CN115418718A - Product based on two-dimensional spinel type ferrite film and preparation method and application thereof - Google Patents
Product based on two-dimensional spinel type ferrite film and preparation method and application thereof Download PDFInfo
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- CN115418718A CN115418718A CN202211090358.9A CN202211090358A CN115418718A CN 115418718 A CN115418718 A CN 115418718A CN 202211090358 A CN202211090358 A CN 202211090358A CN 115418718 A CN115418718 A CN 115418718A
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- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 87
- 239000011029 spinel Substances 0.000 title claims abstract description 60
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 89
- 239000000463 material Substances 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000010408 film Substances 0.000 claims description 39
- 239000002994 raw material Substances 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 239000010445 mica Substances 0.000 claims description 27
- 229910052618 mica group Inorganic materials 0.000 claims description 27
- 239000010409 thin film Substances 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 18
- 239000012159 carrier gas Substances 0.000 claims description 13
- 238000005229 chemical vapour deposition Methods 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 9
- -1 transition metal chalcogenide Chemical class 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 6
- 229910052582 BN Inorganic materials 0.000 claims description 4
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 12
- 239000010703 silicon Substances 0.000 abstract description 12
- 229910052710 silicon Inorganic materials 0.000 abstract description 12
- 230000007547 defect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
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- 239000010453 quartz Substances 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- 230000003287 optical effect Effects 0.000 description 6
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- 238000002425 crystallisation Methods 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 229910003321 CoFe Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
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- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/183—Epitaxial-layer growth characterised by the substrate being provided with a buffer layer, e.g. a lattice matching layer
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
- C30B25/186—Epitaxial-layer growth characterised by the substrate being specially pre-treated by, e.g. chemical or physical means
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
- C30B29/26—Complex oxides with formula BMe2O4, wherein B is Mg, Ni, Co, Al, Zn, or Cd and Me is Fe, Ga, Sc, Cr, Co, or Al
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Abstract
The application discloses a product based on a two-dimensional spinel type ferrite film, a preparation method and an application thereof. According to the method, van der Waals materials are introduced to the surface of the substrate to serve as a lattice mismatch buffer layer, so that the effect of interface stress is effectively reduced, undesirable factors such as interface defects and dislocation are reduced, and the problem of multi-physical mismatch limitation of products based on the two-dimensional spinel type ferrite film is solved, so that the two-dimensional spinel type ferrite film is integrated on different substrates, particularly silicon-based substrates.
Description
Technical Field
The application relates to the technical field of inorganic nano materials, in particular to a method for preparing a two-dimensional spinel type ferrite film based on Van der Waals epitaxy, a product based on the two-dimensional spinel type ferrite film and application of the product.
Background
The development of modern information technology has pushed electronic materials and devices to low-dimensional nano-scale, for example, the current three-star electronic 3nm process chip has been produced in volume. In recent years, two-dimensional layered materials, i.e., materials in which layers are bonded by strong covalent bonds and stacked together by weak van der waals force, have attracted great interest to scientists due to their ultra-thin thickness and excellent device properties. The two-dimensional magnetic material is the leading edge and the hot spot of the current research, provides an ideal platform for researching novel physical phenomena, and provides a new idea for constructing a spintronics device. However, the two-dimensional layered materials that exhibit magnetic properties are of a rather limited variety, and most have curie temperatures below room temperature and poor environmental stability, which greatly limit their application in practical devices.
Compared with two-dimensional layered materials, non-layered materials have richer material systems, have more outstanding physical properties in some aspects, and have strong complementarity with layered materials. Typical materials such as spinel type ferrite have excellent environmental stability and abundant optical, electrical, magnetic and other functions due to the unique electronic structure, and have wide application prospects in the fields of electronic and optoelectronic devices. If the material can be made two-dimensional, the variety of two-dimensional materials can be greatly enriched, and brand new material characteristics and device functions can be brought. Existing growth techniques (e.g., molecular beam epitaxy, pulsed laser deposition) often require a strict lattice match between the two-dimensional product and the growth substrate, and equipment is expensive, limiting their large-scale application. However, the spinel-type ferrite material has an intrinsic three-dimensional covalent bond structure, and it is difficult to prepare a corresponding two-dimensional thin-layer structure by mechanical lift-off, chemical or physical vapor deposition. Therefore, the universal two-dimensional preparation method for exploring the spinel type ferrite material has important significance and value.
