CN110438556B - Preparation method of single crystal copper foil - Google Patents
Preparation method of single crystal copper foil Download PDFInfo
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- CN110438556B CN110438556B CN201910710749.8A CN201910710749A CN110438556B CN 110438556 B CN110438556 B CN 110438556B CN 201910710749 A CN201910710749 A CN 201910710749A CN 110438556 B CN110438556 B CN 110438556B
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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
- C30B29/02—Elements
Abstract
The invention provides a single crystal copper foil and a preparation method thereof, and the method comprises the steps of placing a polycrystalline copper foil in a region with a plurality of temperature regions for annealing to prepare the single crystal copper foil; wherein, in the area with a plurality of warm areas, the temperature difference between adjacent warm areas is 5-200 ℃. The method of the embodiment of the invention has simple process, and can conveniently obtain the copper single crystal with large area, high single crystallinity and high flatness.
Description
Technical Field
The invention relates to preparation of a single crystal copper foil, in particular to a method for statically preparing a large-area single crystal copper foil.
Background
Industrial rolled copper foil or electrolytic copper foil is often a polycrystalline copper foil, and the presence of grain boundaries affects its electrical and mechanical properties. The single crystal copper foil has higher conductivity because no grain boundary scatters electrons; the single crystal copper (111) crystal face can be used as a graphene growth substrate to realize the same orientation epitaxial growth of graphene, so that a large-area single crystal graphene sample can be prepared. Therefore, there is a wide demand for the preparation of large-area single crystal copper foils.
At present, methods for producing a copper single crystal have been reported as follows:
1. annealing at high temperature for a long time; the method can realize the conversion from the polycrystalline copper foil to the single crystal copper foil, but the area of the single crystal is limited;
2. cutting one end of the copper foil into a tip, and then carrying out dynamic annealing on the copper foil; the method can prepare large-area copper foil single crystals, but the annealing furnace device needs a winding and mechanical transmission device, and simultaneously introduces an external force for mechanical traction to the copper foil, and has special requirements on the shape of the tip of the copper foil, and the process and the device of the method are complex in whole view;
3. static suspension stress-free annealing, namely, suspending the metal foil to avoid the contact with a substrate so as to reduce the external stress and realize the preparation of the copper foil single crystal with larger area; however, the method requires the metal foil to be suspended, and the area of the prepared copper foil single crystal is about 32 square centimeters at most.
Disclosure of Invention
The invention provides a preparation method of a single crystal copper foil, which comprises the steps of placing a polycrystalline copper foil in a region with a plurality of temperature regions for annealing to prepare the single crystal copper foil; wherein, in the area with a plurality of warm areas, the temperature difference between adjacent warm areas is 5-200 ℃.
According to an embodiment of the invention, the temperature of at least one of said temperature zones is above 900 ℃.
According to an embodiment of the invention, the temperature of at least one of said temperature zones is above 980 ℃.
According to an embodiment of the present invention, the temperature of the plurality of temperature zones is 800 to 1080 ℃.
According to an embodiment of the present invention, the plurality of temperature zones includes a first temperature zone, a second temperature zone, and a third temperature zone.
According to an embodiment of the invention, the temperature of the first temperature zone is 980-1040 ℃, the temperature of the second temperature zone is 950-1020 ℃, and the temperature of the third temperature zone is 850-1000 ℃.
According to an embodiment of the present invention, the plurality of temperature zones include a first temperature zone, a second temperature zone, a third temperature zone, a fourth temperature zone, and a fifth temperature zone; the temperature of the first temperature zone is 1000-1040 ℃, the temperature of the second temperature zone is 980-1030 ℃, the temperature of the third temperature zone is 950-1020 ℃, the temperature of the fourth temperature zone is 900-1010 ℃, and the temperature of the fifth temperature zone is 850-1000 ℃.
According to an embodiment of the present invention, the temperature difference between the adjacent temperature zones is 10-30 ℃.
