CN112301411A - Method for preparing single crystal copper foil - Google Patents
Method for preparing single crystal copper foil Download PDFInfo
- Publication number
- CN112301411A CN112301411A CN201910710763.8A CN201910710763A CN112301411A CN 112301411 A CN112301411 A CN 112301411A CN 201910710763 A CN201910710763 A CN 201910710763A CN 112301411 A CN112301411 A CN 112301411A
- Authority
- CN
- China
- Prior art keywords
- copper foil
- single crystal
- polycrystalline
- polycrystalline copper
- crystal copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
-
- 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
- C30B29/02—Elements
Abstract
The invention provides a method for preparing a single crystal copper foil, which comprises the step of placing a polycrystalline copper foil obliquely and carrying out annealing treatment to obtain the single crystal copper foil. The method provided by the embodiment of the invention is rapid, high in repeatability and low in cost, and can be used for preparing large-size single crystal copper foil.
Description
Technical Field
The invention relates to copper foil single crystallization, in particular to a method for rapidly preparing a large-size copper foil single crystal.
Background
The electrical properties, mechanical properties and the like of the polycrystalline copper foil are affected due to more grain boundaries, and the single crystal metal has lower resistance due to no grain boundary scattered electrons. In addition, the copper foil is used as a common substrate for growing the graphene, and seamless splicing of graphene domains is easier to realize through single crystallization, so that the single crystal graphene is obtained. Epitaxial growth of other two-dimensional materials such as Boron Nitride (BN) on large area single crystal copper foils is also of interest.
The conventional method for preparing a single crystal copper foil includes a temperature gradient method, a method for growing abnormal grains; in addition, the method of preparing the single crystal copper foil also includes a method of annealing for a long time (more than 6 h). However, these methods have limitations due to their long time consumption and insufficient processing size.
Disclosure of Invention
The invention mainly aims to provide a method for preparing a single crystal copper foil, which comprises the step of placing a polycrystalline copper foil obliquely for annealing treatment to prepare the single crystal copper foil.
According to an embodiment of the present invention, the inclination angle of the poly-crystalline copper foil is 30 to 90 °.
According to an embodiment of the present invention, the inclination angle of the poly-crystal copper foil is 45 to 60 °.
According to one embodiment of the invention, the method comprises the step of heating the polycrystalline copper foil to 800-1084 ℃ and then cooling the polycrystalline copper foil.
According to an embodiment of the present invention, the rate of temperature increase and/or decrease of the polycrystalline copper foil is 0.1 to 20 ℃/min.
According to an embodiment of the present invention, the polycrystalline copper foil may be heated by a cold-wall chemical vapor deposition apparatus (cold-wall CVD) or a hot-wall chemical vapor deposition apparatus (hot-wall CVD).
According to an embodiment of the present invention, the cooling method of the polycrystalline copper foil is air cooling, water cooling or natural cooling.
According to an embodiment of the present invention, the annealing time is 10 to 360 minutes.
According to an embodiment of the invention, the method comprises annealing the polycrystalline copper foil in a gas atmosphere, the gas comprising one or more of hydrogen, argon, nitrogen, carbon dioxide.
According to an embodiment of the present invention, the pressure during the annealing process is 50 to 101325 Pa.
The method provided by the embodiment of the invention is rapid, high in repeatability and low in cost, and can be used for preparing the single crystal copper foil with larger size.
Drawings
FIG. 1 is a drawing showing a real object of a single crystal copper foil produced in example 1 of the present invention;
FIG. 2 is an optical view of a single crystal copper foil produced in example 1 of the present invention;
FIG. 3 is an optical view of a single crystal copper foil produced in example 2 of the present invention;
FIG. 4 is a drawing showing a copper foil produced by the comparative example of the present invention;
FIG. 5 is an optical diagram of a single crystal copper foil produced by comparative example of the present invention.
Detailed Description
Exemplary embodiments that embody features and advantages of the invention are described in detail below. It is to be understood that the invention is capable of other and different embodiments and its several details are capable of modification without departing from the scope of the invention, and that the description is intended to be illustrative in nature and not to be construed as limiting the invention.
