CN101306835B - SnO2 complex three-dimensional nanostructure and method for preparing same - Google Patents
SnO2 complex three-dimensional nanostructure and method for preparing same Download PDFInfo
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- CN101306835B CN101306835B CN2008100364394A CN200810036439A CN101306835B CN 101306835 B CN101306835 B CN 101306835B CN 2008100364394 A CN2008100364394 A CN 2008100364394A CN 200810036439 A CN200810036439 A CN 200810036439A CN 101306835 B CN101306835 B CN 101306835B
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Abstract
The invention discloses a SnO2 complex three-dimensional nano structure. In the SnO2 complex three-dimensional nano structure, the oriented growth direction of a SnO2 one-dimensional nano rod is changed along different three-dimensional directions many times and twisted and bent to form a plurality of inflection points and further form the complex three-dimensional structure; the diameter of the nano rod is between 300 and 700nm; compared with the SnO2 nano structure conventionally synthesized and the method for making the same, the invention has the characteristics that: 1. the SnO2 nano structure synthesized has the novel and unique three-dimensional structure, and compared with the one-dimensional nano rod, the three-dimensional structure has larger specific surface area; 2. the sourcesupply method and the substrate position are particularly designed, namely materials are simultaneously put above and below the vertical substrate; 3. the designed reaction microcavity can better control the reaction atmosphere; 4. the structure has lower requirements on reaction equipment and carrier gases, and a common horizontal pipe type atmosphere furnace and N2 gas are adopted; 5. the structure has a simple method, low cost, good repeatability and capability of being synthesized massively.
Description
Technical field
The present invention relates to a kind of nanostructure, be specifically related to a kind of edge different three-dimensional epitaxial SnO of novelty
2Complex three-dimensional nanostructure and preparation method thereof.Adopt thermal evaporation method, in the reaction microcavity of design construction, at a standard atmospheric pressure with do not have under the condition of catalyzer, high yield ground is synthetic on silicon chip substrate to obtain this structure.Belong to photoelectron material, semiconductor material and device technology field.
Technical background
SnO
2Being a kind of n N-type semiconductorN material with wide direct band gap, also is transparent conductive material and the present widely used gas sensitive that has commercial value the earliest.Compare SnO with ZnO
2Have wideer band gap and the exciton bind energy of Geng Gao, band gap under the room temperature and exciton bind energy are respectively 3.62eV and 130meV.SnO
2Have high visible light transmissivity, high conductivity, high stability, high rigidity and extremely strong erosion resistance, be widely used in fields such as transparent conducting glass, solar cell, flat-panel monitor, high-temperature electronic device and gas sensor.SnO
2As present most widely used a kind of gas sensitive, have physics, chemical stability is good, erosion resistance is strong, and reliability is higher, satisfactory mechanical property; To gas detection is reversible, and absorption, desorption time weak point can use continuously for a long time; Though energy gap broad, donor level are appropriate shallow energy levels, obtain suitable characteristics such as electrical characteristic easily.Therefore with SnO
2Gas sensor for material of main part is made is in middle cardiac status in the metal-oxide semiconductor (MOS) resistance-type gas sensor.SnO
2Be a kind of surperficial control type gas sensitive, SnO
2Sensing capabilities the size of its particle diameter and specific surface area is had very strong dependency, its specific surface area is big more, helps gas adsorption and surface reaction more, the gas sensor that easy more acquisition is highly sensitive, selectivity is good.Because nano material has that granularity is little, specific surface is big, the big advantage of gas impedance variations relatively, thereby can satisfy gas sensitivity height, use temperature is low, sensing range is wide requirement.In recent years, along with the development of nanotechnology, utilized different technologies successfully to prepare SnO
2Structures such as nano wire, nano belt, nanometer rod, nano particle and to and air-sensitive sense characteristic study.Here synthesized in the reaction microcavity of design construction along different three-dimensional epitaxial SnO by thermal evaporation method
2Nanostructure is compared this structure of one dimension Nano structure and is had bigger specific surface area, is expected to further improve SnO
2The air-sensitive sensing capabilities.
Summary of the invention
The purpose of this invention is to provide a kind of SnO
2Complex three-dimensional nanostructure, it has the specific surface area bigger than one dimension Nano structure.
Another object of the present invention is for the preparation method of above-mentioned 3-D nano, structure is provided.
SnO provided by the present invention
2Complex three-dimensional nanostructure is to adopt thermal evaporation method, synthetic obtaining in the reaction microcavity of design construction.This SnO
2Complex three-dimensional nanostructure is SnO
2Monodimension nano stick repeatedly changes the oriented growth direction along different three-dimensionals, reverses, is bent to form a plurality of flex points, and then constitutes complicated three-dimensional structure, and the diameter of nanometer rod is 300-700nm.
