CN115196639B - Two-dimensional ultrathin silicon oxide compound and preparation method thereof - Google Patents

Two-dimensional ultrathin silicon oxide compound and preparation method thereof Download PDF

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CN115196639B
CN115196639B CN202210519041.6A CN202210519041A CN115196639B CN 115196639 B CN115196639 B CN 115196639B CN 202210519041 A CN202210519041 A CN 202210519041A CN 115196639 B CN115196639 B CN 115196639B
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copper foil
dimensional ultrathin
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silicon oxide
copper
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CN115196639A (en
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洪艺伦
郑益
任品云
周亚亭
郑倩颖
连跃彬
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Changzhou Institute of Technology
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    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
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    • C01P2002/89—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by mass-spectroscopy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract

The invention discloses a two-dimensional ultrathin silica compound and a preparation method thereof, which belong to amorphous two-dimensional non-layered materials, have uniform structure and excellent environment, chemical, thermal stability and mechanical properties, and lay a foundation for research and application in the fields of electronic devices, optoelectronic devices, surface-enhanced Raman materials, high-strength films, high-light-transmittance films and the like; the method adopts the bimetallic layer substrate, firstly, the temperature is raised to be higher than the melting point temperature of copper in the deposition process, so that the upper copper is melted and uniformly and evenly spread on the lower transition metal M, copper and the transition metal M cannot be alloyed, and a foundation is laid for the subsequent uniform growth of the two-dimensional ultrathin silicon oxide; the preparation method is carried out under normal pressure, has the characteristics of convenient operation, easy regulation and control, easy large-area preparation and the like, and can obtain two-dimensional ultrathin silica compounds with different thicknesses or large-area films, wherein the size of the films depends on the size of a substrate used in the growth process.

Description

Two-dimensional ultrathin silicon oxide compound and preparation method thereof
Technical Field
The invention relates to the technical field of materials, in particular to a two-dimensional ultrathin silicon oxide compound and a preparation method thereof.
Background
Graphene (Graphene) is a kind of Graphene which is formed by sp 2 New materials with hybridized linked carbon atoms closely packed into a monolayer two-dimensional honeycomb lattice structure. The graphene has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of material science, micro-nano processing, energy sources, biomedicine, drug delivery and the like, and is considered as a revolutionary material in the future.
Meanwhile, successful exfoliation of graphene opens the door for two-dimensional material research. The two-dimensional material has wide application prospect in the fields of electronics, optoelectronics, information, energy, environment, aerospace and the like due to the excellent electrical, optical, thermal, mechanical and other properties. The composition and the structure of the two-dimensional material can lead the two-dimensional material to show different physical and chemical properties and bring new physical effects, so the exploration of the novel two-dimensional material is always the most active research front in the field of the two-dimensional material, and the method has great significance in expanding the physical properties of the two-dimensional material and developing new application.
At present, besides the two-dimensional lamellar material represented by graphene, various novel two-dimensional non-lamellar materials are also prepared successively, including Mo 2 C. WC, moN, etc. However, although the types of the bulk non-lamellar materials are far more than those of the bulk lamellar materials, the two-dimensional non-lamellar materials are limited by the limitation of surface active suspension bonds, and ultrathin forms are difficult to prepare, so that the application and popularization of the two-dimensional non-lamellar materials are limited.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a two-dimensional ultrathin silica compound, belongs to an amorphous two-dimensional non-layered material, has a uniform structure and excellent environmental, chemical, thermal stability and mechanical properties, and lays a foundation for research and application in the fields of electronic devices, optoelectronic devices, surface-enhanced Raman materials, high-strength films, high-light-transmittance films and the like; the method adopts the bimetallic layer substrate, firstly, the temperature is raised to be higher than the melting point temperature of copper in the deposition process, so that the upper copper is melted and uniformly and evenly spread on the lower transition metal M, and copper and the transition metal M cannot be alloyed, thereby laying a foundation for the subsequent uniform growth of the two-dimensional ultrathin silicon oxide; the preparation method is carried out under normal pressure, has the characteristics of convenient operation, easy regulation and control, easy large-area preparation and the like, and can obtain two-dimensional ultrathin silica compounds with different thicknesses or large-area films, wherein the size of the films depends on the size of a substrate used in the growth process.
One of the technical scheme purposes of the invention is to design a two-dimensional ultrathin silica compound, and the chemical structural general formula of the two-dimensional ultrathin silica compound is SiO x ，0<x≤2。
The second technical scheme of the invention provides a preparation method of a two-dimensional ultrathin silica compound, which comprises the following steps:
s1: depositing a two-dimensional ultrathin silicon oxide on a bimetallic layer substrate by adopting a chemical vapor deposition method, wherein the upper layer of the bimetallic layer substrate is copper, the lower layer of the bimetallic layer substrate is transition metal M, the melting point temperature of the transition metal M is higher than that of copper, and the two-dimensional ultrathin silicon oxide is deposited on the upper side surface of copper;
s2: spin-coating a layer of high polymer film on the upper side surface deposited with the two-dimensional ultrathin silicon oxide copper, etching in etching solution to remove copper, and cleaning to obtain the two-dimensional ultrathin silicon oxide supported by the high polymer film;
s3: and transferring the two-dimensional ultrathin silica compound supported by the high polymer film to a target substrate, etching in etching solution to remove the high polymer film, cleaning and drying to obtain the two-dimensional ultrathin silica compound supported by the target substrate.
The preferable technical scheme is that the specific operation of the step S1 is that a bimetallic layer substrate and a silicon oxide precursor are placed in a horizontal reaction furnace, carrier gas is continuously introduced, the temperature is raised to be higher than the melting point temperature of copper, the temperature is lowered to a deposition temperature range of 900-1080 ℃ at a speed of 2-5 ℃/min, the carrier gas is closed, the temperature is kept for 10-2400 min, and then the temperature is lowered to room temperature at a speed of 10-600 ℃/min.
A further preferable technical scheme is that in step S1: the deposition temperature ranges from 1050 ℃ to 1080 ℃, the heat preservation time ranges from 10 min to 240min, and then the temperature is reduced to room temperature at the speed of 200 ℃ to 600 ℃/min.
In a further preferred embodiment, in step S1: the transition metal M is one of molybdenum, tungsten, vanadium, niobium and tantalum; the silicon oxygen precursor is one of quartz, silane, oxygen, silicon simple substance and oxygen; the carrier gas is hydrogen or a mixed gas of hydrogen and inert gas, wherein the volume percentage of the hydrogen is more than or equal to 20%.
A further preferable embodiment further includes the step S1: the thickness of copper on the upper layer of the bimetallic layer substrate is 100 nm-1000 mu M, the purity is 98-99.9999 wt%, and the bimetallic layer substrate is formed by stacking transition metal M and copper, or is obtained by magnetron sputtering or thermal evaporation of copper by the transition metal M.
Further preferable technical scheme is that the thickness of copper on the upper layer of the bimetallic layer substrate is 1-25 mu m, and the purity is 99.5-99.9999 wt%.
In a preferred embodiment, in the step S2: the thickness of the high polymer film is 100 nm-500 mu m, and the spin coating liquid corresponding to the high polymer film is formed by mixing one or more of polymethyl methacrylate, polyethylene, polystyrene and polypropylene; the etching solution is one of an ammonium sulfate aqueous solution, a tin tetrachloride aqueous solution, a ferric chloride aqueous solution, a hydrochloric acid aqueous solution and concentrated ammonia water, wherein the molar concentration range of the ammonium sulfate aqueous solution, the tin tetrachloride aqueous solution, the ferric chloride aqueous solution and the hydrochloric acid aqueous solution is 0.05-2 mol/L.
In a further preferable embodiment, in the step S2, the thickness of the high molecular polymer film is 10 μm to 500. Mu.m.
In the preferred technical scheme, in the step S3, the etching solution is one or more of ketone, chlorinated hydrocarbon, halogenated hydrocarbon and aromatic hydrocarbon organic solvents.
The design concept of the method is as follows:
the influence of surface dangling bonds on the stability of the ultrathin material in the growth process of the silicon oxide is passivated by a reducing gas atmosphere, so that the two-dimensional ultrathin silicon oxide is prepared. In the growth process of the non-lamellar silicon oxide, island growth caused by surface energy constraint is inhibited by a reducing gas atmosphere, so that a two-dimensional ultrathin silicon oxide with uniform thickness is formed; in addition, the bimetallic layer formed by the upper Cu/bottom transition group metal M is used as a growth substrate, and the Cu layer which is subjected to melting and solidifying treatment in advance is used for growing at the reaction temperature which is not higher than the melting point of copper, so that the growth of the two-dimensional ultrathin silicon oxide film with large area and uniform thickness is ensured.
The invention has the advantages and beneficial effects that:
1. according to the preparation method of the two-dimensional ultrathin silica compound, disclosed by the invention, a bimetallic layer substrate is adopted, the temperature is firstly increased to be higher than the melting point temperature of copper in the deposition process, so that upper copper is melted and uniformly and evenly spread on a lower transition metal M, and copper and the transition metal M cannot be alloyed, thereby laying a foundation for the subsequent uniform growth of the two-dimensional ultrathin silica compound.
