CN106702320A - Superconductor-insulator-metal heterogeneous two-dimension crystalline film material and preparing method thereof - Google Patents
Superconductor-insulator-metal heterogeneous two-dimension crystalline film material and preparing method thereof Download PDFInfo
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- CN106702320A CN106702320A CN201510779021.2A CN201510779021A CN106702320A CN 106702320 A CN106702320 A CN 106702320A CN 201510779021 A CN201510779021 A CN 201510779021A CN 106702320 A CN106702320 A CN 106702320A
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Abstract
The invention discloses a superconductor-insulator-metal heterogeneous film material which is of a laminated structure. The superconductor-insulator-metal heterogeneous film material comprises a metal hafnium base layer, a hafnium pentatelluride film structure layer and a hafnium tritelluride film structure layer, and the laminated structure is expanded in a two-dimensional plane. A preparing method includes the steps that a proper amount of high-purity hafnium is evaporated and deposited to the surface of the transition metal hafnium base layer in a vacuum environment; annealing treatment is conducted so that deposited tellurium atoms and metal hafnium atoms on the base interact with each other to form a hafnium pentatelluride two-dimensional orderly crystalline film-shaped structure; and annealing treatment is further conducted, the surface of the formed hafnium pentatelluride two-dimensional orderly crystalline film-shaped structure is subjected to the structure change again to form hafnium tritelluride, finally, the hafnium tritelluride-hafnium pentatelluride-metal hafnium two-dimensional laminated structure is formed, and the superconductor-insulator-metal heterogeneous film material is obtained. The preparing technology is relatively simple, defects of the obtained heterogeneous-structure film are few, an interface is not likely to be polluted, and the quality of the heterogeneous-structure film is improved.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of superconductor-insulator-metal is heterogeneous
Two-dimentional crystalline film material and preparation method thereof.
Background technology
Graphene, represents as the classics of two dimensional crystal material, due to the electronically and physically property of its uniqueness,
It is short to turn into study hotspot highly visible during the decade since being peeled off from its parent graphite from 2004,
The exploration in world wide to New Two Dimensional crystalline material and research boom are triggered.Different physical properties
Two dimensional crystal material superposition, it is most likely that produce some new material structures and physical property, for example,
In the heterogeneous laminated construction of Graphene-boron nitride, new physical property (Hofstadter butterfly has been observed
Butterfly --- the excellent parting pattern of description electronics moving situation in magnetic field)；This Graphene-boron nitride
Heterogeneous laminated construction, is not a kind of simple material stacking, but a kind of new two dimensional crystal material, from
And be used to confirm the theoretical prediction before 40 years, huge work will have been played in electronics and optoelectronic device
With.Nearest theoretical research shows, is become attached to the heterogeneous folded of body and (s ripples) superconductor by studying topology
Rotating fields, it is most likely that observe Maastricht Treaty Rana Fermion, this particle is expected to the shape in quantum calculation
Into the quantum bit of stabilization so that efficient topological quantum computer is possibly realized.Build this lamination knot
Structure has important scientific value and application prospect.
Five telluride hafniums are foretold to be topological insulator (energy gap of 0.4 electron volts) in theory.In addition,
The three telluride hafniums of figure have been reported with superconducting property.The structure and ten split-phases of five telluride hafniums and three telluride hafniums
Seemingly, five telluride hafniums are coupled together by zigzag tellurium chain in the middle of the prism structures of three telluride hafniums,
All there is two-dimensional layer configuration.If this five telluride hafnium of different nature and three telluride can be spontaneously formed
The heterogeneous laminated construction of hafnium, can carry out study on regulation to physical property.For the research in terms of this, in base
Plinth and application aspect all will be with good prospects.The application that two-dimentional dissimilar materials is paid, high-quality material
Preparation be its crucial and basis.But on the experiment preparation method of five telluride hafnium films, particularly atom
The preparation of the sample of level thickness, does not report so far.Experiment preparation method on three telluride hafnium blocks,
Presently mainly prepared with the method for sintering, and the preparation of three telluride hafnium samples of atomic-level thickness, so far
Also do not report.
As a kind of brand-new superconductor-insulator-metal heterofilm material, the telluride hafnium of three telluride hafnium-five
The acquisition of-metal hafnium heterofilm is the premise and condition to its further physical property research and practical application.
