CN100344574C - Core shell type zinc oxide/stancic oxide composite nanometer material and preparation method thereof - Google Patents

Core shell type zinc oxide/stancic oxide composite nanometer material and preparation method thereof Download PDF

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CN100344574C
CN100344574C CNB200510129969XA CN200510129969A CN100344574C CN 100344574 C CN100344574 C CN 100344574C CN B200510129969X A CNB200510129969X A CN B200510129969XA CN 200510129969 A CN200510129969 A CN 200510129969A CN 100344574 C CN100344574 C CN 100344574C
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zinc oxide
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type zinc
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CN1803707A (en
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匡勤
周樨
徐韬
林水潮
江智渊
谢兆雄
谢素原
黄荣彬
郑兰荪
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Xiamen University
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Abstract

The present invention discloses a core-shell type zinc oxide/tin oxide composite nanometer material and a preparation process thereof, which relates to the preparation of a nanometer material, particularly to the core-shell type zinc oxide/tin oxide composite nanometer material and the preparation process thereof. The present invention provides the core-shell type zinc oxide/tin oxide composite nanometer material with a good, clean and flawless interface and the preparation process thereof. The core-shell type zinc oxide/tin oxide composite nanometer material comprises a ZnO core and an SnO2 shell covering the ZnO. Firstly, the nanometer material of the ZnO is prepared, then the precursor of SnH4 is prepared, and the generated gas of the SnH4 is carried by N2 to enter an air bag for growing the SnO2 shell; the ZnO2/SnO2 composite material with a core-shell structure is obtained by growing on a substrate of a silicon chip. The interface formed between the core of the zinc oxide and the shell of the tin oxide is a clean epitaxial interface with fewer flaws, and the core-shell type zinc oxide/tin oxide composite nanometer material has good controllability and abundant forms, and has different fluorescence emission spectrum with the zinc oxide or the tin oxide as the homogenous material.

Description

Core shell type zinc oxide/stancic oxide composite nanometer material and preparation method thereof
Technical field
The present invention relates to a kind of preparation of nano material, especially relate to a kind of core shell type zinc oxide/stancic oxide composite nanometer material and preparation method thereof.
Technical background
Form the multifunctionality that adjustable heterogeneous nano material has shown height, therefore in the manufacturing of following nanometer electronic device great application prospect is arranged, the preparation such as various heterogeneous nano materials such as superlattice nano line, coaxial or twin shaft nano wires has caused the sizable research interest of people.As everyone knows, the most key factor of nano-device performance and reliability that influences is exactly the quality of constructing interface between the heterogeneous nano material of nano-device, because the defective that exists on the heterogeneous interface can greatly worsen the transmission of electronics in device.For a long time, epitaxy is considered to obtain to have the best a kind of method of heterojunction structure of good clean interface.
As everyone knows, many metal oxides all are the semiconductor functional materials of excellent performance, are widely used in fields such as photoelectricity, conversion of solar energy and transmitter.In the middle of numerous oxide compounds, zinc oxide (ZnO) and stannic oxide (SnO 2) be considered to the functional materials of tool application prospect, because they have the energy gap of broad, higher gas sensitization and excellent optical property.ZnO and SnO 2All be the n N-type semiconductorN, its energy gap is respectively 3.37eV and 3.6eV during 300K.Recently, some studies show that: by ZnO and SnO 2The dissimilar materials of constructing shows the physicochemical property more excellent more than its single-material in some aspects, for example by ZnO and SnO 2The compound gas sensor and ZnO or the SnO that constitute 2The gas sensor that single-material constitutes is compared, its sensitivity improved a lot (Costello B.P.J.D., Ewen R.J., Jones P.R.H., Ratcliffe N.M., Wat R.K.M.Sensors and Actuators B 1999,61,199-207).Although about ZnO or SnO 2The heterojunction structure that forms with other semiconductor materials often has report, but because ZnO and SnO 2Have bigger textural difference between two kinds of crystal, also nobody successfully obtains by ZnO and SnO so far 2The epitaxial heterostructures that constitutes.Even the ZnO/SnO that those have been reported 2Matrix material also normally by ball milling (Solid state ionics 2000,135,163-167), the pyrolytic coating method (Guo Sijin, Zheng Shunxuan, in Yongan, SnO 2: the light transmissive gas-sensitive property of ZnO film, Chinese laser, 1991,18 (12); 905-908), (king deposits, Wang Peng, Xu Baiqing, ZnO-SnO in co-precipitation 2Nano composite oxide photocatalyst catalyzed degradation p-Nitroaniline, the catalysis journal, 2004,25 (12): 967-972) etc. method is with ZnO and SnO 2Nano particle simply mixes, and the contact interface between the dissimilar materials is very loose, so synthesis condition such as ball milling time, blended uniformity coefficient etc. all have very large influence to device performance.