2. The preparation method of the two-dimensional ultrathin silica compound disclosed by the invention can be carried out under normal pressure, has the characteristics of convenience in operation, easiness in regulation and control, easiness in large-area preparation and the like, and can be used for obtaining two-dimensional ultrathin silica compounds or large-area films with different thicknesses, wherein the size of the films depends on the size of a substrate used in the growth process.
3. The preparation method of the two-dimensional ultrathin silica compound disclosed by the invention is the biggest difference from the traditional chemical vapor deposition method in that when the furnace temperature reaches the growth temperature and constant-temperature growth starts, the carrier gas in the reducing atmosphere is closed, so that the whole material preparation process is carried out in the static reducing atmosphere, and finally the amorphous two-dimensional ultrathin silica compound is obtained, which is completely different from the crystal material which is usually prepared by the traditional chemical vapor deposition method.
4. The two-dimensional ultrathin silica compound prepared by the preparation method disclosed by the invention belongs to a two-dimensional non-layered material, is uniform in structure, has excellent environment, chemical, thermal stability and mechanical properties, and lays a foundation for research and application of the two-dimensional ultrathin silica compound in the fields of electronic devices, optoelectronic devices, surface-enhanced Raman materials, high-strength films, high-light-transmittance films and the like.
Drawings
FIG. 1 is a schematic diagram of a process for preparing a two-dimensional ultrathin silica compound according to the invention;
FIG. 2 (a), (b), (c) and (d) correspond in sequence to the transfer of the two-dimensional ultrathin silica compounds prepared in examples 1 to 4, respectively, to SiO 2 Optical microscopy pictures on Si substrate;
FIG. 3 (a) is a transfer of the two-dimensional ultrathin silica compound prepared in example 2 to SiO 2 Optical microscopy pictures on Si substrate;
FIG. 3 (b) is a transfer of the two-dimensional ultrathin silica compound prepared in example 4 to SiO 2 Optical micrograph on Si substrate.
FIG. 4 (a) shows that 10X 1mm is used in example 2 3 An atomic force microscope photograph of the two-dimensional ultrathin silica compound obtained after the quartz plate is taken as a precursor and grows for 3 hours, wherein the curve in the figure is a thickness curve of the two-dimensional ultrathin silica compound measured by the atomic force microscope;
FIG. 4 (b) shows that 15X 1mm is used in example 5 3 An atomic force microscope photograph of the two-dimensional ultrathin silicon oxide compound obtained after the quartz plate is taken as a precursor and grows for 3 hours, wherein the curve in the figure is the thickness curve of an ultrathin sample measured by the atomic force microscope;
FIG. 5 (a) is a transmission electron micrograph of the two-dimensional ultrathin silica compound prepared in example 1, showing that the sample surface was uniform;
FIG. 5 (b) is a selected area electron diffraction pattern in the marked area of FIG. 5 (a), showing that the two-dimensional ultrathin silicon oxide in that area is amorphous;
FIG. 6 is a secondary ion mass spectrometry scan of a two-dimensional ultrathin silica compound prepared in example 3, wherein (a) of FIG. 6 is O + A surface scan of ions; FIG. 6 (b) is Si + A surface scan of ions; FIG. 6 (c) is Cu + A surface scan of ions; FIG. 6 (d) is Mo + A facial scan of the ions.
FIG. 7 (a) is a transfer of the two-dimensional ultrathin silica compound prepared in example 3 to SiO 2 Optical microscopy pictures on Si substrate;
FIG. 7 (b) shows a two-dimensional ultrathin silicon oxide and SiO obtained in FIG. 7 (a) 2 Optical microscope photo of Si matrix soaked in 1mol/L hydrochloric acid solution for 24 hr;
FIG. 7 (c) shows a two-dimensional ultrathin silicon oxide and SiO obtained in FIG. 7 (b) 2 Optical microscope pictures of Si matrix taken out from hydrochloric acid solution and soaked in deionized water for 1 week;
FIG. 7 (d) shows a two-dimensional ultrathin silicon oxide and SiO obtained in FIG. 7 (c) 2 The Si substrate was removed from deionized water and left to stand in air for 6 months.
In the figure: 1. a carrier gas inlet; 2. a bimetal layer substrate; 21. copper foil; 22. molybdenum sheets; 3. quartz plates; 4. a horizontal reaction furnace; 5. pyrolyzing the boron nitride inner tube; 6. a quartz outer tube; 7. and a carrier gas outlet.
Detailed Description
The following describes the embodiments of the present invention further with reference to the drawings and examples. The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention.
Example 1
As shown in FIG. 1, the method for preparing the two-dimensional ultrathin silica compound comprises the following steps:
s1: a copper foil/molybdenum sheet bimetal layer substrate 2 (copper foil 5 mm×5 mm×12.5 μm, purity 99.5wt%, molybdenum sheet 5 mm×7 mm×100 μm, purity 99.95 wt%) and a quartz sheet 3 (10 mm×10 mm×1 mm, purity 99.99 wt%) were placed in a central region inside a pyrolytic boron nitride tube 5 (tube inner diameter 16 mm, length 20 cm), wherein the quartz sheet 3 was placed at an end of the pyrolytic boron nitride tube 5 near the carrier gas outlet 7, the quartz sheet 3 was spaced apart from the end of the copper foil/molybdenum sheet bimetal layer substrate 2 by about 5 mm, and then the copper foil/molybdenum sheet bimetal layer substrate 2, the quartz sheet 3 and the pyrolytic boron nitride tube 5 were placed together in a central region of a quartz outer tube 6 inside a horizontal reaction furnace 4 (tube diameter 22 mm, reaction zone length 20 mm); introducing hydrogen into the carrier gas inlet 1, heating to 1090 ℃ to melt the copper foil 21 (the hydrogen flow is 200 milliliters/min in the heating process, the heating speed is 20 ℃/min), rapidly cooling to 1080 ℃ in 2 minutes when the furnace temperature reaches 1090 ℃ to solidify the copper foil 21 on the molybdenum sheet 22, closing the carrier gas inlet 1 and the carrier gas outlet 7 after the furnace temperature is reduced to 1080 ℃, starting to grow the two-dimensional silicon oxide on the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2, and rapidly cooling at 500 ℃/min after the growth is finished to obtain the two-dimensional silicon oxide on the surface of the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2;
S2: dripping a polymethyl methacrylate (PMMA) ethyl lactate solution (the weight percentage of the polymethyl methacrylate is 4 percent) on the surface of a copper foil on which a two-dimensional silicon-oxygen compound grows, coating into a PMMA film with the thickness of about 40 mu m by using a spin coater at 5000 r/min, drying at 120 ℃ for 10 min, then placing into a 0.2mol/L ammonium persulfate aqueous solution, and reacting at 70 ℃ for 20 min to dissolve the copper foil substrate to obtain the two-dimensional ultrathin silicon-oxygen compound (PMMA/silicon-oxygen compound) supported by the polymethyl methacrylate film;
s3: transfer of PMMA/Silicone Compound to SiO 2 Dissolving PMMA on Si substrate with acetone at 55deg.C, cleaning, oven drying, and transferring silicon oxide to obtain SiO 2 Two-dimensional ultrathin silica compounds supported by Si substrates.
The components, crystal structure, morphology and thickness of the prepared two-dimensional ultrathin silica compound are characterized by using an optical microscope, a transmission electron microscope and an atomic force microscope, and the result shows that the obtained two-dimensional ultrathin silica compound is amorphous, has a circular shape, has an average size of 15 mu m and has a thickness of about 1nm.
Example 2
As shown in FIG. 1, the method for preparing the two-dimensional ultrathin silica compound comprises the following steps:
S1: a copper foil/molybdenum sheet bimetal layer substrate 2 (copper foil 5 mm×5 mm×12.5 μm, purity 99.5wt%, molybdenum sheet 5 mm×7 mm×100 μm, purity 99.95 wt%) and a quartz sheet 3 (10 mm×10 mm×1 mm, purity 99.99 wt%) were placed in a central region inside a pyrolytic boron nitride tube 5 (tube inner diameter 16 mm, length 20 cm), wherein the quartz sheet 3 was placed at an end of the pyrolytic boron nitride tube 5 near the carrier gas outlet 7, the quartz sheet 3 was spaced apart from the end of the copper foil/molybdenum sheet bimetal layer substrate 2 by about 5 mm, and then the copper foil/molybdenum sheet bimetal layer substrate 2, the quartz sheet 3 and the pyrolytic boron nitride tube 5 were placed together in a central region of a quartz outer tube 6 inside a horizontal reaction furnace 4 (tube diameter 22 mm, reaction zone length 20 mm); introducing hydrogen into the carrier gas inlet 1, heating to 1090 ℃ to melt the copper foil 21 (the hydrogen flow is 200 milliliters/min in the heating process, the heating speed is 20 ℃/min), rapidly cooling to 1080 ℃ in 2 minutes when the furnace temperature reaches 1090 ℃ to solidify the copper foil 21 on the molybdenum sheet 22, closing the carrier gas inlet 1 and the carrier gas outlet 7 after the furnace temperature is reduced to 1080 ℃, starting to grow the two-dimensional silicon oxide on the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2, and rapidly cooling at 500 ℃/min after the growth is finished to obtain the two-dimensional silicon oxide on the surface of the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2;
S2: dripping a polymethyl methacrylate (PMMA) ethyl lactate solution (the weight percentage of the polymethyl methacrylate is 4 percent) on the surface of a copper foil on which a two-dimensional silicon-oxygen compound grows, coating into a PMMA film with the thickness of about 40 mu m by using a spin coater at 5000 r/min, drying at 120 ℃ for 10 min, then placing into a 0.2mol/L ammonium persulfate aqueous solution, and reacting at 70 ℃ for 20 min to dissolve the copper foil substrate to obtain the two-dimensional ultrathin silicon-oxygen compound (PMMA/silicon-oxygen compound) supported by the polymethyl methacrylate film;
s3: transfer of PMMA/Silicone Compound to SiO 2 Dissolving PMMA on Si substrate with acetone at 55deg.C, cleaning, oven drying, and transferring silicon oxide to obtain SiO 2 Two-dimensional ultrathin silica compounds supported by Si substrates.
