CN104593733B - The pulsed laser deposition preparation method of copper doped zinc oxide nanometer rods - Google Patents
The pulsed laser deposition preparation method of copper doped zinc oxide nanometer rods Download PDFInfo
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- CN104593733B CN104593733B CN201510079267.9A CN201510079267A CN104593733B CN 104593733 B CN104593733 B CN 104593733B CN 201510079267 A CN201510079267 A CN 201510079267A CN 104593733 B CN104593733 B CN 104593733B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
Abstract
The pulsed laser deposition preparation method of copper doped zinc oxide nanometer rods, it relates to the deposition process of a kind of air-sensitive nano material.The present invention is to solve that the existing method preparing copper doped zinc oxide nanometer rods exists that chemical raw material kind is many, course of reaction is complicated, the problem being readily incorporated impurity.This method is as follows: one, copper zinc oxide ceramic target is mixed in preparation；Two, utilize pulse laser that target is carried out ablation, it is thus achieved that inculating crystal layer；Three, laser ablation target 20 120min, must mix copper nano structure of zinc oxide.The present invention uses pulsed laser deposition preparation to mix copper zinc oxide nano rod, uses raw material simple, only needs two kinds of raw materials, and produces in the vacuum chamber, and sample crystalline quality is high, it is to avoid introduce impurity, and doping component controllability is good.The invention belongs to the preparation field of copper doped zinc oxide nanometer rods.
Description
Technical field
The present invention relates to a kind of air-sensitive depositing nano-materials method.
Background technology
Zinc oxide is traditional gas sensitive, to ethanol, NH3、NOxGood air-sensitive is had to respond Deng gas, and the most several
Year along with the progress of science and technology and industrial expansion, hydrogen sulfide in the substantial amounts of use of industrial circle, and hydrogen sulfide gas to be one have
Poison, there is corrosive gas, even if being exposed to same meeting in several hours in the hydrogen sulfide gas of very low concentrations (< 20ppm)
Human body is produced the most serious harm with industrial products.And pure zinc oxide nano material is due to the restriction of material property itself,
Gas the most well response to low concentration hydrogen sulfide, needing just can be to sulfuration in higher temperature (about 300 DEG C)
Hydrogen responds, and greatly reduces the using value that hydrogen sulfide gas is sensed by pure zinc oxide material in the suitability.The most several
Year, people are shown by research, and hydrogen sulfide gas is had preferable air-sensitive to respond by the zinc oxide nano rod of Copper-cladding Aluminum Bar, but
People prepare wet chemical method [Li T, Fan H M, Yi J B, the Herng such as the commonly used hydro-thermal of nano zinc oxide material of Copper-cladding Aluminum Bar
T S, Ma Y W, Huang X L, Xue J M and Ding J, 2010, J.Mater.Chem., 20,5756-5762] and middle promulgated by the State Council
Bright patent [Li Ying etc., copper doped zinc oxide meets the hydrothermal preparing process of lithium iron phosphate positive material, application number:
201110187303.5], raw material time prepared by wet chemical method is more, and step is more complicated, and in the solution of chemical reaction
It is readily incorporated impurity.
Summary of the invention
The present invention is to solve that the existing method preparing copper doped zinc oxide nanometer rods exists that chemical raw material kind is many, course of reaction
Complexity, the problem being readily incorporated impurity, and the pulsed laser deposition preparation method of a kind of copper doped zinc oxide nanometer rods is provided.
