CN109382087A - A kind of stannic oxide-zinc stannate core-shell nano line and preparation method - Google Patents
A kind of stannic oxide-zinc stannate core-shell nano line and preparation method Download PDFInfo
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- 239000011258 core-shell material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910003107 Zn2SnO4 Inorganic materials 0.000 claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 230000008021 deposition Effects 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002070 nanowire Substances 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 239000011701 zinc Substances 0.000 claims abstract description 8
- 238000007740 vapor deposition Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000010792 warming Methods 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000000151 deposition Methods 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000005229 chemical vapour deposition Methods 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052594 sapphire Inorganic materials 0.000 claims description 4
- 239000010980 sapphire Substances 0.000 claims description 4
- 238000005137 deposition process Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 description 13
- 239000012071 phase Substances 0.000 description 13
- 239000011257 shell material Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000003708 ampul Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 239000010439 graphite Substances 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 239000012808 vapor phase Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 4
- 238000000231 atomic layer deposition Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 238000001451 molecular beam epitaxy Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
- C23C16/0281—Deposition of sub-layers, e.g. to promote the adhesion of the main coating of metallic sub-layers
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- 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
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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Abstract
The invention discloses a kind of stannic oxide-zinc stannate core-shell nano line and preparation methods, comprising the following steps: step 1: by SnO2Powder and graphite powder are 1:4 mixing in molar ratio, and grinding uniformly, obtains SnO2+ C powder；It is in molar ratio that 1:1 is mixed by ZnO powder and graphite powder, grinding uniformly, obtains ZnO+C powder；Step 2: after substrate gold-plated film, being placed in crystallizing field and be warming up to 918 DEG C, by SnO2+ C powder is placed in gas-phase deposition system high-temperature region and is heated to 980 DEG C, passes through vapor deposition growth SnO in substrate2Nano wire；Step 3: ZnO+C powder being placed in gas-phase deposition system high-temperature region, passes through vapor deposition growth Zn in substrate2SnO4Shell, up to target product after cooling；The SnO that the present invention is prepared2‑Zn2SnO4Core-shell nano line core shell structure is obvious, and contrast is uniform, and interface is smooth with smooth outer surface, has fabulous epitaxial relationship, and preparation method is simple, easy to maintain.
Description
Technical field
The present invention relates to technical field of nanometer material preparation, and in particular to a kind of stannic oxide-zinc stannate core-shell nano line
And preparation method.
Background technique
With the rapid development of global industry, ecological environment constantly deteriorates, and research and development utilize solar energy highly effective degradation Industry Waste
The material of organic dyestuff has become the hot spot of current research in water；Research of the conductor oxidate nano material as photochemical catalyst
Increasingly it is taken seriously；It is to improve optical energy utilization efficiency and photoproduction is inhibited to carry that material, which improves the main thought of photocatalysis performance, at present
Flow the compound of son；The realization above-mentioned requirements that nucleocapsid heterogeneous structure material can kill two birds with one stone, since light can in core-shell structure
It is therefore effectively improved by the light capture ability of multiple reflections and refraction, material, while the shell for high electron mobility of arranging in pairs or groups
Material；Light induced electron can be guided in time, be reduced the recombination probability of carrier also；Compared to conventional bulk, one
Dimension nano material has higher specific surface area and higher chemical activity, and preparing nanoscale catalysis material is equally to work as premise
One of the effective means of high photocatalysis efficiency.
Stannic oxide and zinc stannate are all environmentally friendly, broad stopband N-type semiconductor oxide materials, they have
Good photocatalysis performance；Wherein zinc stannate electron mobility (10-30cm also with higher2Vs-1) and lower electron-hole
Recombination rate, while its chemical stability is splendid；There is Xiguang Han et al. to realize SnO at present2/Zn2SnO4Hollow structure is received
The preparation of rice material, and SnO2-Zn2SnO4The preparation of core-shell nano line is also never implemented.Chemical vapour deposition technique
(Chemical Vapor Deposition, CVD) is to prepare the most common method of One, Dimensional Semiconductor Nano Materials, is that one kind exists
Under set temperature and atmosphere, the method for vapor-phase reactant deposition growing material in substrate.It is tested in all vapor depositions
In, the growth mechanism of nano material mainly has gas-liquid-solid and two kinds gas-solid.VLS growth mechanism mainly dominates nano wire
Axial growth, vapor-solid process multiaction is in the lateral growth of nano wire.Theoretically, change in nanowire growth process
Become the ingredient of supplied vapor-phase reactant, and utilize vapor-solid process, the system of coaxial heterogeneous core-shell nano line can be realized
It is standby.The general equipment that can be achieved to change reactant ingredient during the growth process has Metallo-Organic Chemical Vapor to deposit (Metal-
Organic Chemical Vapor Deposition, MOCVD), molecular beam epitaxy (Molecular Beam Epitaxy,
MBE) and atomic layer deposition (Atomic Layer Deposition, ALD), but these equipment are not only expensive but also complicated for operation,
Maintenance cost is high.