Summary of the invention
The objective of the invention is at ZnO surface epitaxy SnO 2, so that a kind of have good, core shell type zinc oxide/stancic oxide composite nanometer material cleaning, the zero defect interface to be provided, another object of the present invention is to provide a kind of preparation this hud typed ZnO/SnO 2The universal method of composite nano materials.
Core shell type zinc oxide/stancic oxide composite nanometer material of the present invention comprises that a ZnO kernel and one deck are wrapped in the SnO of ZnO 2Shell.
The size of ZnO kernel is 30~1500nm, SnO 2The thickness of shell is 10~250nm.
Described ZnO nano material is four jiaos of forked ZnO, aircraft shape ZnO, array-like ZnO, hexa-prism ZnO, pyramid shape ZnO or banded ZnO etc.
It is template that the preparation method of core shell type zinc oxide/stancic oxide composite nanometer material of the present invention adopts the ZnO nano material with specific modality that obtains with prepared beforehand, and the method by chemical vapour deposition is at ZnO surface epitaxy one deck SnO 2Shell wraps up the ZnO template fully and promptly to obtain hud typed ZnO/SnO 2Composite nano materials the steps include:
1) preparation of ZnO template: prepare the ZnO nano material by chemical vapour deposition, ionic liquid or laser splash method;
2) SnH 4The preparation of presoma: with SnCl 45H 2The O aqueous solution is added drop-wise to KOH and KBH 4In the mixed aqueous solution, the gas SnH of generation 4Pass through N 2Carry enter in the air bag standby;
3) SnO 2The growth of shell: the ZnO nano material for preparing is dispersed in cuts out on the good silicon chip substrate, be placed on then in the reaction chamber of chemical vapor deposition unit as SnO 2The substrate of growth after the question response chamber vacuumizes, is heated to 600~800 ℃ with silicon chip substrate, feeds the SnH for preparing 4/ N 2Gas mixture, deposition back stop supplies SnH 4/ N 2Gas mixture and the power supply of closing heating controller are lowered the temperature silicon chip naturally, close vacuum system at last, and promptly growth obtains having the ZnO/SnO of nucleocapsid structure on silicon chip substrate 2Matrix material;
In step 1), described ZnO nano material is four jiaos of forked ZnO, aircraft shape ZnO, array-like ZnO, hexa-prism ZnO, pyramid shape ZnO or banded ZnO etc.
In step 2) in, be the SnCl of 0.10~0.30g/ml with concentration 45H 2The O aqueous solution is added drop-wise to KOH and the KBH that concentration is 0.025~0.075g/ml 4Mixed aqueous solution; The mass ratio of each reactant is SNCl 45H 2O: KOH: KBH 4=1: (0.3~0.8): (0.3~0.8) is preferably SnCl 45H 2O: KOH: KBH 4=1: 0.5: 0.5, the gas SnH of generation 4By flow velocity is the N of 100~300sccm 2Carry enter in the air bag standby.
In step 3), feed the SnH for preparing 4/ N 2The flow velocity of gas mixture is 10~80sccm, and depositing time is 1~10min.
With existing ZnO/SnO by ball milling, pyrolytic coating or prepared by co-precipitation 2Matrix material is compared, and the present invention has following outstanding advantage: the 1) ZnO/SnO for preparing of the present invention 2The interface of composite nano materials is not the contact interface that loosens, ZnO kernel and SnO 2The interface that forms between the shell is the few epitaxial interface of defective of cleaning.2) controllability is fine.Because be vapor deposition processes, to SnO 2Can pass through in the lip-deep epitaxially grown control of ZnO SnH 4/ N 2The accurate control of the concentration of gas mixture, flow velocity and depositing time realizes.3) can synthesize the hud typed ZnO/SnO of variform 2Composite nano materials.Because have extremely abundant form, therefore utilize the present invention to prepare to comprise the SnO of four jiaos of forked, aircraft shapes, array-like, hexa-prism, pyramid shape and banded variform as the ZnO of template 2Hollow nano-material.4) the hud typed ZnO/SnO for preparing of the present invention 2Composite nano materials has and its single-material ZnO or SnO 2Different fluorescence emission spectrums, this will have potential to use aspect photoelectric device.
