CN116913605A - Method for precisely growing inch-grade niobium diselenide superconducting film by van der Waals self-epitaxy, product and application - Google Patents
Method for precisely growing inch-grade niobium diselenide superconducting film by van der Waals self-epitaxy, product and application Download PDFInfo
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- CXRFFSKFQFGBOT-UHFFFAOYSA-N bis(selanylidene)niobium Chemical compound [Se]=[Nb]=[Se] CXRFFSKFQFGBOT-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000000407 epitaxy Methods 0.000 title claims abstract description 15
- 239000010408 film Substances 0.000 claims abstract description 100
- 239000000758 substrate Substances 0.000 claims abstract description 66
- 239000010409 thin film Substances 0.000 claims abstract description 43
- 238000002360 preparation method Methods 0.000 claims abstract description 27
- 239000010955 niobium Substances 0.000 claims abstract description 24
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 22
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 9
- 238000000137 annealing Methods 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 6
- 238000001514 detection method Methods 0.000 claims abstract description 5
- ZDYUUBIMAGBMPY-UHFFFAOYSA-N oxalic acid;hydrate Chemical compound O.OC(=O)C(O)=O ZDYUUBIMAGBMPY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 40
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 150000002821 niobium Chemical class 0.000 claims description 5
- 238000004528 spin coating Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910000058 selane Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000006698 induction Effects 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 230000007246 mechanism Effects 0.000 abstract description 3
- 230000000630 rising effect Effects 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 6
- XZLABTOOVBNJCD-UHFFFAOYSA-D O.[Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound O.[Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XZLABTOOVBNJCD-UHFFFAOYSA-D 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 150000003346 selenoethers Chemical class 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000879 optical micrograph Methods 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- -1 transition metal selenide Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000000089 atomic force micrograph Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000000861 blow drying Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 238000004098 selected area electron diffraction Methods 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 description 1
- 238000010218 electron microscopic analysis Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000007431 microscopic evaluation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- GGYFMLJDMAMTAB-UHFFFAOYSA-N selanylidenelead Chemical compound [Pb]=[Se] GGYFMLJDMAMTAB-UHFFFAOYSA-N 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B12/00—Superconductive or hyperconductive conductors, cables, or transmission lines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
Abstract
The invention relates to a Van der Waals self-epitaxy accurate growth inch-grade niobium diselenide (NbSe) 2 ) Methods, products and applications of superconducting thin films. The invention precisely controls the reaction atmosphere by controlling the temperature rising rate, adopts ammonium niobate oxalate hydrate as niobium precursor, and forms Nb on the surface of the niobium precursor film in the high-temperature annealing process 2 Se 9 Intermediate, decomposition to NbSe at higher temperature 2 Epitaxial induction from top to bottom to generate NbSe 2 A film. The growth mechanism of the invention overcomes the defect that the substrate crystal is relative to NbSe 2 Epitaxial induction of crystal can obtain high-quality NbSe on any substrate 2 A superconducting thin film. The invention realizes inch grade NbSe 2 Preparation of superconducting thin film on arbitrary substrate to obtain high quality NbSe 2 The film has higher superconducting performance and can be applied to the preparation of superconducting materials and infrared detection devices.
Description
Technical Field
The invention relates to a transition metal selenide and a preparation method and application thereof, in particular to a method for precisely growing an inch-grade niobium diselenide superconducting film by van der Waals self-epitaxy, a product and application thereof, and belongs to the field of nano materials.
Background
The superconducting material has zero resistance at critical temperature and electromagnetic property which is not possessed by a conventional conductor, so that the superconducting material is widely applied to the fields of superconducting power, superconducting magnet and microwave application, single photon detection and the like. While two-dimensional selenide superconducting thin film (NbSe) 2 ) As the superconducting material with unique Van der Waals layered structure, the superconducting energy gap is smaller so that NbSe 2 Has application prospect as a single photon infrared detector of the superconductive nanowire, and the unique layered structure is NbSe 2 The large-area preparation of ultrathin films is possible. However, due to the complexity of rapid aerodynamic processes and chemical reactions, current growth methods have difficulty achieving one-step preparation of NbSe of extreme vertical dimensions 2 The superconductive film has strong induction effect on Van der Waals structure, and the current growth method does not realize the preparation of NbSe with extreme vertical dimension on any substrate 2 A superconducting thin film. Thus, ultra-thin superconducting NbSe was developed 2 The preparation research of the film is important to the research of two-dimensional superconducting characteristics and mid-infrared single photon detection.