According to an embodiment of the present invention, the gas atmosphere in the annealing process is one or more of hydrogen, argon, helium, and a mixture of argon and oxygen; and/or the annealing time is more than 5 minutes.
An embodiment of the present invention provides a single crystal copper foil manufactured by the above method.
The method of the embodiment of the invention has simple process, and can conveniently obtain the copper single crystal with large area, high single crystallinity and high flatness.
Drawings
FIG. 1 is a partial optical photograph of a large-area single-crystal copper foil produced in example 1 of the present invention;
FIG. 2 is an XRD characterization result of a (111) plane-oriented copper foil single crystal obtained in example 1 of the present invention;
FIG. 3 shows EBSD characterization results of (111) plane-oriented copper foil single crystal obtained in example 1 of the present invention;
FIG. 4 is a partial optical photograph of a sheet of (111) plane-oriented copper foil single crystal obtained in example 3 of the present invention;
FIG. 5 shows EBSD characterization results of a piece of (111) plane oriented copper foil single crystal obtained in example 3 of the present invention;
FIG. 6 is an optical picture of a sheet of (106) plane-oriented copper foil single crystal obtained in example 5 of the present invention;
FIG. 7 shows EBSD characterization results of a piece of (106) plane-oriented copper foil single crystal obtained in example 5 of the present invention;
FIG. 8 shows the XRD characterization results of a piece of (111) plane oriented copper foil single crystal obtained in example 6 of the present invention.
Detailed Description
Exemplary embodiments that embody features and advantages of the invention are described in detail below in the specification. It is to be understood that the invention is capable of other embodiments and that various changes in form and details may be made therein without departing from the scope of the invention and the description and drawings are to be regarded as illustrative in nature and not as restrictive.
One embodiment of the present invention provides a method for preparing a single crystal copper foil, comprising placing a polycrystalline copper foil in a region having a plurality of temperature regions (annealing region) for annealing to prepare a single crystal copper foil; wherein, in the area with a plurality of warm areas, the temperature difference of adjacent warm areas is 5-200 ℃.
In one embodiment, during the annealing process, the poly-crystalline copper foil is located in at least two temperature zones, i.e., the poly-crystalline copper foil passes through the boundary of the two temperature zones.
In one embodiment, the poly-crystalline copper foil is disposed in each temperature zone of the whole annealing region.
In one embodiment, the temperature difference between adjacent temperature zones in the annealing zone may be 5 to 200 ℃, further 5 to 50 ℃, and further 10 to 30 ℃. For example, 6 ℃, 8 ℃, 10 ℃, 12 ℃, 14 ℃, 15 ℃, 16 ℃, 18 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 60 ℃, 70 ℃, 80 ℃, 100 ℃, 120 ℃, 150 ℃, 180 ℃ and the like.
In one embodiment, the annealing zone comprises a plurality of temperature zones connected, such as two temperature zones, three temperature zones, four temperature zones, five temperature zones, six temperature zones, and the like; the temperature of at least one temperature zone is 900 ℃ or higher, preferably 980 ℃ or higher, for example 1000 ℃, 1020 ℃, 1050 ℃, 1080 ℃ or the like, so that part of the copper foil region is in a surface pre-melted state.
In one embodiment, the temperature of the annealing zone(s) is 800-1080 ℃, such as 820 ℃, 840 ℃, 850 ℃, 870 ℃, 880 ℃, 900 ℃, 920 ℃, 940 ℃, 950 ℃, 960 ℃, 980 ℃, 1000 ℃, 1020 ℃, 1050 ℃, 1060 ℃, 1080 ℃ and the like.
In the present application, the number of temperature zones is not limited, and may be determined according to the structure of the annealing furnace body used.
In one embodiment, the plurality of temperature zones includes a first temperature zone and a second temperature zone connected to each other, the first temperature zone may be 1000 ℃, and the second temperature zone may be 900 ℃, 950 ℃, 980 ℃ or 990 ℃.
In one embodiment, the plurality of temperature zones includes a first temperature zone, a second temperature zone, and a third temperature zone, which are connected in sequence.
