CN102020253B - Topological insulator material and preparation method thereof - Google Patents
Topological insulator material and preparation method thereof Download PDFInfo
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- CN102020253B CN102020253B CN2010105370825A CN201010537082A CN102020253B CN 102020253 B CN102020253 B CN 102020253B CN 2010105370825 A CN2010105370825 A CN 2010105370825A CN 201010537082 A CN201010537082 A CN 201010537082A CN 102020253 B CN102020253 B CN 102020253B
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Abstract
The invention provides a topological insulator material and a preparation method thereof, belonging to the preparation field of new materials. The topological insulator material is of a bamboo joint-like bismuth selenide nanostructure array which is formed by bamboo joint-like bismuth selenide nanostructures with uniform size. The preparation method is realized by using a template. In the preparation method, the regular bamboo joint-like bismuth selenide nanostructure array is directly obtained on the template, wherein the bismuth selenide is doped with copper; and the prepared nano material is provided with the topological insulating property capable of regulating materials. Compared with conventional preparation method of the bismuth selenide material, the preparation method of the topological insulator material has the characteristics of simple technology, low cost, one-step molding and the like.
Description
Technical field
The invention belongs to the preparation field of nano material, be specifically related to a kind of topological isolator material and preparation method thereof.
Background technology
According to the difference of electronic state structure, traditional material is divided into " metal " and " isolator " two big types.And topological isolator is a kind of new quantum polymorphic material, and the body electronic state of this polymorphic material is the isolator that energy gap is arranged, and its surface then is the metallic state of no energy gap.Be different from general sense because the surface state that surperficial unsaturated linkage or surface reconstruction cause; The surface metal attitude of topology isolator is that the topological framework by the body electronic state of material determines fully; Receive symmetry protection, therefore do not receive impurity and unordered influence basically.Guaranteed that just because of these key characters topological isolator might obtain important use in the electronic technology development in future, have huge application potential.The majorant topology insulating material that searching has enough big physical efficiency crack and has a chemicalstability becomes important focus and the difficult point that people pay close attention at present.
2009, Inst. of Physics, CAS/Beijing Condensed Matter Physics National Laboratory and Stanford Univ USA deeply cooperated, and had foretold that one type of new majorant topology insulating material system (is mainly V-VI family material, like Bi
2Se
3, Bi
2Te
3And Sb
2Te
3).They have systematically inquired into the physical mechanism that this type material becomes the majorant topology isolator from theoretical with calculating, and have provided the KP Hamiltonian of describing this dirac point, and have calculated a class APRES electronics spectrogram.The topological insulating material of this type has unique advantage, promptly has only a dirac point to exist in the said material surface state, is the simplest majorant topology isolator, and this simplicity is that the research of theoretical model provides good platform.In addition, the physical efficiency crack of said material is very big, especially Bi
2Se
3(0.3 ev), room temperature energy yardstick head and shoulders above, this also means spin electric device (Zhong Fang, Shou-Cheng Zhang, et al., Nature Physics, 2009 (5): 438-442) that might realize the room temperature less energy-consumption.
In theory research, relevant cut-and-try work also makes important progress.The M.Z.Hasan of Princeton university and R.J.Cava professor are at Bi
2Se
3In observed (Y.Xia, D.Qian, D.Hsieh, L.Wray, A.Pal, H.Lin, A.Bansil, D.Grauer, Y.S.Hor, R.J.Cava, et al., Nature Physics, 2009 (5): 398-402) of existing of surface state dirac point.The Fang Zhong of physics institute of the Chinese Academy of Sciences, Dai Xi study group cooperate with the Z.X.Shen professor study group of Stanford University, utilize ARPES to observe Bi
2Te
3Surperficial single dirac point (Y.L.Chen, J.G.Analytis, J.-H.Chu, Z.K.Liu in the material; S.-K.Mo, X.L.Qi, H.J.Zhang, D.H.Lu; X.Dai, Z.Fang, S.C.Zhang, I.R.Fisher; Z.Hussain, and Z.