Disclosure of Invention
The invention aims to: the invention provides a method for precisely growing an inch-grade niobium diselenide superconducting film by van der Waals self-epitaxy, which can prepare an inch-grade thickness-controllable superconducting niobium diselenide superconducting film on any substrate, and a second purpose of providing a product inch-grade niobium diselenide superconducting film obtained by the method.
The technical scheme is as follows: the invention discloses a method for precisely growing an inch-grade niobium diselenide superconducting film by van der Waals self-epitaxy, which comprises the following steps:
(1) Dissolving niobium salt in water, and ultrasonically stirring to obtain a niobium precursor solution;
(2) Cleaning the substrate, and spin-coating the niobium precursor solution on the cleaned substrate;
(3) Placing the substrate spin-coated with the niobium precursor solution in a middle heating area of a tube furnace, taking a small amount of selenium powder, placing the selenium powder at an upper air opening of the tube furnace, vacuumizing the tube furnace, and introducing inert gas and reducing gas; heating to sublimate selenium powder, reacting with niobium precursor solution, annealing, and naturally cooling.
Further, in the step (1), the niobium salt is ammonium niobate oxalate hydrate.
Further, in the step (1), the mass concentration of the niobium precursor solution is 0.09-0.45 g/mL.
Further, in the step (2), the substrate is Al 2 O 3 Substrate, siO 2 Si substrate, si 3 N 4 A substrate or a MgO substrate.
Further, in the step (2), the niobium precursor solution is spin-coated to a substrate of 0.1mL/m 2 。
Further, in the step (3), the inert gas is argon, the reducing gas is hydrogen, and the volume ratio of the argon to the hydrogen is 1:1. The total gas flow was 25sccm.
Further, in the step (3), in the heating and annealing process in the tube furnace, the selenium powder is evaporated to react with hydrogen so as to ensure the hydrogen selenide atmosphere.
Further, in the step (3), when heating to lead selenium powder to sublimate and react with niobium precursor solution, the heating rate of a heating area in the middle of the tube furnace is 20 ℃/min, the heating temperature is kept between 750 and 800 ℃ for 5 to 10min, the heating rate of an upper tuyere position of the tube furnace is 10 ℃/min, and the heating temperature is kept between 350 and 400 ℃ for 5 to 10min.
Further, the heating rate of the intermediate heating area of the tube furnace is 20 ℃/min, the temperature is raised to 800 ℃ and maintained for 10min, the heating rate of the upper tuyere position of the tube furnace is 10 ℃/min, and the temperature is raised to 400 ℃ and maintained for 10min.
The inch-grade niobium diselenide superconducting film obtained by the method of the invention.
Further, the thickness of the inch-grade niobium diselenide superconducting film is 2.1-12.4 nm.
The invention also comprises application of the inch-grade niobium diselenide superconducting film in preparing superconducting materials and single photon detection devices.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages:
(1) According to the method for precisely growing the niobium diselenide inch-grade film by the Van der Waals self-epitaxy, the niobium salt is directly spin-coated on the surface of the substrate to serve as a metal source, so that the process of vaporizing and redeposition of the metal source is avoided, large-area coverage on the surface of the substrate can be realized, the horizontal size of the preparation of the diselenide film is greatly improved, and the size of one inch can be achieved at present. And the metal source is uniformly distributed on the surface of the substrate, the total amount of the metal source is controllable, and the thickness of the grown selenide film can be changed along with the change of the concentration of the niobium precursor solution, so that the preparation of the niobium diselenide film with controllable thickness can be realized.
