CN105947974A - Cross-shaped laser ablation tube-type furnace used for Zinc oxide nanowires and array growth - Google Patents

Cross-shaped laser ablation tube-type furnace used for Zinc oxide nanowires and array growth Download PDF

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CN105947974A
CN105947974A CN201610283003.XA CN201610283003A CN105947974A CN 105947974 A CN105947974 A CN 105947974A CN 201610283003 A CN201610283003 A CN 201610283003A CN 105947974 A CN105947974 A CN 105947974A
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zinc oxide
substrate
density
target
cross
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曹丙强
邱智文
杨晓朋
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University of Jinan
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B3/0004—Apparatus specially adapted for the manufacture or treatment of nanostructural devices or systems or methods for manufacturing the same
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B28/00—Production of homogeneous polycrystalline material with defined structure
    • C30B28/02—Production of homogeneous polycrystalline material with defined structure directly from the solid state
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides

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Abstract

The invention discloses a cross-shaped laser ablation tube-type furnace used for Zinc oxide nanowires and array growth. The cross-shaped laser ablation tube-type furnace comprises a target material control system, a carrier gas flow control system, a liner heating system, a furnace body, a cross-shaped quartz tube, and a vacuum acquisition and control system. The cross-shaped laser ablation tube-type furnace is featured by high vacuum, convenient replacement of target material, flexible and changeable experiment schemes and real-time doping and adjustable sedimentation rate. (1) Through the cross-shaped laser ablation tube-type furnace, Zinc oxide nanowire arrays of high density (10/microns 2) grow on a sapphire liner. (2) Through a layer of Zinc oxide buffer layer growing on a liner, Zinc oxide nanowire arrays of low density (0.1/microns 2) grow on a sapphire liner. (3) density of Zinc oxide nanowire arrays growing the buffer layer varies with the increase of distance between the target material and liners.