In one embodiment, the temperature of the first temperature zone may be 980 ℃ to 1040 ℃, such as 1000 ℃ or 1020 ℃; the temperature of the second temperature zone can be 950-1020 ℃, such as 960 ℃, 980 ℃, 1000 ℃ and the like; the temperature of the third temperature zone may be 850 to 1000 ℃, for example 870 ℃, 900 ℃, 920 ℃, 950 ℃, 980 ℃ and the like.
In one embodiment, the first temperature zone, the second temperature zone, and the third temperature zone may be 1020 ℃, 1000 ℃, 980 ℃, respectively.
In one embodiment, the first, second, and third temperature zones may be 1000 ℃, 950 ℃, 900 ℃, respectively.
In one embodiment, the first, second, and third temperature zones may be 1020 ℃, 950 ℃, 900 ℃, respectively.
In one embodiment, the first, second, and third temperature zones may be 850 ℃, 1020 ℃, 850 ℃ respectively.
In one embodiment, the first temperature zone, the second temperature zone, and the third temperature zone may be 980 ℃, 1020 ℃, 970 ℃, respectively.
In one embodiment, the plurality of temperature zones includes a first temperature zone, a second temperature zone, a third temperature zone, a fourth temperature zone, and a fifth temperature zone, which are connected in sequence.
In one embodiment, the temperature of the first temperature zone may be 1000-1040 ℃, for example, 1020 ℃, 1030 ℃, etc.; the temperature of the second temperature zone can be 980-1030 ℃, for example, 990 ℃, 1000 ℃, 1020 ℃ and the like; the temperature of the third temperature zone may be 950 to 1020 ℃, for example, 960 ℃, 980 ℃, 1000 ℃, 1010 ℃, etc.; the temperature of the fourth temperature zone may be 900 to 1010 ℃, for example, 920 ℃, 950 ℃, 980 ℃, 1000 ℃ and the like; the temperature of the fifth temperature zone may be 850 to 1000 ℃, for example, 860 ℃, 880 ℃, 900 ℃, 920 ℃, 950 ℃, 960 ℃, 980 ℃.
In one embodiment, the plurality of temperature zones in the annealing area are connected, and the temperature of each temperature zone is increased or decreased in sequence by the same or different temperature difference; for example, the temperature of the first, second, and third temperature zones connected may be 1000 ℃, 980 ℃, 900 ℃, or 900 ℃, 980 ℃, 1000 ℃.
In one embodiment, the temperature difference between adjacent temperature zones in the annealing region is the same, i.e., the temperatures of the plurality of temperature zones are increased or decreased stepwise, for example, the temperature difference is increased or decreased by 10 ℃, 20 ℃ or 50 ℃, so as to form a static temperature gradient.
In one embodiment, the temperatures in the plurality of temperature zones connected in the annealing zone are sequentially increased and then decreased, for example, the temperatures in the first temperature zone, the second temperature zone, and the third temperature zone connected in series may be 850 ℃, 1020 ℃, 850 ℃.
In one embodiment, the temperatures in the plurality of temperature zones connected in the annealing zone are sequentially decreased and then increased, for example, the temperatures in the first temperature zone, the second temperature zone, and the third temperature zone connected in series may be 1020 ℃, 900 ℃, and 1000 ℃.
In one embodiment, the annealing process of the polycrystalline copper foil can be completed in an annealing furnace (e.g., a tube furnace), and an annealing area composed of a plurality of temperature zones having temperature differences is set by adjusting the temperature of each temperature zone of the annealing furnace.
In one embodiment, the annealing furnace has one or more heating zones, and the static temperature gradient region in the furnace is set by setting different temperatures in each heating zone.
In one embodiment, when the annealing process of the polycrystalline copper foil is completed in the annealing furnace, the annealing includes a heating temperature zone in the annealing furnace, and may also include a non-heating zone outside the heating temperature zone, that is, the temperature difference between the heating temperature zone and the non-heating zone is defined by the above temperature difference, and the corresponding non-heating zone also belongs to a part of the annealing zone.