-X.Shen, Science, 2009 (325): 178-181).Except research to body phase material topology insulating property, the design of small scale low dimensional structures material synthetic and by dimensional effect introduce to The properties such as electron spinnings, then be another importance that people pay close attention to this field development.Synthesizing of V-VI family nano material comprises that mainly solution is combined to, like hydro-thermal synthetic (Hongjie Zhang, et al., J.AM.CHEM.SOC.; 2006 (128): 16490-16491), microwave synthetic (R.Harpeness, A.Gedanken, New J.Chem., 2003 (27): 1191-1193), electrochemical deposition (Xiaoguang Li, et al.; J.Phys.Chem.B, 2005 (109): 1430-1432) and ultrasonic electrochemical deposition (Xiaofeng Qiu, Clemens Burda, Ruiling Fu; Lin Pu, Hongyuan Chen, and Junjie Zhu, J.AM.CHEM.SOC.; 2004 (126): 16276-16277), and gas phase is synthetic, like chemical vapour deposition (Hongkun Park, et al.; J.AM.CHEM.SOC., 2008,130,6252) and molecular beam epitaxial growth (Molecular Beam Epitaxy; Be called for short MBE) (Kehui Wu, et al., Appl.Phys.Lett, 2009 (95): 053114-1～3).In the traditional molecular beam epitaxial growth and chemical Vapor deposition process; Owing to receive the restriction of the factors such as post-treatment process of complicated preparation technology, expensive material cost and difficulty; Often be difficult to synthetic efficiently a large amount of small size lower-dimensional topology insulating material, and device is simple and easy, the cost of material is low because electrochemical method has, the power consumption few, and is easy to realize the structure of the synthetic various complicacies of design through parameters such as regulating voltages; In V-VI family low dimension small size superstructure synthetic, receive attention (Wei Wang more and more widely; Xiaoguang Li, et al., J.Am.Chem.Soc.2007 (129): 6702-6703; Xincun Dou, Guanghai Li, et al., Nano Lett., 2008 (8): 1286-1290; Wei Wang, Xiaoguang Li, et al., J.Phys.Chem.C, 2008 (112): 15190-15194; F.H.Xue, G.T.Fei, B.Wu, P.Cui, and L.D.Zhang, J.Am.Chem.Soc.2005,127 (44), 15348-15349).Yet; Present electrochemical method institute synthetic superstructure (being mainly template assisted electrochemical deposition V-VI family superlattice nano line array); Only can realize regulation and control to material radial dimension (along nanowire growth direction); For the regulation and control of different fragments axial dimension (the vertical nano-wire direction of growth), so a certain segmental selectivity preparation, be what not appear in the newspapers.And this part work is crucial to the research of material topology insulating property.
Summary of the invention
The purpose of this invention is to provide a kind of topological insulating material and preparation method thereof, this topology insulating material is a ring shape bismuth selenide nano-structure array.
Ring shape bismuth selenide nano-structure array is made up of the ring shape bismuth selenide nanostructure of size homogeneous; Ring shape bismuth selenide nano-structure array thickness (being the length of ring shape bismuth selenide (copper doping) nanostructure) can be 0.5-50 μ m; Wherein the external diameter of ring shape bismuth selenide nanostructure is 20-200nm, the length-to-diameter ratio 2.5-2500 of nanostructure.
Ring shape bismuth selenide nanostructure is doped with copper.
The preparation of ring shape bismuth selenide provided by the invention (copper doping) nano-structure array comprises:
A. the preparation of electrolytic solution: solute is bismuth sulfate, copper sulfate and selenous acid; Solvent can be trolamine (Triethanolamine; Be abbreviated as TEA) and the mixed solution of disodium EDTA (Ethylenediaminetetraacetic acid disodium salt is abbreviated as EDTA-2Na) and water.The composition of principal reaction thing is as shown in the table:
B. electrochemical appliance: be working electrode with the gold-plated anodic oxidation aluminium formwork in the back side (Anodic Aluminum Oxide is called for short AAO, but is not limited to this template), anode is selected platinum electrode for use, and reference electrode is a SCE;
C. deposition is tactful: adopt multistep impulse of current sedimentation (Multi Current Steps), design I
1=1 * 10
-6～9 * 10
-6A/mm
2And I
2=1 * 10
-5～9 * 10
-5A/mm
2Two sections deposition process (like Fig. 1, T
1: T
2=1: 1～4: 1, T wherein
1Form by 1～6 impulse of current), the inner bismuth selenide (Bi that fills in the template duct
2Se
3) and copper doping bismuth selenide (Bi
2-xCu
xSe
3) alternating structure, depositing time is 0.5～5 hour;
D. template is removed, and obtains ring shape bismuth selenide (copper doping) nano-structure array.
Ring shape bismuth selenide (copper doping) nano-structure array that adopts method for preparing to obtain is carried out anneal and can obtain single crystal structure.
Said annealing temperature was regulated and control by following intensification and constant temperature stage:
1) starting temperature of said temperature rise period is selected from the arbitrary temperature between 10 ℃-25 ℃, and final temperature is selected from the arbitrary temperature between 300-600 ℃; Temperature rise rate in the said temperature rise period is 1-20 ℃/min;
2) temperature in said constant temperature stage is 1) described in final temperature; The time in said constant temperature stage is 0.5-10 hour.
The present invention has the following advantages:
Adopt the auxiliary method of template, on template, directly obtain regular ring shape bismuth selenide (copper doping) nano-structure array, compare to the preparation of traditional bismuth selenide material, have characteristics such as technology is simple, with low cost, disposal molding; Through adjusting to invented technology, can obtain ring shape bismuth selenide (copper doping) the nano-structure array layer of different length-to-diameter ratios and crystal formation, and with the topological insulating property of this controlled material.