The pulsed laser deposition preparation method of copper doped zinc oxide nanometer rods follows the steps below:
One, copper zinc oxide ceramic target is mixed in preparation: by cupric oxide powder that purity is 99.9% and Zinc oxide powder according to mole
Than be 1:(9-99) ratio ball milling 24h, 600-700 DEG C of pre-burning 4-8 hour, then under the pressure of 20-30MPa suppress
The disk becoming a diameter of 30-50mm, thickness to be 3mm, sinters 4-8 hour at 1000-1200 DEG C subsequently, is mixed
Copper zinc oxide ceramic target；
Two, clean substrate: to substrate according to acetone ultrasonic cleaning 5min～20min, use deionized water ultrasonic cleaning
5min～20min and be for 1 time a cycle with each ultrasonic cleaning of order of methanol ultrasonic cleaning 5min～20min, repeats clear
Wash 2～3 cycles, the substrate after i.e. being cleaned；
Three, the copper zinc oxide ceramic target of mixing step one obtained loads pulsed laser deposition rotation target position, step 2 is cleaned
After substrate be fixed on can be on rotation sample carrier, and the substrate after cleaning disposes in opposite directions with mixing copper zinc oxide ceramic target, cleans
After substrate and the distance mixed between copper zinc oxide ceramic target be 20mm～100mm；
Four, the vacuum being evacuated to vacuum chamber reaches 1 × 10-3Pa, is passed through buffer gas, controls buffer gas flow and is
1sccm～100sccm；
Five, first regulate underlayer temperature to 400-500 DEG C, be 0.1J/cm at laser energy density2～100J/cm2, laser arteries and veins
Rush width be 25ns, frequency be 1Hz～50Hz, to mix copper zinc oxide ceramic target rotational velocity be 20r/min, substrate rotation
Speed is 15r/min, the pressure of oxygen is to use under conditions of 0.1-100Pa krypton fluoride excimer laser to mixing copper zinc oxide
Ceramic target carries out laser ablation 1-20min, it is thus achieved that inculating crystal layer；
Six, then raise underlayer temperature to 600-750 DEG C, be 0.1J/cm at laser energy density2～100J/cm2, laser arteries and veins
Rush width be 25ns, frequency be 1Hz～50Hz, to mix copper zinc oxide ceramic target rotational velocity be 20r/min, substrate rotation
Speed is 15r/min, the pressure of argon is 10-1000Pa, the pressure of oxygen is to carry out laser ablation under conditions of 0-100Pa
20-120min, must mix copper zinc oxide nano rod；
Seven, after step 6 terminates, stop molecular pump, then stop mechanical pump, open the vent valve of mechanical pump bottom, and to very
Cavity is passed through buffer gas to normal pressure, substrate obtains copper doped zinc oxide nanometer rods；
Substrate described in step 2 is silicon chip, glass, silicon dioxide or gold,platinized silicon chip；
Buffer gas described in step 4 is the mixed gas of one or more in oxygen, nitrogen, argon.
The invention have the benefit that
1, the present invention uses pulsed laser deposition preparation to mix copper zinc oxide nano rod, uses raw material simple, only needs two kinds of raw materials,
And produce in the vacuum chamber, any impurity will not be introduced, generate the cycle short, only 3h-4h；
2, the present invention can reach different doping ratios by copper oxide in regulation target from the ratio of zinc oxide, and preparation facilitates.
What 2, prepared by the present invention mixes copper zinc oxide nano rod, and diameter Distribution is at 50-200nm；Distribution of lengths at 500-6000nm,
Thinner diameter and bigger fineness ratio make to mix copper zinc oxide nano rod and have big specific surface area, first can promote it
Light ability, secondly can all have good response to the hydrogen sulfide gas in wider concentration range.
3, realizing the room temperature to hydrogen sulfide gas to detect, copper doped zinc oxide nanometer rods prepared by PLD is owing to having good crystalline substance
Lattice structure, and the introducing of Copper-cladding Aluminum Bar, i.e. can be to the 15ppm concentration that human body is produced harm by Long contact time in room temperature
Hydrogen sulfide gas realize good detection, and respond recovery rapidly, improve and mix copper zinc oxide range of application.
Accompanying drawing explanation
Fig. 1 is the SEM front elevation of the copper doped zinc oxide nanometer rods of experiment one preparation；
Fig. 2 is the SEM side view of the copper doped zinc oxide nanometer rods of experiment one preparation；
Fig. 3 is the XRD figure of the copper doped zinc oxide nanostructured of experiment one preparation；
Fig. 4 is the EDS power spectrum of the copper doped zinc oxide nanostructured of experiment three preparation；
Fig. 5 is the copper doped zinc oxide nanometer rods room temperature of the experiment three preparation spectral response figure to 15ppm hydrogen sulfide gas,
In figureFor being passed through spectrogram before hydrogen sulfide,For being passed through spectrogram after hydrogen sulfide,For light after discharge hydrogen sulfide
Spectrogram.
Detailed description of the invention
Technical solution of the present invention is not limited to act detailed description of the invention set forth below, and also include between each detailed description of the invention is any
Combination.