Description of drawings
Fig. 1 is the structure and the preparation flow figure thereof of core shell type zinc oxide/stancic oxide composite nanometer material.
The run after fame ZnO nano material of kind of form of Fig. 2.
Fig. 3 (a) is for being raw material with the Zn powder, the transmission electron microscope photo of four jiaos of forked ZnO that prepare by chemical Vapor deposition process; (b) be with SnH 4Be Xi Yuan, at four jiaos of forked ZnO template surface deposition SnO 2After four jiaos of forked hud typed ZnO/SnO obtaining 2The transmission electron microscope photo of composite nano materials; (c) be four jiaos of forked hud typed ZnO/SnO 2The X-ray powder diffraction figure of composite nano materials, in the drawings, X-coordinate is 2 θ (degree), ordinate zou is Intensity (a.u.); (d) be four jiaos of forked hud typed ZnO/SnO 2The high-resolution electron microscope photo of composite nano materials.
Fig. 4 (a) is for being raw material with the Zn powder, by chemical Vapor deposition process prepare the transmission electron microscope photo of aircraft shape ZnO; (b) be with SnH 4Be Xi Yuan, at aircraft shape ZnO template surface deposition SnO 2After the hud typed ZnO/SnO of aircraft shape that obtains 2The electron scanning micrograph of composite nano materials; (c) be the hud typed ZnO/SnO of aircraft shape 2The X-ray energy spectrum figure of composite nano materials.
Fig. 5 (a) is for being raw material with the Zn grain, the electron scanning micrograph of the array ZnO nano wire for preparing by chemical Vapor deposition process; (b) be with SnH 4Be Xi Yuan, at array-like ZnO template surface deposition SnO 2After the hud typed array-like ZnO/SnO that obtains 2The electron scanning micrograph of composite nano-line; (c) be the hud typed ZnO/SnO of array-like 2The X-ray energy spectrum figure of composite nano materials.
Fig. 6 (a) is for being raw material with the Zn grain, the electron scanning micrograph of the hexa-prism ZnO for preparing by the laser splash method; (b) be with SnH 4Be Xi Yuan, at hexa-prism ZnO template surface deposition SnO 2After the hud typed ZnO/SnO of hexa-prism that obtains 2The electron scanning micrograph of composite Nano rod; (c) be the hud typed ZnO/SnO of hexa-prism 2The X-ray energy spectrum figure of composite nano materials.
Fig. 7 (a) decomposes the electron scanning micrograph of the pyramid shape ZnO that obtains for being raw material with the zinc acetate in ionic liquid; (b) be with SnH 4Be Xi Yuan, at pyramid shape ZnO template surface deposition SnO 2After the hud typed ZnO/SnO of pyramid shape that obtains 2The transmission electron microscope photo; (c) be the hud typed ZnO/SnO of pyramid shape 2The X-ray energy spectrum figure of composite nano materials.
Four jiao forked ZnO, the ZnO/SnOs of Fig. 8 for obtaining among the embodiment 1 2, SnO 2The fluorescence spectrum figure of nano material.
Embodiment
The present invention is further illustrated in conjunction with the accompanying drawings below by embodiment.Used in the present embodiment chemical vapor deposition unit adopts the chemical vapor deposition unit (referring to CN1546723A and CN2655310Y patent) that integrates the silicon chip heating deposition, silicon chip both as heating source also as deposition substrate, its basic functional principle is for to be heated to different temperature through the size of current of silicon chip with silicon chip by controlling flow, but to be equally applicable to the tube furnace be the conventional gas-phase deposition apparatus of heating source to this preparation method.