The method for preparing two-dimensional material heterojunction structure conventional at present is to peel off the method for shifting stacking, but this method
The complexity of preparation technology is increased, and the heterojunction structure film defects for obtaining are more, interface is easily dirty
Dye, causes the reduction of its performance.Therefore, experimentally find one kind and prepare the tellurium of three telluride hafnium of high-quality-five
The method for changing hafnium-metal hafnium heterofilm material is particularly important.
The content of the invention
It is an object of the invention to provide a kind of superconductor-insulator-metal heterofilm material and its preparation
Method, preparation method is relatively easy, and the superconductor-insulator-metal heterofilm material property of preparation is more
It is high.
Concrete scheme of the invention is as follows：
A kind of superconductor-insulator-metal heterofilm material, is layer structure, including metal hafnium substrate
Layer, five telluride hafnium membrane structures layer and three telluride hafnium membrane structures layer, the five telluride hafnium membrane structure layer are located at institute
The surface of metal hafnium basalis is stated, the three telluride hafnium membrane structure layer is located at five telluride hafnium membrane structure layer
Surface, the layer structure extends in two dimensional surface.
The invention also discloses a kind of preparation side of above-mentioned superconductor-insulator-metal heterofilm material
Method, comprises the following steps：
Step 1) under vacuum conditions, by appropriate high-purity tellurium hydatogenesis to hafnium transition metal substrate table
Face；
Step 2) made annealing treatment, so that the metal hafnium atom on the tellurium atom and the substrate of deposition
Interact and form five telluride hafnium sequential 2 D crystalline state membrane structures；
Step 3) further make annealing treatment, make the five telluride hafnium membranaceous knot of sequential 2 D crystalline state to be formed
Recurring structure changes to form three telluride hafniums again on the surface of structure, ultimately forms the telluride hafnium of three telluride hafnium-five-gold
Category hafnium two-dimension laminate structure, obtains the superconductor-insulator being made up of the telluride hafnium of three telluride hafnium-five-metal hafnium
- metal heterofilm material.
The high-purity tellurium for wherein using is 99.999% or the tellurium of similar purity.Because five telluride for being formed
This sequential 2 D crystalline state membrane structure of hafnium is insulating material, and three telluriums that five telluride hafnium surfaces are formed
It is a kind of superconduction sequential 2 D crystalline state film to change hafnium, so, the telluride hafnium of three telluride hafnium-five-gold for finally giving
Category hafnium two-dimension laminate structure is superconductor-insulator-metal heterofilm material.
Further, step 1) in tellurium used the mistake is evaporated to by the method for physical vapour deposition (PVD)
Cross metal hafnium substrate surface.
Further, step 2) described in annealing temperature it is interval be 450 DEG C~500 DEG C, annealing time 10-20
Minute.Preferably, the annealing temperature is 500 DEG C, annealing time 15 minutes.
Further, the mistake of the five telluride hafnium sequential 2 D crystalline state membrane structure is formed for growing
The surface for crossing metal hafnium substrate is (0001) face of metal hafnium.
Further, the forming method in (0001) face of the metal hafnium is：First to gold in vacuum chamber
Category hafnium monocrystalline is carried out argon ion sputtering 3-6 hours, then metal hafnium substrate is heated and maintained at into 900 DEG C
High annealing 5-10 minutes, formation can be scanned the periodicity superjunction that tunnel microscope (STM) is characterized
Structure.Preferably, the argon ion sputtering time is carried out for 5 hours, in 900 DEG C of high annealing 8 minutes.
Wherein, the periodicity superstructure that the five telluride hafnium crystalline material is formed in (0001) face of hafnium,
Its typical cycle is 0.34 × 1.09nm, can find to fluctuate with sample temperature.The periodicity superstructure energy
Tunnel microscope (STM) is enough scanned to be characterized.
Further, the Atomic Arrangement energy of the top of the five telluride hafnium sequential 2 D crystalline state membrane structure
Tunnel microscope is enough scanned to be characterized.
Further, the energy gap of 0.4 electron volts of the five telluride hafnium crystalline material can be differentiated conductance
(dI/dV) spectrum is characterized.
Further, step 3) in the annealing temperature it is interval for 500 DEG C~600 DEG C, annealing time
10-20 minutes.Preferably, the annealing temperature is 560 DEG C, and annealing time is 15 minutes.