Detailed description of the invention one: the pulsed laser deposition preparation method of present embodiment copper doped zinc oxide nanometer rods is according to following
Step is carried out:
One, copper zinc oxide ceramic target is mixed in preparation: by cupric oxide powder that purity is 99.9% and Zinc oxide powder according to mole
Than be 1:(9-99) ratio ball milling 24h, 600-700 DEG C of pre-burning 4-8 hour, then under the pressure of 20-30MPa suppress
The disk becoming a diameter of 30-50mm, thickness to be 3mm, sinters 4-8 hour at 1000-1200 DEG C subsequently, is mixed
Copper zinc oxide ceramic target；
Two, clean substrate: to substrate according to acetone ultrasonic cleaning 5min～20min, use deionized water ultrasonic cleaning
5min～20min and be for 1 time a cycle with each ultrasonic cleaning of order of methanol ultrasonic cleaning 5min～20min, repeats clear
Wash 2～3 cycles, the substrate after i.e. being cleaned；
Three, the copper zinc oxide ceramic target of mixing step one obtained loads pulsed laser deposition rotation target position, step 2 is cleaned
After substrate be fixed on can be on rotation sample carrier, and the substrate after cleaning disposes in opposite directions with mixing copper zinc oxide ceramic target, cleans
After substrate and the distance mixed between copper zinc oxide ceramic target be 20mm～100mm；
Four, the vacuum being evacuated to vacuum chamber reaches 1 × 10-3Pa, is passed through buffer gas, controls buffer gas flow and is
1sccm～100sccm；
Five, first regulate underlayer temperature to 400-500 DEG C, be 0.1J/cm at laser energy density2～100J/cm2, laser arteries and veins
Rush width be 25ns, frequency be 1Hz～50Hz, to mix copper zinc oxide ceramic target rotational velocity be 20r/min, substrate rotation
Speed is 15r/min, the pressure of oxygen is to use under conditions of 0.1-100Pa krypton fluoride excimer laser to mixing copper zinc oxide
Ceramic target carries out laser ablation 1-20min, it is thus achieved that inculating crystal layer；
Six, then raise underlayer temperature to 600-750 DEG C, be 0.1J/cm at laser energy density2～100J/cm2, laser arteries and veins
Rush width be 25ns, frequency be 1Hz～50Hz, to mix copper zinc oxide ceramic target rotational velocity be 20r/min, substrate rotation
Speed is 15r/min, the pressure of argon is 10-1000Pa, the pressure of oxygen is to carry out laser ablation under conditions of 0-100Pa
20-120min, must mix copper zinc oxide nano rod；
Seven, after step 6 terminates, stop molecular pump, then stop mechanical pump, open the vent valve of mechanical pump bottom, and to very
Cavity is passed through buffer gas to normal pressure, substrate obtains copper doped zinc oxide nanometer rods；
Substrate described in step 2 is silicon chip, glass, silicon dioxide or gold,platinized silicon chip；
Described substrate and the distance mixed between copper zinc oxide ceramic target are freely regulated by handwheel；
Buffer gas described in step 4 is the mixed gas of one or more in oxygen, nitrogen, argon.
Buffer gas described in present embodiment when being mixed gas between each composition for arbitrarily than.
Detailed description of the invention two: present embodiment in step one unlike detailed description of the invention one in temperature is
1050-1150 DEG C is sintered.Other is identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment is lining unlike one of detailed description of the invention one or two described in step 3
The end and the distance mixed between copper zinc oxide ceramic target are 40-60mm.Other is identical with one of detailed description of the invention one or two.
Detailed description of the invention four: first present embodiment regulates in step 5 unlike one of detailed description of the invention one to three
Underlayer temperature to 420-460 DEG C.Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention five: present embodiment is swashing described in step 5 unlike one of detailed description of the invention one to four
Optical energy density is 1.2-6J/cm2.Other is identical with one of detailed description of the invention one to four.
Detailed description of the invention six: present embodiment is swashing described in step 5 unlike one of detailed description of the invention one to five
The light ablation time is 10-15min.Other is identical with one of detailed description of the invention one to five.
Detailed description of the invention seven: then present embodiment raises in step 6 unlike one of detailed description of the invention one to six
Underlayer temperature to 620-720 DEG C.Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention eight: laser ablation in present embodiment step 6 unlike one of detailed description of the invention one to seven
Time is 60-100min.Other is identical with one of detailed description of the invention one to seven.