Disclosure of Invention
Aiming at the problems that the existing two-dimensional spinel material is poor in crystallization quality and cannot be integrated with silicon base, the embodiment of the application provides a method for preparing a two-dimensional spinel type ferrite film based on Van der Waals epitaxy, a product based on the two-dimensional spinel type ferrite film and application of the product.
In a first aspect, the present application provides a product based on a two-dimensional spinel-type ferrite thin film, the product comprising a growth substrate and a two-dimensional spinel-type ferrite thin film attached to a surface of the growth substrate, the growth substrate being a van der waals material or a substrate having a van der waals material coated thereon.
In some embodiments provided herein, the van der waals material is a layered material with a surface free of dangling bonds, and is selected from any one of mica, boron nitride, graphite, and a transition metal chalcogenide.
In some embodiments of the present invention, a method for preparing a substrate with a surface coated with van der waals material comprises: attaching Van der Waals materials to the surface of the substrate by adopting a mechanical stripping method or a vapor deposition method; the substrate is preferably a silicon wafer.
In some embodiments provided herein, the substrate surface van der waals material has a thickness of 0.3nm to 1mm, and preferably the van der waals material has a thickness of 1 to 20nm.
In some embodiments of the present invention, the spinel ferrite has the formula AB 2 O 4 A is a divalent metal cation including Cr 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ 、Cd 2+ One or more of; b is a trivalent metal cation including Cr 3+ 、Mn 3+ 、Fe 3+ 、Co 3+ 、Ni 3+ 、Ga 3+ One or more of (a).
In some embodiments provided herein, the two-dimensional spinel-type ferrite thin film has a lateral dimension of 3 to 300 μm and a thickness of 1 to 300nm. In some preferred embodiments, the two-dimensional spinel-type ferrite thin film has a lateral dimension of 5 to 50 μm and a thickness of 2 to 5nm.
In a second aspect, the present application provides a method of preparing a product based on a two-dimensional spinel-type ferrite thin film, comprising: and depositing the spinel type ferrite material on a growth substrate by adopting a chemical vapor deposition method to obtain the two-dimensional spinel type ferrite film attached to the surface of the growth substrate.
In some embodiments provided herein, depositing a spinel ferrite material on a growth substrate using a chemical vapor deposition process comprises: placing the reaction raw materials and the growth substrate in a tubular furnace, and carrying out high-temperature reaction under the condition of introducing inert carrier gas; and after the reaction is finished, cooling to obtain the two-dimensional spinel type ferrite film attached to the surface of the growth substrate.
In some embodiments provided by the present invention, the reaction raw material is one or more of pure metal of a and B, oxide powder and chloride powder, and the atomic ratio of the reaction raw materials a and B is 1.
In a third aspect, the present application provides the use of a product based on a two-dimensional spinel-type ferrite thin film in the field of magnetic or electronic devices.
Compared with the prior art, the Van der Waals materials are introduced to the surface of the substrate to serve as the lattice mismatch buffer layer, so that the effect of interface stress is effectively reduced, poor factors such as interface defects and dislocation are reduced, the problem of multi-physical mismatch limitation of products based on the two-dimensional spinel type ferrite film is solved, the two-dimensional spinel type ferrite film is integrated on different substrates, the obtained film is high in crystallization quality, good in environmental stability, low in preparation cost, adjustable in size and thickness and capable of achieving the size of a single unit cell at the thinnest.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a schematic structural view of a two-dimensional spinel-type ferrite thin film-based product prepared in example 1 of the present application.