The components, crystal structure, morphology and thickness of the prepared two-dimensional ultrathin silica compound are characterized by using an optical microscope, a transmission electron microscope and an atomic force microscope, and the result shows that the obtained two-dimensional ultrathin silica compound is amorphous, has a circular shape, has an average size of 70 mu m and has a thickness of about 1nm.
Example 3
As shown in FIG. 1, the method for preparing the two-dimensional ultrathin silica compound comprises the following steps:
S1: a copper foil/molybdenum sheet bimetal layer substrate 2 (copper foil 5 mm×5 mm×12.5 μm, purity 99.5wt%, molybdenum sheet 5 mm×7 mm×100 μm, purity 99.95 wt%) and a quartz sheet 3 (10 mm×10 mm×1 mm, purity 99.99 wt%) were placed in a central region inside a pyrolytic boron nitride tube 5 (tube inner diameter 16 mm, length 20 cm), wherein the quartz sheet 3 was placed at an end of the pyrolytic boron nitride tube 5 near the carrier gas outlet 7, the quartz sheet 3 was spaced apart from the end of the copper foil/molybdenum sheet bimetal layer substrate 2 by about 5 mm, and then the copper foil/molybdenum sheet bimetal layer substrate 2, the quartz sheet 3 and the pyrolytic boron nitride tube 5 were placed together in a central region of a quartz outer tube 6 inside a horizontal reaction furnace 4 (tube diameter 22 mm, reaction zone length 20 mm); introducing hydrogen into the carrier gas inlet 1, heating to 1090 ℃ to melt the copper foil 21 (the hydrogen flow is 200 milliliters/min in the heating process, the heating speed is 20 ℃/min), rapidly cooling to 1080 ℃ in 2 minutes when the furnace temperature reaches 1090 ℃ to solidify the copper foil 21 on the molybdenum sheet 22, closing the carrier gas inlet 1 and the carrier gas outlet 7 after the furnace temperature is reduced to 1080 ℃, starting to grow the two-dimensional silicon oxide on the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2, and rapidly cooling at 500 ℃/min after the growth is finished to obtain the two-dimensional silicon oxide on the surface of the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2;
S2: dripping a polymethyl methacrylate (PMMA) ethyl lactate solution (the weight percentage of the polymethyl methacrylate is 4 percent) on the surface of a copper foil on which a two-dimensional silicon-oxygen compound grows, coating into a PMMA film with the thickness of about 40 mu m by using a spin coater at 5000 r/min, drying at 120 ℃ for 10 min, then placing into a 0.2mol/L ammonium persulfate aqueous solution, and reacting at 70 ℃ for 20 min to dissolve the copper foil substrate to obtain the two-dimensional ultrathin silicon-oxygen compound (PMMA/silicon-oxygen compound) supported by the polymethyl methacrylate film;
s3: transfer of PMMA/Silicone Compound to SiO 2 Dissolving PMMA on Si substrate with acetone at 55deg.C, cleaning, oven drying, and transferring silicon oxide to obtain SiO 2 Two-dimensional ultrathin silica compounds supported by Si substrates.
The components, crystal structure, morphology and thickness of the prepared two-dimensional ultrathin silica compound are characterized by using an optical microscope, a transmission electron microscope and an atomic force microscope, and the result shows that the obtained two-dimensional ultrathin silica compound is amorphous, has a circular shape, has an average size of 180 mu m and has a thickness of about 1nm.
Example 4
As shown in FIG. 1, the method for preparing the two-dimensional ultrathin silica compound comprises the following steps:
S1: a copper foil/molybdenum sheet bimetal layer substrate 2 (copper foil 5 mm×5 mm×12.5 μm, purity 99.5wt%, molybdenum sheet 5 mm×7 mm×100 μm, purity 99.95 wt%) and a quartz sheet 3 (10 mm×10 mm×1 mm, purity 99.99 wt%) were placed in a central region inside a pyrolytic boron nitride tube 5 (tube inner diameter 16 mm, length 20 cm), wherein the quartz sheet 3 was placed at an end of the pyrolytic boron nitride tube 5 near the carrier gas outlet 7, the quartz sheet 3 was spaced apart from the end of the copper foil/molybdenum sheet bimetal layer substrate 2 by about 5 mm, and then the copper foil/molybdenum sheet bimetal layer substrate 2, the quartz sheet 3 and the pyrolytic boron nitride tube 5 were placed together in a central region of a quartz outer tube 6 inside a horizontal reaction furnace 4 (tube diameter 22 mm, reaction zone length 20 mm); introducing hydrogen into the carrier gas inlet 1, heating to 1090 ℃ to melt the copper foil 21 (the hydrogen flow is 200 milliliters/min in the heating process, the heating speed is 20 ℃/min), rapidly cooling to 1080 ℃ in 2 minutes when the furnace temperature reaches 1090 ℃ to solidify the copper foil 21 on the molybdenum sheet 22, closing the carrier gas inlet 1 and the carrier gas outlet 7 after the furnace temperature is reduced to 1080 ℃, starting to grow the two-dimensional silicon oxide on the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2, and rapidly cooling at 500 ℃/min after the growth is finished to obtain the two-dimensional silicon oxide on the surface of the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2;
S2: dripping a polymethyl methacrylate (PMMA) ethyl lactate solution (the weight percentage of the polymethyl methacrylate is 4 percent) on the surface of a copper foil on which a two-dimensional silicon-oxygen compound grows, coating into a PMMA film with the thickness of about 40 mu m by using a spin coater at 5000 r/min, drying at 120 ℃ for 10 min, then placing into a 0.2mol/L ammonium persulfate aqueous solution, and reacting at 70 ℃ for 20 min to dissolve the copper foil substrate to obtain the two-dimensional ultrathin silicon-oxygen compound (PMMA/silicon-oxygen compound) supported by the polymethyl methacrylate film;
s3: transfer of PMMA/Silicone Compound to SiO 2 Dissolving PMMA on Si substrate with acetone at 55deg.C, cleaning, oven drying, and transferring silicon oxide to obtain SiO 2 Two-dimensional ultrathin silica compounds supported by Si substrates.
The components, crystal structure, morphology and thickness of the prepared two-dimensional ultrathin silicon oxide compound are characterized by utilizing an optical microscope, a transmission electron microscope and an atomic force microscope, and the result shows that the prepared two-dimensional ultrathin silicon oxide compound is amorphous and is in a complete film form, and the thickness is about 1nm.
Example 5
As shown in FIG. 1, the method for preparing the two-dimensional ultrathin silica compound comprises the following steps:
S1: a copper foil/molybdenum sheet bimetal layer substrate 2 (copper foil 5 mm×5 mm×12.5 μm, purity 99.5wt%, molybdenum sheet 5 mm×7 mm×100 μm, purity 99.95 wt%) and a quartz sheet 3 (15 mm×15 mm×1 mm, purity 99.99 wt%) were placed in a central region inside a pyrolytic boron nitride tube 5 (tube inner diameter 16 mm, length 20 cm), wherein the quartz sheet 3 was placed at an end of the pyrolytic boron nitride tube 5 near the carrier gas outlet 7, the quartz sheet 3 was spaced apart from the end of the copper foil/molybdenum sheet bimetal layer substrate 2 by about 5 mm, and then the copper foil/molybdenum sheet bimetal layer substrate 2, the quartz sheet 3 and the pyrolytic boron nitride tube 5 were placed together in a central region of a quartz outer tube 6 inside a horizontal reaction furnace 4 (tube diameter 22 mm, reaction zone length 20 mm); introducing hydrogen into the carrier gas inlet 1, heating to 1090 ℃ to melt the copper foil 21 (the hydrogen flow is 200 milliliters/min in the heating process, the heating speed is 20 ℃/min), rapidly cooling to 1080 ℃ in 2 minutes when the furnace temperature reaches 1090 ℃ to solidify the copper foil 21 on the molybdenum sheet 22, closing the carrier gas inlet 1 and the carrier gas outlet 7 after the furnace temperature is reduced to 1080 ℃, starting to grow the two-dimensional silicon oxide on the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2, and rapidly cooling at 500 ℃/min after the growth is finished to obtain the two-dimensional silicon oxide on the surface of the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2;
S2: dripping a polymethyl methacrylate (PMMA) ethyl lactate solution (the weight percentage of the polymethyl methacrylate is 4 percent) on the surface of a copper foil on which a two-dimensional silicon-oxygen compound grows, coating into a PMMA film with the thickness of about 40 mu m by using a spin coater at 5000 r/min, drying at 120 ℃ for 10 min, then placing into a 0.2mol/L ammonium persulfate aqueous solution, and reacting at 70 ℃ for 20 min to dissolve the copper foil substrate to obtain the two-dimensional ultrathin silicon-oxygen compound (PMMA/silicon-oxygen compound) supported by the polymethyl methacrylate film;
s3: transfer of PMMA/Silicone Compound to SiO 2 Dissolving PMMA on Si substrate with acetone at 55deg.C, cleaning, oven drying, and transferring silicon oxide to obtain SiO 2 Two-dimensional ultrathin silica compounds supported by Si substrates.