This SnO
2The preparation method of complex three-dimensional nanostructure, concrete technology is as follows:
1) the crude iron grid is cut into the small pieces of 1cm * 2cm, thin iron railings lattice are cut into the sheet of 3cm * 5cm, ultrasonic cleaning is clean in alcohol then; Silicon chip is cut into the small pieces of 1cm * 2cm, and it is clean to pass through dilute hydrochloric acid, alcohol, acetone and deionized water ultrasonic cleaning successively;
2) the tubular type growth furnace of horizontal positioned is heated to 850-950 ℃ with the speed of 15 ℃/min;
3) with SnO
2Powder and Graphite Powder 99 uniform mixing after as reaction source are put into a quartz boat in by mass ratio at 1: 1, and a slice crude iron grid sheet is covered on the source, with the position of a slice silicon slice placed 1-2mm above crude iron grid sheet, collect resultant of reaction as substrate; With whole source and the substrate of covering of the thin iron railings lattice of a slice sheet, and at thin iron railings lattice sheet lay last layer source material;
4) quartz boat is put into the middle part of the horizontal tube atmosphere furnace that heats in advance;
5) feeding flow is the N of 0.3L/min-1L/min
2Gas reacts 30-120min as carrier gas under a standard atmospheric pressure;
6) take out quartz boat, the fine hair shape material of one deck white is arranged is SnO to face length on silicon chip substrate
23-D nano, structure;
Described crude iron grid is 20 orders;
Described thin iron railings lattice are 300 orders;
Described SnO
2The purity of powder and Graphite Powder 99 is 99.99%;
The horizontal pipe furnace of mentioning in the processing step 2 of the present invention, the diameter of its silica tube are 8cm, and length is 110cm.
The present invention has adopted the unique design of placing raw material in the above and below of substrate simultaneously according to the reaction mechanism of thermal evaporation prepared in reaction nanostructure, is built into the reaction microcavity of local around will substrate, confinement reaction atmosphere, successfully synthesize a kind of SnO of novelty
2Complex three-dimensional nanostructure.With respect to former synthetic SnO
2Nanostructure and preparation method thereof, outstanding feature of the present invention is: (1) synthetic SnO
2Nanostructure has novel unique three-D space structure, has bigger specific surface area than monodimension nano stick; (2) the confession source side method and the substrate location of unique design are about to the above and below that raw material is placed on vertical substrates simultaneously.(3) the reaction microcavity of design construction, it is less demanding to conversion unit and carrier gas better to control reaction atmosphere (4), adopts common horizontal tube atmosphere furnace and N
2Gas (5) method is simple, and cost is low, and good reproducibility can synthesize in a large number.
Description of drawings
Fig. 1 is SnO
2The X-ray diffractogram of complex three-dimensional nanostructure;
Fig. 2 a is a large amount of SnO
2The SEM photo of complex three-dimensional nanostructure;
Fig. 2 b is single SnO
2The SEM photo that complex three-dimensional nanostructure is 10000 times;
Fig. 2 c is single SnO
2The SEM photo that complex three-dimensional nanostructure is 20000 times.
Embodiment
Further specify technical characterstic of the present invention below in conjunction with accompanying drawing and specific embodiment.
Shown in the SEM photo of Fig. 2 a, Fig. 2 b and Fig. 2 c, this SnO
2Complex three-dimensional nanostructure is SnO
2Monodimension nano stick repeatedly changes the oriented growth direction along different three-dimensionals, reverses, is bent to form a plurality of flex points, and then constitutes complicated three-dimensional structure, and the diameter of nanometer rod is 300-700nm.
Embodiment 1
1) clean thin iron railings lattice (300 order) ultrasonic cleaning in spirituous solution of crude iron grid of small pieces (20 order) and sheet; It is clean that the small pieces silicon chip is passed through dilute hydrochloric acid, alcohol, acetone and deionized water ultrasonic cleaning successively;
2) the tubular type atmosphere furnace of horizontal positioned is heated to 850 ℃ with the speed of 15 ℃/min;
3) with SnO
299.99%) and Graphite Powder 99 (purity: 99.99%) be put in the quartz boat powder (purity: by mass ratio 1 to 1 uniform mixing, a slice crude iron grid sheet is covered on the source, with the position of a slice silicon slice placed, collect resultant of reaction as substrate at crude iron grid sheet vertical direction 1mm; With whole source and the substrate of covering of the thin iron railings lattice of a slice sheet, and put one deck source at thin iron railings lattice sheet and expect;
4) quartz boat is put into the middle part of the horizontal pipe furnace that heats in advance;
5) feeding flow is the rare gas element N of 0.3L/min
2As carrier gas, under a standard atmospheric pressure, react 35min;
6) take out quartz boat, face length has the fine hair shape material of one deck white on silicon chip substrate.