Fig. 2 is a schematic diagram illustrating the principle of preparing a two-dimensional spinel-type ferrite thin film on the surface of a mica substrate in example 1 of the present application.
FIG. 3 is a graph showing the results of (a) optical microscope observation and (b) atomic force microscope observation of the product obtained in example 1 of the present application on the surface of a mica substrate.
FIG. 4 is a graph showing the results of optical microscope observation of the product obtained in comparative example 1 of the present application on the surface of a silicon wafer substrate.
Fig. 5 is a raman spectrum of a product obtained on the surface of a mica substrate in example 1 of the present application, and a raman characteristic peak of the product can determine that the component of the product obtained on the surface of the mica substrate in example 1 is cobalt ferrite;
FIG. 6 shows (a) a high resolution transmission electron micrograph, (b) a selected area electron diffraction pattern, and (c) an elemental distribution of the product obtained on the surface of a mica substrate according to example 1 of the present application.
Figure 7 is a current-voltage curve for a sandwich device made in example 1 of the present application.
FIG. 8 shows the magnetic hysteresis loops of the product obtained from example 1 under different temperature conditions in (a) the direction of perpendicular magnetic field and (b) the direction of parallel magnetic field.
Fig. 9 shows (a) an optical microscope observation result, (b) a high-resolution transmission electron microscope image, and (c) an element distribution image of the product obtained in example 2 of the present application on the surface of a mica substrate.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
In a first aspect, the present application provides a product based on a two-dimensional spinel-type ferrite thin film, the product comprising a growth substrate and a two-dimensional spinel-type ferrite thin film attached to a surface of the growth substrate, the growth substrate being a van der waals material or a substrate having a van der waals material coated thereon. The product has the properties of magnetism, ferroelectricity, photoelectricity, resistance change, semiconductors and the like, and can be used for preparing magnetic devices and electronic devices. The method introduces Van der Waals materials to the surface of the substrate to serve as the lattice mismatch buffer layer, effectively reduces the effect of interface stress, reduces undesirable factors such as interface defects and dislocation, and solves the problem of multi-physical mismatch limitation of products based on the two-dimensional spinel type ferrite film, so that the two-dimensional spinel type ferrite film is integrated on different substrates, particularly silicon-based substrates.
In some embodiments provided herein, the van der waals material is a layered material with a surface free of dangling bonds, and is selected from any one of mica, boron nitride, graphite, and a transition metal chalcogenide.
In some embodiments, the method for preparing a substrate with a van der waals coated surface comprises: attaching the van der waals material to the surface of the substrate by adopting a mechanical stripping method or a vapor deposition method; the substrate is preferably a silicon wafer.
In some embodiments provided herein, the substrate surface van der waals material has a thickness of 0.3nm to 1mm, and preferably the van der waals material has a thickness of 1 to 20nm.
In some embodiments of the present invention, the spinel ferrite has the formula AB 2 O 4 A is a divalent metal cation including Cr 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ 、Cd 2+ One or more of (a); b is a trivalent metal cation including Cr 3+ 、Mn 3+ 、Fe 3+ 、Co 3+ 、Ni 3+ 、Ga 3+ One or more of (a).
In some embodiments provided herein, the two-dimensional spinel-type ferrite thin film has a lateral dimension of 3 to 300 μm and a thickness of 1 to 300nm. In some preferred embodiments, the two-dimensional spinel-type ferrite thin film has a lateral dimension of 5 to 50 μm and a thickness of 2 to 5nm.
In a second aspect, the present application provides a method of preparing a two-dimensional spinel-type ferrite thin film-based product, comprising: and depositing the spinel type ferrite material on a growth substrate by adopting a chemical vapor deposition method to obtain the two-dimensional spinel type ferrite film attached to the surface of the growth substrate.
