tunnel aspect was expected fabulous application prospect to obtain efficiently; Its three, the preparation method is easy, materials are few, and are pollution-free, the temperature of reacting required is low and with short production cycle, is suitable for suitability for industrialized production; Its four, by control, can obtain to have the nano-structure array of different most advanced and sophisticated how much patterns to zinc oxide nano rod/tower etching time, the utmost point is beneficial to its application in the adjustable field emission of parameter.
As the further embodiment of beneficial effect, the one, Zinc oxide nano awl is positioned on the substrate, and the array utmost point that is assembled into thus is beneficial to and is applied to construct device; The 2nd, hydrothermal method is made and is placed the step of the zinc oxide nano rod/tower array on the substrate to be preferably: the first step, with massfraction is that 20～30% ammoniacal liquor is added dropwise in the zinc solution that concentration under stirring is 0.05～0.15M and obtains precursor solution, wherein, volume ratio between ammoniacal liquor and zinc solution is 1:800～1000, second step, the substrate that earlier its surface is covered with the young crystal layer of zinc oxide places precursor solution, and will wherein being equipped with precursor solution that the surface is covered with the young crystal layer substrate of zinc oxide again, to place pressure be 2.5～5 * 10
5Pa, temperature are 90～100 ℃ of heating 70～200min down, then, take out substrate down in normal temperature, and the resultant on the water flushing substrate, acquisition places the zinc oxide nano rod/tower array on the substrate, has that technology is succinct, materials are few, and save time, free of contamination advantage; The 3rd, zinc solution is preferably liquor zinci chloridi or zinc acetate solution or zinc nitrate solution, makes the selection of raw material that bigger leeway be arranged, and is not only convenient flexibly, also is beneficial to suitability for industrialized production; The 4th, the drop rate of ammoniacal liquor is preferably 0.6～0.8ml/min, and ammoniacal liquor drips the back to be continued to stir 10～30min, can be easy to and obtain preferably suitable precursor solution; The 5th, the thickness of the young crystal layer of the zinc oxide that substrate surface is covered with is preferably 50～200nm, can make the stay-in-grade zinc oxide nano rod/tower array that places on the substrate; The 6th, substrate can be metal or semi-conductor or isolator, wherein, metal can be zinc or titanium or aluminium, semi-conductor can be silicon or germanium or conductive glass, isolator can be glass or ceramic plate or vitrified pipe, all can grow zinc oxide nano rod/tower array thereon, also be zinc oxide nano rod/tower array growth to substrate without any dependency, can on any substrate, generate; The 7th, water is preferably deionized water or distilled water, the number of times of flushing is 3～6 times, both avoided the introducing of impurity, make the less wash number of its need just can reach the purpose of cleaning again, also promptly can remove the cooperation ion of ammonia residual in resultant and the intermediate product effectively and obtain zinc oxide nano rod/tower array and product; The 8th, the product on separate substrate and its is preferably and uses blade to peel off, not only simply but also quick.
Description of drawings is described in further detail optimal way of the present invention below in conjunction with accompanying drawing.