Description of drawings
Fig. 1 invents the deposition strategy that said electrochemical deposition method adopts for this;
Fig. 2 is the electron scanning micrograph of ring shape bismuth selenide (copper doping) nanostructure of embodiment 1 preparation;
Fig. 3 is the electron scanning micrograph of ring shape bismuth selenide (copper doping) nanostructure of embodiment 2 preparations.
Embodiment
Following examples only are detailed description of the present invention, and should not be construed as qualification of the present invention.
The key step of preparation ring shape bismuth selenide (copper doping) nano-structure array is following in the embodiment of the invention:
Being coated with about 1 centimetre of 10-100nm thick golden film, length and width, thickness with the back side is that the alumina formwork of 5-50 micron is a working electrode; Platinized platinum is a counter electrode; SCE is a reference electrode; With concentration be respectively bismuth sulfate, copper sulfate and the selenous acid of 0.001～0.02mol/L, 0.001～0.02mol/L and 0.003～0.06mol/L trolamine (0.015～0.3mol/L) and disodium EDTA (0.0035～0.07mol/L) with the mixed solution of water be electrolytic solution; Design the condition deposit copper doping bismuth selenide 0.5～5 hour of two sections different deposition behaviors, the current density in two stages is respectively 1 * 10
-6～9 * 10
-6A/mm
2With 1 * 10
-5～9 * 10
-5A/mm
2(T
1: T
2=1: 1～4: 1, T wherein
1Form by 1～6 impulse of current).To at the uniform velocity stir electrolytic solution in the deposition process.
Embodiment 1, template assisted electrochemical sedimentation prepare ring shape bismuth selenide nano-structure array
Being coated with about 1 centimetre of 50nm thick golden film, length and width, thickness with the back side is that 30 microns alumina formwork is a working electrode; Platinized platinum is a counter electrode; SCE is a reference electrode; The mixed solution of trolamine (0.3mol/L) and disodium EDTA (0.07mol/L) and water that is respectively bismuth sulfate, copper sulfate and the selenous acid of 0.02mol/L, 0.02mol/L and 0.06mol/L with concentration is an electrolytic solution; Design the condition deposit bismuth selenide of two sections different deposition behaviors or mix the copper bismuth selenide, the current density in two stages is respectively 9 * 10
-6A/mm
2With 9 * 10
-5A/mm
2(T
1: T
2=2: 1, T wherein
1Form by 2 impulse of current).1.5 will at the uniform velocity stir electrolytic solution in hour deposition process.After electrochemical deposition finished, alumina formwork inside had evenly been filled one deck bismuth selenide or has been mixed the copper bismuth selenide, thick about 10 microns (see figure 2)s, and the external diameter of forming the bamboo knot shaped structure array is 50nm, length-to-diameter ratio is 200.Can know that by figure evenly having filled the ring shape in inside, alumina formwork duct mixes copper bismuth selenide nano-structure array.
Embodiment 2, template assisted electrochemical sedimentation prepare ring shape bismuth selenide nano-structure array
Being coated with about 1 centimetre of 50nm thick golden film, length and width, thickness with the back side is that 30 microns alumina formwork is a working electrode; Platinized platinum is a counter electrode; SCE is a reference electrode; The mixed solution of trolamine (0.015mol/L) and disodium EDTA (0.0035mol/L) and water that is respectively bismuth sulfate, copper sulfate and the selenous acid of 0.001mol/L, 0.001mol/L and 0.003mol/L with concentration is an electrolytic solution; Design the condition deposit bismuth selenide of two sections different deposition behaviors or mix the copper bismuth selenide, the current density in two stages is respectively 1 * 10
-6A/mm
2With 1 * 10
-5A/mm
2(T
1: T
2=1: 1, T wherein
1Form by 6 impulse of current).To at the uniform velocity stir electrolytic solution in 5 hours deposition process.After electrochemical deposition finished, alumina formwork inside had evenly been filled one deck bismuth selenide or has been mixed the copper bismuth selenide, thick about 10 microns (see figure 3)s, and the external diameter of forming the bamboo knot shaped structure array is 50nm, length-to-diameter ratio is 200.Can know that by Fig. 3 evenly having filled the ring shape in inside, alumina formwork duct mixes copper bismuth selenide nano-structure array.
It should be noted that at last the purpose of publicizing and implementing example is to help further to understand the present invention, but it will be appreciated by those skilled in the art that: in the spirit and scope that do not break away from the present invention and appended claim, various replacements and modification all are possible.Therefore, the present invention should not be limited to the disclosed content of embodiment, and the scope that the present invention requires to protect is as the criterion with the scope that claims define.
