CN111690983A - Preparation method of meter-level large single-crystal high-index surface copper foil - Google Patents
Preparation method of meter-level large single-crystal high-index surface copper foil Download PDFInfo
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- CN111690983A CN111690983A CN201910179992.1A CN201910179992A CN111690983A CN 111690983 A CN111690983 A CN 111690983A CN 201910179992 A CN201910179992 A CN 201910179992A CN 111690983 A CN111690983 A CN 111690983A
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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
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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
- C30B1/00—Single-crystal growth directly from the solid state
- C30B1/02—Single-crystal growth directly from the solid state by thermal treatment, e.g. strain annealing
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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
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/64—Flat crystals, e.g. plates, strips or discs
Abstract
The invention provides a preparation method of a meter-scale large single-crystal high-index surface copper foil, which is characterized in that commercial polycrystalline copper foil is used as a raw material, and a series of meter-scale large single-crystal high-index surface copper foils such as Cu (112), Cu (113), Cu (122), Cu (123), Cu (133), Cu (223), Cu (233), Cu (355) and other high-index surfaces are prepared by utilizing a process of pre-oxidation protection and then annealing. The method provided by the invention solves the problems that the price and the preparation cost of the Cu (112), Cu (113), Cu (122), Cu (123), Cu (133), Cu (223), Cu (233), Cu (355) and other high-index surface single crystal copper foils are high and no product is supplied on the market, and realizes the mass preparation of the high-quality meter-grade large single crystal Cu (112), Cu (113), Cu (122), Cu (123), Cu (133), Cu (223), Cu (233), Cu (355) and other high-index surface copper foils by a very simple method.
Description
Technical Field
The invention relates to a method for massively preparing a series of meter-level large single-crystal high-index surface copper foils by using an industrial-grade copper foil based on pre-oxidation protection.
Background
The single crystal copper foil shows a plurality of unusual electrical, mechanical, adsorption and catalytic properties due to the smooth surface without crystal boundary and strong anisotropy. For example, single crystal Cu has lower resistance and ac impedance than polycrystalline Cu, and is important because electron scattering occurs at grain boundaries of polycrystalline Cu, which is an excellent electrical property, so that it has a very broad market prospect in the conventional power transmission field and the new generation of electronic industry field; the single crystal superalloy has more excellent creep resistance because grain boundary slippage is avoided; in addition, the single crystal surface, especially the surface of large-area single crystal copper foil, is also an important substrate material for preparing large-area high-quality two-dimensional materials such as graphene, boron nitride, transition metal chalcogenide and the like by CVD. Meanwhile, the single crystal copper foil substrate with the high crystal face index has a special induction effect in the aspects of preparation of the two-dimensional material single crystal film and preparation of the organic molecule single crystal film, and is beneficial to obtaining the two-dimensional material single crystal film and the organic molecule single crystal film with special structures and functions.
However, the single crystal metals currently commercialized are generally prepared by bulk crystal growth or deposition of thin films on substrates, are expensive, have small areas, and cannot meet the requirements of large-scale applications in the fields of substrates, target markets, microelectronics industry, and traditional power transmission. Meanwhile, the high-surface-index single crystal copper foil with special purposes cannot be accurately obtained. Therefore, an effective means is found to obtain a series of meter-level large single crystal high-index surface copper foils, and the method has important significance for large-scale application of the foils in the fields of substrates, target markets, microelectronic industry and traditional power transmission.