The two-dimensional spinel type ferrite film is prepared on a van der waals substrate through a van der waals epitaxial technology, the film is high in crystallization quality, good in environmental stability, low in preparation cost, adjustable in size and thickness and can be thinned to the size of a single unit cell.
In some embodiments provided herein, depositing a spinel ferrite material on a growth substrate using a chemical vapor deposition process comprises: placing the reaction raw materials and the growth substrate in a tubular furnace, and carrying out high-temperature reaction under the condition of introducing inert carrier gas; and after the reaction is finished, cooling to obtain the two-dimensional spinel type ferrite film attached to the surface of the growth substrate.
In some embodiments, the depositing the spinel-type ferrite material on the growth substrate by chemical vapor deposition comprises the following steps:
placing the reaction raw materials in a high-temperature resistant container;
reversely buckling the growth substrate right above the reaction raw materials;
placing a high-temperature resistant container filled with reaction raw materials and a growth substrate in the center of a tube furnace;
and introducing inert carrier gas into the tubular furnace to perform high-temperature reaction, and cooling after the reaction is finished.
In some embodiments provided by the present invention, the reaction raw material is one or more of pure metal of a and B, oxide powder and chloride powder, and the atomic ratio of the reaction raw materials a and B is 1.
In some embodiments provided herein, the refractory vessel is a quartz boat.
In some embodiments provided herein, depositing the spinel ferrite material on the growth substrate using chemical vapor deposition further comprises: the molecular sieve, the reaction raw materials and the growth substrate are placed in the tubular furnace together, and the molecular sieve is uniformly paved on the surface of the reaction raw materials, so that the uniform evaporation of the reaction raw materials can be promoted, and a relatively more stable growth environment is created.
In some embodiments provided by the present invention, the carrier gas is at least one of argon and nitrogen, or a mixture of at least one of argon and nitrogen and oxygen, and the flow rate of the carrier gas is 50-300sccm. In some preferred embodiments, the carrier gas is argon or oxygen-argon mixture gas, and the flow rate of the carrier gas is 100-200sccm.
In some embodiments provided herein, the tube furnace is heated from room temperature to 600-800 ℃ over 10-30 minutes and held for 5-30 minutes. In some preferred embodiments, the tube furnace is raised from room temperature to 650-750 ℃ over 10-20 minutes and held for 5-15 minutes.
In a third aspect, the present application provides the use of a product based on a two-dimensional spinel-type ferrite thin film in the field of magnetic or electronic devices.
Further, the present application provides a method for preparing a two-dimensional spinel type ferrite thin film based on van der waals epitaxy, comprising the steps of:
step S101, placing reaction raw materials in a quartz boat; wherein the reaction raw material is one or more of pure metals of Cr, mn, fe, co, ni, cu, zn, cd and Ga, oxide powder and chloride powder.
Step S102, reversely buckling the growth substrate right above the reaction raw materials; the growth substrate is Van der Waals material or silicon chip with Van der Waals material on surface, the Van der Waals material is any one of mica, boron nitride, graphite or layered material without dangling bonds on surface such as transition metal chalcogenide, and the Van der Waals material has a thickness of 0.3nm-1mm.
Step S103, a quartz boat containing the reaction raw materials and the growth substrate is placed in the center of the tube furnace.
Step S104, introducing inert gases such as argon, nitrogen and the like or mixed gas of the inert gases and oxygen as carrier gas into the tubular furnace, heating the mixture from room temperature to 600-800 ℃ for 10-30 minutes, keeping the temperature for 5-30 minutes for heating reaction, and cooling the mixture after the reaction is finished to obtain the two-dimensional spinel-type ferrite material with the chemical formula AB 2 O 4 (ii) a Wherein the flow rate of the carrier gas is 50-300sccm.
The transverse dimension of the two-dimensional spinel type ferrite material prepared by the method is 3-300 mu m, and the thickness is 1-300nm.
The method for preparing a two-dimensional spinel type ferrite thin film based on van der waals epitaxy, the product based on the two-dimensional spinel type ferrite thin film and the application thereof provided by the present application will be described in detail with reference to the following examples.