In one embodiment, the annealing of the polycrystalline copper foil is performed using a three-temperature zone annealing furnace, and the temperatures of the three temperature zones in the annealing furnace may be 1020 ℃, 1000 ℃, 980 ℃, or 1000 ℃, 950 ℃, 900 ℃ in this order.
In one embodiment, the poly-crystalline copper foil may be placed on a carrier, and the carrier may be placed in an annealing zone (annealing furnace) for high temperature annealing, and the structure of the carrier may be the structure of the carrier used for annealing.
In one embodiment, the number of the carriers may be one, or may be multiple, and is used for placing one or more pieces of polycrystalline copper foil; when a plurality of polycrystalline copper foils are placed using a plurality of carriers, batch production of single crystal copper foils can be realized.
In one embodiment, the atmosphere during the annealing process may be one or more of hydrogen, argon, helium, and a mixture of argon and oxygen.
In one embodiment, the atmosphere during the annealing process is 500sccm hydrogen.
In one embodiment, the annealing time is 5 minutes or more, for example, 10 minutes, 30 minutes, 60 minutes, and the like.
The method for preparing a single crystal copper foil according to an embodiment of the present invention includes the steps of:
s1: placing the polycrystalline copper foil on a carrier;
s2: placing the carrier with the copper foil in an annealing furnace;
s3: heating the annealing furnace to a specified temperature to form an annealing area with a plurality of temperature areas, and carrying out high-temperature annealing on the polycrystalline copper foil;
s3: and cooling the annealing furnace to room temperature to obtain a single crystal copper foil sample.
According to the method provided by the embodiment of the invention, a plurality of carriers are configured, so that annealing treatment can be performed on a plurality of pieces of polycrystalline copper foil at one time, and batch static preparation of single crystal copper foil is realized.
The method of the embodiment has no specific requirements on the shape of the polycrystalline copper foil, and the length and the width of the copper foil single crystal are only limited by the size of the furnace body, so that large-area batch production can be realized.
According to the method provided by the embodiment of the invention, the large-area single crystal copper foil can be prepared in batch without a complicated mechanical transmission device and without hanging the polycrystalline copper foil.
The method of the embodiment of the invention has the advantages that the process is simpler and more convenient, the used device is simple, and the annealing furnaces such as a common tube furnace and the like can meet the preparation requirement of the single crystal copper foil; mechanical transmission and a winding device are not needed, and the static annealing mode does not generate extra mechanical stretching on the copper foil, so that the obtained single crystal copper foil is smoother.
The following will further explain a method for manufacturing a single crystal copper foil according to an embodiment of the present invention with reference to the accompanying drawings and specific examples. Wherein, the raw materials are all obtained from the market.
EXAMPLE 1 annealing with three-temperature zone annealing furnace to obtain monolithic Single-crystal copper foil
In this embodiment, the annealing furnace used is a three-zone annealing furnace. The length of each temperature zone is 20 cm. The temperature settings of the three temperature zones are as follows in sequence: 1020 deg.C, 1000 deg.C and 980 deg.C. The method comprises the following specific steps:
(1) cutting a single industrial copper foil into a length of 40cm, placing the single industrial copper foil on a copper foil carrier, and placing the copper foil carrier in an annealing furnace to enable the copper foil to be in three temperature zones;
(2) starting a mechanical pump to vacuumize the annealing furnace, and then introducing 500sccm hydrogen;
(3) and (3) raising the temperature of three temperature zones of the annealing furnace to a set temperature: 1020 ℃, 1000 ℃ and 980 ℃;
(4) annealing the copper foil at a set temperature for 30 minutes;
(5) after the temperature of the annealing furnace is reduced to room temperature, the gas is closed and is communicated with the atmosphere, and a large-area copper (111) single crystal sample is obtained. The picture of a partial copper foil single crystal as shown in fig. 1 shows that the area size of the copper foil single crystal is 182 cm.
