CN101671007B - Nanometer zinc selenide with quadruped structure and preparing method thereof - Google Patents
Nanometer zinc selenide with quadruped structure and preparing method thereof Download PDFInfo
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- CN101671007B CN101671007B CN2009101965932A CN200910196593A CN101671007B CN 101671007 B CN101671007 B CN 101671007B CN 2009101965932 A CN2009101965932 A CN 2009101965932A CN 200910196593 A CN200910196593 A CN 200910196593A CN 101671007 B CN101671007 B CN 101671007B
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Abstract
The invention discloses a nanometer zinc selenide with a quadruped structure. The zinc selenide nanocrystal is composed of two crystalline phases, in particular, a cubic crystal nucleus and four symmetrical hexagonal branch feet. The preparing method comprises the following steps: taking zinc selenide powder and active carbon powder to be mixed in the mole ratio of 3-5:1 to serve as a raw material; taking high-purity nitrogen as carrier gas; performing thermal evaporation reaction at the raw material zone in the quartz tube of a high-temperature resistance furnace at the temperature of 1000-1200 DEG C for 30-120 minutes. After reaction, a deposited product collected in the zone under the temperature of 250-400 DEG C when reaction occurs in the quartz tube is the nanometer zinc selenide with a quadruped structure. Based on the preparation of semiconductor material with low cost and simple operation, it is possible to develop the novel semiconductor nanometer material with new photoelectric properties.
Description
Technical field
The present invention relates to a kind of structure, preparation method of nanometer zinc selenide material and may use, more particularly, the present invention relates to structure, the preparation method of zinc selenide (ZnSe) nano particle of a kind of quadruped structure (Tetrapods).Belong to the nano semiconductor material technical field.
Background technology
Zinc selenide (ZnSe) is as important II-VI family semi-conductor, and its block materials at room temperature energy gap is 2.70eV.The widespread use of zinc selenide based nano-material in a plurality of fields is the very interested problems of people, photoelectric device, photodetector [Haase such as photodiode (LED), solar cell, blue light range, M.A., et al., Znse-Znsse Electrooptic Wave-Guide Modulators.Applied Physics Letters, p.3228-3229.] and round-the-clock infra-red material etc. 1991.59 (25):.Compare with gallium arsenide (exciton bind energy is 4.2meV), zinc selenide has noticeable exciton bind energy (21meV).In recent years, many study group have prepared the zinc selenide of multiple pattern by several different methods, for example: selenizing zinc wire, band, rod, sheet, nucleocapsid structure and hollow ball structure etc.Since six sides thermodynamic (al) unstable under general environment of zinc selenide, the zinc selenide nano materials that majority is reported all be zink sulphide (cube) structure.
The semiconductor nano material of special construction possesses many novel characteristics, so its very potential functional elements that becomes nanoscale photoelectron material and device, has caused that people pay close attention to widely.The semiconductor nano material of preparation structure unanimity, pattern complexity might be developed new function material.The complex construction of nano semiconductor material is its key element [Duan that becomes functional material or further be integrated into nano-device, X.F., et al., Single-nanowire electrically driven lasers.Nature, 2003.421 (6920): p.241-245.].The four-footed zinc selenide is nanocrystalline to be noticeable a kind of in the complicated zinc selenide structure, and once the quadruped structure of Bao Dao this type of zinc selenide or sulphur selenium zinc ternary compound all was single wurtzite (six a sides) structure.
Given this, the inventor attempts by thermal evaporation techniques, and it is nanocrystalline to prepare the quadruped structure zinc selenide with non-single phase, reaches by the special construction that obtains zinc selenide and seeks its new application aims.
Summary of the invention
The objective of the invention is to prepare a kind of special quadruped structure zinc selenide.This four-footed zinc selenide has a cube of nucleus and is six sides symmetric minute stempoda mutually with four.This structure is different from the four-footed zinc selenide of common single phase, and special structure will be brought zinc selenide possible new function and application aspect photoelectric material.
Another object of the present invention provides a kind of above-mentioned four-footed zinc selenide preparation of nanomaterials.
Embodiment of the present invention are as follows:
A kind of nanometer zinc selenide of quadruped structure, it is characterized in that: this zinc selenide is nanocrystalline to be made of two crystalline phases, be specially a cube of nucleus and be six sides symmetric minute stempoda mutually with four, cube nucleus is a cube phase zincblende lattce structure nucleus, and six sides are wurtzite structure mutually.
The preparation method of the nanometer zinc selenide of above-mentioned quadruped structure:
A. the zinc selenide powder is mixed as raw material with the activated carbon powder, the mass ratio of zinc selenide and carbon dust is to be positioned over the heating zone of silica tube in 1.4: 0.2 or 1.4: 0.12.
B. continue to feed high pure nitrogen, as the carrier gases of thermal evaporation reaction, the flow control of nitrogen is at the nitrogen of 400～800ml/min, and air pressure remains 1atm.
