阅读说明：本技术 一种单晶金属箔材及其制备方法 (Single crystal metal foil and preparation method thereof ) 是由 黄德萍 史浩飞 张永娜 李昕 李占成 于 2020-05-15 设计创作，主要内容包括：本发明提供一种单晶金属箔材的制备方法,其中,方法包括以下步骤：(1)在多晶金属箔材两端施加应力；(2)在步骤(1)施加应力的同时将所述多晶金属箔材进行弯曲,并同时进行高温退火处理；(3)在多晶金属箔材两端施加逐渐定量增加的应力,获得单晶金属箔材。通过以上方法能制备大面积的单晶二维材料；此方法简单可控,可用于大需求的生产。(The invention provides a preparation method of a single crystal metal foil, which comprises the following steps: (1) applying stress to two ends of the polycrystalline metal foil; (2) bending the polycrystalline metal foil while applying stress in the step (1), and simultaneously performing high-temperature annealing treatment; (3) and applying gradually and quantitatively increased stress to two ends of the polycrystalline metal foil to obtain the monocrystalline metal foil. The method can prepare large-area single crystal two-dimensional materials; the method is simple and controllable, and can be used for production with large demand.)

1. A preparation method of a single crystal metal foil is characterized by comprising the following steps:

(1) applying stress to two ends of the polycrystalline metal foil;

(2) bending the polycrystalline metal foil while applying stress in the step (1), and simultaneously performing high-temperature annealing treatment;

(3) and applying gradually and quantitatively increased stress to two ends of the polycrystalline metal foil to obtain the monocrystalline metal foil.

2. The method of claim 1, wherein the polycrystalline metal foil has a thickness of 1 to 100 μm and a size of 1mm²-1000mm²。

3. The method according to claim 2, wherein the polycrystalline metal is cut into an I-shape having a width greater at both ends than at the middle, and a hole is formed at the center of each of the wider ends, and a stress-pulling device is installed through the hole to apply the stress.

4. The method for preparing the alloy material according to claim 1, wherein the method for applying stress in the step (1) comprises the stress applying effects caused by pulling, pressing and gravity, and the stress is 0-300 MPa.

5. The production method according to claim 1, wherein the polycrystalline metal foil in the step (2) is bent at a bending radius of 0.01mm to 100mm and a bending angle of 0 ° to 360 °.

6. The preparation method according to claim 1, wherein the specific steps of performing the high-temperature annealing treatment are as follows:

introducing one or more of argon gas with the flow of 1-1000sccm, nitrogen gas with the flow of 1-1000sccm and hydrogen with the flow of 1-500sccm as protective gas;

raising the annealing temperature to 1200 ℃ at the temperature rise rate of 1-20 ℃/s, continuing to cool for 1-200h, and then cooling at the temperature rise rate of 1-50 ℃/s.

7. The method of claim 1, wherein the polycrystalline metal foil comprises a face centered cubic metal including copper, nickel, platinum, palladium, gold, and aluminum.

8. The method of claim 7, wherein the metal has a purity of greater than 99%.

9. The production method according to claim 1, wherein the surface crystal planes of the single-crystal metal foil obtained in the step (3) include (111), (110), (100), (212), (223), (116), (335), (233) crystal planes.

10. Single-crystal metal foil obtained by the production method according to any one of claims 1 to 9, wherein the single-crystal metal foil has a thickness of 1 to 100 μm and a size of 1mm²-1000mm²(ii) a Wherein the metal is face-centered cubic metalIncluding copper, nickel, platinum, palladium, gold, aluminum.

Technical Field

The invention belongs to the technical field of single crystal metal material preparation, and particularly relates to a single crystal metal foil and a preparation method thereof.

Background

Single crystals are very important in the field of research of materials, and they generally exhibit excellent properties in terms of electricity, magnetism, light, heat, and the like, and thus are useful as high-performance electronic devices, semiconductor devices, and the like.

In the preparation of the two-dimensional material film, the metal material can be generally used as a catalyst substrate for the growth of the two-dimensional material, and the epitaxial relationship between the two-dimensional material and the metal substrate and the lattice matching between the two have great influence on the performance of the two-dimensional material.