The invention provides a method for preparing a single crystal copper foil by adjusting stress, which comprises the step of placing a polycrystalline copper foil obliquely for annealing treatment to prepare the single crystal copper foil.
In the invention, the raw material copper foil is obliquely arranged according to a certain angle so as to reduce the stress concentration of the copper foil in the temperature rising process.
In one embodiment, the inclination angle of the poly-crystal copper foil is 30 to 90 °, preferably 45 to 60 °, for example, the inclination angle may be 40 °, 50 °, 55 °, 65 °, 70 °, 80 °, and the like.
In one embodiment, the poly-crystalline copper foil may be disposed on the inclined member so as to maintain a certain inclination angle.
In one embodiment, the tilting means comprises an adjustable tilting surface, tilting frame or support to keep the poly-crystalline copper foil tilted.
In one embodiment, the material of the inclined member may be one or more of quartz, graphite, alumina, nickel, and molybdenum.
In one embodiment, the polycrystalline copper foil is annealed in a certain gas atmosphere to prepare a single crystal copper foil.
In one embodiment, the gas atmosphere for processing the poly-crystalline copper foil may be one or more of hydrogen, argon, nitrogen, and carbon dioxide, and the gas flow rate may be 100-2000 sccm, such as 200sccm, 500sccm, 800sccm, 1000sccm, 1200sccm, 1500sccm, 1800sccm, and the like.
In one embodiment, the pressure during the annealing process of the poly-crystalline copper foil may be 50 to 101325Pa, such as 100Pa, 500Pa, 1000Pa, 5000Pa, 10000Pa, 50000Pa, etc.
In one embodiment, the temperature of the poly-crystal copper foil is raised to 800 to 1084 ℃ and then the temperature of the poly-crystal copper foil is lowered, for example, the temperature of the poly-crystal copper foil is raised to 900 ℃ or 1000 ℃.
In one embodiment, the temperature increase/decrease rate of the poly-crystalline copper foil may be 0.1-20 ℃/min, such as 0.5 ℃/min, 1 ℃/min, 5 ℃/min, 10 ℃/min, 15 ℃/min, and the like.
In one embodiment, the polycrystalline copper foil may be heated by a conventional heating method, such as a cold-wall CVD (cold-wall CVD) or a hot-wall CVD (hot-wall CVD).
In one embodiment, the cooling method of the poly-crystal copper foil may be air cooling, water cooling or natural cooling.
In one embodiment, the annealing time is not less than 10 minutes, preferably 10 to 360 minutes, such as 30 minutes, 60 minutes, 90 minutes, 120 minutes, 150 minutes, 300 minutes, and the like.
In the present invention, the brand, model, supplier, and the like of the raw copper foil used are not limited.
In one embodiment, the size of the raw copper foil used may vary from sub-centimeter to meter, depending on the size of the vacuum chamber used.
In one embodiment, the purity of the raw copper foil used may be 95 to 99.99999%.
The method of one embodiment of the invention can realize simultaneous treatment of 1-50 copper foils at one time.
The single crystal copper foil substrate prepared by the embodiment of the invention can be used for growing high-quality two-dimensional materials such as single crystal graphene and hexagonal boron nitride.
The method for preparing the single crystal copper foil is a treatment method for preparing the single crystal copper foil with the advantages of high release capacity, high repeatability and low cost, and has good industrial prospect.
Compared with the prior art, the method provided by the embodiment of the invention can be used for preparing the single crystal copper foil with larger size.
Hereinafter, a method for manufacturing a single crystal copper foil according to an embodiment of the present invention will be described in detail with reference to specific examples. Wherein the raw material copper foil is purchased from electronic technology of Power Generation, Inc. of Kunshan, Lu, and other raw materials can be obtained from open commercial sources unless otherwise specified; the optical images involved were all measured by light microscopy (Nikon).
