CN102115339A - Laser ablation growing method of zinc oxide nanowire array with controllable density - Google Patents
Laser ablation growing method of zinc oxide nanowire array with controllable density Download PDFInfo
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- CN102115339A CN102115339A CN2010100116029A CN201010011602A CN102115339A CN 102115339 A CN102115339 A CN 102115339A CN 2010100116029 A CN2010100116029 A CN 2010100116029A CN 201010011602 A CN201010011602 A CN 201010011602A CN 102115339 A CN102115339 A CN 102115339A
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Abstract
The invention relates to a high-voltage laser ablation preparation method of a zinc oxide nanowire material, and the method is especially used for realizing the extensive regulation of the growing density of a nanowire array. The extensive regulation of the growing density of the zinc oxide nanowire array is realized through introducing a zinc oxide buffer layer and regulating the distance between a target material and a substrate. By adopting a high-voltage pulse laser ablation technology, not only can the growth of the high-density zinc oxide nanowire array be realized, but also the growth of the low-density zinc oxide nanowire array is realized by virtue of the buffer layer. In addition, through the regulation of the distance between the target material and the substrate, the extensive regulation of the growing density of the zinc oxide nanowire is realized.
Description
Technical field
The present invention relates to a kind of high pressure laser ablation preparation method of zinc-oxide nano wire material, especially realized regulation and control on a large scale the nano-wire array stand density.
Background technology
Zinc oxide is a kind of novel II～direct wide bandgap compound semiconductors material of VI family, have excellent optics and electrology characteristic, band gap under the room temperature is 3.37eV, exciton bind energy is 60meV, greater than the hot ionization energy (25meV) under the room temperature, possessed the supremacy clause of emission blue light or near-ultraviolet light, can develop multiple luminescent devices such as ultraviolet, blue light, green glow.Zinc oxide nanowire is the emphasis that people study owing to having unique size, dimension and novel physical character.The zinc oxide nano-wire array of growing on substrate owing to have the unified direction of growth, can be used for assemble nanometer laser line generator, Field Emission Display and nano wire generator etc.The preparation method of zinc oxide nano-wire array can be divided into two kinds of liquid phase method and vapor phase processs.As having disclosed " a kind of method of low temperature controllable preparation of zinc oxide nano line and application thereof " among the disclosed Chinese invention patent ublic specification of application CN 101319372A on December 10th, 2008.It provides sedimentary in advance zinc oxide of a kind of usefulness or metallic zinc as the seed of zinc oxide nanowire growth, realizes the regulation and control of zinc oxide nanowire stand density.But this preparation method exists weak point: at first, the thickness that needs strictness to control Seed Layer is realized the control to nanowire growth density; Secondly, use the bad control of the orientation of zinc oxide nanowire on substrate of solution growth.This will directly influence the application in fields such as zinc oxide nano-wire array emission on the scene, nano wire generator.Disclosed among the disclosed Chinese invention patent ublic specification of application CN 101311358A on November 26th, 2008 for another example in a kind of " method of preparing zinc oxide nanometer wire array by femtosecond laser and device thereof ".It provides a kind of control by two-dimentional accurate displacement on the zinc oxide target with the femtosecond laser radiation field to realize that zinc oxide nanowire periodically grows.But this preparation method also exists weak point: at first, this method is direct grow nanowire on target, and prepared nano wire is unfavorable for second stage employ; Secondly, need the precision optical machinery supervisory control desk to realize the periodicity growth of nano wire, and can't realize density control.
Summary of the invention
The objective of the invention is to overcome above-mentioned technological deficiency, realized the regulation and control on a large scale of zinc oxide nano-wire array stand density by the distance between introducing zinc bloom buffer layer and adjusting target and the substrate.
Zinc oxide nano-wire array can be divided into high-density zinc oxide nano-wire array and low density zinc oxide nano-wire array.
Said high-density is meant that the stand density numerical value of zinc oxide nanowire on substrate is at 1/ μ m
2More than.