Fig. 1 be to be positioned at take the photograph after product on the substrate uses Sirion 200 type scanning electronic microscope (SEM) to observe one of SEM photo.Can find out that by Fig. 1 (a) product is intensive shape and is distributed on the substrate equably.Fig. 1 (b) is the enlarged view of Fig. 1 (a), can see that by it product is that the directly about 200nm of auger, most advanced and sophisticated awl directly are the nano awl shape structure of 6～15nm;
Fig. 2 be take the photograph after using JEM-2010 type transmission electron microscope (TEM) and JEOL-2010 type high resolution transmission electron microscope (TEM) to observe to product shown in Figure 1 the TEM photo.Can find out that by Fig. 2 (a) length of nano awl is that 2～2.5 μ m and diameter Distribution are more even.Fig. 2 (b) is the enlarged view of the single nano awl among Fig. 2 (a), by its tip diameter that can see nano awl about 6nm, the growth of nano awl is along [0001] direction, the interior illustration in Fig. 2 (b) lower left corner is its selected area electron diffraction photo, and it has showed the monocrystalline that nano awl is good;
Fig. 3 uses the resulting XRD spectra in Phlips X ' Pert type X-ray diffraction (XRD) instrument test back to product shown in Figure 1, can be found out that by this XRD spectra products therefrom is a hexagonal wurtzite zinc oxide structure, and [0001] preferred orientation of height is arranged;
Fig. 4 be to adopt that hydrothermal method of the present invention makes place zinc oxide nano rod/tower array on the substrate to use Sirion 200 type scanning electronic microscope (SEM) to observe after take the photograph one of SEM photo, can find out that by Fig. 4 (a) zinc oxide nano rod of acquisition/tower array is intensive shape and is distributed on the substrate equably.Fig. 4 (b) is the enlarged view of Fig. 4 (a), can see that by it zinc oxide nano rod/tower is nanometer rod/tower structure of the about 50nm of rod/tower diameter of the about 200nm of rod/tower diameter, end;
Fig. 5 is to be after 0.5% ammoniacal liquor corrodes the different time respectively to zinc oxide nano rod shown in Figure 4/tower array functional quality mark, re-use take the photograph after Sirion 200 type scanning electronic microscope (SEM) are observed it the SEM photo, wherein, Fig. 5 (a) is corrosion 2h, Fig. 5 (b) is corrosion 3h, Fig. 5 (c) is corrosion 4h, and Fig. 5 (d) is corrosion 5.5h.Can find out by Fig. 5 (a)～(d),, can obtain having the Zinc oxide nano awl array of the high sharpness of different tops pattern, illustrate that these nanostructures can be applied in the adjustable field emission of parameter along with the prolongation of etching time;
Fig. 6 is after the hydrothermal method of using prior art or chemical Vapor deposition process are obtained to place zinc oxide nano rod/tower array on the substrate, re-use preparation method of the present invention and make product, afterwards, take the photograph after using Sirion 200 type scanning electronic microscope (SEM) that product is observed the SEM photo.Can see that by Fig. 6 (a) being thick with rod/tower diameter on the substrate is the array of zinc oxide nano rod/tower formation of 70nm.Fig. 6 (b) is for using the Zinc oxide nano awl array with high sharpness that obtains after preparation method's corrosion of the present invention to the zinc oxide nano rod/tower array shown in Fig. 6 (a), the sharpness of the zinc oxide nano rod/tower structure before as seen from the figure, the Zinc oxide nano awl that obtains after preparation method of the present invention handles is handled has improved significantly.Can draw thus, this normal temperature chemical corrosion method is pervasive to the Zinc oxide nano awl array of preparation different diameter.
Embodiment at first makes with ordinary method or buys ammoniacal liquor from market, liquor zinci chloridi, zinc acetate solution and zinc nitrate solution as zinc solution, zinc, titanium, aluminium, silicon, germanium, conductive glass, glass, ceramic plate and vitrified pipe as substrate, the surface of above-mentioned substrate all is covered with the young crystal layer of zinc oxide, as the deionized water and the distilled water of water.Then, earlier substrate is cleaned up in advance, afterwards,