The components, crystal structure, morphology and thickness of the prepared two-dimensional ultrathin silica compound are characterized by using an optical microscope, a transmission electron microscope and an atomic force microscope, and the result shows that the obtained two-dimensional ultrathin silica compound is amorphous, has a circular shape, has an average size of 80 mu m and has a thickness of about 2nm.
Example 6
As shown in FIG. 1, the method for preparing the two-dimensional ultrathin silica compound comprises the following steps:
S1: a copper foil/molybdenum sheet bimetal layer substrate 2 (copper foil 5 mm×5 mm×12.5 μm, purity 99.5wt%, molybdenum sheet 5 mm×7 mm×100 μm, purity 99.95 wt%) and a quartz sheet 3 (10 mm×10 mm×1 mm, purity 99.99 wt%) were placed in a central region inside a pyrolytic boron nitride tube 5 (tube inner diameter 16 mm, length 20 cm), wherein the quartz sheet 3 was placed at an end of the pyrolytic boron nitride tube 5 near the carrier gas outlet 7, the quartz sheet 3 was spaced apart from the end of the copper foil/molybdenum sheet bimetal layer substrate 2 by about 5 mm, and then the copper foil/molybdenum sheet bimetal layer substrate 2, the quartz sheet 3 and the pyrolytic boron nitride tube 5 were placed together in a central region of a quartz outer tube 6 inside a horizontal reaction furnace 4 (tube diameter 22 mm, reaction zone length 20 mm); introducing hydrogen into the carrier gas inlet 1, heating to 1090 ℃ to melt the copper foil 21 (the hydrogen flow is 200 milliliters/min in the heating process, the heating speed is 20 ℃/min), rapidly cooling to 1080 ℃ in 2 minutes when the furnace temperature reaches 1090 ℃ to solidify the copper foil 21 on the molybdenum sheet 22, closing the carrier gas inlet 1 and the carrier gas outlet 7 after the furnace temperature is reduced to 1050 ℃, starting to grow the two-dimensional silicon oxide on the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2, and rapidly cooling at 500 ℃/min after the growth is finished to obtain the two-dimensional silicon oxide on the surface of the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2;
S2: dripping a polymethyl methacrylate (PMMA) ethyl lactate solution (the weight percentage of the polymethyl methacrylate is 4 percent) on the surface of a copper foil on which a two-dimensional silicon-oxygen compound grows, coating into a PMMA film with the thickness of about 40 mu m by using a spin coater at 5000 r/min, drying at 120 ℃ for 10 min, then placing into a 0.2mol/L ammonium persulfate aqueous solution, and reacting at 70 ℃ for 20 min to dissolve the copper foil substrate to obtain the two-dimensional ultrathin silicon-oxygen compound (PMMA/silicon-oxygen compound) supported by the polymethyl methacrylate film;
s3: transfer of PMMA/Silicone Compound to SiO 2 Dissolving PMMA on Si substrate with acetone at 55deg.C, cleaning, oven drying, and transferring silicon oxide to obtain SiO 2 Two-dimensional ultrathin silica compounds supported by Si substrates.
The components, crystal structure, morphology and thickness of the prepared two-dimensional ultrathin silica compound are characterized by using an optical microscope, a transmission electron microscope and an atomic force microscope, and the result shows that the obtained two-dimensional ultrathin silica compound is amorphous, has a circular shape, has an average size of 50 mu m and has a thickness of about 1nm.
Example 7
As shown in FIG. 1, the method for preparing the two-dimensional ultrathin silica compound comprises the following steps:
S1: a copper foil/molybdenum sheet bimetal layer substrate 2 (copper foil 5 mm×5 mm×12.5 μm, purity 99.5wt%, molybdenum sheet 5 mm×7 mm×100 μm, purity 99.95 wt%) and a quartz sheet 3 (10 mm×10 mm×1 mm, purity 99.99 wt%) were placed in a central region inside a pyrolytic boron nitride tube 5 (tube inner diameter 16 mm, length 20 cm), wherein the quartz sheet 3 was placed at an end of the pyrolytic boron nitride tube 5 near the carrier gas outlet 7, the quartz sheet 3 was spaced apart from the end of the copper foil/molybdenum sheet bimetal layer substrate 2 by about 5 mm, and then the copper foil/molybdenum sheet bimetal layer substrate 2, the quartz sheet 3 and the pyrolytic boron nitride tube 5 were placed together in a central region of a quartz outer tube 6 inside a horizontal reaction furnace 4 (tube diameter 22 mm, reaction zone length 20 mm); introducing hydrogen into the carrier gas inlet 1, heating to 1090 ℃ to melt the copper foil 21 (the hydrogen flow is 200 milliliters/min in the heating process, the heating speed is 20 ℃/min), rapidly cooling to 1080 ℃ in 2 minutes when the furnace temperature reaches 1090 ℃ to solidify the copper foil 21 on the molybdenum sheet 22, closing the carrier gas inlet 1 and the carrier gas outlet 7 after the furnace temperature is reduced to 1000 ℃, starting to grow the two-dimensional silicon oxide on the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2, and rapidly cooling at 500 ℃/min after the growth is finished to obtain the two-dimensional silicon oxide on the surface of the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2;
S2: dripping a polymethyl methacrylate (PMMA) ethyl lactate solution (the weight percentage of the polymethyl methacrylate is 4 percent) on the surface of a copper foil on which a two-dimensional silicon-oxygen compound grows, coating into a PMMA film with the thickness of about 40 mu m by using a spin coater at 5000 r/min, drying at 120 ℃ for 10 min, then placing into a 0.2mol/L ammonium persulfate aqueous solution, and reacting at 70 ℃ for 20 min to dissolve the copper foil substrate to obtain the two-dimensional ultrathin silicon-oxygen compound (PMMA/silicon-oxygen compound) supported by the polymethyl methacrylate film;
s3: transfer of PMMA/Silicone Compound to SiO 2 Dissolving PMMA on Si substrate with acetone at 55deg.C, cleaning, oven drying, and transferring silicon oxide to obtain SiO 2 Two-dimensional ultrathin silica compounds supported by Si substrates.
The components, crystal structure, morphology and thickness of the prepared two-dimensional ultrathin silica compound are characterized by using an optical microscope, a transmission electron microscope and an atomic force microscope, and the result shows that the obtained two-dimensional ultrathin silica compound is amorphous, has a circular shape, has an average size of 20 mu m and has a thickness of about 1nm.
Example 8
As shown in FIG. 1, the method for preparing the two-dimensional ultrathin silica compound comprises the following steps:
S1: a copper foil/molybdenum sheet bimetal layer substrate 2 (copper foil 5 mm×5 mm×12.5 μm, purity 99.5wt%, molybdenum sheet 5 mm×7 mm×100 μm, purity 99.95 wt%) and a quartz sheet 3 (10 mm×10 mm×1 mm, purity 99.99 wt%) were placed in a central region inside a pyrolytic boron nitride tube 5 (tube inner diameter 16 mm, length 20 cm), wherein the quartz sheet 3 was placed at an end of the pyrolytic boron nitride tube 5 near the carrier gas outlet 7, the quartz sheet 3 was spaced apart from the end of the copper foil/molybdenum sheet bimetal layer substrate 2 by about 5 mm, and then the copper foil/molybdenum sheet bimetal layer substrate 2, the quartz sheet 3 and the pyrolytic boron nitride tube 5 were placed together in a central region of a quartz outer tube 6 inside a horizontal reaction furnace 4 (tube diameter 22 mm, reaction zone length 20 mm); introducing hydrogen into the carrier gas inlet 1, heating to 1090 ℃ to melt the copper foil 21 (the hydrogen flow is 200 milliliters/min in the heating process, the heating speed is 20 ℃/min), rapidly cooling to 1080 ℃ in 2 minutes when the furnace temperature reaches 1090 ℃ to solidify the copper foil 21 on the molybdenum sheet 22, closing the carrier gas inlet 1 and the carrier gas outlet 7 after the furnace temperature is reduced to 900 ℃, starting to grow the two-dimensional silicon oxide on the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2, and rapidly cooling at 500 ℃/min after the growth is finished to obtain the two-dimensional silicon oxide on the surface of the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2;
S2: dripping a polymethyl methacrylate (PMMA) ethyl lactate solution (the weight percentage of the polymethyl methacrylate is 4 percent) on the surface of a copper foil on which a two-dimensional silicon-oxygen compound grows, coating into a PMMA film with the thickness of about 40 mu m by using a spin coater at 5000 r/min, drying at 120 ℃ for 10 min, then placing into a 0.2mol/L ammonium persulfate aqueous solution, and reacting at 70 ℃ for 20 min to dissolve the copper foil substrate to obtain the two-dimensional ultrathin silicon-oxygen compound (PMMA/silicon-oxygen compound) supported by the polymethyl methacrylate film;
s3: transfer of PMMA/Silicone Compound to SiO 2 Dissolving PMMA on Si substrate with acetone at 55deg.C, cleaning, oven drying, and transferring silicon oxide to obtain SiO 2 Two-dimensional ultrathin silica compounds supported by Si substrates.