Embodiment 2
1) clean thin iron railings lattice (300 order) ultrasonic cleaning in spirituous solution of crude iron grid of small pieces (20 order) and sheet; It is clean that the small pieces silicon chip is passed through dilute hydrochloric acid, alcohol, acetone and deionized water ultrasonic cleaning successively;
2) the tubular type atmosphere furnace of horizontal positioned is heated to 900 ℃ with the speed of 15 ℃/min;
3) with SnO
299.99%) and Graphite Powder 99 (purity: 99.99%) be put in the quartz boat powder (purity: by mass ratio 1 to 1 uniform mixing, a slice crude iron grid sheet is covered on the source, with the position of a slice silicon slice placed, collect resultant of reaction as substrate at crude iron grid sheet vertical direction 2mm; With whole source and the substrate of covering of the thin iron railings lattice of a slice sheet, and put one deck source at thin iron railings lattice sheet and expect;
4) quartz boat is put into the middle part of the horizontal pipe furnace that heats in advance;
5) feeding flow is the rare gas element N of 1L/min
2As carrier gas, under a standard atmospheric pressure, react 60min;
6) take out quartz boat, face length has the fine hair shape material of one deck white on silicon chip substrate.
Embodiment 3
1) clean thin iron railings lattice (300 order) ultrasonic cleaning in spirituous solution of crude iron grid of small pieces (20 order) and sheet; It is clean that the small pieces silicon chip is passed through dilute hydrochloric acid, alcohol, acetone and deionized water ultrasonic cleaning successively;
2) the tubular type atmosphere furnace of horizontal positioned is heated to 950 ℃ with the speed of 15 ℃/min;
3) with SnO
299.99%) and Graphite Powder 99 (purity: 99.99%) be put in the quartz boat powder (purity: by mass ratio 1 to 1 uniform mixing, a slice crude iron grid sheet is covered on the source, with the position of a slice silicon slice placed, collect resultant of reaction as substrate at crude iron grid sheet vertical direction 2mm; With whole source and the substrate of covering of the thin iron railings lattice of a slice sheet, and put one deck source at thin iron railings lattice sheet and expect;
4) quartz boat is put into the middle part of the horizontal pipe furnace that heats in advance;
5) feeding flow is the rare gas element N of 1L/min
2As carrier gas, under a standard atmospheric pressure, react 120min;
6) take out quartz boat, face length has the fine hair shape material of one deck white on silicon chip substrate.
Embodiment 4
1) clean thin iron railings lattice (300 order) ultrasonic cleaning in spirituous solution of crude iron grid of small pieces (20 order) and sheet; It is clean that the small pieces silicon chip is passed through dilute hydrochloric acid, alcohol, acetone and deionized water ultrasonic cleaning successively;
2) the tubular type atmosphere furnace of horizontal positioned is heated to 920 ℃ with the speed of 15 ℃/min;
3) with SnO
299.99%) and Graphite Powder 99 (purity: 99.99%) be put in the quartz boat powder (purity: by mass ratio 1 to 1 uniform mixing, a slice crude iron grid sheet is covered on the source, with the position of a slice silicon slice placed, collect resultant of reaction as substrate at crude iron grid sheet vertical direction 1.5mm; With whole source and the substrate of covering of the thin iron railings lattice of a slice sheet, and put one deck source at thin iron railings lattice sheet and expect;
4) quartz boat is put into the middle part of the horizontal pipe furnace that heats in advance;
5) feeding flow is the rare gas element N of 0.8L/min
2As carrier gas, under a standard atmospheric pressure, react 80min;
6) take out quartz boat, face length has the fine hair shape material of one deck white on silicon chip substrate.
The product that aforesaid method obtains is SnO
23-D nano, structure, its X-ray diffractogram as shown in Figure 1, contrast standard diffraction spectra card shows that synthetic product is purified cubic rutile-type SnO
2, the diffraction peak of representing among the figure all is SnO
2The four directions rutile structure is produced, and does not have the impurity peaks such as other oxide compounds of Sn or Sn to occur.
Scanning electron microscope picture as Fig. 2 a shows: synthesized the SnO with complex three-dimensional space structure on silicon chip substrate in a large number
2Nanostructure.