Embodiment 1: finish preparation according to the following steps successively: a) use hydrothermal method to make the zinc oxide nano rod/tower array that places on the substrate earlier, its step is, the first step, with massfraction is that 30% ammoniacal liquor is added dropwise in the zinc solution that concentration under stirring is 0.05M and obtains precursor solution, and ammoniacal liquor in the precursor solution and the volume ratio between zinc solution are 1:800; Wherein, zinc solution is a liquor zinci chloridi, and the drop rate of ammoniacal liquor is 0.8ml/min, and ammoniacal liquor drips the back and continues to stir 10min.In second step, the substrate that earlier its surface is covered with the young crystal layer of zinc oxide places precursor solution, and will wherein being equipped with precursor solution that the surface is covered with the young crystal layer substrate of zinc oxide again, to place pressure be 2.5 * 10
5Pa, temperature are 90 ℃ of heating 200min down; Wherein, the thickness of the young crystal layer of the zinc oxide that substrate surface is covered with is 50nm, and substrate is a silicon chip.Then, take out substrate down in normal temperature, and the resultant on the water flushing substrate; Wherein, water is deionized water, and the number of times of flushing is 3 times, obtains to be similar to the zinc oxide nano rod/tower array on the substrate of placing shown in Fig. 4 (a) and Fig. 4 (b).Perhaps, use the hydrothermal method of prior art or chemical Vapor deposition process to obtain to be similar to the zinc oxide nano rod/tower array on the substrate of placing shown in Fig. 6 (a).B) refabrication Zinc oxide nano awl, its step be, earlier substrate and the zinc oxide nano rod/tower array on it being placed massfraction is that 0.5% ammonia soln is placed 5.5h, again with substrate with the intermediate product on it takes out and the water flushing; Wherein, water is deionized water, and the number of times of flushing is 3 times.Then, separate substrate and the product on it, wherein, separate substrate and the product on it are peeled off for using blade, make and be similar to shown in Fig. 1 (a), Fig. 1 (b), Fig. 2 (a) and Fig. 2 (b), shown in the curve among Fig. 3, and the Zinc oxide nano awl shown in Fig. 5 (d).
Embodiment 2: finish preparation according to the following steps successively: a) use hydrothermal method to make the zinc oxide nano rod/tower array that places on the substrate earlier, its step is, the first step, with massfraction is that 28% ammoniacal liquor is added dropwise in the zinc solution that concentration under stirring is 0.08M and obtains precursor solution, and ammoniacal liquor in the precursor solution and the volume ratio between zinc solution are 1:850; Wherein, zinc solution is a liquor zinci chloridi, and the drop rate of ammoniacal liquor is 0.75ml/min, and ammoniacal liquor drips the back and continues to stir 15min.In second step, the substrate that earlier its surface is covered with the young crystal layer of zinc oxide places precursor solution, and will wherein being equipped with precursor solution that the surface is covered with the young crystal layer substrate of zinc oxide again, to place pressure be 3 * 10
5Pa, temperature are 93 ℃ of heating 170min down; Wherein, the thickness of the young crystal layer of the zinc oxide that substrate surface is covered with is 80nm, and substrate is a silicon chip.Then, take out substrate down in normal temperature, and the resultant on the water flushing substrate; Wherein, water is deionized water, and the number of times of flushing is 4 times, obtains to be similar to the zinc oxide nano rod/tower array on the substrate of placing shown in Fig. 4 (a) and Fig. 4 (b).Perhaps, use the hydrothermal method of prior art or chemical Vapor deposition process to obtain to be similar to the zinc oxide nano rod/tower array on the substrate of placing shown in Fig. 6 (a).B) refabrication Zinc oxide nano awl, its step be, earlier substrate and the zinc oxide nano rod/tower array on it being placed massfraction is that 0.6% ammonia soln is placed 4h, again with substrate with the intermediate product on it takes out and the water flushing; Wherein, water is deionized water, and the number of times of flushing is 4 times.Then, separate substrate and the product on it, wherein, separate substrate and the product on it are peeled off for using blade, make and be similar to shown in Fig. 1 (a), Fig. 1 (b), Fig. 2 (a) and Fig. 2 (b), shown in the curve among Fig. 3, and be similar to the Zinc oxide nano awl shown in Fig. 5 (c).