Five telluride hafnium surfaces of the three telluride hafnium crystalline material on (0001) face of metal hafnium form
Periodicity superstructure, typical cycle is 0.38 × 0.47nm, may find to fluctuate with sample temperature, should
Periodicity superstructure can be scanned tunnel microscope and be characterized.
Further, the Atomic Arrangement of the three telluride hafnium crystalline material top can be scanned tunnel show
Micro mirror (STM) is characterized.
Further, the superconducting energy gap of the three telluride hafnium crystalline material can be differentiated conductance (dI/dV)
Characterized.
A kind of superconductor-insulator-metal heterofilm material that the present invention is provided and preparation method thereof, leads to
Cross the telluride hafnium of three telluride hafnium-five-metal hafnium crystalline substance that molecular beam epitaxial method has grown large-area high-quality
State thin-film material, has abandoned the conventional method for peeling off transfer stacking, reduces superconductor-insulator-metal
The complexity of heterofilm material technology, meanwhile, the heterojunction structure film defects of acquisition are few, and interface is difficult
It is contaminated, improve the quality of heterojunction structure film.The thin-film material is the newcomer of the heterogeneous family of superconduction,
The research field of superconduction heterofilm is expanded, has been had in terms of Future Information electronics and device developmental research
Be widely used potentiality.
Brief description of the drawings
Fig. 1 is by the schematic diagram of high-purity tellurium hydatogenesis to hafnium transition metal substrate surface in the present invention；
Fig. 2 for the present invention in for the first time make annealing treatment after hafnium transition metal substrate surface formed five telluride
The schematic diagram of hafnium membrane structure layer；
Fig. 3 is five telluride hafnium membrane structure layer surfaces, three telluride of formation after second annealing in the present invention
The schematic diagram of hafnium membrane structure layer；
Fig. 4 is the telluride hafnium of three telluride hafnium-five-metal hafnium heterofilm material ultimately formed in the present invention
Side view；
Fig. 5 is the scanning of the coverage tellurium particle high deposited on (0001) surface of metal hafnium in the present invention
Tunnel microscope image；
Fig. 6 is sweeping for the telluride hafnium film of high-quality five that is prepared on (0001) face of metal hafnium in the present invention
Retouch tunnel microscope image；
Fig. 7 is the differential conductance of the telluride hafnium of high-quality five prepared on (0001) face of hafnium in the present invention
Spectrum；
Fig. 8 is the telluride hafnium of three telluride hafnium of high-quality-five prepared on (0001) face of hafnium in the present invention
The PSTM image of laminated material；
Fig. 9 is the telluride hafnium of three telluride hafnium of high-quality-five prepared on (0001) face of hafnium in the present invention
The differential conductance spectrum of laminated material.
Specific embodiment
Below in conjunction with the accompanying drawings to the present invention provide a kind of superconductor-insulator-metal heterofilm material and
The specific embodiment of its preparation method elaborates.
Fig. 1 is by the schematic diagram of high-purity tellurium hydatogenesis to hafnium transition metal substrate surface in the present invention；
Fig. 2 for the present invention in for the first time make annealing treatment after hafnium transition metal substrate surface formed five telluride hafnium films
The schematic diagram of structure sheaf；Fig. 3 is five telluride hafnium membrane structure layer surfaces after second annealing in the present invention
Form the schematic diagram of three telluride hafnium membrane structures layer；Fig. 4 is the three telluride hafniums-five ultimately formed in the present invention
The side view of telluride hafnium-metal hafnium heterofilm material.
High-quality superconductor-insulator-metal heterofilm material is prepared on hafnium transition metal surface, it is whole
As Figure 1-Figure 4, Fig. 1 shows in the present invention in (0001) of hafnium production procedure effect diagram
The tellurium particle of the coverage high of surface room temperature deposition；Fig. 2 show in the present invention after sample annealing
Five telluride hafnium membrane materials of the sequential 2 D that (0001) superficial growth of hafnium goes out；Fig. 3 shows the present invention
The tellurium of three telluride hafnium-five of the sequential 2 D gone out in (0001) superficial growth of hafnium after middle sample annealing
Change hafnium lamination membrane material, in the lateral plan of Fig. 4, clearly demonstrate the telluride hafnium of three telluride hafnium-five-
The arrangement of metal hafnium, the structure extends in two dimensional surface periodically.