The components, crystal structure, morphology and thickness of the prepared two-dimensional ultrathin silica compound are characterized by using an optical microscope, a transmission electron microscope and an atomic force microscope, and the result shows that the obtained two-dimensional ultrathin silica compound is amorphous, has a circular shape, has an average size of 8 mu m and has a thickness of about 1nm.
Example 9
As shown in FIG. 1, the method for preparing the two-dimensional ultrathin silica compound comprises the following steps:
S1: a copper foil/molybdenum sheet bimetal layer substrate 2 (copper foil 10 mm×10 mm×25 μm, purity 99.99wt%, molybdenum sheet 10 mm×12 mm×100 μm, purity 99.95 wt%) and a quartz sheet 3 (10 mm×10 mm×1 mm, purity 99.99 wt%) were placed in a central region inside a pyrolytic boron nitride tube 5 (tube inside diameter 16 mm, length 20 cm), wherein the quartz sheet 3 was placed at one end of the pyrolytic boron nitride tube 5 near the carrier gas outlet 7, the quartz sheet 3 was spaced apart from the end of the copper foil/molybdenum sheet bimetal layer substrate 2 by about 5 mm, and then the copper foil/molybdenum sheet bimetal layer substrate 2, the quartz sheet 3 and the pyrolytic boron nitride tube 5 were placed together in a central region inside a quartz outer tube 6 inside a horizontal reaction furnace 4 (tube diameter 22 mm, reaction region length 20 mm); introducing hydrogen into the carrier gas inlet 1, heating to 1090 ℃ to melt the copper foil 21 (the hydrogen flow is 200 milliliters/min in the heating process, the heating speed is 20 ℃/min), rapidly cooling to 1080 ℃ in 2 minutes when the furnace temperature reaches 1090 ℃ to solidify the copper foil 21 on the molybdenum sheet 22, closing the carrier gas inlet 1 and the carrier gas outlet 7 after the furnace temperature is reduced to 1080 ℃, starting to grow the two-dimensional silicon oxide on the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2, and rapidly cooling at 500 ℃/min after the growth is finished to obtain the two-dimensional silicon oxide on the surface of the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2;
S2: dripping a polymethyl methacrylate (PMMA) ethyl lactate solution (the weight percentage of the polymethyl methacrylate is 4 percent) on the surface of a copper foil on which a two-dimensional silicon-oxygen compound grows, coating into a PMMA film with the thickness of about 40 mu m by using a spin coater at 5000 r/min, drying at 120 ℃ for 10 min, then placing into a 0.2mol/L ammonium persulfate aqueous solution, and reacting at 70 ℃ for 20 min to dissolve the copper foil substrate to obtain the two-dimensional ultrathin silicon-oxygen compound (PMMA/silicon-oxygen compound) supported by the polymethyl methacrylate film;
s3: transfer of PMMA/Silicone Compound to SiO 2 Dissolving PMMA on Si substrate with acetone at 55deg.C, cleaning, oven drying, and transferring silicon oxide to obtain SiO 2 Two-dimensional ultrathin silica compounds supported by Si substrates.
The components, crystal structure, morphology and thickness of the prepared two-dimensional ultrathin silica compound are characterized by using an optical microscope, a transmission electron microscope and an atomic force microscope, and the result shows that the obtained two-dimensional ultrathin silica compound is amorphous, has a circular shape, has an average size of 30 mu m and has a thickness of about 1nm.
Example 10
The method for preparing the two-dimensional ultrathin silica compound comprises the following steps:
S1: placing a copper foil/tungsten plate bimetal layer substrate (copper foil 5 mm×5 mm×12.5 micrometers, purity 99.5wt%, tungsten plate 5 mm×7 mm×100 micrometers, purity 99.95 wt%) and a quartz plate (10 mm×10 mm×1 mm, purity 99.99 wt%) in a central region inside a pyrolytic boron nitride tube (tube inner diameter 16 mm, length 20 cm), wherein the quartz plate is placed at one end of the pyrolytic boron nitride tube near a carrier gas outlet, the quartz plate is approximately 5 mm apart from the end of the copper foil/tungsten plate bimetal layer substrate, and then placing the copper foil/tungsten plate bimetal layer substrate, the quartz plate and the pyrolytic boron nitride tube together in a central region inside a quartz outer tube inside a horizontal reaction furnace (tube diameter 22 mm, reaction zone length 20 mm); introducing hydrogen into the carrier gas inlet, heating to 1090 ℃ to melt the copper foil (the hydrogen flow is 200 milliliters/min in the heating process, the heating speed is 20 ℃/min), rapidly cooling to 1080 ℃ in 2 minutes when the furnace temperature reaches 1090 ℃ to solidify the copper foil on the tungsten sheet, closing the carrier gas inlet and the carrier gas outlet after the furnace temperature is reduced to 1080 ℃, starting to grow a two-dimensional silicon oxide on the copper foil of the copper foil/tungsten sheet double-metal layer substrate, and rapidly cooling at the speed of 500 ℃/min after the growth is finished for 1 hour to obtain the two-dimensional silicon oxide on the copper foil surface of the copper foil/tungsten sheet double-metal layer substrate;
S2: dripping a polymethyl methacrylate (PMMA) ethyl lactate solution (the weight percentage of the polymethyl methacrylate is 4 percent) on the surface of a copper foil on which a two-dimensional silicon-oxygen compound grows, coating into a PMMA film with the thickness of about 40 mu m by using a spin coater at 5000 r/min, drying at 120 ℃ for 10 min, then placing into a 0.2mol/L ammonium persulfate aqueous solution, and reacting at 70 ℃ for 20 min to dissolve the copper foil substrate to obtain the two-dimensional ultrathin silicon-oxygen compound (PMMA/silicon-oxygen compound) supported by the polymethyl methacrylate film;
s3: transfer of PMMA/Silicone Compound to SiO 2 Dissolving PMMA on Si substrate with acetone at 55deg.C, cleaning, oven drying, and transferring silicon oxide to obtain SiO 2 Two-dimensional ultrathin silica compounds supported by Si substrates.
The components, crystal structure, morphology and thickness of the prepared two-dimensional ultrathin silica compound are characterized by using an optical microscope, a transmission electron microscope and an atomic force microscope, and the result shows that the obtained two-dimensional ultrathin silica compound is amorphous, has a circular shape, has an average size of 15 mu m and has a thickness of about 1nm.
Example 11
The method for preparing the two-dimensional ultrathin silica compound comprises the following steps:
S1: placing a copper foil/niobium sheet bimetal layer substrate (copper foil 5 mm×5 mm×12.5 micrometers, purity 99.5wt%, niobium sheet 5 mm×7 mm×100 micrometers, purity 99.95 wt%) and a quartz sheet (10 mm×10 mm×1 mm, purity 99.99 wt%) in a central region inside a pyrolytic boron nitride tube (tube inner diameter 16 mm, length 20 cm), wherein the quartz sheet is placed at one end of the pyrolytic boron nitride tube near a carrier gas outlet, the quartz sheet is spaced apart from the end of the copper foil/niobium sheet bimetal layer substrate by about 5 mm, and then placing the copper foil/niobium sheet bimetal layer substrate, the quartz sheet and the pyrolytic boron nitride tube together in a central region inside a quartz outer tube inside a horizontal reaction furnace (tube diameter 22 mm, reaction zone length 20 mm); introducing hydrogen into the carrier gas inlet, heating to 1090 ℃ to melt the copper foil (the hydrogen flow is 200 milliliters/min in the heating process, the heating speed is 20 ℃/min), rapidly cooling to 1080 ℃ in 2 minutes when the furnace temperature reaches 1090 ℃ to solidify the copper foil on the niobium sheet 2, closing the carrier gas inlet and the carrier gas outlet after the furnace temperature is reduced to 1080 ℃, starting to grow a two-dimensional silicon-oxygen compound on the copper foil of the copper foil/niobium sheet double-metal layer substrate, and rapidly cooling at the speed of 500 ℃/min after the growth is finished for 1 hour to obtain the two-dimensional silicon-oxygen compound on the copper foil surface of the copper foil/niobium sheet double-metal layer substrate;
S2: dripping a polymethyl methacrylate (PMMA) ethyl lactate solution (the weight percentage of the polymethyl methacrylate is 4 percent) on the surface of a copper foil on which a two-dimensional silicon-oxygen compound grows, coating into a PMMA film with the thickness of about 40 mu m by using a spin coater at 5000 r/min, drying at 120 ℃ for 10 min, then placing into a 0.2mol/L ammonium persulfate aqueous solution, and reacting at 70 ℃ for 20 min to dissolve the copper foil substrate to obtain the two-dimensional ultrathin silicon-oxygen compound (PMMA/silicon-oxygen compound) supported by the polymethyl methacrylate film;
s3: transfer of PMMA/Silicone Compound to SiO 2 Dissolving PMMA on Si substrate with acetone at 55deg.C, cleaning, oven drying, and transferring silicon oxide to obtain SiO 2 Two-dimensional ultrathin silica compounds supported by Si substrates.