Detailed description of the invention nine: present embodiment is the oxygen described in step 6 unlike one of detailed description of the invention one to eight
The pressure of gas is 1-10Pa.Other is identical with one of detailed description of the invention one to eight.
Detailed description of the invention ten: present embodiment is the argon described in step 6 unlike one of detailed description of the invention one to nine
The pressure of gas is 100-150Pa, and the pressure of oxygen is 0Pa.Other is identical with one of detailed description of the invention one to nine.
Use following experimental verification effect of the present invention:
Experiment one:
The pulsed laser deposition preparation method of copper doped zinc oxide nanometer rods follows the steps below:
One, copper zinc oxide ceramic target is mixed in preparation: by purity be 99.9% cupric oxide powder be 99.9% oxide powder and zinc with purity
End is according to the ratio ball milling 24h that mol ratio is 1:99,700 DEG C of pre-burnings 4 hours, then suppresses under the pressure of 20MPa
The disk becoming a diameter of 30mm, thickness to be 3mm, at 1150 DEG C, sintering makes its molding and densification in 6 hours subsequently,
Obtain mixing copper zinc oxide ceramic target；
Two, substrate is cleaned: to substrate according to acetone ultrasonic cleaning 10min, by deionized water ultrasonic cleaning 10min and use
The each ultrasonic cleaning of order of methanol ultrasonic cleaning 10min is for 1 time a cycle, 2 cycles of repeated washing, i.e. obtains clear
Substrate after washing；
Three, the copper zinc oxide ceramic target of mixing step one obtained loads pulsed laser deposition rotation target position, step 2 is cleaned
After substrate be fixed on can be on rotation sample carrier, and the substrate after cleaning disposes in opposite directions with mixing copper zinc oxide ceramic target, cleans
After substrate and the distance mixed between copper zinc oxide ceramic target be 40mm；
Four, the vacuum being evacuated to vacuum chamber reaches 1 × 10-3Pa, is passed through buffer gas, controls buffer gas flow and is
50sccm；
Five, first regulate underlayer temperature to 450 DEG C, be 1.5J/cm at laser energy density2, laser pulse width be 25ns,
Frequency is 8Hz, mix copper zinc oxide ceramic target rotational velocity is 20r/min, substrate rotational velocity is 15r/min, oxygen
Pressure is to use under conditions of 5Pa krypton fluoride excimer laser to carry out laser ablation to mixing copper zinc oxide ceramic target
10min, it is thus achieved that inculating crystal layer；
Six, then raise underlayer temperature to 700 DEG C, be 1.5J/cm at laser energy density2, laser pulse width be 25ns,
Frequency is 8Hz, mix copper zinc oxide ceramic target rotational velocity is 20r/min, substrate rotational velocity is 15r/min, argon
Pressure is 120Pa, the pressure of oxygen is to carry out laser ablation 60min under conditions of 0Pa, must mix copper zinc oxide nano rod；
Seven, after step 6 terminates, stop molecular pump, then stop mechanical pump, open the vent valve of mechanical pump bottom, and to very
Cavity is passed through buffer gas to normal pressure, substrate obtains copper doped zinc oxide nanometer rods；
Substrate described in step 2 is silicon chip；
Buffer gas described in step 4 is oxygen.
The copper doped zinc oxide nanometer rods of experiment one preparation is carried out electron microscope scanning and X-ray diffraction analysis to it,
Fig. 1 is the SEM front elevation of the copper doped zinc oxide nanometer rods of experiment one preparation, and as can be seen from the figure prepared by experiment one
Copper doped zinc oxide nanometer rods, diameter 80-120nm, length 5000-6000nm, Fig. 2 is the Copper-cladding Aluminum Bar of experiment one preparation
The SEM side view of zinc oxide nano rod.Fig. 3 is the XRD figure of the copper doped zinc oxide nanometer rods of experiment one preparation, from
Figure can be seen that into ZnO crystal structure diffraction peak, illustrate that copper is all mixed with in the crystal of ZnO.