(2) In the reaction process of the method, nbSe firstly formed on the surface of the film 2 The film can epitaxially induce the conversion of the bottom precursor niobium, so that the epitaxial induction effect brought by different substrates can be avoided, and the preparation of the superconductive selenide on any substrate is realized.
(3) The method adopts a unique temperature rising rate to prepare NbSe 2 Compared with other heating rates and methods adopted in the current research, the method avoids the consequences of incomplete splicing caused by the too low heating rate and severe reaction and vertical growth of grains caused by the too high heating rate. The selenide prepared at the temperature rising rate has high quality and good crystallinity, and the grown selenide film can be used for researching the two-dimensional superconducting characteristic and the preparation of a single photon detector due to the expandability of the area and the thickness controllability of the niobium diselenide film.
Drawings
Fig. 1 is a schematic process diagram and a corresponding optical microscope image of the niobium diselenide thin film prepared in example 1.
FIG. 2 is an optical photograph of various thicknesses of niobium diselenide thin films and substrates prepared in examples 1 to 5;
FIG. 3 is an AFM image of niobium diselenide films of different thicknesses prepared in examples 1-5;
FIG. 4 is an SEM image of a niobium diselenide film of example 1;
fig. 5 is a Raman graph of niobium diselenide films of different thicknesses prepared in examples 1 to 5.
FIG. 6 is a high resolution transmission electron microscope image of the niobium diselenide film of example 1.
FIG. 7 is a graph showing the low-temperature electrical properties of niobium diselenide films prepared in examples 1 to 5.
FIG. 8 is an optical photograph of niobium diselenide thin films on different substrates prepared in example 1, example 6 to example 9;
fig. 9 is an XRD pattern and low temperature electrical property pattern of niobium diselenide thin films on different substrates prepared in example 1, example 6 to example 9.
Fig. 10 is an SEM image of the niobium diselenide thin film prepared in example 10.
Fig. 11 is an SEM image of the niobium diselenide thin film prepared in example 11.
Fig. 12 is an SEM image of the niobium diselenide thin film prepared in example 12.
Fig. 13 is an SEM image of the niobium diselenide thin film prepared in comparative example 1.
FIG. 14 is a schematic diagram showing the growth mechanism process for preparing a niobium diselenide film in example 1.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
EXAMPLE 1 preparation of high quality ultra thin superconducting niobium diselenide film
(1) Dissolving 0.45g of ammonium niobate niobium oxalate hydrate in 5mL of ultrapure water, and stirring for 5min by ultrasonic to clarify and transparent solution to obtain niobium precursor solution;
(2) Taking alumina (Al) 2 O 3 ) The substrate (horizontal size is 10mm×10mm), respectively ultrasonic cleaning with acetone, ethanol and water for 15min, and blow drying with nitrogen after the substrate is clear. Blow-drying Al 2 O 3 The substrate was placed on a spin coater, and 0.01mL of niobium precursor solution was appliedDripping into Al 2 O 3 Uniformly spreading the solution on the surface of the substrate, setting the rotating speed of a spin coater to be 3000rpm, and spin-coating for 30 s;
(3) After the spin coating is finished, al spin-coated with niobium precursor solution 2 O 3 Placing the substrate in a clean porcelain boat, and placing the porcelain boat in the center of a tube furnace (middle heating zone); placing 0.1g selenium powder at one end of air inlet of tube furnace (i.e. air inlet position of tube furnace), vacuumizing, and charging argon-hydrogen mixture (50% H) 2 ) Heating and annealing at a flow rate of 25sccm, and maintaining an argon-hydrogen atmosphere in the heating and annealing process; setting a heating program of a tube furnace: the heating rate of the middle heating zone of the tube furnace is 20 ℃/min, the temperature is maintained for 10min after reaching 800 ℃, the heating rate of the upper tuyere position where selenium powder is placed is 10 ℃/min, and the temperature is maintained for 10min after reaching 400 ℃; naturally cooling after finishing, and can be performed on Al 2 O 3 The surface of the substrate is obtained with high quality NbSe 2 The superconducting thin film has a thickness of 12.1nm and a horizontal dimension of 10mm×10mm. NbSe 2 Van der Waals self-epitaxy precise growth process of superconducting film and NbSe 2 An optical microscopic view of the surface of the superconducting thin film is shown in fig. 1.