C. open high temperature resistance furnace, the temperature in raw material district is 1000～1200 ℃ when reacting in the control silica tube, and the reaction times is 30～120min.
D. after reaction finishes, treat the burner hearth cool to room temperature after, collected yellow final product in 250～400 ℃ of (during reaction) warm area positions of silica tube.
The zinc selenide that the preparation method of the nanometer zinc selenide of above-mentioned quadruped structure makes is nanocrystalline structurally to exist two crystalline phases simultaneously: zink sulphide (cube phase) nucleus and four wurtzites symmetrical branch of (six sides mutually); Each branched length and diameter are respectively 50～150nm and 80～120nm.
Structural characterization
Utilize x-ray diffractometer (XRD), scanning electronic microscope (SEM) and transmission electron microscope (TEM) characterize resulting product.According to its XRD figure spectrum, this material comprises a cube phase (lattice parameter respectively
) with six sides (lattice parameter a=3.996 mutually
); By SEM figure and TEM figure, can see that this material is the short nanorod structure of pattern homogeneous, grow symmetric four bar-shaped branches from nucleus respectively, each branch is the hexa-prism structure of rule, have the hexagonal cross-section (001) of better crystal face, each branched length and diameter are respectively 50～150nm and 80～120nm.
Characteristics of the present invention and purposes
Zinc selenide quadruped structure of the present invention is nanocrystalline for thermal evaporation reaction under the catalyst-free situation makes, and the preparation that is different from the zinc selenide four-footed nanocrystalline structure of having reported generally adopts tin (Sn) as catalyzer; On the structure by zink sulphide (cube) and wurtzite (six sides) constitute, be specially the branch foot that cube nucleus epitaxy goes out four six side's phases, also be different from reported be the four-footed zinc selenide of single six side's phases.
Nanocrystalline complex topography and the consistent three-dimensional structure of being prepared to may promote it and further be used and become novel functional material, the nanocrystalline general block zinc selenide of the zinc selenide of complex construction has special luminous peak position, the four-footed zinc selenide is nanocrystalline to have significantly fluorescent emission at orange and blue wave band, might develop novel photoelectric material.
Description of drawings
Each Figure of description is done schematic illustration:
Fig. 1 has shown the X-ray diffracting spectrum of synthetic product.The result shows that product possesses fine crystallinity, is made up of with (* peak position) two kinds of crystalline phases cube mutually mutually six sides.
Fig. 2 is product SEM image of (a-c) under different resolution.The result shows, product is the comparatively four-footed nanostructure of homogeneous of pattern and size.
Fig. 3 is the TEM image of (a-c) under product different resolution and the different angles.As can be seen, symmetric four the branch stempodas of product are corynebacterium six prisms among the figure, and the cross section is comparatively regular hexagon.
Fig. 4 is the HRTEM image of (a-c) under the product different resolution.The result shows that the branch part of product is six side's phases along the growth of [001] direction; Its nucleus is a cube phase.(111) face of nucleus and branched (010) face have coupling (interplanar distance is respectively 0.33nm and 0.34nm) preferably.
Embodiment
Further specify the present invention below by embodiment and Comparative Examples, but the present invention is limited to embodiment absolutely not.
Embodiment 1
At first get 1.40g zinc selenide powder and the 0.20g activated carbon powder mixes, mixed powder is put into the heating zone of high temperature resistance furnace silica tube, vacuumize after airtight.Feed nitrogen subsequently in pipe, continuing to feed flow is the nitrogen of 600ml/min, and is a normal atmosphere in the holding tube.The opening resistor stove, control raw material district temperature is closed resistance furnace at 1100 ℃ behind the heating 60min, and the nitrogen that remains the feeding constant current in the entire reaction course is as carrier gases.After treating that silica tube is cooled to room temperature, be that the yellow reaction product is obtained in 280～300 ℃ deposition region when the pipe internal heating.
Utilize X-ray diffractometer (XRD), scanning electronic microscope (SEM) and transmission electron microscope (TEM) that resulting product is characterized.Characterization result shows, products therefrom by cube and two crystalline phases of six sides form, be the quadruped structure zinc selenide of pattern homogeneous, each divides stempoda is the hexagon stub that length and diameter are respectively 80nm and 100nm, pile up with (001) direction, along the growth of [001] direction.
Embodiment 2
At first get 1.40g zinc selenide powder and the 0.20g activated carbon powder mixes, mixed powder is put into the heating zone of high temperature resistance furnace silica tube, vacuumize after airtight.Feed nitrogen subsequently in pipe, continuing to feed flow is the nitrogen of 600ml/min, and is a normal atmosphere in the holding tube.The opening resistor stove, control raw material district temperature is closed resistance furnace at 1100 ℃ behind the heating 90min, and the nitrogen that remains the feeding constant current in the entire reaction course is as carrier gases.After treating that silica tube is cooled to room temperature, be that the yellow reaction product is obtained in 280～320 ℃ deposition region when the pipe internal heating.