Example 1:
the principle of the method for preparing the two-dimensional spinel type ferrite thin film based on van der waals epitaxy provided by the embodiment is shown in fig. 2, and the method specifically comprises the following steps:
(1) 0.2 g of Fe 2 O 3 Powder, 0.1 g CoO powder and 0.04 g FeCl 3 Uniformly mixing the powder, and placing the mixture as a reaction raw material in a quartz boat;
(2) Uniformly paving the molecular sieve on the surface of the reaction raw material;
(3) Reversely buckling a mica substrate right above the reaction raw materials to serve as a growth substrate;
(4) Placing a quartz boat filled with reaction raw materials, a molecular sieve and a mica substrate in the center of a tube furnace;
(5) Continuously introducing high-purity argon with the flow of 150sccm into the tubular furnace as carrier gas;
(6) Heating the mica substrate to 700 deg.C for 15 min in a tube furnace, maintaining for 15 min, and naturally cooling to room temperature to obtain two-dimensional spinel-type ferrite film (CoFe) on the surface of the mica substrate 2 O 4 ) To obtain a mica substrate to which a two-dimensional spinel-type ferrite film is attached.
The result of observing the mica substrate surface product by using an optical microscope and an atomic force microscope is shown in fig. 3, and it can be seen from fig. 3 that the mica substrate surface product is uniform and clean, the crystal is triangular, and the structural schematic diagram is shown in fig. 1.
The mica substrate surface product is further observed by using a high-resolution transmission electron microscope and selective area electron diffraction, and the result is shown in fig. 6, and as can be seen from fig. 6, the lattice fringes of the mica substrate surface product and selective area electron diffraction spots are very clear, the crystallinity is very good, and the element distribution is very uniform.
The magnetic properties of the mica substrate surface product were measured by a physical property measurement system, and the results are shown in fig. 8, and it can be seen from fig. 8 that the mica substrate surface product has hard magnetic properties, and curie temperature exceeding 390K is superior to that of the existing two-dimensional spinel type ferrite.
The application of the product based on the two-dimensional spinel type ferrite film in the field of magnetic devices or electronic devices provided by the embodiment is as follows:
the traditional photoetching process and the metal coating process are combined to prepare a sandwich type device structure of metal Au/two-dimensional spinel type ferrite film/metal Cr, and the electronic application performance of the sandwich type device structure is detected. Wherein, the metal Au is positioned below the two-dimensional spinel type ferrite film, and the thickness is 30nm; the metal Cr is positioned above the two-dimensional spinel type ferrite film and is 10nm in thickness, and the metal Cr is covered with 30nm metal Au so as to prevent the metal Cr from being oxidized.
FIG. 7 is a current-voltage curve for a sandwich device prepared in example 1; as can be seen from fig. 7, the resistance of the sandwich type device reversibly changes between the high resistance state and the low resistance state, exhibiting resistance change behavior, illustrating that the two-dimensional spinel type ferrite thin film prepared in example 1 can be used for a two-dimensional electronic device;
example 2:
the method for preparing the two-dimensional spinel type ferrite thin film based on Van der Waals epitaxy provided by the embodiment comprises the following steps of:
(1) 0.2 g of Fe 2 O 3 Powder, 0.1 gram MnO powder and 0.04 gram FeCl 3 Uniformly mixing the powder, and placing the powder serving as a reaction raw material in a quartz boat;
(2) Uniformly paving the molecular sieve on the surface of the reaction raw material;
(3) Reversely buckling a mica substrate right above the reaction raw materials to serve as a growth substrate;
(4) Placing a quartz boat filled with reaction raw materials, a molecular sieve and a mica substrate in the center of a tube furnace;
(5) Continuously introducing high-purity argon with the flow rate of 150sccm into the tubular furnace as carrier gas;
(6) The temperature of the tube furnace is raised from room temperature to 700 ℃ after 15 minutes, the tube furnace is naturally cooled to room temperature after being kept for 15 minutes,namely, a two-dimensional spinel type ferrite film (MnFe) is obtained on the surface of the mica substrate 2 O 4 ) To obtain a mica substrate to which a two-dimensional spinel-type ferrite thin film is attached.