FIG. 1 is a schematic illustration of a niobium diselenide film prepared in example 1 and a corresponding optical microscope image, wherein a is NbSe 2 Van der Waals self-epitaxy precise growth process schematic diagram of superconducting film, b is a solution film optical microscope image after spin coating, c is a precursor film surface optical microscope image after high-temperature annealing, d is a finished product NbSe after high-temperature selenization reaction 2 Optical microscopy of the surface of the film. As can be seen from FIG. 1, the precursor solution film is subjected to high Wen Tui fire and reacts with Se to synthesize NbSe 2 The film, and the surface of the finished film is flat and smooth, which proves that the method can synthesize NbSe with larger size 2 A film.
For NbSe prepared in this example 2 The result of scanning electron microscopic analysis of the superconducting thin film is shown in FIG. 4, and FIG. 4 is a scanning electron microscopic image of the niobium diselenide thin film in example 1, wherein a is an SEM image at 20 μm and b is an SEM image at 1 μm. As can be seen from FIG. 4, the electrical properties of the film surface are flattenedAnd (5) uniformity.
For NbSe prepared in this example 2 The superconducting thin film was subjected to High Resolution Transmission Electron Microscopy (HRTEM) analysis, and the results are shown in fig. 6. FIG. 6 is a transmission electron microscope image of a niobium diselenide thin film of example 1, wherein a is an HRTEM image at 5nm and b is a corresponding Selected Area Electron Diffraction (SAED) image. As can be seen from FIG. 6, the synthesized NbSe 2 The film had a standard hexagonal phase lattice arrangement.
Example 2
This example provides a high quality ultra-thin two-dimensional superconducting transition metal selenide (niobium diselenide) film prepared in substantially the same manner as in example 1, except that: in the step (1), the mass of the ammonium niobate niobium oxalate hydrate is 0.22g, and high-quality NbSe is obtained 2 The thickness of the superconducting thin film was 6.4nm.
Example 3
This example provides a high quality ultra-thin niobium diselenide superconducting film, the preparation process is substantially identical to that of example 1, except that: in the step (1), the mass of the ammonium niobate niobium oxalate hydrate is 0.15g, and high-quality NbSe is obtained 2 The thickness of the superconducting thin film was 4.2nm.
Example 4
This example provides a high quality ultra-thin niobium diselenide superconducting film, the preparation process is substantially identical to that of example 1, except that: in the step (1), the mass of the ammonium niobate niobium oxalate hydrate is 0.11g, and high-quality NbSe is obtained 2 The thickness of the superconducting thin film was 3.0nm.
Example 5
This example provides a high quality ultra-thin niobium diselenide superconducting film, the preparation process is substantially identical to that of example 1, except that: in the step (1), the mass of the ammonium niobate niobium oxalate hydrate is 0.09g, and high-quality NbSe is obtained 2 The thickness of the superconducting thin film was 2.1nm.
The niobium diselenide films and substrates prepared in examples 1 to 5 were optically analyzed to have different thicknesses, and the results are shown in fig. 2. FIG. 2 is an optical photograph of various thicknesses of niobium diselenide thin films and substrates prepared in examples 1 to 5; as can be seen from FIG. 2, the niobium diselenide thin films of different thicknesses can be prepared by the method of the invention, and the films have relatively uniform quality at different thicknesses.
Atomic force microscopic analysis was performed on the niobium diselenide films of different thicknesses prepared in examples 1 to 5, and the results are shown in fig. 3. FIG. 3 is an AFM image of niobium selenide films of varying thicknesses prepared in examples 1-5; as can be seen from fig. 3, the niobium diselenide film has a flat surface at the atomic level, which indicates that the resultant film has high uniformity and flatness.
Raman spectrum analysis was performed on the niobium diselenide thin films of different thicknesses prepared in examples 1 to 5, and the results are shown in fig. 5. Fig. 5 is a Raman graph of niobium diselenide films of different thicknesses prepared in examples 1 to 5. As can be seen from fig. 5, the film prepared by this method is a standard niobium diselenide film.