Said low density is meant that the stand density numerical value of zinc oxide nanowire on substrate is at 1/ μ m
2Below.
On ethereal blue jewel substrate, by the high-voltage pulse laser ablation methods, but growing high density 10-50/ μ m
2Zinc oxide nano-wire array;
Growth one deck zinc bloom buffer layer on Sapphire Substrate, by the high-voltage pulse laser ablation methods, the low density of can growing 0.01-1/ μ m
2Zinc oxide nano-wire array;
Said zinc bloom buffer layer is meant that a layer thickness that is grown on the Sapphire Substrate by the conventional low pulsed laser deposition is the zinc-oxide film of 20nm-500nm.
Zinc-oxide nano line length density of the present invention regulation and control from low to high are meant that nanowire growth density is from 0.1/ μ m
2To 10/ μ m
2Between change.
Wherein adopt the high pressure laser ablation method directly to prepare the method for high-density zinc oxide nano-wire array, its concrete steps are:
The high pressure laser ablation method is that this KrF laser is arrived on the zinc oxide target along the silica tube axial line later on through lens focus, and the right on of target is placed with a sapphire Al
2O
3The oxygen and the zinc of plasma state is melted and be evaporated to growth substrates because target absorbs the high-energy of laser, rapidly; Wavelength of Laser is 248nm, and energy density is 1-3J/cm
2, frequency is 1Hz-10Hz, and the growth pressure in the silica tube is 20mbar-100mbar, and growth temperature is 750 ℃-800 ℃, and growth time is 10 minutes-30 minutes; Distance between target and the substrate is 6mm～15mm; Under the conveying of the carrier gas high-purity argon gas Ar that flows, the oxygen of plasma state and zinc deposit on substrate and grow into the unidimensional zinc oxide nano-wire array.
Wherein adopt the method for the low-density zinc oxide nano-wire array of high pressure Prepared with Laser Ablation, its concrete steps are:
Adopt the conventional low pulsed laser deposition at sapphire Al
2O
3Growth one deck zinc bloom buffer layer on the substrate, wherein the thickness of zinc bloom buffer layer is 20nm-500nm, and Wavelength of Laser is 248nm, and energy density is 2J-3J/cm
2Frequency is 2Hz-10Hz, and through arriving on the zinc oxide target along the silica tube axial line after the lens focus, the right on of target is placed with a growth substrates with this KrF laser, because target absorbs the high-energy of laser, melted and be evaporated to the oxygen and the zinc of plasma state rapidly; Growth pressure in the silica tube is 20mbar-100mbar, and growth temperature is 800 ℃, and growth time is 10 minutes-30 minutes; Distance between target and the substrate is 6mm～15mm.
Silica tube wherein recited above is shaped as the T type.
Beneficial effect of the present invention is: by the high-voltage pulse laser ablation technology, not only realized the growth of high-density zinc oxide nano-wire array, and utilize the buffer layer technology to realize the growth of low density zinc oxide nanowire, and then, the regulation and control on a large scale of zinc oxide nanowire stand density have been realized by regulating the distance between target and the substrate.This invention growth technique is simple, good reproducibility, and the preparation efficiency height, prepared zinc oxide nano-wire array is even, and the crystal mass height can satisfy zinc oxide nanowire and must use aspect Field Emission Display and the photoelectric device.
Description of drawings
Accompanying drawing 1 is a growth apparatus synoptic diagram of the present invention.The KrF excimer laser that wavelength is 248 nanometers is through arriving on the zinc oxide target along the silica tube axial line after the lens focus.The right on of target is placed with a growth substrates.Because target absorbs the high-energy of laser, melted and be evaporated to the oxygen and the zinc of plasma state rapidly.Under the conveying of mobile carrier gas shown in the figure, the oxygen of plasma state and zinc deposit on substrate and grow into the unidimensional zinc oxide nano-wire array.