The chemical vapor deposition unit that integrates the silicon chip heating deposition is provided with 1) boost-up circuit, the external silicon chip (load) that is heated of boost-up circuit output terminal, be used for when silicon chip is in cold state, voltage of supply is boosted with the startup silicon chip, and reduce voltage in real time along with silicon chip heats up.2) pulse-width modulation circuit, its pulse-width signal output termination boost-up circuit control signal input terminus, for boost-up circuit provides pulse-width signal, the current signal output end of over-current signal input termination boost-up circuit is for boost-up circuit provides overcurrent protection.3) overpressure protection circuit, its superpressure is judged the external silicon chip that is heated of signal input part, its superpressure shutdown signal is exported the modulation signal input terminus of termination pulse-width modulation circuit, is used for monitoring in real time the output voltage of boost-up circuit.4) constant-current circuit, the external silicon chip that is heated of its input terminus is used to control the silicon chip electric current, to realize the purpose of control silicon temperature.5) boost or switching circuit is judged in the step-down constant current automatically, connect boost-up circuit and constant-current circuit respectively, the work that is used for boost-up circuit and constant-current circuit is switched.6) interface circuit, its current sample port connects constant-current circuit, is heated the external silicon chip that is heated of silicon chip both end voltage sample port, is computer or micro-chip control temperature interface, and monitors silicon chip both end voltage, current sample port.7) power supply connects boost-up circuit, pulse-width modulation circuit, overpressure protection circuit, constant-current circuit respectively, boosts or switching circuit and interface circuit etc. are judged in the step-down constant current automatically.
Embodiment 1
Hud typed ZnO/SnO 2The structure of composite nano materials and preparation flow are referring to Fig. 1.Core shell type zinc oxide/stancic oxide composite nanometer material comprises that the thickness that ZnO kernel that a size is 30~1500nm and one deck are wrapped in ZnO is the SnO of 10~250nm 2Shell.
During preparation, 1) four jiaos of forked ZnO kernels of preparation; Take by weighing the 0.1gZn powder, place on the silicon chip substrate of the chemical vapor deposition unit that integrates the silicon chip heating deposition, start the heating controller power supply, setting electric current is that 5A is that temperature is 800 ℃, heating Zn powder, four jiaos of forked ZnO that evaporation obtains were collected at the 1cm place directly over the silicon slice placed of tailoring with other a slice placed the Zn powder simultaneously;
2) SnH 4The preparation of presoma: take by weighing KBH respectively 4With each 15g of KOH, be mixed with in the three-necked flask of packing into behind the 200ml aqueous solution; Take by weighing 30g SnCl 45H 2O is mixed with the 100ml aqueous solution, in the constant pressure funnel of packing into.Three-necked flask intermediary eck is connected with constant pressure funnel, and all the other two ecks are N 2The import of (carrier gas/carrier gas) and outlet.With the SnCl in the constant pressure funnel 45H 2The O aqueous solution dropwise adds KOH and KBH in the three-necked flask 4Mixed aqueous solution, the SnH of generation 4Gas is the N of 300sccm by flow velocity 2Carrier gas carries that to enter an airbag standby;
3) SnO 2The growth of shell: the silicon chip that will deposit four jiaos of forked ZnO is fixed on two electrodes of reaction unit, after treating that the silica tube reaction chamber vacuumizes, start silicon chip microcell heating controller power supply, setting electric current is that 5A is that temperature is 800 ℃, feeds the SnH for preparing with the flow velocity of 60sccm 4/ N 2Gas mixture is closed silicon chip microcell heating controller power supply through behind the 5min, closes vacuum system.The sample collection that is deposited on the silicon chip is got off promptly to obtain four jiaos of forked hud typed ZnO/SnO 2Composite nano materials.
The sedimentation products that each step obtains is all passed through transmission electron microscope and X-ray powder diffraction analysis.That obtained by chemical Vapor deposition process is four jiaos of forked ZnO of high yield, and the diameter of every nanometer rod is that (Fig. 3 a) for 30~100nm; Through SnO 2After the coating, the size of four jiaos of forks increases to some extent, and the increasing diameter of every nanometer rod adds as 40~130nm (Fig. 3 b); To four jiaos of forked hud typed ZnO/SnO 2The X-ray powder diffraction analysis that composite nano materials is done (Fig. 3 c) shows that material is by rutile-type SnO 2Form with wurtzite-type ZnO, further high resolution transmission electron microscopy sign (Fig. 3 d) shows ZnO kernel and SnO 2Interface between the shell is good, defective is less, has epitaxial relationship.