Description

A kind of cross for zinc oxide nanowire and array growth ( + ) type laser ablation tube furnace
Technical field
The present invention relates toA kind of cross for zinc oxide nanowire and array growth ( + ) type laser ablation tube furnace, it is achieved the growth of zinc oxide nanowire, especially achieve the regulation and control on a large scale to nanowire array growth density.
Background technology
Zinc oxide is a kind ofNovelII～VI race's direct wide bandgap compound semiconductors material, there is the optically and electrically characteristic of excellence, band gap under room temperature is 3.37eV, exciton bind energy is 60meV, big hot ionization energy (25meV) at room temperature, possess transmitting blue light or the supremacy clause of black light, the multiple luminescent device such as ultraviolet, blue and green light can have been developed.Zinc oxide nanowire is the emphasis that people study owing to having the physical property of size, dimension and the novelty of uniqueness.At the zinc oxide nano-wire array of Grown, owing to having the unified direction of growth, can be used to assemble nanometer laser line generator, EED and nano wire electromotor etc..The preparation method of zinc oxide nano-wire array can be divided into liquid phase method and vapor phase method two kinds.As disclosed " a kind of method of low temperature controllable preparation of zinc oxide nano line and application thereof " in Chinese invention patent application prospectus CN 101319372A disclosed in December in 2008 10 days.It is intended to provide a kind of seed grown with the zinc oxide being previously deposited or metallic zinc as zinc oxide nanowire, realizes the regulation and control of zinc oxide nanowire stand density.But, this preparation method also exists weak point, firstly, it is necessary to the thickness strictly controlling Seed Layer realizes the control to nanowire growth density；Secondly, with the bad control of the orientation on substrate of the zinc oxide nanowire of solution growth.This will directly affect the zinc oxide nano-wire array application in fields such as Flied emission, nano wire electromotors.For another example in Chinese invention patent application prospectus CN 101311358A disclosed in 26 days November in 2008, disclose one " method of preparing zinc oxide nanometer wire array by femtosecond laser and device thereof ".It is intended to provide one femtosecond laser radiation field to control to realize zinc oxide nanowire cyclical growth by two dimension accurate displacement on zinc oxide target.But, this preparation method there is also weak point, and first, this method is directly to grow nano wire on target, and prepared nano wire is unfavorable for that secondary utilizes；Secondly, need precision optical machinery control station to realize the cyclical growth of nano wire, and density domination cannot be realized.
Summary of the invention
It is an object of the invention to overcome the deficiency of above-mentioned existing technologies, there is provided a kind of cross for oxide nano thread and array growth (+) type laser ablation tube furnace, this device has target and changes conveniently, experimental program is flexible and changeable, can adulterate in real time, the advantages such as sedimentation rate is adjustable, this device of what is more important can regulate the stand density of zinc oxide nanowire on a large scale.
The inventive method technical solution is: realize the regulation and control on a large scale of zinc oxide nano-wire array stand density by introducing the distance between zinc bloom buffer layer and regulation target and substrate, it specifically comprises the following steps that
(1) use cross (+) type laser ablation tube furnace on a sapphire substrate, direct growth high-density zinc oxide nano-wire array；
(2) by introducing one layer of zinc bloom buffer layer on a sapphire substrate, the growth of low-density zinc oxide nano-wire array is realized；
(3) by the distance between regulation target and substrate, it is achieved the regulation and control from low to high of zinc oxide nanowire stand density.
Described high pressure laser ablation is that the pulsed excimer laser with wavelength as 248nm irradiates pure zinc oxide target, and energy density is at 1-3J/cm2Between, and under Ar gas transport effect, deposit in Sapphire Substrate.
Described high density refers to that zinc oxide nanowire stand density numerical value on substrate is in 1/ μm2Above.
Described zinc bloom buffer layer refers to by the traditional laser pulse deposition growing zinc-oxide film that a layer thickness is 20-50nm on a sapphire substrate.
Described low-density refers to that zinc oxide nanowire stand density numerical value on substrate is in 1/ μm2Below.
The regulation and control from low to high of described zinc-oxide nano line length density refer to that nanowire growth density is from 0.1/ μm2To 10/ μm2Between change.
The invention has the advantages that: utilize buffer layer technique to achieve the growth of low-density zinc oxide nanowire, and by the distance between regulation target and substrate, it is achieved that the regulation and control on a large scale of zinc oxide nanowire stand density.This invention growth technique is simple, reproducible, and preparation efficiency is high, and prepared zinc oxide nano-wire array is uniform, and crystal mass is high, can meet zinc oxide nanowire and must apply in terms of FED and photoelectric device.
Accompanying drawing explanation
Figure 1Cross for oxide nano thread and array growth used in the present invention (+) signal of type laser ablation tube furnaceFigure。
Figure 2UseFigure 1In equipment, the electron scanning micrograph of the high-density zinc oxide nano-wire array grown on a sapphire substrate.