The components, crystal structure, morphology and thickness of the prepared two-dimensional ultrathin silica compound are characterized by using an optical microscope, a transmission electron microscope and an atomic force microscope, and the result shows that the obtained two-dimensional ultrathin silica compound is amorphous, has a circular shape, has an average size of 15 mu m and has a thickness of about 1nm.
Example 12
As shown in FIG. 1, the method for preparing the two-dimensional ultrathin silica compound comprises the following steps:
S1: a copper foil/molybdenum sheet bimetal layer substrate 2 (copper foil 5 mm×5 mm×12.5 μm, purity 99.5wt%, molybdenum sheet 5 mm×7 mm×100 μm, purity 99.95 wt%) and a quartz sheet 3 (10 mm×10 mm×1 mm, purity 99.99 wt%) were placed in a central region inside a pyrolytic boron nitride tube 5 (tube inner diameter 16 mm, length 20 cm), wherein the quartz sheet 3 was placed at an end of the pyrolytic boron nitride tube 5 near the carrier gas outlet 7, the quartz sheet 3 was spaced apart from the end of the copper foil/molybdenum sheet bimetal layer substrate 2 by about 5 mm, and then the copper foil/molybdenum sheet bimetal layer substrate 2, the quartz sheet 3 and the pyrolytic boron nitride tube 5 were placed together in a central region of a quartz outer tube 6 inside a horizontal reaction furnace 4 (tube diameter 22 mm, reaction zone length 20 mm); introducing hydrogen into the carrier gas inlet 1, heating to 1090 ℃ to melt the copper foil 21 (the hydrogen flow is 200 milliliters/min in the heating process, the heating speed is 20 ℃/min), rapidly cooling to 1080 ℃ in 2 minutes when the furnace temperature reaches 1090 ℃ to solidify the copper foil 21 on the molybdenum sheet 22, closing the carrier gas inlet 1 and the carrier gas outlet 7 after the furnace temperature is reduced to 1080 ℃, starting to grow the two-dimensional silicon oxide on the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2, and rapidly cooling at 500 ℃/min after the growth is finished to obtain the two-dimensional silicon oxide on the surface of the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2;
S2: dripping a polystyrene ethyl lactate solution (the weight percentage of the polystyrene is 4 percent) on the surface of a copper foil on which a two-dimensional silicon-oxygen compound grows, coating a layer of polystyrene film by using a spin coater at 4000 rpm, drying the film at 120 ℃ for 10 minutes, then placing the film into a 0.5mol/L tin tetrachloride aqueous solution, and reacting for 30 minutes at 50 ℃ to dissolve the copper foil substrate, thereby obtaining the two-dimensional ultrathin silicon-oxygen compound (polystyrene/silicon-oxygen compound) supported by the polystyrene film;
s3: transfer of polystyrene/Silicone Compound to SiO 2 Dissolving polystyrene on Si substrate with chloroform at 55deg.C, cleaning and oven drying to obtain SiO 2 Two-dimensional ultrathin silica compounds supported by Si substrates.
The components, crystal structure, morphology and thickness of the prepared two-dimensional ultrathin silica compound are characterized by using an optical microscope, a transmission electron microscope and an atomic force microscope, and the result shows that the obtained two-dimensional ultrathin silica compound is amorphous, has a circular shape, has an average size of 15 mu m and has a thickness of about 1nm.
Example 13
As shown in FIG. 1, the method for preparing the two-dimensional ultrathin silica compound comprises the following steps:
S1: a copper foil/molybdenum sheet bimetal layer substrate 2 (copper foil 5 mm×5 mm×12.5 μm, purity 99.5wt%, molybdenum sheet 5 mm×7 mm×100 μm, purity 99.95 wt%) and a quartz sheet 3 (10 mm×10 mm×1 mm, purity 99.99 wt%) were placed in a central region inside a pyrolytic boron nitride tube 5 (tube inner diameter 16 mm, length 20 cm), wherein the quartz sheet 3 was placed at an end of the pyrolytic boron nitride tube 5 near the carrier gas outlet 7, the quartz sheet 3 was spaced apart from the end of the copper foil/molybdenum sheet bimetal layer substrate 2 by about 5 mm, and then the copper foil/molybdenum sheet bimetal layer substrate 2, the quartz sheet 3 and the pyrolytic boron nitride tube 5 were placed together in a central region of a quartz outer tube 6 inside a horizontal reaction furnace 4 (tube diameter 22 mm, reaction zone length 20 mm); introducing hydrogen into the carrier gas inlet 1, heating to 1090 ℃ to melt the copper foil 21 (the hydrogen flow is 200 milliliters/min in the heating process, the heating speed is 20 ℃/min), rapidly cooling to 1080 ℃ in 2 minutes when the furnace temperature reaches 1090 ℃ to solidify the copper foil 21 on the molybdenum sheet 22, closing the carrier gas inlet 1 and the carrier gas outlet 7 after the furnace temperature is reduced to 1080 ℃, starting to grow the two-dimensional silicon oxide on the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2, and rapidly cooling at 500 ℃/min after the growth is finished to obtain the two-dimensional silicon oxide on the surface of the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2;
S2: dripping polyethylene ethyl lactate solution (the weight percentage of the polyethylene is 4 wt%) on the surface of a copper foil on which a two-dimensional silicon-oxygen compound grows, coating a layer of polyethylene film with the thickness of 500 μm by a spin coater at 500 r/min, baking for 10 min at 120 ℃ and then placing into a 0.2mol/L ammonium persulfate aqueous solution, and reacting for 30 min at 50 ℃ to dissolve the copper foil substrate to obtain the two-dimensional ultrathin silicon-oxygen compound (polyethylene/silicon-oxygen compound) supported by the polyethylene film;
s3: transfer of polyethylene/Silicone Compound to SiO 2 Dissolving polyethylene on Si substrate with toluene at 55deg.C, cleaning, oven drying, and transferring silicon oxide to obtain SiO 2 Two-dimensional supersupport for Si substratesThin silicone compounds.
The components, crystal structure, morphology and thickness of the prepared two-dimensional ultrathin silica compound are characterized by using an optical microscope, a transmission electron microscope and an atomic force microscope, and the result shows that the obtained two-dimensional ultrathin silica compound is amorphous, has a circular shape, has an average size of 15 mu m and has a thickness of about 1nm.
Example 14
As shown in FIG. 1, the method for preparing the two-dimensional ultrathin silica compound comprises the following steps:
S1: a copper foil/molybdenum sheet bimetal layer substrate 2 (copper foil 5 mm×5 mm×12.5 μm, purity 99.5wt%, molybdenum sheet 5 mm×7 mm×100 μm, purity 99.95 wt%) and a quartz sheet 3 (10 mm×10 mm×1 mm, purity 99.99 wt%) were placed in a central region inside a pyrolytic boron nitride tube 5 (tube inner diameter 16 mm, length 20 cm), wherein the quartz sheet 3 was placed at an end of the pyrolytic boron nitride tube 5 near the carrier gas outlet 7, the quartz sheet 3 was spaced apart from the end of the copper foil/molybdenum sheet bimetal layer substrate 2 by about 5 mm, and then the copper foil/molybdenum sheet bimetal layer substrate 2, the quartz sheet 3 and the pyrolytic boron nitride tube 5 were placed together in a central region of a quartz outer tube 6 inside a horizontal reaction furnace 4 (tube diameter 22 mm, reaction zone length 20 mm); introducing mixed gas of 50% hydrogen and 50% argon into the carrier gas inlet 1, heating to 1090 ℃ to melt the copper foil 21 (the hydrogen flow is 200 milliliters/minute in the heating process, the heating speed is 20 ℃/minute), rapidly cooling to 1080 ℃ in 2 minutes when the furnace temperature reaches 1090 ℃ to solidify the copper foil 21 on the molybdenum sheet 22, closing the carrier gas inlet 1 and the carrier gas outlet 7 after the furnace temperature is reduced to 1080 ℃, starting to grow the two-dimensional silicon oxide on the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2, and rapidly cooling at 500 ℃/minute after the growth is finished, so as to obtain the two-dimensional silicon oxide on the surface of the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2;
S2: dripping a polymethyl methacrylate (PMMA) ethyl lactate solution (the weight percentage of the polymethyl methacrylate is 4 percent) on the surface of a copper foil on which a two-dimensional silicon-oxygen compound grows, coating into a PMMA film with the thickness of about 40 mu m by using a spin coater at 5000 r/min, drying at 120 ℃ for 10 min, then placing into a 0.2mol/L ammonium persulfate aqueous solution, and reacting at 70 ℃ for 20 min to dissolve the copper foil substrate to obtain the two-dimensional ultrathin silicon-oxygen compound (PMMA/silicon-oxygen compound) supported by the polymethyl methacrylate film;
s3: transfer of PMMA/Silicone Compound to SiO 2 Dissolving PMMA on Si substrate with acetone at 55deg.C, cleaning, oven drying, and transferring silicon oxide to obtain SiO 2 Two-dimensional ultrathin silica compounds supported by Si substrates.