Embodiment 3: finish preparation according to the following steps successively: a) use hydrothermal method to make the zinc oxide nano rod/tower array that places on the substrate earlier, its step is, the first step, with massfraction is that 25% ammoniacal liquor is added dropwise in the zinc solution that concentration under stirring is 0.1M and obtains precursor solution, and ammoniacal liquor in the precursor solution and the volume ratio between zinc solution are 1:900; Wherein, zinc solution is a liquor zinci chloridi, and the drop rate of ammoniacal liquor is 0.7ml/min, and ammoniacal liquor drips the back and continues to stir 20min.In second step, the substrate that earlier its surface is covered with the young crystal layer of zinc oxide places precursor solution, and will wherein being equipped with precursor solution that the surface is covered with the young crystal layer substrate of zinc oxide again, to place pressure be 4 * 10
5Pa, temperature are 95 ℃ of heating 130min down; Wherein, the thickness of the young crystal layer of the zinc oxide that substrate surface is covered with is 120nm, and substrate is a silicon chip.Then, take out substrate down in normal temperature, and the resultant on the water flushing substrate; Wherein, water is deionized water, and the number of times of flushing is 5 times, obtains the zinc oxide nano rod/tower array on the substrate of placing shown in Fig. 4 (a) and Fig. 4 (b).Perhaps, use the hydrothermal method of prior art or chemical Vapor deposition process to obtain to be similar to the zinc oxide nano rod/tower array on the substrate of placing shown in Fig. 6 (a).B) refabrication Zinc oxide nano awl, its step be, earlier substrate and the zinc oxide nano rod/tower array on it being placed massfraction is that 0.8% ammonia soln is placed 3h, again with substrate with the intermediate product on it takes out and the water flushing; Wherein, water is deionized water, and the number of times of flushing is 5 times.Then, separate substrate and the product on it, wherein, separate substrate and the product on it are peeled off for using blade, make shown in Fig. 1 (a), Fig. 1 (b), Fig. 2 (a) and Fig. 2 (b), shown in the curve among Fig. 3, and be similar to the Zinc oxide nano awl shown in Fig. 5 (b).
Embodiment 4: finish preparation according to the following steps successively: a) use hydrothermal method to make the zinc oxide nano rod/tower array that places on the substrate earlier, its step is, the first step, with massfraction is that 23% ammoniacal liquor is added dropwise in the zinc solution that concentration under stirring is 0.13M and obtains precursor solution, and ammoniacal liquor in the precursor solution and the volume ratio between zinc solution are 1:950; Wherein, zinc solution is a liquor zinci chloridi, and the drop rate of ammoniacal liquor is 0.65ml/min, and ammoniacal liquor drips the back and continues to stir 25min.In second step, the substrate that earlier its surface is covered with the young crystal layer of zinc oxide places precursor solution, and will wherein being equipped with precursor solution that the surface is covered with the young crystal layer substrate of zinc oxide again, to place pressure be 4.5 * 10
5Pa, temperature are 98 ℃ of heating 100min down; Wherein, the thickness of the young crystal layer of the zinc oxide that substrate surface is covered with is 160nm, and substrate is a silicon chip.Then, take out substrate down in normal temperature, and the resultant on the water flushing substrate; Wherein, water is deionized water, and the number of times of flushing is 5 times, obtains to be similar to the zinc oxide nano rod/tower array on the substrate of placing shown in Fig. 4 (a) and Fig. 4 (b).Perhaps, use the hydrothermal method of prior art or chemical Vapor deposition process to obtain to be similar to the zinc oxide nano rod/tower array on the substrate of placing shown in Fig. 6 (a).B) refabrication Zinc oxide nano awl, its step be, earlier substrate and the zinc oxide nano rod/tower array on it being placed massfraction is that 1% ammonia soln is placed 2h, again with substrate with the intermediate product on it takes out and the water flushing; Wherein, water is deionized water, and the number of times of flushing is 5 times.Then, separate substrate and the product on it, wherein, separate substrate and the product on it are peeled off for using blade, make and be similar to shown in Fig. 1 (a), Fig. 1 (b), Fig. 2 (a) and Fig. 2 (b), shown in the curve among Fig. 3, and be similar to the Zinc oxide nano awl shown in Fig. 5 (b).