Disclosure of Invention
The invention firstly provides a macroscopic preparation method of a meter-scale large single-crystal high-index surface copper foil, which comprises the steps of carrying out oxidation protection on an industrial-scale commercial polycrystalline copper foil in advance, then carrying out annealing, and utilizing high temperature to drive oxidation protection to ensure that nucleation sites of the high-index surface grow up to obtain the meter-scale large single-crystal high-index surface copper foil; the method comprises the following steps:
firstly, placing the polycrystalline copper foil on a high-temperature-resistant substrate or in a high-temperature-resistant substrate interlayer, starting to heat to more than 80 ℃ in an oxygen-containing atmosphere, keeping the temperature for more than 1 minute, and then cooling to room temperature to obtain the polycrystalline copper foil protected by pre-oxidation;
secondly, placing the pre-oxidation-protected polycrystalline copper foil on a high-temperature-resistant substrate or in a high-temperature-resistant substrate interlayer, placing the substrate into chemical vapor deposition equipment, and introducing inert gas and H2Then starting to increase the temperature;
thirdly, when the temperature is increased to 800-1100 ℃, keeping the flow components of the introduced gas unchanged, and carrying out an annealing process, wherein the annealing duration is longer than 10 minutes;
and (IV) after the annealing is finished, naturally cooling to room temperature to obtain the high-index surface single crystal copper foil.
Preferably, in the above method, the large-scale single-crystal high-index-surface copper foil includes, but is not limited to, Cu (112), Cu (113), Cu (122), Cu (123), Cu (133), Cu (223), Cu (233), or Cu (355) single-crystal copper foil.
Preferably, in the above method, the high-index surface is an index surface other than three low-index surfaces of Cu (001), Cu (011), and Cu (111).
Preferably, in the above method, the polycrystalline copper foil is put into a heating stage, an annealing furnace or a chemical vapor deposition apparatus to be heated in the step (one).
Preferably, in the above method, the oxygen-containing atmosphere in the step (one) is an air atmosphere or a pure oxygen atmosphere.
Preferably, in the above method, the inert gas in the step (two) is N2Or Ar.
Preferably, in the above method, the method comprises the steps of:
placing industrial grade commercial polycrystalline copper foil without any surface treatment on a high-temperature-resistant substrate or a high-temperature-resistant substrate interlayer, placing the industrial grade commercial polycrystalline copper foil into a heating table, an annealing furnace or chemical vapor deposition equipment, starting to heat up to 80-450 ℃ in air atmosphere, keeping for 1 min-24 h, and then cooling to room temperature to obtain the polycrystalline copper foil with pre-oxidation protection;
secondly, placing the pre-oxidation-protected polycrystalline copper foil on a high-temperature-resistant substrate or in a high-temperature-resistant substrate interlayer, placing the substrate into chemical vapor deposition equipment, and introducing inert gas and H2The flow rate of the inert gas is 200-2000 sccm, H2The flow rate is 20-500 sccm, then the temperature rise is started, and the inert gas is N2Or Ar;
and (III) when the temperature is raised to 800-1100 ℃, keeping the flow components of the introduced gas unchanged, and carrying out an annealing process for 10 minutes-24 hours.
And (IV) after the annealing is finished, keeping the flow components of the introduced gas unchanged, and naturally cooling to room temperature to obtain the high-index-surface single crystal copper foil.
Preferably, in the above process, steps one, two, three and four are all carried out under atmospheric conditions.
Preferably, in the above method, the refractory substrate interlayer is 2 to several hundred layers.
Preferably, in the above method, more than 1 piece of polycrystalline copper foil is placed in the high temperature resistant substrate interlayer to simultaneously prepare more than 1 piece of large single crystal high index surface copper foil in meter scale.
Preferably, in the above method, the single crystal copper foil has a length of 0.005m to 500m and a width of 0.005m to 5 m.
The invention also provides a meter-scale large monocrystal high-index surface copper foil, which is prepared by any one of the methods, and the length of the meter-scale large monocrystal high-index surface copper foil is 0.005-500 m, and the width of the meter-scale large monocrystal high-index surface copper foil is 0.005-5 m.
Preferably, the industrial-grade commercial polycrystalline copper foil is not subjected to any surface treatment, i.e., industrial-grade commercial polycrystalline copper foil obtained from the open commercial sources is directly used in the present process without any surface pretreatment.