Example 1
1) Placing a copper foil on a quartz plate;
2) placing the quartz plate with the copper foil in a chemical vapor deposition furnace with an inclination angle of 45 degrees;
3) and (3) heating to 1000 ℃ in a hydrogen atmosphere of 1000sccm, annealing for 1 hour at the pressure of about 530Pa, rapidly cooling, and taking out the quartz plate loaded with the copper foil to obtain the single crystal copper foil with the size of a decimeter, wherein a physical diagram is shown in figure 1, and an optical diagram is shown in figure 2.
Example 2
1) Placing a copper foil on a quartz plate;
2) placing the quartz plate with the copper foil in a chemical vapor deposition furnace in an inclined way of 90 degrees;
3) raising the temperature to 1000 ℃ in a hydrogen atmosphere of 1000sccm, annealing for 1 hour at a pressure of about 530Pa, rapidly cooling, and taking out the quartz plate loaded with the copper foil to obtain copper foil crystal grains as shown in FIG. 3.
Comparative example
1) Placing a copper foil on a quartz plate;
2) horizontally placing the quartz plate with the copper foil in a chemical vapor deposition furnace;
3) raising the temperature to 1000 ℃ in a hydrogen atmosphere of 1000sccm, annealing for 1 hour at a pressure of about 530Pa, rapidly reducing the temperature, taking out the quartz plate loaded with the copper foil, and obtaining a copper foil material object diagram as shown in FIG. 4 and a copper foil crystal grain as shown in FIG. 5. Compared with the single crystal copper foil prepared in example 1, the grain size of the horizontally placed copper foil is only in the order of hundred microns, which is significantly smaller than the grain size of the copper foil when obliquely placed. In addition, in the optical diagram, the smaller the crystal grain size, the rougher the surface of the copper foil looks due to scattering or the like, and the brighter the surface of the single-crystal copper foil. The larger the single crystallization size of the copper foil is, the more beneficial effect is on preparing high-quality graphene and other two-dimensional materials.
Unless otherwise defined, all terms used herein have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are for illustrative purposes only and are not intended to limit the scope of the present invention, and those skilled in the art may make various other substitutions, alterations, and modifications within the scope of the present invention, and thus, the present invention is not limited to the above-described embodiments but only by the claims.
Claims (10)
1. A method for preparing a single crystal copper foil comprises the step of placing a polycrystalline copper foil obliquely for annealing treatment to obtain the single crystal copper foil.
2. The method according to claim 1, wherein the angle of inclination of the polycrystalline copper foil is 30 to 90 °.
3. The method according to claim 2, wherein the angle of inclination of the polycrystalline copper foil is 45 to 60 °.
4. The method according to claim 1, comprising heating the polycrystalline copper foil to 800-1084 ℃ and then cooling the polycrystalline copper foil.
5. The method according to claim 1, wherein the rate of temperature rise and/or decrease of the temperature of the polycrystalline copper foil is 0.1 to 20 ℃/min.
6. The method of claim 1, wherein the polycrystalline copper foil is heated by a cold wall chemical vapor deposition apparatus or a hot wall chemical vapor deposition apparatus.
7. The method according to claim 1, wherein the polycrystalline copper foil is cooled by air cooling, water cooling or natural cooling.
8. The method according to claim 1, wherein the annealing treatment time is 10 to 360 minutes.
9. The method of claim 1, comprising annealing the polycrystalline copper foil in a gas atmosphere comprising one or more of hydrogen, argon, nitrogen, carbon dioxide.