The physical property measurement system is used for detecting the magnetic property of the product on the surface of the mica substrate, and the result is shown in fig. 9, and as can be seen from fig. 9, the product obtained on the surface of the mica substrate in example 2 is triangular, has a uniform and clean surface, has very clear lattice stripes, has very good crystallinity, and has very uniform element distribution.
The product based on the two-dimensional spinel type ferrite film provided by the embodiment is applied to the field of magnetic devices or electronic devices as follows:
the traditional photoetching process and the metal coating process are combined to prepare a sandwich type device structure of metal Au/two-dimensional spinel type ferrite film/metal Cr, and the electronic application performance of the sandwich type device structure is detected. Wherein, the metal Au is positioned below the two-dimensional spinel type ferrite film, and the thickness is 30nm; the metal Cr is positioned above the two-dimensional spinel type ferrite film, the thickness of the metal Cr is 10nm, and the metal Cr is covered with 30nm metal Au to prevent the metal Cr from being oxidized.
Comparative example 1
The present comparative example provides a method for preparing a two-dimensional spinel-type ferrite thin film, the growth conditions of the present comparative example are the same as those of example 1 of the present application, except that van der waals materials are not introduced as a growth substrate, comprising the steps of:
(1) 0.2 g of Fe 2 O 3 Powder, 0.1 g CoO powder and 0.04 g FeCl 3 Uniformly mixing the powder, and placing the mixture as a reaction raw material in a quartz boat;
(2) Uniformly paving the molecular sieve on the surface of the reaction raw material;
(3) A silicon chip substrate is reversely buckled right above the reaction raw materials to be used as a growth substrate;
(4) Placing a quartz boat filled with reaction raw materials, a molecular sieve and a silicon wafer substrate in the center of a tube furnace;
(5) Continuously introducing high-purity argon with the flow rate of 150sccm into the tubular furnace as carrier gas;
(6) And (3) heating the tube furnace from room temperature to 700 ℃ for 15 minutes, keeping the temperature for 15 minutes, and naturally cooling the tube furnace to the room temperature to obtain a corresponding product on the surface of the silicon wafer substrate.
The product on the surface of the silicon wafer substrate is observed by using an optical microscope, and as a result shown in fig. 4, it can be seen from fig. 4 that comparative example 1 only generates some small particles on the surface of the silicon wafer substrate, and an ideal two-dimensional spinel-type ferrite film cannot be obtained, which proves the importance of van der waals materials in the preparation process of the two-dimensional spinel-type ferrite film.
In the description herein, reference to the description of the terms "one embodiment/mode," "some embodiments/modes," "example," "specific example" or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment/mode or example is included in at least one embodiment/mode or example of the application. In this specification, the schematic representations of the terms used above are not necessarily intended to be the same embodiment/mode or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments/modes or examples. Furthermore, the various embodiments/modes or examples and features of the various embodiments/modes or examples described in this specification can be combined and combined by one skilled in the art without being mutually inconsistent.
It is noted that, in the present application, relational terms such as "first" and "second", and the like, are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrases "comprising one of 8230; \8230;" 8230; "does not exclude the presence of additional like elements in a process, method, article, or apparatus that comprises the element. In this application, "plurality" means at least two, e.g., two, three, etc., unless specifically stated otherwise.
The previous description is only an example of the present application, and is provided to enable any person skilled in the art to understand or implement the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A product based on a two-dimensional spinel type ferrite film is characterized by comprising a growth substrate and the two-dimensional spinel type ferrite film attached to the surface of the growth substrate, wherein the growth substrate is a van der Waals material or a substrate with van der Waals materials coated on the surface.