Prepare the specific steps of the superconductor-insulator-metal heterofilm material：
Embodiment 1：
Multiple argon ion sputtering is carried out nearly 5 hours to hafnium monocrystalline in vacuum chamber, then by by metal hafnium
Substrate is heated and maintained at 900 DEG C of high annealings 8 minutes, obtains clean smooth (0001) crystal face.
Under vacuum conditions, appropriate high-purity tellurium is existed metallic tellurium uniform deposition by silica crucible evaporation source
Hafnium substrate (0001) surface that is clean smooth and remaining room temperature.Tellurium particle as shown in Figure 1 is in substrate table
Face is in random distribution, as shown in the PSTM image of Fig. 5, will deposit the sample for having tellurium particle
Product are annealed 15 minutes at 500 DEG C so that be covered in the tellurium atom and base on hafnium substrate (0001) surface
Bottom hafnium atom interacts, and five telluride hafnium membrane materials is formed, as shown in fig. 6, the membrane material is energy
The periodicity superstructure that tunnel microscope is characterized enough is scanned, this also causes to be deposited on hafnium substrate originally
(0001) the tellurium particle on surface is disappeared.The differential conductance spectrum of Fig. 7 shows that the energy gap of the structure has (arrow
Shown in head), belong to insulating material.Above-mentioned sample is further annealed 15 minutes at 560 DEG C,
So that the five telluride hafniums in top react, three telluride hafnium membrane materials are formed, as shown in figure 8,
The three telluride hafnium membrane materials for being formed are characterized by periodic structure can be scanned tunnel microscope.Fig. 9's
Differential conductance spectrum shows that the superconducting energy gap of the structure is present (shown in arrow), belongs to superconductor material.Institute
To finally give the superconductor-insulator-metal being made up of the telluride hafnium of three telluride hafnium-five-metal hafnium heterogeneous
Thin-film material.
Embodiment 2：
Multiple argon ion sputtering is carried out nearly 3 hours to hafnium monocrystalline in vacuum chamber, then by by metal hafnium
Substrate is heated and maintained at 900 DEG C of high annealings 5 minutes, obtains clean smooth (0001) crystal face.
Under vacuum conditions, appropriate high-purity tellurium is existed metallic tellurium uniform deposition by silica crucible evaporation source
Hafnium substrate (0001) surface that is clean smooth and remaining room temperature.Tellurium particle is in substrate surface in random
Distribution, the sample that will deposit has tellurium particle is annealed 10 minutes at 450 DEG C so that be covered in hafnium substrate
(0001) tellurium atom on surface and substrate hafnium atom interact, and form five telluride hafnium membrane materials,
The membrane material is can be scanned the periodicity superstructure that tunnel microscope is characterized, and this also causes original heavy
Tellurium particle of the product on hafnium substrate (0001) surface is disappeared.Show the energy gap of the structure through differential conductance spectrum
In the presence of belonging to insulating material.Above-mentioned sample is further annealed 20 minutes at 600 DEG C so that
The five telluride hafniums in top react, and form three telluride hafnium membrane materials, three telluride hafnium films of formation
Material is characterized by periodic structure can be scanned tunnel microscope.Show the structure through differential conductance spectrum
Superconducting energy gap exist, belong to superconductor material.So, finally give by the telluride hafnium of three telluride hafnium-five-
Superconductor-insulator-metal heterofilm material that metal hafnium is constituted.
Embodiment 3：
Multiple argon ion sputtering is carried out nearly 6 hours to hafnium monocrystalline in vacuum chamber, then by by metal hafnium
Substrate is heated and maintained at 900 DEG C of high annealings 10 minutes, obtains clean smooth (0001) crystal face.
Under vacuum conditions, appropriate high-purity tellurium is existed metallic tellurium uniform deposition by silica crucible evaporation source
Hafnium substrate (0001) surface that is clean smooth and remaining room temperature.Tellurium particle is in substrate surface in random
Distribution, the sample that will deposit has tellurium particle is annealed 10 minutes at 500 DEG C so that be covered in hafnium substrate
(0001) tellurium atom on surface and substrate hafnium atom interact, and form five telluride hafnium membrane materials,
The membrane material is can be scanned the periodicity superstructure that tunnel microscope is characterized, and this also causes original heavy
Tellurium particle of the product on hafnium substrate (0001) surface is disappeared.Show the energy gap of the structure through differential conductance spectrum
In the presence of belonging to insulating material.Above-mentioned sample is further annealed 10 minutes at 500 DEG C so that
The five telluride hafniums in top react, and form three telluride hafnium membrane materials, three telluride hafnium films of formation
Material is characterized by periodic structure can be scanned tunnel microscope.Show the structure through differential conductance spectrum
Superconducting energy gap exist, belong to superconductor material.So, finally give by the telluride hafnium of three telluride hafnium-five-
Superconductor-insulator-metal heterofilm material that metal hafnium is constituted.