10. The method of claim 1, wherein the pressure during the annealing treatment is 50 to 101325 Pa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910710763.8A CN112301411A (en) | 2019-08-02 | 2019-08-02 | Method for preparing single crystal copper foil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910710763.8A CN112301411A (en) | 2019-08-02 | 2019-08-02 | Method for preparing single crystal copper foil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112301411A true CN112301411A (en) | 2021-02-02 |
Family
ID=74486505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910710763.8A Pending CN112301411A (en) | 2019-08-02 | 2019-08-02 | Method for preparing single crystal copper foil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112301411A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140014030A1 (en) * | 2012-07-10 | 2014-01-16 | William Marsh Rice University | Methods for production of single-crystal graphenes |
| CN107904654A (en) * | 2017-01-12 | 2018-04-13 | 北京大学 | A kind of preparation method of large size single crystal copper foil |
| CN108950684A (en) * | 2018-06-08 | 2018-12-07 | 中国科学院物理研究所 | A method of preparing single-crystal metal foil |
| CN109477237A (en) * | 2016-07-12 | 2019-03-15 | 基础科学研究院 | Single-crystal metal foil and its manufacturing method |
| CN109537043A (en) * | 2018-12-28 | 2019-03-29 | 北京大学 | Control the preparation method of the monocrystalline copper foil of crystal face exposure orientation |
-
2019
- 2019-08-02 CN CN201910710763.8A patent/CN112301411A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140014030A1 (en) * | 2012-07-10 | 2014-01-16 | William Marsh Rice University | Methods for production of single-crystal graphenes |
| CN109477237A (en) * | 2016-07-12 | 2019-03-15 | 基础科学研究院 | Single-crystal metal foil and its manufacturing method |
| CN107904654A (en) * | 2017-01-12 | 2018-04-13 | 北京大学 | A kind of preparation method of large size single crystal copper foil |
| CN108950684A (en) * | 2018-06-08 | 2018-12-07 | 中国科学院物理研究所 | A method of preparing single-crystal metal foil |
| CN109537043A (en) * | 2018-12-28 | 2019-03-29 | 北京大学 | Control the preparation method of the monocrystalline copper foil of crystal face exposure orientation |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5068423B2 (en) | Silicon carbide single crystal ingot, silicon carbide single crystal wafer, and manufacturing method thereof | |
| CN103715069B (en) | A kind of reduce the method for defect in silicon carbide epitaxial film | |
| EP2484815A1 (en) | Sic single crystal and method for producing same | |
| CN104928649A (en) | Local-area carbon supply device and method for manufacturing wafer-level graphene monocrystalline based on local-area carbon supply | |
| CN101910476A (en) | Method for growing silicon carbide single crystal | |
| WO2018165910A1 (en) | Porous gallium nitride single crystal material, preparation method therefor and use thereof | |
| TW201202490A (en) | Method for producing single crystal 3C-SiC substrate and single crystal 3C-SiC substrate produced by the same | |
| CN101965419B (en) | Method for growing silicon carbide single crystal | |
| US9347149B2 (en) | Method for growing epitaxial diamond | |
| WO2011099199A1 (en) | Method for producing silicon carbide crystal and silicon carbide crystal | |
| WO2007013286A1 (en) | AlN CRYSTAL AND METHOD FOR GROWING THE SAME, AND AlN CRYSTAL SUBSTRATE | |
| CN111819311A (en) | Method for producing silicon carbide single crystal | |
| JP2008001569A (en) | SINGLE CRYSTAL SiC AND PRODUCTION METHOD THEREFOR, AND APPARATUS FOR PRODUCING SINGLE CRYSTAL SiC | |
| CN109183143B (en) | Method for improving AlN single crystal purity by using reducing gas | |
| JP2013056807A (en) | METHOD FOR PRODUCING SiC SINGLE CRYSTAL, AND SiC SINGLE CRYSTAL OBTAINED THEREBY | |
| CN109852944A (en) | Graphene preparation method based on microwave plasma CVD | |
| WO2009107188A1 (en) | METHOD FOR GROWING SINGLE CRYSTAL SiC | |
| JP3508519B2 (en) | Epitaxial growth apparatus and epitaxial growth method | |
| JP4494856B2 (en) | Seed crystal for silicon carbide single crystal growth, method for producing the same, and crystal growth method using the same | |
| CN112301411A (en) | Method for preparing single crystal copper foil | |
| JP5761264B2 (en) | Method for manufacturing SiC substrate | |
| Zhao et al. | Effect of C/Si ratio on the characteristics of 3C-SiC films deposited on Si (100) base on the four-step non-cooling process | |
| JP5428706B2 (en) | Method for producing SiC single crystal | |
| JP2002255692A (en) | Silicon carbide epitaxial substrate and manufacturing method thereof | |
| JP2018043891A (en) | Production method of gallium nitride laminate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210202 |