Experiment two:
The pulsed laser deposition preparation method of copper doped zinc oxide nanometer rods follows the steps below:
One, copper zinc oxide ceramic target is mixed in preparation: by purity be 99.9% cupric oxide powder be 99.9% oxide powder and zinc with purity
End is according to the ratio ball milling 24h that mol ratio is 1:19,650 DEG C of pre-burnings 4 hours, then suppresses under the pressure of 20MPa
The disk becoming a diameter of 30mm, thickness to be 3mm, sinters 6 hours subsequently at 1100 DEG C, obtains mixing copper zinc oxide pottery
Porcelain target；
Two, substrate is cleaned: to substrate according to acetone ultrasonic cleaning 10min, by deionized water ultrasonic cleaning 10min and use
The each ultrasonic cleaning of order of methanol ultrasonic cleaning 10min is for 1 time a cycle, 3 cycles of repeated washing, i.e. obtains clear
Substrate after washing；
Three, the copper zinc oxide ceramic target of mixing step one obtained loads pulsed laser deposition rotation target position, step 2 is cleaned
After substrate be fixed on can be on rotation sample carrier, and the substrate after cleaning disposes in opposite directions with mixing copper zinc oxide ceramic target, cleans
After substrate and the distance mixed between copper zinc oxide ceramic target be 40mm；
Four, the vacuum being evacuated to vacuum chamber reaches 1 × 10-3Pa, is passed through buffer gas, controls buffer gas flow and is
50sccm；
Five, first regulate underlayer temperature to 450 DEG C, be 1.5J/cm at laser energy density2, laser pulse width be 25ns,
Frequency is 10Hz, mix copper zinc oxide ceramic target rotational velocity is 20r/min, substrate rotational velocity is 15r/min, oxygen
Pressure be to use under conditions of 5Pa krypton fluoride excimer laser to carry out laser ablation to mixing copper zinc oxide ceramic target
10min, it is thus achieved that inculating crystal layer；
Six, then raise underlayer temperature to 700 DEG C, be 1.5J/cm at laser energy density2, laser pulse width be 25ns,
Frequency is 8Hz, mix copper zinc oxide ceramic target rotational velocity is 20r/min, substrate rotational velocity is 15r/min, argon
Pressure is 120Pa, the pressure of oxygen is to carry out laser ablation 60min under conditions of 1Pa, must mix copper zinc oxide nano rod；
Seven, after step 6 terminates, stop molecular pump, then stop mechanical pump, open the vent valve of mechanical pump bottom, and to very
Cavity is passed through buffer gas to normal pressure, substrate obtains copper doped zinc oxide nanometer rods；
Substrate described in step 2 is silicon chip；
Buffer gas described in step 4 is oxygen.
Experiment three:
The pulsed laser deposition preparation method of copper doped zinc oxide nanometer rods follows the steps below:
One, copper zinc oxide ceramic target is mixed in preparation: by purity be 99.9% cupric oxide powder be 99.9% oxide powder and zinc with purity
End, according to the ratio ball milling 24h that mol ratio is 1:9,600 DEG C of pre-burnings 4 hours, then is pressed under the pressure of 20MPa
A diameter of 30mm, thickness are the disk of 3mm, sinter 6 hours subsequently, obtain mixing copper zinc oxide ceramics at 1050 DEG C
Target；
Two, substrate is cleaned: to substrate according to acetone ultrasonic cleaning 10min, by deionized water ultrasonic cleaning 10min and use
The each ultrasonic cleaning of order of methanol ultrasonic cleaning 10min is for 1 time a cycle, 3 cycles of repeated washing, i.e. obtains clear
Substrate after washing；
Three, the copper zinc oxide ceramic target of mixing step one obtained loads pulsed laser deposition rotation target position, step 2 is cleaned
After substrate be fixed on can be on rotation sample carrier, and the substrate after cleaning disposes in opposite directions with mixing copper zinc oxide ceramic target, cleans
After substrate and the distance mixed between copper zinc oxide ceramic target be 40mm；
Four, the vacuum being evacuated to vacuum chamber reaches 1 × 10-3Pa, is passed through buffer gas, controls buffer gas flow and is
50sccm；
Five, first regulate underlayer temperature to 450 DEG C, be 1.5J/cm at laser energy density2, laser pulse width be 25ns,
Frequency is 8Hz, mix copper zinc oxide ceramic target rotational velocity is 20r/min, substrate rotational velocity is 15r/min, oxygen
Pressure is to use under conditions of 5Pa krypton fluoride excimer laser to carry out laser ablation to mixing copper zinc oxide ceramic target
10min, it is thus achieved that inculating crystal layer；
Six, then raise underlayer temperature to 700 DEG C, be 1.5J/cm at laser energy density2, laser pulse width be 25ns,
Frequency is 8Hz, mix copper zinc oxide ceramic target rotational velocity is 15r/min, substrate rotational velocity is 20r/min, argon
Pressure is 120Pa, the pressure of oxygen is to carry out laser ablation 60min under conditions of 10Pa, must mix copper zinc oxide nano rod；
Seven, after step 6 terminates, stop molecular pump, then stop mechanical pump, open the vent valve of mechanical pump bottom, and to very
Cavity is passed through buffer gas to normal pressure, substrate obtains copper doped zinc oxide nanometer rods；
Substrate described in step 2 is silicon chip, glass, silicon dioxide or gold,platinized silicon chip；
Buffer gas described in step 4 is the mixed gas in nitrogen, argon, the volume ratio of two kinds of gases be arbitrarily than.