The components, crystal structure, morphology and thickness of the prepared two-dimensional ultrathin silica compound are characterized by using an optical microscope, a transmission electron microscope and an atomic force microscope, and the result shows that the obtained two-dimensional ultrathin silica compound is amorphous, has a circular shape, has an average size of 15 mu m and has a thickness of about 1nm.
Example 15
As shown in FIG. 1, the method for preparing the two-dimensional ultrathin silica compound comprises the following steps:
S1: a copper foil/molybdenum sheet bimetal layer substrate 2 (copper foil 5 mm×5 mm×12.5 μm, purity 99.5wt%, molybdenum sheet 5 mm×7 mm×100 μm, purity 99.95 wt%) and a quartz sheet 3 (10 mm×10 mm×1 mm, purity 99.99 wt%) were placed in a central region inside a pyrolytic boron nitride tube 5 (tube inner diameter 16 mm, length 20 cm), wherein the quartz sheet 3 was placed at an end of the pyrolytic boron nitride tube 5 near the carrier gas outlet 7, the quartz sheet 3 was spaced apart from the end of the copper foil/molybdenum sheet bimetal layer substrate 2 by about 5 mm, and then the copper foil/molybdenum sheet bimetal layer substrate 2, the quartz sheet 3 and the pyrolytic boron nitride tube 5 were placed together in a central region of a quartz outer tube 6 inside a horizontal reaction furnace 4 (tube diameter 22 mm, reaction zone length 20 mm); introducing hydrogen into the carrier gas inlet 1, heating to 1090 ℃ to melt the copper foil 21 (the hydrogen flow is 200 milliliters/min in the heating process, the heating speed is 20 ℃/min), rapidly cooling to 1080 ℃ in 2 minutes when the furnace temperature reaches 1090 ℃ to solidify the copper foil 21 on the molybdenum sheet 22, closing the carrier gas inlet 1 and the carrier gas outlet 7 after the furnace temperature is reduced to 1080 ℃, starting to grow the two-dimensional silicon oxide on the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2, and rapidly cooling at 500 ℃/min after the growth is finished to obtain the two-dimensional silicon oxide on the surface of the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2;
S2: dripping a polymethyl methacrylate (PMMA) ethyl lactate solution (the weight percentage of the polymethyl methacrylate is 4 percent) on the surface of a copper foil on which a two-dimensional silicon-oxygen compound grows, coating into a PMMA film with the thickness of about 40 mu m by using a spin coater at 5000 r/min, drying at 120 ℃ for 10 min, then placing into a 0.05mol/L ferric chloride water solution, and reacting at 50 ℃ for 1 hour to dissolve the copper foil substrate, thus obtaining the two-dimensional ultrathin silicon-oxygen compound (PMMA/silicon-oxygen compound) supported by the polymethyl methacrylate film;
s3: transfer of PMMA/Silicone Compound to Al 2 O 3 Dissolving PMMA on the matrix with ethyl lactate at 55deg.C, cleaning, oven drying, and finally transferring silicone compound to obtain Al 2 O 3 Two-dimensional ultrathin silica compounds supported by a substrate.
The components, crystal structure, morphology and thickness of the prepared two-dimensional ultrathin silica compound are characterized by using an optical microscope, a transmission electron microscope and an atomic force microscope, and the result shows that the obtained two-dimensional ultrathin silica compound is amorphous, has a circular shape, has an average size of 15 mu m and has a thickness of about 1nm.
Example 16
As shown in FIG. 1, the method for preparing the two-dimensional ultrathin silica compound comprises the following steps:
S1: a copper foil/molybdenum sheet bimetal layer substrate 2 (copper foil 5 mm×5 mm×12.5 μm, purity 99.5wt%, molybdenum sheet 5 mm×7 mm×100 μm, purity 99.95 wt%) and a quartz sheet 3 (10 mm×10 mm×1 mm, purity 99.99 wt%) were placed in a central region inside a pyrolytic boron nitride tube 5 (tube inner diameter 16 mm, length 20 cm), wherein the quartz sheet 3 was placed at an end of the pyrolytic boron nitride tube 5 near the carrier gas outlet 7, the quartz sheet 3 was spaced apart from the end of the copper foil/molybdenum sheet bimetal layer substrate 2 by about 5 mm, and then the copper foil/molybdenum sheet bimetal layer substrate 2, the quartz sheet 3 and the pyrolytic boron nitride tube 5 were placed together in a central region of a quartz outer tube 6 inside a horizontal reaction furnace 4 (tube diameter 22 mm, reaction zone length 20 mm); introducing hydrogen into the carrier gas inlet 1, heating to 1090 ℃ to melt the copper foil 21 (the hydrogen flow is 200 milliliters/min in the heating process, the heating speed is 20 ℃/min), rapidly cooling to 1080 ℃ in 2 minutes when the furnace temperature reaches 1090 ℃ to solidify the copper foil 21 on the molybdenum sheet 22, closing the carrier gas inlet 1 and the carrier gas outlet 7 after the furnace temperature is reduced to 1080 ℃, starting to grow the two-dimensional silicon oxide on the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2, and rapidly cooling at 500 ℃/min after the growth is finished to obtain the two-dimensional silicon oxide on the surface of the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2;
S2: dripping a polymethyl methacrylate (PMMA) ethyl lactate solution (the weight percentage of the polymethyl methacrylate is 4 percent) on the surface of a copper foil on which a two-dimensional silicon-oxygen compound grows, coating into a PMMA film with the thickness of about 40 mu m by using a spin coater at 5000 r/min, drying at 120 ℃ for 10 min, then placing into a 0.5mol/L tin tetrachloride aqueous solution, and reacting at 50 ℃ for 10 min to dissolve the copper foil substrate, thus obtaining the two-dimensional ultrathin silicon-oxygen compound (PMMA/silicon-oxygen compound) supported by the polymethyl methacrylate film;
s3: and transferring the PMMA/silica compound to a germanium sheet matrix, dissolving the PMMA by using ethyl lactate at the temperature of 55 ℃, cleaning and drying to finally realize successful transfer of the silica compound, thus obtaining the two-dimensional ultrathin silica compound supported by the germanium sheet matrix.
The components, crystal structure, morphology and thickness of the prepared two-dimensional ultrathin silica compound are characterized by using an optical microscope, a transmission electron microscope and an atomic force microscope, and the result shows that the obtained two-dimensional ultrathin silica compound is amorphous, has a circular shape, has an average size of 15 mu m and has a thickness of about 1nm.
Example 17
As shown in FIG. 1, the method for preparing the two-dimensional ultrathin silica compound comprises the following steps:
S1: a copper foil/molybdenum sheet bimetal layer substrate 2 (copper foil 5 mm×5 mm×12.5 μm, purity 99.5wt%, molybdenum sheet 5 mm×7 mm×100 μm, purity 99.95 wt%) and a quartz sheet 3 (10 mm×10 mm×1 mm, purity 99.99 wt%) were placed in a central region inside a pyrolytic boron nitride tube 5 (tube inner diameter 16 mm, length 20 cm), wherein the quartz sheet 3 was placed at an end of the pyrolytic boron nitride tube 5 near the carrier gas outlet 7, the quartz sheet 3 was spaced apart from the end of the copper foil/molybdenum sheet bimetal layer substrate 2 by about 5 mm, and then the copper foil/molybdenum sheet bimetal layer substrate 2, the quartz sheet 3 and the pyrolytic boron nitride tube 5 were placed together in a central region of a quartz outer tube 6 inside a horizontal reaction furnace 4 (tube diameter 22 mm, reaction zone length 20 mm); introducing hydrogen into the carrier gas inlet 1, heating to 1090 ℃ to melt the copper foil 21 (the hydrogen flow is 200 milliliters/min in the heating process, the heating speed is 20 ℃/min), rapidly cooling to 1080 ℃ in 2 minutes when the furnace temperature reaches 1090 ℃ to solidify the copper foil 21 on the molybdenum sheet 22, closing the carrier gas inlet 1 and the carrier gas outlet 7 after the furnace temperature is reduced to 1080 ℃, starting to grow the two-dimensional silicon oxide on the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2, and rapidly cooling at the speed of 200 ℃/min after the growth is finished to obtain the two-dimensional silicon oxide on the surface of the copper foil 21 of the copper foil/molybdenum sheet bimetallic layer substrate 2;
S2: dripping a polymethyl methacrylate (PMMA) ethyl lactate solution (the weight percentage of the polymethyl methacrylate is 4 percent) on the surface of a copper foil on which a two-dimensional silicon-oxygen compound grows, coating into a PMMA film with the thickness of about 40 mu m by using a spin coater at 5000 r/min, drying at 120 ℃ for 10 min, then placing into a 0.2mol/L ammonium persulfate aqueous solution, and reacting at 70 ℃ for 20 min to dissolve the copper foil substrate to obtain the two-dimensional ultrathin silicon-oxygen compound (PMMA/silicon-oxygen compound) supported by the polymethyl methacrylate film;
s3: transfer of PMMA/Silicone Compound to SiO 2 Dissolving PMMA on Si substrate with acetone at 55deg.C, cleaning, oven drying, and transferring silicon oxide to obtain SiO 2 Two-dimensional ultrathin silica compounds supported by Si substrates.