Example 2 annealing with three-temperature annealing furnace to obtain multiple batch single crystal copper foils
In this embodiment, the annealing furnace used is a three-zone annealing furnace. The length of each temperature zone is 20 cm. The temperature settings of the three temperature zones are as follows in sequence: 1020 deg.C, 1000 deg.C and 980 deg.C. The method comprises the following specific steps:
(1) cutting a plurality of industrial copper foils into a length of 45cm, placing each copper foil on a copper foil carrier, vertically stacking the copper foil carriers, and then placing the copper foils in an annealing furnace to enable the copper foils to be in three temperature zones;
(2) starting a mechanical pump to vacuumize the annealing furnace, and then introducing 500sccm hydrogen;
(3) and (3) raising the temperature of three temperature zones of the annealing furnace to a set temperature: 1020 ℃, 1000 ℃ and 980 ℃;
(4) annealing the copper foil at a set temperature for 30 minutes;
(5) and after the temperature of the annealing furnace is reduced to room temperature, closing the gas and communicating the atmosphere to obtain a plurality of large-area copper (111) single crystal samples.
Example 3 annealing with three-temperature annealing furnace to obtain multiple batch single crystal copper foils
In this embodiment, the annealing furnace is a three-zone annealing furnace. The length of each temperature zone is 20 cm. The temperature settings of the three temperature zones are as follows in sequence: 1020 ℃, 950 ℃ and 900 ℃. The difference between this embodiment and embodiment 2 is that the temperature settings of the three temperature zones are different, so that the temperature difference between adjacent temperature zones is different. The method comprises the following specific steps:
(1) cutting a plurality of industrial copper foils into a length of 45cm, placing each copper foil on a copper foil carrier, vertically stacking the copper foil carriers, and then placing the copper foils in an annealing furnace to enable the copper foils to be in three temperature zones;
(2) starting a mechanical pump to vacuumize the annealing furnace, and then introducing 500sccm hydrogen;
(3) and (3) raising the temperature of three temperature zones of the annealing furnace to a set temperature: 1020 ℃, 950 ℃ and 900 ℃;
(4) annealing the copper foil at a set temperature for 30 minutes;
(5) and after the temperature of the annealing furnace is reduced to room temperature, closing the gas and communicating the atmosphere to obtain a plurality of large-area copper (111) single crystal samples.
It should be noted that: in this example, since a large temperature difference was set, the temperature of a part of the region was lower than the pre-melting temperature of the copper foil, and the length of the single crystal region of the prepared copper foil sample was smaller than that of example 2, but the single crystallinity was not affected.
FIG. 4 is a partial optical photograph of a piece of (111) plane-oriented copper foil single crystal obtained in example 3, and since the temperature of a part of the copper foil is low, the boundary between the single crystal region (left) and the polycrystalline region (right) can be clearly seen.
Example 4 annealing with Single-temperature-zone annealing furnace to obtain multiple batch single-crystal copper foils
In this example, the annealing furnace used was a single-temperature zone annealing furnace, and the length of the temperature zone was 30 cm. The temperature of the temperature zone is set as follows: 1020 ℃. The method comprises the following specific steps:
(1) a plurality of industrial copper foils are cut into 40cm in length, each copper foil is placed on a copper foil carrier, the copper foil carriers are vertically stacked, and then the copper foil carriers are placed in an annealing furnace. Because the length of the copper foil is longer than the length of the temperature zone, the partial area of the copper foil is positioned outside the heating temperature zone of the annealing furnace;
(2) starting a mechanical pump to vacuumize the annealing furnace, and then introducing 500sccm hydrogen or 500sccm argon;
(3) heating the heating zone temperature of the annealing furnace to a set temperature: 1020 ℃, the temperature of the two ends of the copper foil outside the heating zone is about 850 ℃;
(4) annealing the copper foil at a set temperature for 30 minutes;
(5) and after the temperature of the annealing furnace is reduced to room temperature, closing the gas and communicating the atmosphere to obtain a plurality of large-area copper (111) single crystal samples.