To it, copper doped zinc oxide nanometer rods of experiment three preparation is carried out EDS energy spectrum analysis, and Fig. 4 is experiment three preparation
The EDS power spectrum of copper doped zinc oxide nanometer rods, it can be seen that have Zn element simultaneously to exist with Cu element, sends out through calculating
Existing Cu element accounts for the 13.9% of the total amount of Zn, Cu element, the most corresponding with the content of the Cu element of 10% in target.
Fig. 5 is the spectrum sensing to hydrogen sulfide gas of the copper doped zinc oxide nanometer rods of experiment three preparation, it can be seen that
The hydrogen sulfide gas of 15ppm concentration is had good response, the change of total spectral intensity to be about by the zinc-oxide nano bar mixing copper
70%, it can be seen that at room temperature prepare and mix copper zinc oxide nano rod hydrogen sulfide gas is had good spectral response characteristic.
Claims (9)
1. the pulsed laser deposition preparation method of copper doped zinc oxide nanometer rods, it is characterised in that copper doped zinc oxide nanometer rods
Pulsed laser deposition preparation method follows the steps below:
One, copper zinc oxide ceramic target is mixed in preparation: by cupric oxide powder that purity is 99.9% and Zinc oxide powder according to mole
Than be 1:(9-99) ratio ball milling 24h, 600-700 DEG C of pre-burning 4-8 hour, then be pressed under the pressure of 20-30MPa
A diameter of 30-50mm, thickness are the disk of 3mm, sinter 4-8 hour subsequently, obtain mixing copper oxygen at 1000-1200 DEG C
Change zinc ceramic target；
Two, clean substrate: to substrate according to acetone ultrasonic cleaning 5min～20min, use deionized water ultrasonic cleaning
5min～20min and be for 1 time a cycle with each ultrasonic cleaning of order of methanol ultrasonic cleaning 5min～20min, repeated washing
2～3 cycles, the substrate after i.e. being cleaned；
Three, the copper zinc oxide ceramic target of mixing step one obtained loads pulsed laser deposition rotation target position, step 2 is cleaned
After substrate be fixed on can be on rotation sample carrier, and the substrate after cleaning disposes in opposite directions with mixing copper zinc oxide ceramic target, cleans
After substrate and the distance mixed between copper zinc oxide ceramic target be 20mm～100mm；
Four, the vacuum being evacuated to vacuum chamber reaches 1 × 10-3Pa, is passed through buffer gas, controls buffer gas flow and is
1sccm～100sccm；
Five, first regulate underlayer temperature to 400-500 DEG C, be 0.1J/cm at laser energy density2～100J/cm2, laser pulse
Width is 25ns, frequency is 1Hz～50Hz, mix copper zinc oxide ceramic target rotational velocity is 20r/min, substrate rotational velocity
It is to use krypton fluoride excimer laser to mixing copper zinc oxide ceramics under conditions of 0.1-100Pa for the pressure of 15r/min, oxygen
Target carries out laser ablation 1-20min, it is thus achieved that inculating crystal layer；
Six, then raise underlayer temperature to 600-750 DEG C, be 0.1J/cm at laser energy density2～100J/cm2, laser pulse
Width is 25ns, frequency is 1Hz～50Hz, mix copper zinc oxide ceramic target rotational velocity is 20r/min, substrate rotational velocity
For the pressure of 15r/min, argon be 10-1000Pa, the pressure of oxygen be to carry out laser ablation under conditions of 0-100Pa
20-120min, must mix copper zinc oxide nano rod；
Seven, after step 6 terminates, stop molecular pump, then stop mechanical pump, open the vent valve of mechanical pump bottom, and to very
Cavity is passed through buffer gas to normal pressure, substrate obtains copper doped zinc oxide nanometer rods；
Substrate described in step 2 is silicon chip, glass, silicon dioxide or gold,platinized silicon chip；
Buffer gas described in step 4 is the mixed gas of one or more in oxygen, nitrogen, argon.