Claims (10)
1. a topological insulating material is characterized in that, this material is bismuth selenide nanostructure and array thereof, and wherein, the bismuth selenide nanostructure is the ring shape, and its array is made up of the ring shape bismuth selenide nanostructure of many size homogeneous.
2. topological insulating material as claimed in claim 1 is characterized in that, said bismuth selenide nanostructure is doped with the copper metallic element.
3. topological insulating material as claimed in claim 1 is characterized in that, ring shape bismuth selenide nano-structure array thickness is 0.5-50 μ m.
4. topological insulating material as claimed in claim 1 is characterized in that, the external diameter of ring shape bismuth selenide nanostructure is 20-200nm, the length-to-diameter ratio 2.5-2500 of nanostructure.
5. the preparation method of ring shape bismuth selenide nano-structure array as claimed in claim 1, concrete steps comprise:
1) preparation of electrolytic solution: solute is bismuth sulfate, copper sulfate and selenous acid, and solvent is the mixed solution of trolamine and disodium EDTA and water;
2) electrochemical appliance: the nano ordered vesicular template gold-plated with the back side is working electrode, and anode is selected platinum electrode for use, and reference electrode is a SCE;
3) deposition strategy: adopt multistep impulse of current sedimentation, inner bismuth selenide and the copper doping bismuth selenide alternating structure of filling in the template duct;
4) template is removed, and obtains ring shape bismuth selenide nano-structure array.
6. method as claimed in claim 5; It is characterized in that; The concentration of bismuth sulfate, copper sulfate and selenous acid is respectively 0.001～0.02mol/L, 0.001～0.02mol/L and 0.003～0.06mol/L, trolamine: the proportioning of disodium EDTA is 0.015～0.3mol/L: 0.0035～0.07mol/L.
7. method as claimed in claim 5 is characterized in that, said template is anodised aluminium or the ordered porous template of polycarbonate nano level.
8. method as claimed in claim 5 is characterized in that, said multistep impulse of current sedimentation comprises two sections deposition process I
1=1 * 10
-6～9 * 10
-6A/mm
2And I
2=1 * 10
-5～9 * 10
-5A/mm
2, T in two sections deposition process
1: T
2=1: 1～4: 1, depositing time is 0.5～5 hour.
9. method as claimed in claim 8 is characterized in that T
1Form by 1～6 impulse of current.
10. method as claimed in claim 5 is characterized in that, the ring shape bismuth selenide nano-structure array that adopts method for preparing to obtain is carried out anneal, and concrete annealing temperature was regulated and control by following intensification and constant temperature stage:
1) starting temperature of said temperature rise period is selected from the arbitrary temperature between 10 ℃-25 ℃, and final temperature is selected from the arbitrary temperature between 300-600 ℃; Temperature rise rate in the said temperature rise period is 1-20 ℃/min;
2) described final temperature is the temperature in constant temperature stage, and the time in said constant temperature stage is 0.5-10 hour.
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| CN105483790B (en) * | 2015-12-17 | 2018-01-12 | 山东建筑大学 | A kind of method that bismuth selenide thermal electric film is prepared with bismuth oxide |
| CN108461382B (en) * | 2018-02-06 | 2020-06-19 | 天津理工大学 | Preparation method for realizing Cu doping of bismuth selenide nano material of topological insulator |
| WO2022045965A1 (en) * | 2020-08-25 | 2022-03-03 | Nanyang Technological University | A product and process of nanoforming |
| CN114864927B (en) * | 2022-05-20 | 2023-12-29 | 青岛大学 | High-performance zinc ion battery anode material copper-doped bismuth selenide and preparation method thereof |
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|---|---|---|---|---|
| CN101475149A (en) * | 2009-01-20 | 2009-07-08 | 宁波大学 | Preparation of bismuth selenide nanoparticle |
| CN101513994A (en) * | 2009-03-10 | 2009-08-26 | 中国科学院上海硅酸盐研究所 | Bismuth base hydrogen storage material and preparation method thereof |
| CN101746738A (en) * | 2009-09-29 | 2010-06-23 | 武汉理工大学 | Preparing method of nano laminar thermoelectric Bi2Se3 compound |
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| CN101475149A (en) * | 2009-01-20 | 2009-07-08 | 宁波大学 | Preparation of bismuth selenide nanoparticle |
| CN101513994A (en) * | 2009-03-10 | 2009-08-26 | 中国科学院上海硅酸盐研究所 | Bismuth base hydrogen storage material and preparation method thereof |
| CN101746738A (en) * | 2009-09-29 | 2010-06-23 | 武汉理工大学 | Preparing method of nano laminar thermoelectric Bi2Se3 compound |
Non-Patent Citations (1)
| Title |
|---|
| 王娟等.无还原剂一步湿化学反应法合成Bi2Se3超薄六边形纳米片.《材料科学与工程学报》.2010,第28卷(第2期),283-286. * |
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