Embodiment 5: finish preparation according to the following steps successively: a) use hydrothermal method to make the zinc oxide nano rod/tower array that places on the substrate earlier, its step is, the first step, with massfraction is that 20% ammoniacal liquor is added dropwise in the zinc solution that concentration under stirring is 0.15M and obtains precursor solution, and ammoniacal liquor in the precursor solution and the volume ratio between zinc solution are 1:1000; Wherein, zinc solution is a liquor zinci chloridi, and the drop rate of ammoniacal liquor is 0.6ml/min, and ammoniacal liquor drips the back and continues to stir 30min.In second step, the substrate that earlier its surface is covered with the young crystal layer of zinc oxide places precursor solution, and will wherein being equipped with precursor solution that the surface is covered with the young crystal layer substrate of zinc oxide again, to place pressure be 5 * 10
5Pa, temperature are 100 ℃ of heating 70min down; Wherein, the thickness of the young crystal layer of the zinc oxide that substrate surface is covered with is 200nm, and substrate is a silicon chip.Then, take out substrate down in normal temperature, and the resultant on the water flushing substrate; Wherein, water is deionized water, and the number of times of flushing is 6 times, obtains to be similar to the zinc oxide nano rod/tower array on the substrate of placing shown in Fig. 4 (a) and Fig. 4 (b).Perhaps, use the hydrothermal method of prior art or chemical Vapor deposition process to obtain to be similar to the zinc oxide nano rod/tower array on the substrate of placing shown in Fig. 6 (a).B) refabrication Zinc oxide nano awl, its step be, earlier substrate and the zinc oxide nano rod/tower array on it being placed massfraction is that 1.25% ammonia soln is placed 1h, again with substrate with the intermediate product on it takes out and the water flushing; Wherein, water is deionized water, and the number of times of flushing is 6 times.Then, separate substrate and the product on it, wherein, separate substrate and the product on it are peeled off for using blade, make and be similar to shown in Fig. 1 (a), Fig. 1 (b), Fig. 2 (a) and Fig. 2 (b), shown in the curve among Fig. 3, and be similar to the Zinc oxide nano awl shown in Fig. 5 (a).
Select liquor zinci chloridi or zinc acetate solution or zinc nitrate solution more respectively for use as zinc solution, zinc or titanium or aluminium or silicon or germanium or conductive glass or glass or ceramic plate or vitrified pipe as substrate, the surface of above-mentioned substrate all is covered with the young crystal layer of zinc oxide, and as the deionized water or the distilled water of water, repeat the foregoing description 1～5, make equally as or be similar to Fig. 1 (a), Fig. 1 (b), shown in Fig. 2 (a) and Fig. 2 (b), shown in the curve among Fig. 3, and as or be similar to the Zinc oxide nano awl shown in Fig. 5 (a) or Fig. 5 (b) or Fig. 5 (c) or Fig. 5 (d).
If the Zinc oxide nano awl that makes is used in the mode of array, can in step, save the technology of the product on separate substrate and its in preparation at that time, can obtain being positioned at the Zinc oxide nano awl on the substrate.
Obviously, those skilled in the art can carry out various changes and modification to Zinc oxide nano awl of the present invention and preparation method thereof and not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (10)
1, a zinc oxide nano cone comprises zinc oxide, it is characterized in that said zinc oxide is the nano awl shape, and the awl length of said nano awl shape is that 2～2.5 μ m, auger directly are that 200～250nm, tapering are 3～15 degree.
2, Zinc oxide nano awl according to claim 1 is characterized in that the awl point diameter of nano awl is 6～15nm.
3, Zinc oxide nano awl according to claim 1 is characterized in that Zinc oxide nano awl is positioned on the substrate.
4, the preparation method of Zinc oxide nano awl according to claim 1, comprise that use hydrothermal method or chemical Vapor deposition process obtain to place the zinc oxide nano rod/tower array on the substrate, it is characterized in that finishing according to the following steps: earlier substrate and the zinc oxide nano rod/tower array on it being placed massfraction is that 0.5～1.25% ammonia soln is placed 1～5.5h, again substrate and the intermediate product on it are taken out also water flushing, then, separate substrate and the product on it make Zinc oxide nano awl.