Accompanying drawing 2 is with the growth apparatus in the accompanying drawing 1, the electron scanning micrograph of the high-density zinc oxide nano-wire array of growing on Sapphire Substrate.Usually its density can be up to 10/ μ m
2. the substrate that is adopted is the sapphire (Al of a orientation
2O
3), the carrier gas of being adopted is high-purity argon gas (Ar), and Wavelength of Laser is 248nm, and energy density is 2J/cm
2, frequency is 10Hz, growth time is 10 minutes.Growth pressure in the silica tube is 100mbar, and growth temperature is 800 ℃.Distance between target and the substrate is 15mm.
Accompanying drawing 3 is with the growth apparatus in the accompanying drawing 1, at the sapphire (Al of one deck zinc bloom buffer layer that grown
2O
3) electron scanning micrograph of the low density zinc oxide nano-wire array of growing on the substrate, its density only is 0.1/ μ m
2. zinc bloom buffer layer prepares with the conventional low pulsed laser deposition, and thickness is 30nm.The carrier gas of being adopted is high-purity argon gas (Ar), and Wavelength of Laser is 248nm, and energy density is 2J/cm
2, frequency is 10 hertz, growth time is 10 minutes.Growth pressure in the silica tube is 100mbar, and growth temperature is 800 ℃.Distance between target and the substrate is 7mm.
Accompanying drawing 4 is electron scanning micrographs of the zinc oxide nano-wire array with different densities of being grown with the growth apparatus among Fig. 1, and its density is between 1/ μ m
2-0.1/ μ m
2Between. the substrate that is adopted is the sapphire (Al of one deck zinc bloom buffer layer of having grown
2O
3).Zinc bloom buffer layer prepares with traditional pulsed laser deposition, and thickness is 30nm.The carrier gas of being adopted is high-purity argon gas (Ar), and the energy density of laser is 2J/cm
2, frequency is 10 hertz, growth time is 10 minutes.Growth pressure in the silica tube is 100mbar, and growth temperature is 800 ℃.The target of three the stereoscan photograph correspondences in upper, middle and lower and the distance between the substrate are respectively 12mm, 9mm, 6mm among Fig. 4.
The modification scope of the zinc oxide nano-wire array stand density that accompanying drawing 5 the present invention are realized: from 0.1/ μ m
2To 10/ μ m
2
Embodiment
Further specify technical scheme of the present invention below by embodiment, but technical scheme of the present invention is not exceeded with embodiment.
Embodiment 1
The growth of high-density zinc oxide nanowire (10/ μ m
2)
(1) is that 99.999% Zinc oxide powder is a raw material with purity,, makes the target of zinc oxide through compressing tablet and sintering process.
(2) target is fixed in position shown in the accompanying drawing 1, and drives at the uniform velocity (20-30 rev/min) rotation by external motors.
(3) diameter of silica tube is 50mm, and growth temperature is 825 ℃, and carrier gas is a high-purity argon gas, and flow is 50SCCM, and substrate is the sapphire (Al of a trend
2O
3), size 1 * 1cm
2
(4) working conditions of laser is: wavelength 248nm, frequency 10Hz, energy density 2J/cm
2
(5) growth air pressure is 100mbar; Growth time is 20 minutes.
(6) distance between target and the substrate is 15mm.
Embodiment 2
The growth of low density zinc oxide nanowire (0.1/ μ m
2)
(1) substrate that adopts is the sapphire (Al of a trend of zinc bloom buffer layer of having grown
2O
3), size 1 * 1cm
2, the thickness 40nm of buffer layer; Wherein the pulsed laser deposition growth conditions of buffer layer is: growth air pressure 10-4mbar, and background atmosphere is oxygen, 625 ℃ of growth temperatures; The working conditions of laser is: wavelength 248nm, frequency 10Hz, energy density 3J/cm
2, growth time is 2 minutes;
(2) be that 99.999% Zinc oxide powder is a raw material with purity,, make the target of zinc oxide through compressing tablet and sintering process;
(3) target is fixed in position shown in Figure 1, and (20-30 rev/min) rotates by driving at the uniform velocity with external motors;
(4) diameter of silica tube is 50mm, and growth temperature is 825 ℃, and carrier gas is a high-purity argon gas, and flow is 50SCCM; Growth air pressure is 100mbar; Growth time is 20 minutes;
(5) distance between target and the substrate is 6mm.