The preparation of large-area single-crystal two-dimensional materials is the bottleneck faced by the preparation and application research of the current two-dimensional materials, and the single-crystal metal substrate has important significance for the growth of the single-crystal two-dimensional materials, for example, single-crystal graphene can be prepared on the surfaces of Cu (111) and Cu (110), and single-crystal boron nitride can be grown on the surface of Cu (110) with a specific step; therefore, the controllable preparation of the single crystal metal substrate is the basis for growing the single crystal two-dimensional material, but the current single crystal metal preparation usually needs long-time high-temperature annealing, and the large-area preparation is difficult to realize.

Disclosure of Invention

In view of the above, an object of the present invention is to provide a method for preparing a single crystal metal foil, which is used to prepare a single crystal metal substrate and is simple and controllable.

In order to achieve the purpose, the technical scheme of the invention is as follows:

a preparation method of a single crystal metal foil comprises the following steps:

(1) applying stress to two ends of the polycrystalline metal foil;

(2) bending the polycrystalline metal foil while applying stress in the step (1), and simultaneously performing high-temperature annealing treatment;

(3) and applying gradually and quantitatively increased stress to two ends of the polycrystalline metal foil to obtain the monocrystalline metal foil.

Further, the thickness of the polycrystalline metal foil is 1-100 μm, and the size is 1mm²-1000mm²。

Furthermore, the polycrystalline metal is cut into an I-shaped shape with the width of two ends larger than the width of the middle part, the center positions of the two ends with the large width are respectively provided with a hole, and a stress pulling device is arranged through the holes to provide applied stress.

Further, the method for applying stress in step (1) includes a stress application effect caused by pulling, pressing and gravity.

Further, the stress is 0-300 MPa.

Further, the bending radius is 0.01mm-100 mm.

Further, the bending angle is 0-360 degrees.

Further, the specific steps of performing the high-temperature annealing treatment are as follows:

introducing one or more of argon gas with the flow of 1-1000sccm, nitrogen gas with the flow of 1-1000sccm and hydrogen with the flow of 1-500sccm as protective gas;

raising the annealing temperature to 1200 ℃ at the temperature rise rate of 1-20 ℃/s, continuing to cool for 1-200h, and then cooling at the temperature rise rate of 1-50 ℃/s.

Further, the metal species of the polycrystalline metal foil include face-centered cubic metals such as copper, nickel, platinum, palladium, gold, and aluminum.

Further, the purity of the metal is greater than 99%.

Further, the surface crystal planes of the single-crystal metal foil obtained in the step (3) include (111), (110), (211), (223), (116), (335), and (233) crystal planes.

Meanwhile, the invention also provides a single crystal metal foil obtained by the method of one of the objects, wherein the thickness of the single crystal metal foil is 1-100 mu m, and the size of the single crystal metal foil is 1mm²-1000mm²(ii) a The metal species include face centered cubic metals such as copper, nickel, platinum, palladium, gold, and aluminum.

Advantageous effects

The invention provides a preparation method of a single crystal metal foil, which can prepare the single crystal metal foil with a required crystal face through simple bending and stress adjustment, is simple to operate and controllable in process, and avoids complex or long preparation processes such as long-time annealing, seed crystal induction and the like in the conventional single crystal preparation method; meanwhile, the invention also provides a method for obtaining any crystal face single crystal metal foil through controllable modulation by changing the stress magnitude, the direction and the like. On the other hand, the invention also provides a single crystal metal foil.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive exercise.

FIG. 1 is a flow chart illustrating an embodiment of a method for manufacturing a single crystal metal foil according to the present invention;

FIG. 2 is a schematic view of a stress applying manner in a method for manufacturing a single crystal metal foil according to the present invention;

FIG. 3 is a schematic structural diagram illustrating an annealing process performed in a single crystal metal foil manufacturing method according to an embodiment of the present invention;

FIG. 4 is a schematic view of the bending angle of the polycrystalline metal foil during the annealing process;

FIG. 5 is a schematic view showing the conversion of a polycrystalline metal foil into a single crystal metal foil in the method for producing a single crystal metal foil according to the present invention;

FIG. 6a is a graph showing the results of an experiment using a single-crystal metal foil according to example 1 of the present invention;

FIG. 6b is a graph showing the ESBD results of a single-crystal metal foil in example 1 of the present invention;

FIG. 7a is a graph showing the results of an experiment using a single-crystal metal foil according to example 2 of the present invention;

FIG. 7b is a graph showing the ESBD results of a single-crystal metal foil in example 2 of the present invention;

FIG. 8a is a graph showing the results of an experiment using a single-crystal metal foil according to example 3 of the present invention;

FIG. 8b is a graph showing the ESBD results of a single-crystal metal foil in example 3 of the present invention;