The components, crystal structure, morphology and thickness of the prepared two-dimensional ultrathin silica compound are characterized by using an optical microscope, a transmission electron microscope and an atomic force microscope, and the result shows that the obtained two-dimensional ultrathin silica compound is amorphous, has a circular shape, has an average size of 15 mu m and has a thickness of about 1nm.
FIG. 2 (a), (b), (c) and (d) correspond in sequence to the transfer of the two-dimensional ultrathin silica compounds prepared in examples 1 to 4, respectively, to SiO 2 As can be seen from the optical microscope photograph on the Si substrate, the two-dimensional ultrathin silica compound prepared by the method is round, the round shape is unchanged along with the extension of the growth time, the size is gradually increased, and finally the two-dimensional ultrathin silica compound film with large area size is formed by connecting together.
FIG. 3 (a) is a transfer of the two-dimensional ultrathin silica compound prepared in example 2 to SiO 2 Optical microscopy pictures on Si substrate; FIG. 3 (b) is a transfer of the two-dimensional ultrathin silica compound prepared in example 4 to SiO 2 As can be seen from the optical microscope photograph of the Si substrate, the two-dimensional ultrathin silica compound is always connected with SiO in the process from independent circular samples to film formation along with the extension of the growth time 2 The Si substrate maintains consistent optical contrast, indicating that the two-dimensional ultrathin silicon oxide is uniform in thickness and unchanged.
FIG. 4 (a) shows that 10X 1mm is used in example 2 3 An atomic force microscope photograph of the two-dimensional ultrathin silica compound obtained after the quartz plate is taken as a precursor and grows for 3 hours, wherein the curve in the figure is a thickness curve of the two-dimensional ultrathin silica compound measured by the atomic force microscope; FIG. 4 (b) shows that 15X 1mm is used in example 5 3 The atomic force microscope photograph of the two-dimensional ultrathin silica compound obtained after the quartz plate is used as a precursor and grows for 3 hours, wherein the curve in the figure is the thickness curve of an ultrathin sample measured by an atomic force microscope, and as can be seen from the figure, different growth parameters can regulate and control the thickness of the two-dimensional ultrathin silica compound, the atomic force microscope photograph shows that the surface of the film material is smooth and flat, the structure is complete, and the thickness of the thinnest silica compound is kept at about 1 nm.
FIG. 5 (a) is a transmission electron micrograph of the two-dimensional ultrathin silica compound prepared in example 1, showing that the sample surface was uniform; FIG. 5 (b) is an electron diffraction pattern of selected regions within the marked region of FIG. 5 (a), showing that the two-dimensional ultrathin silicon oxide within that region is amorphous, illustrating that the two-dimensional ultrathin silicon oxide prepared by the method of the invention is amorphous.
FIG. 6 is a secondary ion mass spectrometry scan of a two-dimensional ultrathin silica compound prepared in example 3, wherein (a) of FIG. 6 is O + A surface scan of ions; FIG. 6 (b) is Si + A surface scan of ions; FIG. 6 (c) is Cu + A surface scan of ions; FIG. 6 (d) is Mo + As can be seen from the graph, the two-dimensional ultrathin silica compound prepared by the method is a compound composed of silicon and oxygen, and Cu and Mo elements in the substrate are not doped into the two-dimensional ultrathin silica compound.
FIG. 7 (a) is a transfer of the two-dimensional ultrathin silica compound prepared in example 3 to SiO 2 Optical microscopy pictures on Si substrate; FIG. 7 (b) shows a two-dimensional ultrathin silicon oxide and SiO obtained in FIG. 7 (a) 2 As can be seen from the optical microscope photograph of the Si substrate immersed in 1mol/L hydrochloric acid solution for 24 hours, the two-dimensional ultrathin silica compound before and after being placed in chemical reagent, air and water oxygen environment for a long time is always consistent with SiO 2 the/Si substrate maintains consistent optical contrast and the structure remains intact, indicating that the two-dimensional ultrathin silicon oxide has excellent environmental and chemical stability.
The test results indicated that: the method takes low-melting-point metal copper with catalytic activity and easy corrosion removal as a growth substrate, takes another high-melting-point transition metal M as a substrate for uniformly spreading molten low-melting-point metal copper, and realizes the preparation of the two-dimensional ultrathin silicon oxide with large size and uniform thickness on the surface of the low-melting-point metal with catalytic activity by a simple CVD method in a normal-pressure high Wen Jingtai reducing atmosphere by introducing Si element and O element; and finally, removing low-melting-point metal copper by etching, and transferring the two-dimensional ultrathin silicon oxide compound to any target matrix. The method has the characteristics of simple preparation process, easy regulation and control of the thickness and the size of the product and easy preparation of a large-area film. The two-dimensional ultrathin silicon oxide obtained by the CVD method has an amorphous structure and excellent environmental and chemical stability, and lays a foundation for the research and application of the two-dimensional ultrathin silicon oxide in the fields of electronic devices, optoelectronic devices, surface-enhanced Raman materials, high-strength films, high-light-transmittance films and the like.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that it will be apparent to those skilled in the art that several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the scope of the invention.

Claims (7)

1. A preparation method of a two-dimensional ultrathin silica compound is characterized in that the chemical structural general formula of the two-dimensional ultrathin silica compound is SiO x ，0<x is less than or equal to 2, comprising the following steps:
s1: depositing a two-dimensional ultrathin silicon oxide on a bimetallic layer substrate by adopting a chemical vapor deposition method, wherein the upper layer of the bimetallic layer substrate is copper, the lower layer of the bimetallic layer substrate is transition metal M, the melting point temperature of the transition metal M is higher than that of copper, and the two-dimensional ultrathin silicon oxide is deposited on the upper side surface of copper;
s2: spin-coating a layer of high polymer film on the upper side surface deposited with the two-dimensional ultrathin silicon oxide copper, etching in etching solution to remove copper, and cleaning to obtain the two-dimensional ultrathin silicon oxide supported by the high polymer film;
s3: transferring the two-dimensional ultrathin silica compound supported by the high polymer film to a target substrate, etching in etching solution to remove the high polymer film, cleaning and drying to obtain the two-dimensional ultrathin silica compound supported by the target substrate;
The specific operation of the step S1 is that a bimetallic layer substrate and a silicon oxide precursor are placed in a horizontal reaction furnace, carrier gas is continuously introduced, the temperature is raised to be higher than the melting point temperature of copper, the temperature is lowered to a deposition temperature range of 900-1080 ℃ at a speed of 2-5 ℃/min, the carrier gas is closed, the temperature is kept for 10-2400 min, and then the temperature is lowered to the room temperature at a speed of 10-600 ℃/min;
in step S1: the transition metal M is one of molybdenum, tungsten, vanadium, niobium and tantalum; the silicon oxide precursor is quartz; the carrier gas is hydrogen or a mixed gas of hydrogen and inert gas, wherein the volume percentage of the hydrogen is more than or equal to 20%.
2. The method for preparing a two-dimensional ultrathin silica compound according to claim 1, wherein in step S1: the deposition temperature ranges from 1050 ℃ to 1080 ℃, the heat preservation time ranges from 10 minutes to 240 minutes, and then the temperature is reduced to room temperature at a speed of 200 ℃ to 600 ℃/min.
3. The method for preparing a two-dimensional ultrathin silica compound according to claim 2, wherein in the step S1: the thickness of copper on the upper layer of the bimetallic layer substrate is 100 nm-1000 mu M, the purity is 98-99.9999 wt%, and the bimetallic layer substrate is formed by stacking transition metal M and copper, or is obtained by magnetron sputtering or thermal evaporation of copper by the transition metal M.
4. The method for preparing a two-dimensional ultrathin silica compound according to claim 3, wherein the thickness of copper on the upper layer of the base of the bimetal layer is 1-25 μm, and the purity is 99.5-99.9999 wt%.
5. The method for preparing a two-dimensional ultrathin silica compound according to claim 1, wherein in the step S2: the thickness of the high polymer film is 100 nm-500 mu m, and the spin coating liquid corresponding to the high polymer film is formed by mixing one or more of polymethyl methacrylate, polyethylene, polystyrene and polypropylene; the etching solution is one of ammonium persulfate aqueous solution, tin tetrachloride aqueous solution and ferric chloride aqueous solution, wherein the molar concentration range of the ammonium persulfate aqueous solution, the tin tetrachloride aqueous solution and the ferric chloride aqueous solution is 0.05-2 mol/L.
6. The method for preparing a two-dimensional ultrathin silica compound according to claim 5, wherein the thickness of the high molecular polymer film in the step S2 is 10 μm to 500. Mu.m.
7. The method for preparing a two-dimensional ultrathin silica compound according to claim 1, wherein in the step S3, the etching solution is one or more of ketone, chlorinated hydrocarbon and aromatic hydrocarbon organic solvents.
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CN104120404A (en) * 2014-07-23 2014-10-29 国家纳米科学中心 Ultra-thin silicon oxide film material and manufacturing method thereof
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