The invention uses industrial grade commercial polycrystalline copper foil as a raw material, and prepares meter-scale large single crystal Cu (112), Cu (113), Cu (122), Cu (123), Cu (133), Cu (223), Cu (233), Cu (355) and other high index surface copper foils by using a special annealing process. The method provided by the invention solves the problems that the price and the preparation cost of the Cu (112), Cu (113), Cu (122), Cu (123), Cu (133), Cu (223), Cu (233), Cu (355) and other high-index surface single crystal copper foils are high and no product is supplied on the market, and realizes the mass preparation of the high-quality meter-grade large single crystal Cu (112), Cu (113), Cu (122), Cu (123), Cu (133), Cu (223), Cu (233), Cu (355) and other high-index surface copper foils by a very simple method.
The invention has the advantages that:
1. the invention firstly proposes that the pre-oxidation protection of commercial copper foil can promote the preparation of the large single crystal Cu (112), Cu (113), Cu (122), Cu (123), Cu (133), Cu (223), Cu (233), Cu (355) and other high index surface copper foils;
2. according to the invention, the commercially available industrial grade commercial polycrystalline copper foil is selected as a raw material, and the meter-grade large single crystal copper foils of Cu (112), Cu (113), Cu (122), Cu (123), Cu (133), Cu (223), Cu (233), Cu (355) and other high-index surface copper foils can be prepared without carrying out complex surface pretreatment on the copper foil, so that the preparation cost is greatly reduced;
3. the method is simple and effective, has low cost, and is beneficial to the practical application and industrial production of meter-scale large single crystal Cu (112), Cu (113), Cu (122), Cu (123), Cu (133), Cu (223), Cu (233), Cu (355) and other high-index surface copper foils.
Drawings
FIG. 1 is a schematic diagram of a high index surface single crystal copper foil obtained by pre-oxidation protection of a commercial industrial grade polycrystalline copper foil followed by annealing.
Fig. 2 is an X-ray diffraction (XRD) result of the copper foil obtained after annealing of a pre-oxidation protected commercial polycrystalline copper foil.
FIG. 3 is a single crystal X-ray diffraction result of a copper foil obtained after annealing a pre-oxidation protected commercial grade polycrystalline copper foil.
Fig. 4 is a back scattered electron diffraction (EBSD) result of a copper foil obtained after annealing a pre-oxidation protected commercial polycrystalline copper foil.
Fig. 5 is a characterization of the copper foil obtained after annealing a partially pre-oxidation protected commercial grade polycrystalline copper foil, the pre-oxidation protected portion being a high index face single crystal copper foil Cu (236) and the non-pre-oxidation protected portion being a low index face single crystal copper foil Cu (111).
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are conventional unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
The first embodiment is as follows: a method for preparing single crystal Cu (112), Cu (113), Cu (122), Cu (123), Cu (133), Cu (223), Cu (233), Cu (355) and other high index facets by pre-oxidation protection and annealing of commercial polycrystalline copper foil of industrial grade, comprising the steps of:
placing the industrial grade commercial polycrystalline copper foil without any surface treatment on a high-temperature-resistant substrate or a high-temperature-resistant substrate interlayer, placing the industrial grade commercial polycrystalline copper foil into a heating table, an annealing furnace or chemical vapor deposition equipment, starting to heat up to 80-450 ℃ in the air atmosphere, keeping the temperature for 1 min-24 h, and then cooling to room temperature to obtain the pre-oxidation-protected polycrystalline copper foil.
Placing the pre-oxidized and protected polycrystalline copper foil on a high-temperature-resistant substrate or a high-temperature-resistant substrate interlayer, placing the substrate or the interlayer in chemical vapor deposition equipment, and introducing inert gas and H2The flow rate of the inert gas is 200-2000 sccm, H2The flow rate is 20-500 sccm, then the temperature rise is started, and the inert gas is N2Or Ar;
and thirdly, when the temperature is raised to 800-1100 ℃, keeping the flow components of the introduced gas unchanged, and carrying out an annealing process for 1 minute-48 hours.
And fourthly, after the annealing is finished, keeping the flow components of the introduced gas unchanged, and naturally cooling to room temperature to obtain the Cu (112), Cu (113), Cu (122), Cu (123), Cu (133), Cu (223), Cu (233), Cu (355) and other high-index-face single crystal copper foils.