Embodiment 2
Preparation process is similar to embodiment 1, just KBH in the process (2) 4Respectively take by weighing 5g and SnCl with KOH 45H 2O takes by weighing 10g, carrier gas N 2Flow velocity be 100sccm; Flow velocity with 80sccm in the process (3) feeds the SnH for preparing 4/ N 2Gas mixture, depositing time are 10min.
The sedimentation products that each step obtains all passes through scanning electronic microscope and X-ray energy spectrum characterizes.The product that is obtained by chemical Vapor deposition process also contains the ZnO of a spot of aircraft shape, smooth surface (Fig. 4 b) except that four jiaos of a large amount of forked ZnO; Through SnO 2After the coating, the size of this aircraft shape structure increases to some extent, and it is coarse that the surface becomes, SnO 2Layer thickness is 20~50nm (Fig. 4 b); Hud typed ZnO/SnO to the aircraft shape 2The X-ray energy spectrum analysis that composite nano materials is done (Fig. 4 c) shows that material contains Zn, Sn, three kinds of elements of O, illustrates SnO 2Be deposited on the ZnO template.
Embodiment 3
1) be raw material with the Zn grain, obtain array-like ZnO nano wire by chemical Vapor deposition process deposition on the good silicon chip substrate of sanction, its diameter is 100~200nm, and length is 1~20 μ m;
2) process (2) (3) is substantially the same manner as Example 1, just KBH in the process (2) 4Respectively take by weighing 10g and SnCl with KOH 45H 2O takes by weighing 20g, carrier gas N 2Flow velocity be 200sccm; The ZnO nano wire that will deposit array-like in the process (3) is as SnO 2Sedimentary substrate, the current settings by silicon chip is that 4A is that temperature is 750 ℃, feeds the SnH for preparing with the flow velocity of 40sccm 4/ N 2Gas mixture, depositing time are 8min.
The sedimentation products that each step obtains all passes through scanning electronic microscope and X-ray energy spectrum characterizes.The ZnO that is prepared by chemical Vapor deposition process is that (Fig. 5 a) for the nano wire of array-like; At SnO subsequently 2The ZnO/SnO that obtains in the deposition process 2Composite nano-line is keeping array-like still perpendicular to silicon chip substrate, but surface ratio is more coarse, SnO 2Layer thickness is 50~100nm (Fig. 5 b).Hud typed ZnO/SnO to array-like 2The X-ray energy spectrum analysis that composite nano materials is done (Fig. 5 c) shows that material contains Zn, Sn, three kinds of elements of O, and SnO is described 2Be deposited on the ZnO template.
Embodiment 4
1) be raw material with the Zn grain, deposition obtains the ZnO nanometer rod to the method by laser splash on the good silicon chip substrate cutting out, and its diameter is 250~500nm, and length is 1.5~3 μ m;
2) process (3) is substantially the same manner as Example 1, just will deposit the ZnO nanometer rod as SnO in the process (3) 2Sedimentary substrate, the current settings by silicon chip is that 2.5A is that temperature is set at 600 ℃.
The sedimentation products that each step obtains all passes through scanning electronic microscope and X-ray energy spectrum characterizes.The ZnO that obtains by the laser splash method is the nanometer rod of hexa-prism, and its diameter is that (Fig. 6 a) for 200~500nm; At SnO subsequently 2The ZnO/SnO that obtains in the deposition process 2Composite nano materials is keeping the shape of the initial hexagonal cross-section of ZnO nanometer rod, but surface ratio is more coarse, SnO 2Layer thickness is 100~200nm (Fig. 6 b).Hud typed ZnO/SnO to hexa-prism 2The X-ray energy spectrum analysis that composite nano materials is done (Fig. 6 c) shows that material contains Zn, Sn, three kinds of elements of O, and SnO is described 2Be deposited on the ZnO template.