More than, although several embodiments of the invention is illustrated, but these implementation methods are intended only as
What example was proposed, it is not intended to limit the scope of the present invention.For these new implementation methods, can be with
Other various modes are implemented, and are not departing from the range of idea of the invention, can carry out various provinces
Slightly, displacement and change.These implementation methods and its deformation, are contained in scope and spirit of the present invention
While, in the invention being also contained in described in claims and its equivalency range.
Claims (10)
1. a kind of superconductor-insulator-metal heterofilm material, it is characterised in that be layer structure,
Including metal hafnium basalis, five telluride hafnium membrane structures layer and three telluride hafnium membrane structures layer, the five telluride hafnium
Membrane structure layer is located at the surface of the metal hafnium basalis, and the three telluride hafnium membrane structure layer is located at described five
The surface of telluride hafnium membrane structure layer, the layer structure extends in two dimensional surface.
2. the preparation of a kind of superconductor as claimed in claim 1-insulator-metal heterofilm material
Method, it is characterised in that comprise the following steps：
Step 1) under vacuum conditions, by appropriate high-purity tellurium hydatogenesis to hafnium transition metal substrate table
Face；
Step 2) made annealing treatment, so that the metal hafnium atom on the tellurium atom and the substrate of deposition
Interact and form five telluride hafnium sequential 2 D crystalline state membrane structures；
Step 3) further make annealing treatment, make the five telluride hafnium membranaceous knot of sequential 2 D crystalline state to be formed
Recurring structure changes to form three telluride hafniums again on the surface of structure, ultimately forms the telluride hafnium of three telluride hafnium-five-gold
Category hafnium two-dimension laminate structure, obtains the superconductor-insulator being made up of the telluride hafnium of three telluride hafnium-five-metal hafnium
- metal heterofilm material.
3. preparation method according to claim 2, it is characterised in that step 1) in tellurium used
The hafnium transition metal substrate surface is evaporated to by the method for physical vapour deposition (PVD).
4. preparation method according to claim 2, it is characterised in that step 2) described in anneal
Temperature range is 450 DEG C~500 DEG C, annealing time 10-20 minutes.
5. the preparation method according to claim any one of 2-4, it is characterised in that for growing shape
It is gold into the surface of the hafnium transition metal substrate of the five telluride hafnium sequential 2 D crystalline state membrane structure
Belong to (0001) face of hafnium.
6. preparation method according to claim 5, it is characterised in that (0001) of the metal hafnium
The forming method in face is：Metal hafnium monocrystalline is carried out argon ion sputtering 3-6 hours in vacuum chamber first, then
Metal hafnium substrate is heated and maintained at high annealing 5-10 minutes of 900 DEG C, formation can be scanned tunnel
The periodicity superstructure that road microscope is characterized.
7. preparation method according to claim 6, it is characterised in that the five telluride hafnium two dimension
The Atomic Arrangement of the top of orderly crystalline state membrane structure can be scanned tunnel microscope and be characterized.
8. preparation method according to claim 7, it is characterised in that the five telluride hafnium crystalline state
The energy gap of 0.4 electron volts of material can be differentiated conductance spectrum and be characterized.
9. preparation method according to claim 2, it is characterised in that step 3) in described move back
Fiery temperature range is 500 DEG C~600 DEG C, annealing time 10-20 minutes.
10. preparation method according to claim 2, it is characterised in that the three telluride hafnium crystalline state
The Atomic Arrangement of material top can be scanned tunnel microscope and be characterized, and the three telluride hafnium is brilliant
The superconducting energy gap of state material can be differentiated conductance spectrum and be characterized.
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| CN115369359A (en) * | 2022-08-17 | 2022-11-22 | 南京航空航天大学 | Method for removing gold (100) surface reconstruction layer |
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