2. The two-dimensional spinel ferrite film-based product of claim 1, wherein: the Van der Waals material is any one of mica, boron nitride, graphite and transition metal chalcogenide.
3. The two-dimensional spinel ferrite film-based product of claim 1, wherein: the thickness of the van der Waals material on the surface of the substrate is 0.3nm-1mm.
4. The two-dimensional spinel ferrite film-based product of claim 1, wherein: the spinel type ferrite has a chemical formula of AB 2 O 4 (ii) a Wherein A is a divalent metal cation, and is Cr 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ 、Cd 2+ One or more of; b is a trivalent metal cation, is Cr 3+ 、Mn 3+ 、Fe 3+ 、Co 3+ 、Ni 3+ 、Ga 3+ One or more of (a).
5. The two-dimensional spinel ferrite film-based product of claim 1, wherein: the transverse dimension of the two-dimensional spinel type ferrite film is 3-300 mu m, and the thickness of the two-dimensional spinel type ferrite film is 1-300nm.
6. A method for preparing a product based on a two-dimensional spinel-type ferrite thin film according to any one of claims 1 to 5, comprising: and depositing the spinel type ferrite material on a growth substrate by adopting a chemical vapor deposition method to obtain the two-dimensional spinel type ferrite film attached to the surface of the growth substrate.
7. The method for preparing a product based on a two-dimensional spinel-type ferrite thin film according to claim 6, wherein: the depositing of the spinel ferrite material on the growth substrate using a chemical vapor deposition process comprises:
placing the reaction raw materials and the growth substrate in a tubular furnace, and carrying out high-temperature reaction under the condition of introducing carrier gas;
and after the reaction is finished, cooling to obtain the two-dimensional spinel type ferrite film attached to the surface of the growth substrate.
8. The method for preparing a product based on a two-dimensional spinel-type ferrite thin film according to claim 7, wherein: the reaction raw materials are one or more of pure metals A and B, oxide powder and chloride powder, and the atomic ratio of the reaction raw materials A to B is 1.
9. The method for preparing a product based on a two-dimensional spinel-type ferrite thin film according to claim 7, wherein: the depositing of the spinel ferrite material on the growth substrate using chemical vapor deposition further comprises: the molecular sieve is placed in a tube furnace along with the reaction feed and the growth substrate.
10. Use of a product based on a two-dimensional spinel ferrite thin film according to any one of claims 1 to 5 in the field of magnetic or electronic devices.
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| WO2002009159A2 (en) * | 2000-07-24 | 2002-01-31 | Motorola, Inc. | Thin-film metallic oxide structure and process for fabricating same |
| US20030209189A1 (en) * | 2002-05-13 | 2003-11-13 | Tetsuo Kado | Magnetic material and method for preparation thereof |
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| CN113990739A (en) * | 2021-10-26 | 2022-01-28 | 西安电子科技大学 | Transfer printing method of gallium oxide epitaxial layer based on Van der Waals film |
| WO2022089181A1 (en) * | 2020-10-29 | 2022-05-05 | 王晓靁 | Gan-on-si epitaxial substrate having 2d material interlayer |
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- 2022-09-07 CN CN202211090358.9A patent/CN115418718A/en not_active Withdrawn
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| WO2002009159A2 (en) * | 2000-07-24 | 2002-01-31 | Motorola, Inc. | Thin-film metallic oxide structure and process for fabricating same |
| US20030209189A1 (en) * | 2002-05-13 | 2003-11-13 | Tetsuo Kado | Magnetic material and method for preparation thereof |
| CN111816741A (en) * | 2020-07-07 | 2020-10-23 | 中国科学院长春光学精密机械与物理研究所 | GaN-based monolithic integrated white light LED based on Van der Waals epitaxy and preparation method thereof |
| WO2022089181A1 (en) * | 2020-10-29 | 2022-05-05 | 王晓靁 | Gan-on-si epitaxial substrate having 2d material interlayer |
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