Figure 3Zinc bloom buffer layer thick for one layer of 50nm of growth the most on a sapphire substrate, then utilizesFigure 2In the electron scanning micrograph of the low-density zinc oxide nano-wire array prepared by growth conditions.
Figure 4There is the sapphire of zinc bloom buffer layer as substrate with growth, useFigure 2In method, the distance between regulation target and substrate, and the zinc oxide nano-wire array of the different densities grown.Figure 4-1, 4-2,4-3 distance between corresponding target and substrate respectively be 12,9,6mm.
Figure 5The modification scope of the zinc oxide nano-wire array stand density that the present invention is realized: from 0.1/ μm2To 10/ μm2。
Detailed description of the invention
Below in conjunction withAccompanying drawingPresent disclosure is described in further detail, but the invention is not restricted to the specific examples being exemplified below.
Attached Figure 1It it is used growth apparatus signalFigure.One wavelength is the KrF laser of 248 nanometers, arrives on zinc oxide target along quartz ampoule axial line after lens focus.The dead ahead of target is placed with a growth substrates.Owing to target absorbs the high-energy of laser, melted rapidly and be evaporated to oxygen and the zinc of plasma state.?In figureUnder the conveying of shown flowing carrier gas, the oxygen of plasma state and zinc deposit on substrate and grow into one-dimensional zinc oxide nano-wire array.
Attached Figure 2Be withAccompanying drawing 1The highdensity zinc oxide nano-wire array of middle method growth, generally its density can be up to 10/ μm2. the substrate used is the sapphire (Al of a orientation2O3), the carrier gas used is high-purity argon gas (Ar), and the wavelength of laser is 248nm, and energy density is 2J/cm2, frequency is 10Hz, and growth time is 10 minutes.Growth pressure in quartz ampoule is 100mbar, and growth temperature is 800 ° of C.Distance between target and substrate is 15mm.
Attached Figure 3Be withAccompanying drawing 1The low-density zinc oxide nano-wire array of middle method growth, generally its density is only 0.1/ μm2.The substrate used is the sapphire (Al of a orientation that grown one layer of zinc bloom buffer layer2O3) substrate.Prepared by zinc bloom buffer layer traditional laser pulse sedimentation, thickness is 30nm.The carrier gas used is high-purity argon gas (Ar), and the wavelength of laser is 248nm, and energy density is 2J/cm2, frequency is 10 hertz, and growth time is 10 minutes.Growth pressure in quartz ampoule is 100mbar, and growth temperature is 800 ° of C.Distance between target and substrate is 7mm.
Accompanying drawing 4 is that its density is between 1/ μm with the low-density zinc oxide nano-wire array of method growth in Fig. 12-0.1/μm2Between. the substrate used is the sapphire (Al of a orientation that grown one layer of zinc bloom buffer layer2O3).Prepared by zinc bloom buffer layer traditional laser pulse sedimentation, thickness is 30nm.The carrier gas used is high-purity argon gas (Ar), and the energy density of laser is 2J/cm2, frequency is 10Hz, and growth time is 10 minutes.Growth pressure in quartz ampoule is 100mbar, and growth temperature is 800 ° of C.Distance between target and substrate that Fig. 4-1, tri-stereoscan photograph of 4-2,4-3 are corresponding is respectively 12mm, 9mm, 6mm.
Embodiment 1(growth of high-density zinc oxide nano wire)
(1) with Zinc oxide powder that purity is 99.999% as raw material, through tabletting and sintering process, the target of zinc oxide is made；
(2) target is fixed onAccompanying drawing 1Shown position, and drive at the uniform velocity (20-30 rev/min) to rotate by external motors；
(3) diameter of quartz ampoule is 50mm, and growth temperature is 825 ° of C, and carrier gas is high-purity argon gas, and flow is 50SCCM, and substrate is the sapphire (Al that a tends to2O3), size 1 × 1cm2；
(4) working condition of laser is: wavelength 248nm, frequency 10Hz, energy density 2J/cm2, growth air pressure is 100mbar；Growth time is 20 minutes；
(5) distance between target and substrate can be between 10mm-35mm.
Embodiment 2(growth of low-density zinc oxide nanowire)
(1) used substrate is to grown the sapphire (Al that a of zinc bloom buffer layer tends to2O3), size 1 × 1cm2, the thickness 20nm-50nm of cushion；
(2) the pulsed laser deposition growth conditions of zinc bloom buffer layer is: growth air pressure 10-4Mbar, background gas is oxygen, 625 ° of C of growth temperature；The working condition of laser is: wavelength 248nm, frequency 10Hz, energy density 3J/cm2, growth time is 2 minutes；
(3) with Zinc oxide powder that purity is 99.999% as raw material, through tabletting and sintering process, the target of zinc oxide is made；
(4) target is fixed onFigure 1Shown position, and by driving at the uniform velocity (20-30 rev/min) to rotate with external motors；
(5) diameter of quartz ampoule is 50mm, and growth temperature is 825 ° of C, and carrier gas is high-purity argon gas, and flow is 50SCCM；
(6) growth air pressure is 100mbar；Growth time is 20 minutes；
(7) typical range between target and substrate is 6mm.
Embodiment 3(growth of the zinc oxide nano-wire array of different densities)
(1)-(6) are with above-described embodiment 2；
(7) distance between target and substrate is increased to 9mm, 12mm and 15mm successively from 6mm.Research shows, along with target and the increase of the spacing of substrate, the density of zinc oxide nanowire arrays is gradually increased.
To sum up experimental result, can realize the controllable growth of zinc oxide nano-wire array by the present invention, and its stand density can be from 0.1/ μm2To 10/ μm2Regulation between four orders of magnitude, asAccompanying drawing 5Shown in.The growth of the zinc oxide nano-wire array that density is controlled is respectively provided with vital science and realistic meaning to semiconductor heterostructure, field emission display and the nano generator of assembling zinc oxide nano wire.