Show as 10000 times the scanning electron microscope picture of Fig. 2 b with as 20000 times the scanning electron microscope picture of Fig. 2 c: SnO
2The complex three-dimensional space structure is repeatedly to change the oriented growth direction by monodimension nano stick, reverses, is bent to form.
Claims (5)
1. SnO
2Complex three-dimensional nanostructure is characterized in that: this SnO
2Complex three-dimensional nanostructure is to adopt thermal evaporation method, synthetic obtaining in the reaction microcavity of design construction; Be SnO
2Monodimension nano stick repeatedly changes the oriented growth direction along different three-dimensionals, reverses, is bent to form a plurality of flex points, and then constitutes complicated three-dimensional structure, and the diameter of nanometer rod is 300-700nm.
2. SnO as claimed in claim 1
2The preparation method of complex three-dimensional nanostructure, concrete technology is as follows:
1) the crude iron grid is cut into the small pieces of 1cm * 2cm, thin iron railings lattice are cut into the sheet of 3cm * 5cm, ultrasonic cleaning is clean in alcohol then; Silicon chip is cut into the small pieces of 1cm * 2cm, and it is clean to pass through dilute hydrochloric acid, alcohol, acetone and deionized water ultrasonic cleaning successively;
2) the tubular type growth furnace of horizontal positioned is heated to 850-950 ℃ with the speed of 15 ℃/min;
3) with SnO
2Powder and Graphite Powder 99 uniform mixing after as reaction source are put into a quartz boat in by mass ratio at 1: 1, and a slice crude iron grid sheet is covered on the source, with the position of a slice silicon slice placed 1-2mm above crude iron grid sheet, collect resultant of reaction as substrate; With whole source and the substrate of covering of the thin iron railings lattice of a slice sheet, and at thin iron railings lattice sheet lay last layer source material;
4) quartz boat is put into the middle part of the horizontal tube atmosphere furnace that heats in advance;
5) feeding flow is the N of 0.3L/min-1L/min
2Gas reacts 30-120min as carrier gas under a standard atmospheric pressure;
6) take out quartz boat, the fine hair shape material of one deck white is arranged is the SnO2 3-D nano, structure to face length on silicon chip substrate.
3. SnO according to claim 2
2The preparation method of complex three-dimensional nanostructure is characterized in that: described crude iron grid is 20 orders; Described thin iron railings lattice are 300 orders.
4. SnO according to claim 2
2The preparation method of complex three-dimensional nanostructure is characterized in that: described SnO
2The purity of powder and Graphite Powder 99 is 99.99%.
5. SnO according to claim 2
2The preparation method of complex three-dimensional nanostructure is characterized in that: the tubular type growth furnace of mentioning in the processing step 2, the diameter of its silica tube are 8cm, and length is 110cm.
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| CN102030362B (en) * | 2010-10-08 | 2012-08-29 | 四川大学 | Method for preparing SnO2 nanomaterial by hydride deposition |
| CN104213098B (en) * | 2013-06-04 | 2017-07-18 | 西安邮电大学 | A kind of nanometer wall construction being made up of sheet tin oxide and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6787231B1 (en) * | 2003-04-11 | 2004-09-07 | Electroplated Metal Solutions, Inc. | Tin (IV) oxide nanopowder and methods for preparation and use thereof |
| CN1530325A (en) * | 2003-03-10 | 2004-09-22 | 中南大学 | Method for preparing stannic anhydride nanometer crystal with solid phase reaction |
| CN1724383A (en) * | 2005-06-21 | 2006-01-25 | 电子科技大学 | Process for preparing one-dimensional nano tin dioxide material |
| CN1896732A (en) * | 2006-06-22 | 2007-01-17 | 上海交通大学 | Production of tubing network-structured nano-stannic oxide gas-sensing material |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1530325A (en) * | 2003-03-10 | 2004-09-22 | 中南大学 | Method for preparing stannic anhydride nanometer crystal with solid phase reaction |
| US6787231B1 (en) * | 2003-04-11 | 2004-09-07 | Electroplated Metal Solutions, Inc. | Tin (IV) oxide nanopowder and methods for preparation and use thereof |
| CN1724383A (en) * | 2005-06-21 | 2006-01-25 | 电子科技大学 | Process for preparing one-dimensional nano tin dioxide material |
| CN1896732A (en) * | 2006-06-22 | 2007-01-17 | 上海交通大学 | Production of tubing network-structured nano-stannic oxide gas-sensing material |
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| JP特开2006-69823A 2006.03.16 |
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