Summary of the invention
The present invention provides a kind of chemical vapour deposition technique realization stannic oxide-zinc stannate easy to operate, low-cost
The preparation of core-shell nano line.
The technical solution adopted by the present invention is that: a kind of preparation method of stannic oxide-zinc stannate core-shell nano line, including with
Lower step:
Step 1: by SnO2Powder and graphite powder are 1:4 mixing in molar ratio, and grinding uniformly, obtains SnO2+ C powder；By ZnO
Powder and graphite powder are 1:1 mixing in molar ratio, and grinding uniformly, obtains ZnO+C powder；
Step 2: after substrate gold-plated film, being placed in crystallizing field and be warming up to 918 DEG C, by SnO2+ C powder is placed in gas-phase deposition system
High-temperature region is heated to 980 DEG C, passes through vapor deposition growth SnO in substrate2Nano wire；
Step 3: ZnO+C powder being placed in gas-phase deposition system high-temperature region, passes through vapor deposition growth Zn in substrate2SnO4
Shell, up to target product after cooling.
Further, flow is passed through as the argon gas of 50sccm and the oxygen of 5sscm in the step 2 and step 3 deposition process
Gas, holding pressure are 1Torr.
Further, the reaction time is 20min in the step 2.
Further, step 3 reaction time is 60min.
Further, ZnO+C powder is placed at chemical vapor deposition high temperature district center upstream 30cm in the step 1, step 3
In by magnetic force propulsion device be sent into high-temperature region.
Further, the substrate is c-plane sapphire, and 10nm thick gold membrane is plated on surface.
Further, low-temperature space and high-temperature region heating rate with the heating rate of 10 DEG C/min rise to 600 in the step 2
DEG C, the oxygen of argon gas and 5sscm that flow is 50sccm is then passed to, holding pressure is 1Torr；The atmosphere item of argon gas and oxygen
High-temperature region is risen to 980 DEG C from 600 DEG C in 40min under part, low-temperature space rises to 918 DEG C from 600 DEG C.
A kind of SnO2-Zn2SnO4Core-shell nano line, the SnO2-Zn2SnO4Core-shell nano line, core SnO2, shell is
Zn2SnO4。
Further, the Zn2SnO4Shell is that muti-piece crystal is spliced.
The beneficial effects of the present invention are:
(1) SnO that the present invention is prepared2-Zn2SnO4Core-shell nano line, SnO2And Zn2SnO4Two-phase crystallinity is good；
(2) SnO that the present invention is prepared2-Zn2SnO4Its core-shell structure of core-shell nano line is obvious, and contrast is uniform, interface
It is smooth with smooth outer surface, there is fabulous epitaxial relationship.
(3) SnO that the present invention is prepared2-Zn2SnO4Core-shell nano line, shell material are spliced to form for muti-piece, crystalline
Free from admixture is measured.The result successfully discloses the epitaxial relationship of stannic oxide and zinc stannate: tape spool parallel relation is SnO2
[101]//Zn2SnO4[101], crystal face parallel relation is
(4) present invention is prepared by CVD method, cheap, easy to operate, easy to maintain, can by magnetic force propulsion device
It effectively realizes and changes reaction source in the case where not changing vacuum environment.
Detailed description of the invention
Fig. 1 is the SnO that the embodiment of the present invention is prepared2-Zn2SnO4The X-ray diffractogram of core-shell nano line.
Fig. 2 is the SnO that the embodiment of the present invention is prepared2-Zn2SnO4Single SnO in core-shell nano line2-Zn2SnO4Nucleocapsid
The transmission electron microscope figure of nano wire.
Fig. 3 is the SnO that the embodiment of the present invention is prepared2-Zn2SnO4Single SnO in core-shell nano line2-Zn2SnO4Nucleocapsid
The transmission electron microscope figure of nano wire.
Fig. 4 is the SnO that the embodiment of the present invention is prepared2-Zn2SnO4The projection electron of core-shell nano line cross-sectional sample is aobvious
Micro mirror figure.
Fig. 5 is the SnO that the embodiment of the present invention is prepared2-Zn2SnO4The elemental line scan of core-shell nano line cross-sectional sample
Figure.
Fig. 6 is the SnO that the embodiment of the present invention is prepared2-Zn2SnO4The transmitted electron of core-shell nano line cross-sectional sample is aobvious
Micro- its corresponding electron diffraction diagram of image.
Specific embodiment
The present invention will be further described in the following with reference to the drawings and specific embodiments.