FIG. 1 is a schematic view of a process for obtaining a high index face single crystal copper foil from a commercial polycrystalline copper foil, which advances in step oneA pre-oxidation protection process in which amorphous Cu is formed on the surface of commercial poly-crystalline copper foil2And O protective layer. In the annealing process in the third step, high-index surface crystal nuclei are firstly formed on the surface of the polycrystalline copper foil, and the high-index surface crystal nuclei grow abnormally along with the extension of the annealing time, so that the commercial polycrystalline copper foil is finally converted into the high-index surface single crystal copper foil.
The interlayer of the high-temperature resistant substrate is 2 to hundreds of layers, and the polycrystalline copper foil is placed in the interlayer, so that more than 2 polycrystalline copper foils can be processed at the same time, and the processing efficiency of the polycrystalline copper foil and the preparation efficiency of the single crystal copper foil are greatly improved.
XRD characterization was performed on the annealed copper foil, and the result is shown in fig. 2. As can be seen from fig. 2, the front and back surfaces of the annealed copper foil have diffraction peaks in only one direction, namely, Cu (112), Cu (113), Cu (122), Cu (123), Cu (133), Cu (223), Cu (233), Cu (355) and other high-index surfaces, indicating that the annealed copper foil as a whole has formed a perfect single crystal of Cu (112), Cu (113), Cu (122), Cu (123), Cu (133), Cu (223), Cu (233), Cu (355) and other high-index surfaces. Single crystal X-ray diffraction (fig. 3) and back-scattered electron diffraction (EBSD) (fig. 4) can further demonstrate Cu (112), Cu (113), Cu (122), Cu (123), Cu (133), Cu (223), Cu (233), Cu (355), and other high index facet single crystals. Therefore, the copper foil is subjected to pre-oxidation protection, and the nucleation sites of the high-index surfaces in the copper foil are protected by oxidation and grow up under the drive of high temperature, so that the growth of single crystals of Cu (112), Cu (113), Cu (122), Cu (123), Cu (133), Cu (223), Cu (233), Cu (355) and other high-index surfaces is promoted, and the large-size single crystal copper foils of Cu (112), Cu (113), Cu (122), Cu (123), Cu (133), Cu (223), Cu (233), Cu (355) and other high-index surfaces are prepared.
The sizes of the Cu (112), Cu (113), Cu (122), Cu (123), Cu (133), Cu (223), Cu (233), Cu (355) and other high-index-face single crystal copper foils prepared by the method are 0.005-5 m and 0.005-500 m in width.
The beneficial effects of the invention are verified by the following tests:
test one: one method of this test, in which commercial multicrystalline copper foil of technical grade was pre-oxidation protected and then annealed to produce single crystal Cu (112), Cu (113), Cu (122), Cu (123), Cu (133), Cu (223), Cu (233), Cu (355) and other high index facets, was as follows:
firstly, placing the industrial-grade commercial polycrystalline copper foil without any surface treatment on a high-temperature-resistant substrate or in a high-temperature-resistant substrate interlayer, placing the industrial-grade commercial polycrystalline copper foil into a heating table, an annealing furnace or chemical vapor deposition equipment, starting to heat up to 150 ℃ in the air atmosphere, keeping for 1 hour, and then cooling to room temperature to obtain the pre-oxidation-protected polycrystalline copper foil.
Secondly, placing the pre-oxidation-protected polycrystalline copper foil on a high-temperature-resistant substrate or in a high-temperature-resistant substrate interlayer, placing the substrate into chemical vapor deposition equipment, and introducing Ar and H2Ar flow rate of 600sccm, H2The flow rate is 60sccm, and then the temperature is raised;
and thirdly, when the temperature is raised to 1000 ℃, keeping the flow components of the introduced gas unchanged, and carrying out an annealing process for 4 hours.
And fourthly, after the annealing is finished, keeping the flow components of the introduced gas unchanged, and naturally cooling to room temperature to obtain the Cu (112), Cu (113), Cu (122), Cu (123), Cu (133), Cu (223), Cu (233), Cu (355) and other high-index surface single crystal copper foils.