5, the preparation method of Zinc oxide nano awl according to claim 4, it is characterized in that the hydrothermal method making places the step of the zinc oxide nano rod/tower array on the substrate to be: the first step, with massfraction is that 20～30% ammoniacal liquor is added dropwise in the zinc solution that concentration under stirring is 0.05～0.15M and obtains precursor solution, wherein, the volume ratio between ammoniacal liquor and zinc solution is 1: 800～1000; In second step, the substrate that earlier its surface is covered with the young crystal layer of zinc oxide places precursor solution, and will wherein being equipped with precursor solution that the surface is covered with the young crystal layer substrate of zinc oxide again, to place pressure be 2.5～5 * 10
5Pa, temperature are 90～100 ℃ of heating 70～200min down, then, take out substrate down in normal temperature, and the resultant on the water flushing substrate, obtain to place the zinc oxide nano rod/tower array on the substrate.
6, the preparation method of Zinc oxide nano awl according to claim 5 is characterized in that zinc solution is liquor zinci chloridi or zinc acetate solution or zinc nitrate solution.
7, the preparation method of Zinc oxide nano awl according to claim 5, the drop rate that it is characterized in that ammoniacal liquor is 0.6～0.8ml/min, ammoniacal liquor drips the back and continues to stir 10～30min.
8, the preparation method of Zinc oxide nano awl according to claim 5 is characterized in that the thickness of the young crystal layer of zinc oxide that substrate surface is covered with is 50～200nm.
9, the preparation method of Zinc oxide nano awl according to claim 5 is characterized in that substrate is metal or semi-conductor or isolator.
10, according to the preparation method of claim 4 or 5 described Zinc oxide nano awls, it is characterized in that water is deionized water or distilled water, the number of times of flushing is 3～6 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101914077A CN101457396B (en) | 2007-12-14 | 2007-12-14 | Zinc oxide nano awl and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101914077A CN101457396B (en) | 2007-12-14 | 2007-12-14 | Zinc oxide nano awl and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101457396A true CN101457396A (en) | 2009-06-17 |
| CN101457396B CN101457396B (en) | 2011-09-07 |
Family
ID=40768507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101914077A Expired - Fee Related CN101457396B (en) | 2007-12-14 | 2007-12-14 | Zinc oxide nano awl and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101457396B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491405A (en) * | 2011-11-18 | 2012-06-13 | 华东理工大学 | Composite nano-zinc oxide material and its preparation method |
| CN102644100A (en) * | 2011-02-18 | 2012-08-22 | 中国科学院合肥物质科学研究院 | Rod - acicular nanometer array and preparation method thereof |
| CN102024637B (en) * | 2009-09-17 | 2013-01-23 | 深圳华映显示科技有限公司 | Method for preparing zinc oxide nano column array field emission component |
| CN103303967A (en) * | 2012-03-08 | 2013-09-18 | 国家纳米科学中心 | Tower-shaped layered zinc oxide nanometer rod, and preparation method and application thereof |
| CN106290481A (en) * | 2015-05-11 | 2017-01-04 | 北京化工大学 | ZnO nano cone gas sensitive of Au load and its production and use |
| CN109459475A (en) * | 2018-12-28 | 2019-03-12 | 哈尔滨理工大学 | Au NPs/ zinc-oxide nano bores array/foamy graphite alkene electrode preparation and application |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011256B (en) * | 2012-12-28 | 2015-04-01 | 上海交通大学 | Method for preparing zinc oxide nanorod arrays in extra-large area |
-
2007
- 2007-12-14 CN CN2007101914077A patent/CN101457396B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102024637B (en) * | 2009-09-17 | 2013-01-23 | 深圳华映显示科技有限公司 | Method for preparing zinc oxide nano column array field emission component |