Embodiment 5
1) being raw material with the zinc acetate, is solvent with the ionic liquid, prepares pyramid shape ZnO by thermolysis.The pyramid shape ZnO powder for preparing is dispersed in the dehydrated alcohol, gets a little ZnO suspension liquid with dropper and dropwise drop on the good silicon chip substrate of sanction, under infrared lamp, dry;
2) process (3) is substantially the same manner as Example 1, just will deposit the silicon chip of pyramid shape ZnO as SnO in the process (3) 2Sedimentary substrate, the current settings by silicon chip is that 3.5A is that temperature is 700 ℃ of SnH 4/ N 2The flow rate control of gas mixture is at 10~40sccm, and the time is controlled at 1~3min.
The sedimentation products that each step obtains all passes through scanning electronic microscope and X-ray energy spectrum characterizes.The ZnO that obtains by the ionic liquid method is the hecaprismo of pyramid shape, and its bottom surface diameter is that (Fig. 7 a) for 1~1.5 μ m; At SnO subsequently 2The ZnO/SnO that obtains in the deposition process 2Composite nano materials is keeping the initial Pyramid of ZnO hecaprismo, but surface ratio is more coarse, SnO 2Layer thickness is 50~250nm (Fig. 7 b).Hud typed ZnO/SnO to pyramid shape 2The X-ray energy spectrum analysis that composite nano materials is done (Fig. 7 c) shows that material contains Zn, Sn, three kinds of elements of O, and SnO is described 2Be deposited on the ZnO template.
Embodiment 6
1) with the zinc powder be raw material, deposition obtains the ZnO nano belt to the method by chemical vapour deposition on the good silicon chip substrate cutting out, and its width is 50~300nm, and thickness is 10~50nm, and length is 10~200 μ m;
2) process (3) is substantially the same manner as Example 1, just will deposit the silicon chip of banded ZnO as SnO in the process (3) 2Sedimentary substrate.
Embodiment 7
Photoluminescence experiment (photoluminescence, PL): respectively four jiaos of forked ZnO powders that embodiment 1 is obtained, have four jiaos of forked ZnO/SnO of nucleocapsid structure 2The SnO that powder, acid corrosion obtain 2The hollow material powder is dispersed in the dehydrated alcohol that heavily steamed, and is placed on that ultrasonic 15min fully disperses it in the ultrasonic cleaner.In scattered suspension liquid impouring fluorescence pond, be the optical excitation sample of 325nm with the wavelength, survey its fluorescence emission spectrum, the results are shown in Figure 8.
Four jiaos of forked ZnO powders have the very big ultraviolet emission peak of an intensity at the 380nm place, this is the semi-conductive band edge emission of ZnO; Hollow four jiaos of forked SnO 2Powder has a faint emission peak at the 400nm place, this is SnO 2The fluorescent emission that the surface oxygen vacancies causes; And have four jiaos of forked ZnO/SnO of nucleocapsid structure 2Powder has a greenbelt emission peak at 450~600nm place except above-mentioned two emission peaks, hud typed ZnO/SnO is described 2Composite nano materials shows and ZnO or SnO 2Different photoluminescent properties.
If adopt chemical Vapor deposition process to prepare the ZnO nano material, generally the Zn powder can be placed on the reaction chamber central authorities of chemical vapor deposition unit, place silicon chip as the sedimentary substrate of ZnO at its downstream direction, after the question response chamber vacuumizes, reaction chamber is heated to 600~800 ℃, close the power supply of heating controller after the deposition and lower the temperature naturally, close vacuum system at last, promptly growth obtains the ZnO nano material on silicon chip substrate.
If adopt the ionic liquid legal system to be equipped with the ZnO nano material, generally the oxysalt of zinc can be joined in the ionic liquid that constitutes by quadrol (or trioctylamine or 30% aqueous methylamine solution) and oleic acid, then at 270-400 ℃ of following constant temperature 20-240min, cooling at room temperature at last, take off the faint yellow precipitation of layer and clean up repeatedly, promptly obtain the ZnO nano material with normal hexane and ethanol.
If adopt the laser splash legal system to be equipped with the ZnO nano material, generally the Zn grain can be placed on the reaction chamber bottom of an end closure, place silicon chip as the sedimentary substrate of ZnO at its downstream direction, after the question response chamber vacuumizes, silicon chip is heated to 600~800 ℃ also makes its evaporation with laser radiation Zn grain, close the power supply of laser and heating controller after the deposition and lower the temperature naturally, close vacuum system at last, promptly growth obtains the ZnO nano material on silicon chip substrate.