And (2) test II: one method of this test, in which commercial multicrystalline copper foil of technical grade was pre-oxidation protected and then annealed to produce single crystal Cu (112), Cu (113), Cu (122), Cu (123), Cu (133), Cu (223), Cu (233), Cu (355) and other high index facets, was as follows:
firstly, placing the industrial-grade commercial polycrystalline copper foil without any surface treatment on a high-temperature-resistant substrate or in a high-temperature-resistant substrate interlayer, placing the industrial-grade commercial polycrystalline copper foil into a heating table, an annealing furnace or chemical vapor deposition equipment, starting to heat up to 200 ℃ in the air atmosphere, keeping the temperature for 0.5 hour, and then cooling to room temperature to obtain the pre-oxidation-protected polycrystalline copper foil.
Secondly, placing the pre-oxidation protected polycrystalline copper foil on a high-temperature resistant linerPlacing on the substrate or in the interlayer of the high temperature resistant substrate into a chemical vapor deposition device, and introducing N2And H2，N2The flow rate is 800sccm, H2The flow rate is 40sccm, and then the temperature is raised;
and thirdly, when the temperature is increased to 900 ℃, keeping the flow components of the introduced gas unchanged, and carrying out an annealing process for 10 hours.
And fourthly, after the annealing is finished, keeping the flow components of the introduced gas unchanged, and naturally cooling to room temperature to obtain the Cu (112), Cu (113), Cu (122), Cu (123), Cu (133), Cu (223), Cu (233), Cu (355) and other high-index surface single crystal copper foils.
Comparative example: pre-oxidation protection is carried out on the industrial grade commercial polycrystalline copper foil part, and then annealing is carried out, wherein the pre-oxidation protection is carried out according to the following steps:
firstly, horizontally placing the industrial grade commercial polycrystalline copper foil without any surface treatment on a high-temperature-resistant substrate, partially placing the industrial grade commercial polycrystalline copper foil on a heating table, starting to heat up to 150 ℃ in the air atmosphere, keeping for 1 hour, and then cooling to room temperature to obtain the partially pre-oxidized and protected polycrystalline copper foil.
Secondly, placing the partially pre-oxidized and protected polycrystalline copper foil on a high-temperature resistant substrate, placing the substrate into chemical vapor deposition equipment, and introducing Ar and H2Ar flow rate of 600sccm, H2The flow rate is 60sccm, and then the temperature is raised;
and thirdly, when the temperature is raised to 1000 ℃, keeping the flow components of the introduced gas unchanged, and carrying out an annealing process for 4 hours.
And fourthly, after the annealing is finished, keeping the flow components of the introduced gas unchanged, and naturally cooling to room temperature to obtain the copper foil of the comparative example.
The partially pre-oxidized protective copper foil after the annealing was characterized by back scattered electron diffraction (EBSD) and single crystal X-ray diffraction, and the results are shown in fig. 5. As shown in fig. 5, the pre-oxidation protected portion is the high-index-surface single crystal copper foil Cu (236), and the non-pre-oxidation protected portion is the low-index-surface single crystal copper foil Cu (111). It can be seen that without prior oxidation protection, the copper foil cannot be recrystallized to form large single crystal Cu (112), Cu (113), Cu (122), Cu (123), Cu (133), Cu (223), Cu (233), Cu (355) and other high index surface copper foils, but can only form single crystal Cu (111) low index surface copper foils.
Claims (12)
1. A preparation method of a meter-level large single crystal high-index surface copper foil is characterized in that a polycrystalline copper foil is subjected to oxidation protection in advance, then annealing is carried out, and the growth of nucleation sites of the high-index surface is driven by high temperature to be oxidized and protected to obtain the meter-level large single crystal high-index surface copper foil;
the method comprises the following steps:
firstly, placing the polycrystalline copper foil on a high-temperature-resistant substrate or in a high-temperature-resistant substrate interlayer, starting to heat to more than 80 ℃ in an oxygen-containing atmosphere, keeping the temperature for more than 1 minute, and then cooling to room temperature to obtain the polycrystalline copper foil protected by pre-oxidation;
secondly, placing the pre-oxidation-protected polycrystalline copper foil on a high-temperature-resistant substrate or in a high-temperature-resistant substrate interlayer, placing the substrate into chemical vapor deposition equipment, and introducing inert gas and H2Then starting to increase the temperature;
thirdly, when the temperature is increased to 800-1100 ℃, keeping the flow components of the introduced gas unchanged, and carrying out an annealing process, wherein the annealing duration is longer than 10 minutes; and (IV) after the annealing is finished, naturally cooling to room temperature to obtain the high-index surface single crystal copper foil.