A kind of SnO2-Zn2SnO4The preparation method of core-shell nano line, comprising the following steps:
Step 1: by SnO2Powder and graphite powder are 1:4 mixing in molar ratio, and grinding uniformly, obtains SnO2+ C being placed in of powder
Learn gas-phase deposition system high-temperature region；It is in molar ratio that 1:1 is mixed by ZnO powder and graphite powder, grinding uniformly, obtains ZnO+C powder
It is placed at chemical gaseous phase system high temperature district center upstream 30cm.
Step 2: selection c-plane sapphire is growth substrate, plates 10nm thick gold membrane on its surface by magnetron sputtering, then sets
In the low-temperature space of chemical gas-phase deposition system；It is passed through the oxygen of argon gas and 5sscm that flow is 50sccm, holding pressure is
1Torr；High-temperature region rises to 980 DEG C, and low-temperature space rises to 918 DEG C, reaches set temperature and maintains 20min, realizes that SnO2 nano wire exists
Growth in low-temperature space substrate.
Step 3: being placed on the ZnO+C powder at gas-phase deposition system high temperature district center upstream 30cm and pass through magnetic force moving device
It is sent into high-temperature region；Under conditions of keeping parameters constant, Zn is realized in low-temperature space2SnO4The growth of shell；The process continues
60min, time reach rear chemical gas-phase deposition system and are down to room temperature from 980 DEG C with 5 DEG C/min, obtain target product.
Embodiment
SnO is prepared according to the following steps2-Zn2SnO4Core-shell nano line:
Step 1: selection c-plane sapphire is growth substrate, and plates 10nm thick gold membrane on its surface by magnetron sputtering technique,
It is subsequently placed in that length is 300mm, diameter is right half part in the quartz ampoule of 30mm；
The high-purity SnO for being 99.99% by purity2Powder and graphite are that 1:4 is mixed, and is ground uniformly, so according to molar ratio
Mixed-powder is placed in the left end in quartz ampoule afterwards；
The quartz ampoule for being placed with substrate and powder source is put into the reaction cavity of chemical gas-phase deposition system, wherein substrate
Positioned at the center of reaction chamber low-temperature space, powder source is located at the center of reaction chamber high-temperature region；
By purity be 99.99% high-purity ZnO powder and graphite be in molar ratio 1:1 mix, grinding uniformly, by mixed powder
End is placed in the half opening quartz ampoule that length is 50mm, radius is 30mm, and the quartz ampoule is then placed on the chemical gas of distance
At the 30cm of phase depositing system high-temperature region center upstream.
Step 2: chemical gas-phase deposition system being evacuated to 0.2Torr, and by high-temperature region and low-temperature space simultaneously from room temperature
600 DEG C are risen to the heating rate of 10 DEG C/min；
It is passed through the high-purity argon gas that purity is 99.99% and the oxygen that purity is 99.99%, throughput is respectively 50sccm
(standard cubic centimeter per minute) and 5sccm, system air pressure are maintained at 1.0Torr；
High-temperature region risen to from 600 DEG C in 40min 980 DEG C, low-temperature space from 600 rise to 918 DEG C, after reaching set temperature
SnO2Carbothermic reduction reaction occurs with graphite and discharges vapor-phase reactant, 20min is maintained to realize SnO2Nano wire is in low-temperature space substrate
Growth.
Step 3: the quartz for filling ZnO Yu graphite mixed-powder of chemical gas-phase deposition system upstream will be placed in step 1
Pipe is sent into high-temperature region through magnetic force moving device, the quartz ampoule being close in step 1；
It keeps experiment parameter constant, so that ZnO and graphite is carried out carbothermic reduction reaction, release second of vapor-phase reactant,
Zn is realized by being blended in low temperature with existing vapor-phase reactant2SnO4The growth of shell, the process continue 60min；
Chemical gas-phase deposition system is down to room temperature from 980 DEG C with 5 DEG C/min, obtains target product.
The SnO that the present embodiment is prepared2-Zn2SnO4Core-shell nano line sample does X-ray diffraction, as shown in Figure 1；From
As can be seen that product only has SnO in figure2And Zn2SnO4Two-phase, free from admixture and sharp diffraction maximum prove that its crystal property is good
It is good.
Fig. 2 and Fig. 3 is the SnO that the present embodiment is prepared2-Zn2SnO4Single SnO in core-shell nano line2-Zn2SnO4Core
The projection electron microscope figure of shell nano wire；As ingredient it is different from thickness caused by contrast difference, can be significantly from figure
Out, with core-shell structure；SnO2-Zn2SnO4Its contrast of core-shell nano line is uniform, and interface is smooth with smooth outer surface, crystallization
Property it is good, have fabulous epitaxial relationship.