Claims (7)

1. the cross for zinc oxide nanowire and array growth (+) type laser ablation tube furnace, including target control system, carrier gas flux control system, substrate heating system, body of heater, cross quartz ampoule, vacuum acquirement and control system, its concrete technology step is as follows:
Selecting wavelength is the pulse laser of 248nm, in a convex lens focus to oxide target material；
The substrate selected is sapphire, monocrystal silicon and zinc bloom buffer layer, and target is the oxide ceramics sheet after sintering, and thickness is 10mm-15mm, a diameter of 27mm-30mm；
By controlling pulse laser single pulse energy 100mJ-700mJ, pulse frequency 1Hz-20Hz, make laser action on zinc oxide target, grow air pressure 80mbar-350mbar, the distance between regulation and control target and substrate, nano-wire array can be obtained on substrate；
By high-voltage pulse laser ablation methods, can growing high density (10/ μm on a sapphire substrate2) zinc oxide nano-wire array；
By at one layer of zinc bloom buffer layer of Grown, (0.1/ μm can be substantially reduced with the zinc-oxide nano line density of above-mentioned high-voltage pulse laser ablation methods growth2)；
The density of the zinc oxide nano-wire array grown on the buffer layer, along with target increases with the increase of the spacing of substrate.
Density the most according to claim 1 is controlled, it is characterised in that: its density values excursion is from 0.1/ μm2To 10/ μm2。
High-voltage pulse laser ablation methods the most according to claim 1, it is characterised in that: growth pressure is 80mbar-350mbar, and quartz ampoule is shaped as cross.
Sapphire Substrate the most according to claim 1, it is characterised in that: crystal face is a face or c face, and monocrystalline substrate crystal face is (100).
Target the most according to claim 1 and the spacing of substrate, it is characterised in that: its numerical value is between 5mm-35mm.
Zinc bloom buffer layer the most according to claim 1, it is characterised in that: the thickness of cushion is between 20nm-50nm.
The density of the zinc oxide nano-wire array grown on the buffer layer the most according to claim 1 increases with the increase of the spacing of substrate along with target, it is characterised in that: its change in value scope is from 0.1/ μm2To 1/ μm2。
CN201610283003.XA 2016-05-03 2016-05-03 Cross-shaped laser ablation tube-type furnace used for Zinc oxide nanowires and array growth Pending CN105947974A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108115146A (en) * 2017-12-20 2018-06-05 东南大学 A kind of preparation method of zinc oxide@zinc microballoons

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101030596A (en) * 2007-03-30 2007-09-05 中山大学 Heterogeneous p-n nano-line array, its production and use
CN102115339A (en) * 2010-01-06 2011-07-06 济南大学 Laser ablation growing method of zinc oxide nanowire array with controllable density
CN102115027A (en) * 2010-01-06 2011-07-06 济南大学 Preparation method and application of zinc oxide thin film

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101030596A (en) * 2007-03-30 2007-09-05 中山大学 Heterogeneous p-n nano-line array, its production and use
CN102115339A (en) * 2010-01-06 2011-07-06 济南大学 Laser ablation growing method of zinc oxide nanowire array with controllable density
CN102115027A (en) * 2010-01-06 2011-07-06 济南大学 Preparation method and application of zinc oxide thin film

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108115146A (en) * 2017-12-20 2018-06-05 东南大学 A kind of preparation method of zinc oxide@zinc microballoons
CN108115146B (en) * 2017-12-20 2019-10-11 东南大学 A kind of preparation method of zinc oxide@zinc microballoon

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Application publication date: 20160921