Example 6
This example provides a high quality ultra-thin niobium diselenide superconducting film, the preparation process is substantially identical to that of example 1, except that: in the step (2), the substrate used is SiO 2 Si substrate, obtaining high quality NbSe 2 The thickness of the superconducting thin film was 12.1nm.
Example 7
This example provides a high quality ultra-thin niobium diselenide superconducting film, the preparation process is substantially identical to that of example 1, except that: in the step (2), the substrate adopted is a Si substrate, and the high-quality NbSe is obtained 2 The thickness of the superconducting thin film was 12.0nm.
Example 8
This example provides a high quality ultra-thin niobium diselenide superconducting film, the preparation process is substantially identical to that of example 1, except that: in the step (2), the substrate used is Si 3 N 4 A substrate, obtaining high-quality NbSe 2 The thickness of the superconducting thin film was 12.4nm.
Example 9
This example provides a high quality ultra-thin niobium diselenide superconducting film, the process of preparation and the process of preparation of example 1The process is basically consistent, except that: in the step (2), the substrate adopted is MgO substrate, thus obtaining high-quality NbSe 2 The thickness of the superconducting thin film was 12.3nm.
The niobium diselenide thin films and substrates on the different substrates prepared in example 1, example 6 to example 9 were optically analyzed, and the results are shown in fig. 8. FIG. 8 is an optical photograph of niobium diselenide thin films on different substrates prepared in example 1, example 6 to example 9; as can be seen from fig. 8, the method can prepare large-area niobium diselenide films on different substrates and has high uniformity.
XRD analysis was performed on the niobium diselenide films prepared in examples 1, 6-9 on different substrates, as shown in FIG. 9, which demonstrates that the films prepared on different substrates by this method are all standard niobium diselenide and have a good degree of crystallization.
Example 10
This example provides a high quality ultra-thin niobium diselenide superconducting film, the preparation process is substantially identical to that of example 1, except that: in the step (3), the heating rate of the intermediate heating zone of the tube furnace is 10 ℃/min, and the heating rate of the upper tuyere position where the selenium powder is placed is 10 ℃/min, thus obtaining high-quality NbSe 2 The thickness of the superconducting thin film was 12.5nm.
Example 11
This example provides a high quality ultra-thin niobium diselenide superconducting film, the preparation process is substantially identical to that of example 1, except that: in the step (3), the heating rate of the intermediate heating zone of the tube furnace is 40 ℃/min, the heating rate of the upper tuyere position where the selenium powder is placed is 20 ℃/min, and the high-quality NbSe is obtained 2 The thickness of the superconducting thin film was 12.0nm.
Example 12
This example provides a high quality ultra-thin niobium diselenide superconducting film, the preparation process is substantially identical to that of example 1, except that: in the step (3), the heating rate of the intermediate heating zone of the tube furnace is 20 ℃/min, and the temperature is maintained for 10min after reaching 700 ℃, thus obtaining high-quality NbSe 2 The thickness of the superconducting thin film was 12.0nm.
Comparative example 1
This example provides a high quality ultra-thin niobium diselenide superconducting film, the preparation process is substantially identical to that of example 1, except that: in the step (2), a magnetron sputtering niobium film is adopted to replace spin-coated niobium salt solution as a precursor, so as to obtain NbSe 2 The thickness of the film was 10.8nm.