2. The method of claim 1, wherein the meter large single crystal high index faced copper foil includes, but is not limited to, Cu (112), Cu (113), Cu (122), Cu (123), Cu (133), Cu (223), Cu (233), or Cu (355) single crystal copper foil.
3. The method of claim 1, wherein the high index surface is an index surface other than three low index surfaces of Cu (001), Cu (011), and Cu (111).
4. The method according to any one of claims 1 to 3, wherein the polycrystalline copper foil is put into a heating stage, an annealing furnace or a chemical vapor deposition apparatus for temperature rise in the step (one).
5. The method according to any one of claims 1 to 3, wherein the oxygen-containing atmosphere in the step (one) is an air atmosphere or a pure oxygen atmosphere.
6. The method according to any one of claims 1 to 3, wherein the inert gas in the step (two) is N2Or Ar.
7. A method according to any of claims 1-3, characterized in that the method comprises the steps of:
placing industrial grade commercial polycrystalline copper foil without any surface treatment on a high-temperature-resistant substrate or a high-temperature-resistant substrate interlayer, placing the industrial grade commercial polycrystalline copper foil into a heating table, an annealing furnace or chemical vapor deposition equipment, starting to heat up to 80-450 ℃ in air atmosphere, keeping for 1 min-24 h, and then cooling to room temperature to obtain the polycrystalline copper foil with pre-oxidation protection;
secondly, placing the pre-oxidation-protected polycrystalline copper foil on a high-temperature-resistant substrate or in a high-temperature-resistant substrate interlayer, placing the substrate into chemical vapor deposition equipment, and introducing inert gas and H2The flow rate of the inert gas is 200-2000 sccm, H2The flow rate is 20-500 sccm, then the temperature rise is started, and the inert gas is N2Or Ar;
and (III) when the temperature is raised to 800-1100 ℃, keeping the flow components of the introduced gas unchanged, and carrying out an annealing process for 10 minutes-24 hours.
And (IV) after the annealing is finished, keeping the flow components of the introduced gas unchanged, and naturally cooling to room temperature to obtain the high-index-surface single crystal copper foil.
8. A process according to any one of claims 1 to 3, wherein steps one, two, three and four are all carried out under atmospheric conditions.
9. The method of any of claims 1-3, wherein the refractory substrate interlayer is 2 to hundreds of layers.
10. The method of claim 9, wherein more than 1 piece of polycrystalline copper foil is placed in the high temperature resistant substrate interlayer to simultaneously prepare more than 1 piece of large single crystal high index face copper foil on a meter scale.
11. The method according to any one of claims 1 to 3, wherein the single-crystal copper foil has a length of 0.005m to 500m and a width of 0.005m to 5 m.
12. A meter-scale large single-crystal high-index surface copper foil is characterized in that the meter-scale large single-crystal high-index surface copper foil is prepared by the method of any one of claims 1 to 11, and the length of the meter-scale large single-crystal high-index surface copper foil is 0.005 m-500 m, and the width of the meter-scale large single-crystal high-index surface copper foil is 0.005 m-5 m.
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| CN112522775B (en) * | 2020-11-26 | 2021-09-28 | 深圳大学 | Preparation method of wafer-level single crystal copper foil and preparation method of regular graphene |
| CN113463201A (en) * | 2021-06-30 | 2021-10-01 | 南京大学 | Annealing method for converting polycrystalline silver foil into high-index crystal-face silver foil |
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