Utilize X-ray diffractometer (XRD), scanning electronic microscope (SEM) and transmission electron microscope (TEM) and uv-visible absorption spectra instrument (UV-Visible Spectrophotometer) that resulting product is characterized.Characterization result is similar to Example 1.
Embodiment 3
At first get 1.40g zinc selenide powder and the 0.12g activated carbon powder mixes, mixed powder is put into the heating zone of high temperature resistance furnace silica tube, vacuumize after airtight.Feed nitrogen subsequently in pipe, continuing to feed flow is the nitrogen of 600ml/min, and is a normal atmosphere in the holding tube.The opening resistor stove, control raw material district temperature is closed resistance furnace at 1100 ℃ behind the heating 90min, and the nitrogen that remains the feeding constant current in the entire reaction course is as carrier gases.After treating that silica tube is cooled to room temperature, be that the yellow reaction product is obtained in 280～300 ℃ deposition region when the pipe internal heating.
Utilize X-ray diffractometer (XRD), scanning electronic microscope (SEM) and transmission electron microscope (TEM) that resulting product is characterized.Characterization result shows, products therefrom by cube and two crystalline phases of six sides form, be the quadruped structure zinc selenide of pattern homogeneous, each divides stempoda is the hexagon stub that length and diameter are respectively 60nm and 100nm, other characterization results are similar to Example 1.
Embodiment 4
At first get 1.40g zinc selenide powder and the 0.20g activated carbon powder mixes, mixed powder is put into the heating zone of high temperature resistance furnace silica tube, vacuumize after airtight.Feed nitrogen subsequently in pipe, continuing to feed flow is the nitrogen of 600ml/min, and is a normal atmosphere in the holding tube.The opening resistor stove, control raw material district temperature is closed resistance furnace at 1100 ℃ behind the heating 60min, and the nitrogen that remains the feeding constant current in the entire reaction course is as carrier gases.After treating that silica tube is cooled to room temperature, be that the yellow reaction product is obtained in 240～270 ℃ deposition region when the pipe internal heating.
Utilize X-ray diffractometer (XRD), scanning electronic microscope (SEM) and transmission electron microscope (TEM) that resulting product is characterized.Characterization result shows, products therefrom by cube and two crystalline phases of six sides form, be the quadruped structure zinc selenide of pattern homogeneous, each divides stempoda is the hexagon stub that length and diameter are respectively 60nm and 90nm, other characterization results are similar to Example 1.
Comparative Examples 1
At first get 1.40g zinc selenide powder and 0.20g activated carbon powder and 0.10g tin protoxide (SnO) powder mixes is even, mixed powder is put into the heating zone of high temperature resistance furnace silica tube, vacuumize after airtight.Feed nitrogen subsequently in pipe, continuing to feed flow is the nitrogen of 600ml/min, and is a normal atmosphere in the holding tube.The opening resistor stove, control raw material district temperature is closed resistance furnace at 1100 ℃ behind the heating 60min, and the nitrogen that remains the feeding constant current in the entire reaction course is as carrier gases.After treating that silica tube is cooled to room temperature, be that the yellow reaction product is obtained in 280～300 ℃ deposition region when the pipe internal heating.
Utilize X-ray diffractometer (XRD), scanning electronic microscope (SEM) and transmission electron microscope (TEM) that resulting product is characterized.Characterization result shows that products therefrom is the quadruped structure zinc selenide of pattern homogeneous by single six side's phase composites, and each divides stempoda is the hexagon stub that length and diameter are respectively 60nm and 100nm, piles up with (001) direction, along the growth of [001] direction.
Claims (2)
1. the nanometer zinc selenide of a quadruped structure, it is characterized in that: this zinc selenide is nanocrystalline to be made of two crystalline phases, be specially by a cube of nucleus epitaxy and go out four symmetric minute stempodas that are six side's phases, cube nucleus is a cube phase zincblende lattce structure nucleus, and six sides are wurtzite structure mutually.
2. the preparation method of the nanometer zinc selenide of quadruped structure according to claim 1, it is characterized in that adopting following concrete steps: with the zinc selenide powder and the mass ratio of activated carbon powder is to mix as raw material in 1.4: 0.2 or 1.4: 0.12, with the high pure nitrogen is delivery gas, in the silica tube of high temperature resistance furnace, react 30～120min in raw material district temperature of reaction 1000～1200 ℃ of thermal evaporations, after the reaction, warm area when reacting in silica tube is 240～320 ℃ of sedimentation products that collect in the zone, is the nanometer zinc selenide material of quadruped structure.
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Cited By (1)
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| US9493351B2 (en) | 2011-12-07 | 2016-11-15 | East China University Of Science And Technology | Methods of producing cadmium selenide multi-pod nanocrystals |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9493351B2 (en) | 2011-12-07 | 2016-11-15 | East China University Of Science And Technology | Methods of producing cadmium selenide multi-pod nanocrystals |
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