Embodiment 3
The growth of the zinc oxide nano-wire array of different densities
(1)-(6) with above-mentioned embodiment 2.
(7) distance between target and the substrate increases successively from 6mm and is 9mm, 12mm and 15mm.The result shows that along with the increase of distance between target and the substrate, it is 0.3/ μ m that the density of zinc oxide rice noodles array increases gradually
2, 0.5/ μ m
2, 1/ μ m
2
Experimental result to sum up can realize the controllable growth of zinc oxide nano-wire array by the present invention, and its stand density can be realized from 0.1/ μ m
2To 10/ μ m
2Adjusting between four orders of magnitude, as shown in Figure 5.The growth of the zinc oxide nano-wire array of controllable density all has vital science and realistic meaning to semiconductor heterostructure, field emission display and the nano generator of assembling zinc oxide nano wire.
Claims (4)
1. the preparation method of a controllable density zinc oxide nano-wire array is characterized in that: on ethereal blue jewel substrate, and by the high-voltage pulse laser ablation methods, the growth of zinc oxide nano linear array.
2. the preparation method of controllable density zinc oxide nano-wire array as claimed in claim 1 is characterized in that: growth one deck zinc bloom buffer layer on Sapphire Substrate, growth low density zinc oxide nano-wire array.
3. the preparation method of controllable density zinc oxide nano-wire array as claimed in claim 1 or 2, it is characterized in that: by regulating the distance between target and the substrate, realize the regulation and control from low to high of zinc oxide nanowire stand density, wherein the distance between target and the substrate is 6mm～15mm.
4. the preparation method of controllable density zinc oxide nano-wire array as claimed in claim 2 is characterized in that: the thickness of described zinc bloom buffer layer is 20nm-500nm.
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|---|---|---|---|
| CN2010100116029A CN102115339A (en) | 2010-01-06 | 2010-01-06 | Laser ablation growing method of zinc oxide nanowire array with controllable density |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103526165A (en) * | 2013-10-21 | 2014-01-22 | 京东方科技集团股份有限公司 | Transparent conducting thin film as well as preparation method thereof, display base plate and display device |
| CN105839055A (en) * | 2016-03-21 | 2016-08-10 | 王烨 | Method for preparation of one-dimensional-nanostructure zinc oxide by thin film deposition |
| CN105947974A (en) * | 2016-05-03 | 2016-09-21 | 济南大学 | Cross-shaped laser ablation tube-type furnace used for Zinc oxide nanowires and array growth |
| CN107344868A (en) * | 2016-05-06 | 2017-11-14 | 山东大学 | A kind of method for the single-layer graphene for preparing no cushion on sic substrates |
-
2010
- 2010-01-06 CN CN2010100116029A patent/CN102115339A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103526165A (en) * | 2013-10-21 | 2014-01-22 | 京东方科技集团股份有限公司 | Transparent conducting thin film as well as preparation method thereof, display base plate and display device |
| WO2015058551A1 (en) * | 2013-10-21 | 2015-04-30 | 京东方科技集团股份有限公司 | Transparent conductive film and preparation method, display substrate and display device therefor |
| CN105839055A (en) * | 2016-03-21 | 2016-08-10 | 王烨 | Method for preparation of one-dimensional-nanostructure zinc oxide by thin film deposition |
| CN105947974A (en) * | 2016-05-03 | 2016-09-21 | 济南大学 | Cross-shaped laser ablation tube-type furnace used for Zinc oxide nanowires and array growth |
| CN107344868A (en) * | 2016-05-06 | 2017-11-14 | 山东大学 | A kind of method for the single-layer graphene for preparing no cushion on sic substrates |
| CN107344868B (en) * | 2016-05-06 | 2019-08-27 | 山东大学 | A method of preparing the single-layer graphene of no buffer layer on sic substrates |
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Application publication date: 20110706 |