The niobium diselenide films prepared in examples 10 to 12 and comparative example 1 were subjected to scanning electron microscope analysis, and the results are shown in fig. 10 to 13. As can be seen from FIGS. 10 to 13, nbSe prepared in example 1 2 The niobium diselenide films prepared in examples 10 to 12 and comparative example 1 all had a rough surface compared to SEM images of the films. For the specific heating rate in example 2, for the finished product NbSe 2 The contribution of the flat surface of the film, we have studied in depth the NbSe under this condition 2 And a corresponding schematic is drawn as shown in fig. 14. FIG. 14 is a schematic diagram showing the growth mechanism of the niobium diselenide film prepared in example 1, showing the unique Van der Waals self-epitaxial growth process of Nb 2 O 5 The film started to selenize at 400 ℃ to form a rod-shaped Nb on the surface 2 Se 9 Then converted into NbSe 2 Species. Subsequently, the top vdW NbSe 2 The species being seed, nb at the bottom 2 O 5 Self-epitaxial selenization, thereby eliminating a strong dependence on the epitaxial force of the substrate. Thus, nbSe 2 The film can be made of NbSe 2 Well synthesized on any substrate with good lattice matching, not just Al 2 O 3 A substrate.
Example 13 electrical Property testing
The niobium diselenide films prepared in examples 1 to 12 and comparative example 1 were subjected to performance test as follows (i.e., the electrical properties at low temperature of the niobium diselenide films prepared in examples 1 to 12 and comparative example 1):
(1) The films prepared in examples 1 to 12 and comparative example 1 were first placed on a PCB, respectively, and the films and the PCB were led using an electric welder. And then the PCB with the film is placed into a refrigerator for cooling and connected with a Keithlay 2450 analyzer for low-temperature electrical measurement. The results are shown in fig. 7 and 9 and table 1.
(2) During measurement, whether the sample is in a superconducting state or not can be judged by testing the resistance value of the sample. Normalizing the resistance of the sample at the low temperature to the resistance at 15K, wherein the superconducting transformation temperature is the temperature at which the resistance of the sample reaches 10%; the superconducting transition width is the temperature change value of the process that the resistance of the sample is reduced from 90% to 10%.
FIG. 7 is a graph showing the low-temperature electrical properties of niobium diselenide films prepared in examples 1 to 5. The thicknesses of the samples in examples 1 to 5 were identified by AFM, and were 12.1nm, 6.4nm, 4.2nm, 3.0nm, and 2.1nm, respectively. As can be seen from fig. 7, when the temperature was reduced to 5K, the sample resistances of examples 1 and 2 had been reduced to 0 ohms, indicating that the samples had reached a superconducting state. This is the highest superconducting transition temperature that can be achieved in all niobium diselenide films prepared at present, and shows that the niobium diselenide films obtained by the method of the invention have very high crystalline quality, which is comparable to the HRTEM image in example 1.
Fig. 9 is an XRD pattern and a low-temperature electrical property pattern of niobium diselenide thin films on different substrates prepared in example 1, example 6 to example 9, wherein a is an XRD pattern and b is a low-temperature electrical property pattern. From fig. 9, it can be seen that the niobium diselenide thin films prepared by the method of the present invention have similar low temperature electrical property patterns, so it can be inferred that the method of the present invention can prepare large-area high-quality niobium diselenide thin films on arbitrary substrates.
By preparing superconductive NbSe on different substrates in example 1, example 6-example 9 2 The films were tested and analyzed. The optical pictures show NbSe prepared on five different substrates 2 The film surface was smooth and uniform (see FIG. 8), demonstrating NbSe at macroscopic dimensions 2 Successful preparation of the film. Identification of NbSe prepared on five substrates of example 1, example 6-example 9 by XRD patterns 2 The crystallographic orientation of the film (see FIG. 9 a), demonstrated NbSe prepared on five substrates 2 The films all haveThe same crystal orientation and very high crystallinity. FIG. 9b shows low temperature electrical measurements of NbSe prepared on five substrates 2 The films have similar and higher superconducting performance, which indicates that the invention can prepare the superconducting two-dimensional transition metal selenide film on any substrate.