| CN102644100A (en) * | 2011-02-18 | 2012-08-22 | 中国科学院合肥物质科学研究院 | Rod - acicular nanometer array and preparation method thereof |
| CN102644100B (en) * | 2011-02-18 | 2014-07-16 | 中国科学院合肥物质科学研究院 | Rod - acicular nanometer array and preparation method thereof |
| CN102491405A (en) * | 2011-11-18 | 2012-06-13 | 华东理工大学 | Composite nano-zinc oxide material and its preparation method |
| CN103303967A (en) * | 2012-03-08 | 2013-09-18 | 国家纳米科学中心 | Tower-shaped layered zinc oxide nanometer rod, and preparation method and application thereof |
| CN103303967B (en) * | 2012-03-08 | 2014-10-01 | 国家纳米科学中心 | Tower-shaped layered zinc oxide nanometer rod, and preparation method and application thereof |
| CN106290481A (en) * | 2015-05-11 | 2017-01-04 | 北京化工大学 | ZnO nano cone gas sensitive of Au load and its production and use |
| CN109459475A (en) * | 2018-12-28 | 2019-03-12 | 哈尔滨理工大学 | Au NPs/ zinc-oxide nano bores array/foamy graphite alkene electrode preparation and application |
| CN109459475B (en) * | 2018-12-28 | 2020-10-27 | 哈尔滨理工大学 | Preparation and application of Au NPs/zinc oxide nanocone array/foam graphene electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101457396B (en) | 2011-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101457396B (en) | Zinc oxide nano awl and preparation method thereof | |
| Zhang et al. | Low‐temperature fabrication of highly crystalline SnO2 nanorods | |
| Qiu et al. | Sol–gel assisted ZnO nanorod array template to synthesize TiO2 nanotube arrays | |
| Hu et al. | Development of a wet chemical method for the synthesis of arrayed ZnO nanorods | |
| Hiralal et al. | Growth and process conditions of aligned and patternable films of iron (III) oxide nanowires by thermal oxidation of iron | |
| KR101102098B1 (en) | Method for Producing Branched Nanowire | |
| CN1884091A (en) | Process for preparing nano ZnO | |
| CN102079506A (en) | Preparation method of bent silicon nanowire array with changeable direction | |
| CN102024637B (en) | Method for preparing zinc oxide nano column array field emission component | |
| KR20080084193A (en) | Method for mass producing nanostructure using mesoporous template and nanostructure made thereof | |
| TWI683786B (en) | Two-dimensional semiconductor with geometry structure and generating method thereof | |
| Nam et al. | Rutile structured SnO2 nanowires synthesized with metal catalyst by thermal evaporation method | |
| CN103864460A (en) | Preparation method of sequenced tungsten oxide nanowire array structure | |
| Xie et al. | In situ formation of indium catalysts to synthesize crystalline silicon nanowires on flexible stainless steel substrates by PECVD | |
| CN100336722C (en) | One-dimensional ring shaped Nano silicon material and preparation | |
| Jeon et al. | Synthesis of gallium-catalyzed silicon nanowires by hydrogen radical-assisted deposition method | |
| Le Shim et al. | Large enhancement of field emission from ZnO nanocone arrays via patterning process | |
| Shan et al. | Controlled growth of highly ordered CdSe one-dimensional nanostructures | |
| CN102644100A (en) | Rod - acicular nanometer array and preparation method thereof | |
| Bai et al. | Nucleation and growth of boron nanowires on diamond particles | |
| Hamidinezhad et al. | Vertically-tapered silicon nanowire arrays prepared by plasma enhanced chemical vapor deposition: Synthesis, structural characterization and photoluminescence | |
| CN1944267A (en) | Process for preparing tipped gallium nitride conical stick using self catalytic mode | |
| CN1958877A (en) | Periodic monocrystalline Nano structure of castellated ZnO, preparation method | |
| Das et al. | Synthesis of ZnO nanowire by MOCVD technique: effect of substrate and growth parameter | |
| CN104401936B (en) | A kind of method at substrate level direction controllable growth carbon nano-tube bundle |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110907 Termination date: 20131214 |