FIG. 9a is a graph showing the results of an experiment using a single-crystal metal foil according to example 4 of the present invention;

FIG. 9b is a graph showing the ESBD results of a single-crystal metal foil in example 4 of the present invention;

FIG. 10a is a graph showing the results of an experiment using a single-crystal metal foil according to example 5 of the present invention;

FIG. 10b is a graph showing the ESBD results of a single-crystal metal foil in example 5 of the present invention;

FIG. 11a is a graph showing the results of an experiment using a single-crystal metal foil according to example 6 of the present invention;

FIG. 11b is a graph showing the results of ESBD in the single-crystal metal foil in example 6 of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The examples are given for the purpose of better illustration of the invention, but the invention is not limited to the examples. Therefore, those skilled in the art should make insubstantial modifications and adaptations to the embodiments of the present invention in light of the above teachings and remain within the scope of the invention.

Referring to fig. 1, a method for preparing a single crystal metal foil according to the present invention, specifically, a method for preparing a single crystal metal foil includes the steps of:

s100: applying stress to two ends of the polycrystalline metal foil; then step S200 is executed;

in the embodiment, firstly, a polycrystalline metal foil is cut into an I-shaped shape with the width of two ends larger than the width of the middle, the centers of the two ends with the larger width are respectively provided with a hole, a hole is arranged with a tension device to apply quantitative tension to provide quantitative stress, and the stress is 0-300 MPa; the specific shape can be referred to fig. 2, wherein F1, F1' are applied tensile forces, 2 and 4 are holes, and 3 is an annealing target region;

preferably, the polycrystalline metal foil has a thickness of 1-100 μm and a size of 1mm²-1000mm²The metal types of the polycrystalline metal foil comprise face-centered cubic metals such as copper, nickel, platinum, palladium, gold and aluminum, and the purity of the metals is more than 99%.

S200: simultaneously carrying out high-temperature annealing treatment on the polycrystalline metal foil;

further, the polycrystalline metal foil 2 is placed in a tube furnace as shown in fig. 3 for a high temperature annealing process while applying stress in step S100, wherein 2 is the polycrystalline metal foil, 1 is a quartz tube, 5 is an upper heating wire, 6 is a lower heating wire, and 2 is a bending angle adjusting device.

Further, the bending angle adjusting device 2 has the function of bending the metal surface under the action of high temperature and tensile force, so that the metal surface is subjected to bending stress, and the direction of the tensile force is changed, thereby promoting the change of the crystal orientation of the surface.

Furthermore, the crystal planes of the surface are changed differently through the bending with different bending radii and angles, so that the generation of different crystal planes is regulated and controlled.

Specifically, the annealing process comprises: introducing one or more of argon gas with the flow rate of 1-1000sccm, nitrogen gas with the flow rate of 1-1000sccm and hydrogen with the flow rate of 1-500sccm into the quartz tube 1 as protective gas; raising the annealing temperature to 1200 ℃ at the temperature rise rate of 1-20 ℃/s, continuing to cool for 1-200h, and then cooling at the temperature rise rate of 1-50 ℃/s.

S300: and applying gradually and quantitatively increased stress to two ends of the polycrystalline metal foil to obtain the monocrystalline metal foil.

In this embodiment, while the high temperature annealing is performed in step S200, the polycrystalline metal foil is bent by the applied tension, specifically, according to the manner shown in fig. 4, F1 and F1 'are tension, r is the bending radius of the angle adjusting device, θ is the bending angle, and the direction of F1' is controllable, so that θ is in the range of 0 to 360 ° and r is in the range of 0.1mm to 100mm, the bending degree of the metal foil is adjusted by the change of r, and the tension of the stress pulling device is controlled, so that the stress is changed between 0 to 300Mpa during the temperature-rising annealing process. After the annealing treatment, a single crystal metal foil can be obtained in the annealing target region 3, and the surface crystal orientation of the single crystal metal foil includes common crystal planes (111), (110), (100), (211), (223), (116), (335), (233), (017), (014), and (212). The invention can regulate and control different single crystal faces to dominate in a sample according to different pulling force and curved surface annealing modes.

FIG. 5 is a schematic view of the transition of a polycrystalline metal foil to a single crystal metal foil according to the present invention, wherein 7 is the polycrystalline metal foil before annealing, 8 is a normal grain boundary, and 9 is a twin grain boundary; 10 is an annealing process, and 11 is a single crystal metal foil obtained after annealing.