TABLE 1 Low temperature measurement data sheets for niobium diselenide films prepared in examples 1-12 and comparative example 1
| Film thickness/nm | Superconducting transition temperature/K | Superconducting transition width/K | |
| Example 1 | 12.1 | 5.2 | 0.28 |
| Example 2 | 6.4 | 5.1 | 0.35 |
| Example 3 | 4.2 | 4.0 | 0.50 |
| Example 4 | 3.0 | 3.3 | 0.87 |
| Example 5 | 2.1 | 2.1 | 1.36 |
| Example 6 | 12.1 | 4.7 | 0.29 |
| Example 7 | 12.0 | 4.6 | 0.31 |
| Example 8 | 12.4 | 4.6 | 0.30 |
| Example 9 | 12.3 | 4.8 | 0.28 |
| Example 10 | 12.5 | 3.3 | 0.59 |
| Example 11 | 12.0 | 4.1 | 0.48 |
| Example 12 | 12.0 | 4.3 | 0.49 |
| Comparative example 1 | 10.8 | 2.9 | 0.42 |
As can be seen from Table 1, nbSe having a thickness of 2.1nm to 12.1nm can be prepared by the methods of examples 1 to 5 2 Thin films with better superconducting properties and quality, in examples 1, 6-9, we can prepare high quality NbSe on different substrates 2 Films, demonstrating the applicability of the method on different substrates. In examples 10 to 13 we used different preparation conditions, the test results showed that the 20 ℃/min heating rate and 800 ℃ growth temperature mentioned in example 1 were used to prepare high quality NbSe 2 Is a preferred condition of (2).
Claims (10)
1. The method for precisely growing the inch-grade niobium diselenide superconducting film by van der Waals self-epitaxy is characterized by comprising the following steps of:
(1) Dissolving ammonium niobate oxalate hydrate in water, and carrying out ultrasonic stirring to obtain niobium precursor solution;
(2) Cleaning the substrate, and spin-coating niobium precursor solution on the cleaned substrate;
(3) Placing the substrate spin-coated with the niobium precursor solution in a middle heating area of a tubular furnace, placing selenium powder at an upper air port of the tubular furnace, vacuumizing the tubular furnace, and introducing inert gas and reducing gas; heating to sublimate selenium powder, reacting with niobium precursor solution, annealing, and naturally cooling.
2. The method for precisely growing an inch-grade niobium diselenide superconducting film by van der waals self-epitaxy according to claim 1, wherein in the step (1), the organic niobium salt is ammonium niobate oxalate hydrate, and the mass concentration of the niobium precursor solution is 0.09-0.45 g/mL.
3. The method for precisely growing an inch-sized niobium diselenide superconducting thin film by van der waals self-epitaxy according to claim 1, wherein in the step (2), the substrate is Al 2 O 3 Substrate, siO 2 Si substrate, si 3 N 4 A substrate or a MgO substrate.
4. The method for precisely growing an inch-sized niobium diselenide superconducting thin film from epitaxial van der waals according to claim 1, wherein in the step (2), the niobium precursor solution is spin-coated to a substrate of 1mL/m 2 。
5. The method for precisely growing an inch-sized niobium diselenide superconducting thin film by van der waals self-epitaxy according to claim 1, wherein in the step (3), the inert gas is argon, the reducing gas is hydrogen, and the volume ratio of the argon to the hydrogen is 1:1.
6. The method for precisely growing the inch-grade niobium diselenide superconducting film by van der waals self-epitaxy according to claim 1, wherein in the step (3), in the tube furnace heating and annealing process, selenium powder is evaporated to react with hydrogen so as to ensure the hydrogen selenide atmosphere.
7. The method for precisely growing the inch-grade niobium diselenide superconducting film by van der waals self-epitaxy according to claim 1, wherein in the step (3), when heating to enable selenium powder to sublimate and react with a niobium precursor solution, the heating rate of a middle heating area of a tube furnace is 20 ℃/min, the heating is carried out to 750-800 ℃ for 5-10 min, the heating rate of an upper tuyere position of the tube furnace is 10 ℃/min, and the heating is carried out to 350-400 ℃ for 5-10 min.
8. An inch grade niobium diselenide inch grade superconducting film obtained by the method of any one of claims 1 to 7.
9. The inch grade niobium diselenide superconducting film of claim 8, wherein the thickness of the inch grade niobium diselenide superconducting film is 2.1-12.4 nm.
10. The use of the inch-grade niobium diselenide superconducting thin film of claim 8 in the preparation of superconducting materials and single photon detection devices.
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