Fig. 4 is the SnO that the present embodiment is prepared2-Zn2SnO4The transmission electron microscope of core-shell nano line cross-sectional sample
Figure；As can be seen from the figure its shell material is spliced by six pieces of crystal, and the structure is extremely novel in core-shell nano material.
Fig. 5 is the SnO that the present embodiment is prepared2-Zn2SnO4The elemental line scan figure of core-shell nano line cross-sectional sample
Piece；；Wherein a is the scanning transmission electron micrograph image of the core-shell nano line cross-sectional sample, b is core-shell nano line line scanning result
In Zn elemental distribution, c be Sn elemental distribution in core-shell nano line line scanning result, d is core-shell nano line line
O elemental distribution in scanning result, as can be seen from the figure in shell Zn enrichment of element and have a certain amount of Sn element,
The kernel Sn enrichment of element and shortage of Zn element, oxygen element are distributed in nucleocapsid part, the provable structure core is SnO2, shell
For Zn2SnO4。
Fig. 6 is the SnO that the embodiment of the present invention is prepared2-Zn2SnO4The transmitted electron of core-shell nano line cross-sectional sample is aobvious
Micro- its corresponding image K-M (b) of image (a).Three sets of electron diffraction diagrams can have been calibrated from its electron micrograph image
Case, they are belonging respectively to SnO2[101], Zn2SnO4[101] andThe result successfully disclose stannic oxide with
The epitaxial relationship of zinc stannate: tape spool parallel relation is SnO2[101]//Zn2SnO4[101], crystal face parallel relation is
The SnO that the present invention is prepared2-Zn2SnO4Core-shell nano cable architecture is novel, good crystallinity, and epitaxial growth relationship is bright
Really, the shell structurre of muti-piece splice type is extremely novel；Can be prepared by chemical vapor deposition, can by being simple and efficient,
Cheap method realizes the preparation of coaxial heterogeneous core-shell nano line.
Claims (9)
1. a kind of stannic oxide-zinc stannate core-shell nano line preparation method, which comprises the following steps:
Step 1: by SnO2Powder and graphite powder are 1:4 mixing in molar ratio, and grinding uniformly, obtains SnO2+ C powder；By ZnO powder
It is in molar ratio 1:1 mixing with graphite powder, grinding uniformly, obtains ZnO+C powder；
Step 2: after substrate gold-plated film, being placed in crystallizing field and be warming up to 918 DEG C, by SnO2+ C powder is placed in gas-phase deposition system high temperature
Area is heated to 980 DEG C, passes through vapor deposition growth SnO in substrate2Nano wire；
Step 3: ZnO+C powder being placed in gas-phase deposition system high-temperature region, passes through vapor deposition growth Zn in substrate2SnO4Shell,
Up to target product after cooling.
2. a kind of stannic oxide according to claim 1-zinc stannate core-shell nano line preparation method, which is characterized in that
The oxygen of argon gas and 5sscm that flow is 50sccm is passed through in the step 2 and step 3 deposition process, holding pressure is
1Torr。
3. a kind of stannic oxide according to claim 1-zinc stannate core-shell nano line preparation method, which is characterized in that
The reaction time is 20min in the step 2.
4. a kind of stannic oxide according to claim 1-zinc stannate core-shell nano line preparation method, which is characterized in that
Step 3 reaction time is 60min.
5. a kind of stannic oxide according to claim 1-zinc stannate core-shell nano line preparation method, which is characterized in that
ZnO+C powder is placed at chemical vapor deposition high temperature district center upstream 30cm in the step 1, is promoted and is filled by magnetic force in step 3
It sets and is sent into high-temperature region.
6. a kind of stannic oxide according to claim 1-zinc stannate core-shell nano line preparation method, which is characterized in that
The substrate is c-plane sapphire, and 10nm thick gold membrane is plated on surface.
7. a kind of stannic oxide according to claim 1-zinc stannate core-shell nano line preparation method, which is characterized in that
Low-temperature space and high-temperature region heating rate rise to 600 DEG C with the heating rate of 10 DEG C/min in the step 2, and then passing to flow is
The argon gas of 50sccm and the oxygen of 5sscm, holding pressure are 1Torr；It will be high in 40min under the atmospheric condition of argon gas and oxygen
Warm area rises to 980 DEG C from 600 DEG C, and low-temperature space rises to 918 DEG C from 600 DEG C.
8. a kind of system of stannic oxide-zinc stannate core-shell nano line as described in any one claim as described in claim 1~7
SnO made from Preparation Method2-Zn2SnO4Core-shell nano line, which is characterized in that the SnO2-Zn2SnO4Core-shell nano line, core are
SnO2, shell Zn2SnO4。
9. a kind of SnO according to claim 82-Zn2SnO4Core-shell nano line, which is characterized in that the Zn2SnO4Shell is
Muti-piece crystal is spliced.
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