Claims (10)

1, core shell type zinc oxide/stancic oxide composite nanometer material is characterized in that comprising that a ZnO kernel and one deck are wrapped in the SnO of ZnO 2Shell.
2, core shell type zinc oxide/stancic oxide composite nanometer material as claimed in claim 1, the size that it is characterized in that described ZnO kernel is 30~1500nm, SnO 2The thickness of shell is 10~250nm, and described ZnO nano material is four jiaos of forked ZnO, aircraft shape ZnO, array-like ZnO, hexa-prism ZnO, pyramid shape ZnO or banded ZnO.
3, core shell type zinc oxide/stancic oxide composite nanometer material preparation method is characterized in that its step is as follows:
1) preparation of ZnO template: prepare the ZnO nano material by chemical vapour deposition, ionic liquid or laser splash method;
2) SnH 4The preparation of presoma: with SnCl 45H 2The O aqueous solution is added drop-wise to KOH and KBH 4In the mixed aqueous solution, the gas SnH of generation 4Pass through N 2Carry enter in the air bag standby;
3) SnO 2The growth of shell: the ZnO nano material for preparing is dispersed in cuts out on the good silicon chip substrate, be placed on then in the reaction chamber of chemical vapor deposition unit as SnO 2The substrate of growth after the question response chamber vacuumizes, is heated to 600~800 ℃ with silicon chip substrate, feeds the SnH for preparing 4/ N 2Gas mixture, deposition back stop supplies SnH 4/ N 2Gas mixture and the power supply of closing heating controller are lowered the temperature silicon chip naturally, close vacuum system at last, and promptly growth obtains having the ZnO/SnO of nucleocapsid structure on silicon chip substrate 2Matrix material.
4, core shell type zinc oxide/stancic oxide composite nanometer material preparation method as claimed in claim 3, it is characterized in that in step 1) described ZnO nano material is four jiaos of forked ZnO, aircraft shape ZnO, array-like ZnO, hexa-prism ZnO, pyramid shape ZnO or banded ZnO.
5, core shell type zinc oxide/stancic oxide composite nanometer material preparation method as claimed in claim 3 is characterized in that in step 2) in, be the SnCl of 0.10~0.30g/ml with concentration 45H 2The O aqueous solution is added drop-wise to KOH and the KBH that concentration is 0.025~0.075g/ml 4Mixed aqueous solution.
6, core shell type zinc oxide/stancic oxide composite nanometer material preparation method as claimed in claim 3 is characterized in that in step 2) in, SnCl 45H 2O, KOH and KBH 4Mass ratio be 1: 0.3~0.8: 0.3~0.8.
7, core shell type zinc oxide/stancic oxide composite nanometer material preparation method as claimed in claim 6 is characterized in that in step 2) in, SnCl 45H 2O: KOH: KBH 4=1: 0.5: 0.5.
8, core shell type zinc oxide/stancic oxide composite nanometer material preparation method as claimed in claim 3 is characterized in that in step 2) in, the gas SnH of generation 4By flow velocity is the N of 100~300sccm 2Carry enter in the air bag standby.
9, core shell type zinc oxide/stancic oxide composite nanometer material preparation method as claimed in claim 3 is characterized in that in step 3), feeds the SnH for preparing 4/ N 2The flow velocity of gas mixture is 10~80sccm.
10, core shell type zinc oxide/stancic oxide composite nanometer material preparation method as claimed in claim 3 is characterized in that in step 3), and depositing time is 1~10min.
CNB200510129969XA 2005-12-16 2005-12-16 Core shell type zinc oxide/stancic oxide composite nanometer material and preparation method thereof Expired - Fee Related CN100344574C (en)

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CN1460544A (en) * 2003-05-26 2003-12-10 中国科学院广州地球化学研究所 Preparation method of nano ZnO-SnO2 composite oxide photo-catalyst

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CN1414644A (en) * 2001-10-26 2003-04-30 中国科学院半导体研究所 Manufacturing method of single/multiple layer hetero quntum point structure
CN1460544A (en) * 2003-05-26 2003-12-10 中国科学院广州地球化学研究所 Preparation method of nano ZnO-SnO2 composite oxide photo-catalyst

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