The pulsed laser deposition preparation method of copper doped zinc oxide nanometer rods the most according to claim 1, it is characterised in that step
It is 40-60mm for substrate and the distance mixed between copper zinc oxide ceramic target described in rapid three.
The pulsed laser deposition preparation method of copper doped zinc oxide nanometer rods the most according to claim 1, it is characterised in that step
First underlayer temperature to 420-460 DEG C is regulated in rapid five.
The pulsed laser deposition preparation method of copper doped zinc oxide nanometer rods described in 1 the most as requested, it is characterised in that step 5
Described in laser energy density be 1.2-6J/cm2。
The pulsed laser deposition preparation method of copper doped zinc oxide nanometer rods described in 1 the most as requested, it is characterised in that step 5
Described in laser ablation time be 10-15min.
The pulsed laser deposition preparation method of copper doped zinc oxide nanometer rods described in 1 the most as requested, it is characterised in that step 6
In then raise underlayer temperature to 620-720 DEG C.
The pulsed laser deposition preparation method of copper doped zinc oxide nanometer rods described in 1 the most as requested, it is characterised in that step 6
Middle laser ablation time is 60-100min.
The pulsed laser deposition preparation method of copper doped zinc oxide nanostructured rod described in 1 the most as requested, it is characterised in that step
The pressure of the oxygen described in rapid six is 1-10Pa.
The pulsed laser deposition preparation method of copper doped zinc oxide nanostructured rod described in 1 the most as requested, it is characterised in that step
The pressure of the argon described in rapid six is 100-150Pa, and the pressure of oxygen is 0Pa.
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| CN101424653A (en) * | 2008-12-02 | 2009-05-06 | 上海工程技术大学 | Zinc oxide doped air-sensitive film preparation method |
| CN101768728A (en) * | 2010-01-15 | 2010-07-07 | 深圳大学 | Method for preparing doped ZnO-based film through magnetron sputtering |
| CN101781749A (en) * | 2010-02-03 | 2010-07-21 | 中国科学院半导体研究所 | Preparation method of Cu doped p type ZnO thin film |
| CN102372500A (en) * | 2011-05-31 | 2012-03-14 | 安徽大学 | Method for preparing Cu diffusion doped ZnO base semiconductor by adopting laser pulse deposition method |
| CN102719792A (en) * | 2012-06-18 | 2012-10-10 | 上海交通大学 | Method applying magnetron sputtering method to preparation of transparent conductive film |
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2015
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101424653A (en) * | 2008-12-02 | 2009-05-06 | 上海工程技术大学 | Zinc oxide doped air-sensitive film preparation method |
| CN101768728A (en) * | 2010-01-15 | 2010-07-07 | 深圳大学 | Method for preparing doped ZnO-based film through magnetron sputtering |
| CN101781749A (en) * | 2010-02-03 | 2010-07-21 | 中国科学院半导体研究所 | Preparation method of Cu doped p type ZnO thin film |
| CN102372500A (en) * | 2011-05-31 | 2012-03-14 | 安徽大学 | Method for preparing Cu diffusion doped ZnO base semiconductor by adopting laser pulse deposition method |
| CN102719792A (en) * | 2012-06-18 | 2012-10-10 | 上海交通大学 | Method applying magnetron sputtering method to preparation of transparent conductive film |
Non-Patent Citations (1)
| Title |
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| "锡掺杂氧化锌薄膜乙醇气敏性的研究";白翠彩等;《天津工业大学学报》;20120228;第31卷(第1期);第13-16页 * |
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