EXAMPLE 5 annealing in three-temperature zone annealing furnace to obtain multiple batch single-crystal copper foils
In this embodiment, the annealing furnace used is a three-temperature-zone annealing furnace, and the temperature settings of the three temperature zones are as follows: 1020 ℃, 950 ℃ and 900 ℃. In this example, a crystal plane copper foil single crystal other than the (111) crystal plane is shown.
The method comprises the following specific steps:
(1) a plurality of industrial copper foils are cut into 45cm long, and each copper foil is placed on a copper foil carrier. Vertically stacking the copper foil carriers, and then placing the copper foil carriers in an annealing furnace to enable the copper foil to be in three temperature zones;
(2) starting a mechanical pump to vacuumize the annealing furnace, and then introducing 500sccm hydrogen;
(3) heating the annealing furnace to a set temperature: 1020 ℃, 950 ℃ and 900 ℃;
(4) annealing the copper foil at a set temperature for 60 minutes;
(5) and after the temperature of the annealing furnace is reduced to room temperature, closing the gas and communicating the atmosphere to obtain a plurality of large-area copper (106) single crystal samples.
FIG. 6 is an optical photograph of a piece of (106) plane-oriented copper foil single crystal obtained in example 5, and it is apparent that the boundary between the single crystal region (left) and the polycrystalline region (right). The area of the partial copper foil single crystal shown in fig. 4 of this example is 53 cm square.
EXAMPLE 6 preparation of Single-Crystal copper foil by five-temperature zone annealing furnace
In this example, the annealing furnace used was a five-zone annealing furnace, and the length of each zone was 30 cm.
The temperature settings of the five temperature zones are as follows in sequence: 1040 deg.C, 1025 deg.C, 1005 deg.C, 990 deg.C, 975 deg.C.
The method comprises the following specific steps:
(1) a plurality of industrial copper foils are cut into 150cm long, and each copper foil is placed on a copper foil carrier. Vertically stacking the copper foil carriers, and then placing the copper foil carriers in an annealing furnace to enable the copper foil to be positioned in five temperature zones;
(2) starting a mechanical pump to vacuumize the annealing furnace, and then introducing 2000sccm hydrogen;
(3) heating the annealing furnace to a set temperature: 1040 deg.C, 1025 deg.C, 1005 deg.C, 990 deg.C, 975 deg.C;
(4) annealing the copper foil at a set temperature for 60 minutes;
(5) and after the temperature of the annealing furnace is reduced to room temperature, closing the gas and communicating the atmosphere to obtain a plurality of large-area copper (111) single crystal samples.
EXAMPLE 7 annealing in three-temperature zone annealing furnace to obtain monolithic Single-crystal copper foil
In this embodiment, the annealing furnace used is a three-zone annealing furnace. The length of each temperature zone is 20 cm. The temperature settings of the three temperature zones are as follows in sequence: 980 ℃, 1020 ℃ and 970 ℃. One of the differences between this embodiment and embodiment 1 is that: in this embodiment, the temperature of the middle temperature zone of the three temperature zones is set to be the highest. The method comprises the following specific steps:
(1) cutting a single industrial copper foil into 50cm long, placing the single industrial copper foil on a copper foil carrier, and placing the copper foil carrier in an annealing furnace to enable the copper foil to be in three temperature zones;
(2) starting a mechanical pump to vacuumize the annealing furnace, and then introducing 500sccm hydrogen and 500sccm argon;
(3) and (3) raising the temperature of three temperature zones of the annealing furnace to a set temperature: 1020 ℃, 1000 ℃ and 980 ℃;
(4) annealing the copper foil at a set temperature for 60 minutes;
(5) and after the temperature of the annealing furnace is reduced to the room temperature, closing the gas and communicating the atmosphere to obtain the copper single crystal sample.
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 (7)
1. A preparation method of a single crystal copper foil comprises the steps of placing a polycrystalline copper foil in an annealing furnace with a plurality of temperature areas for static annealing to prepare the single crystal copper foil; the polycrystalline copper foil is positioned in at least two temperature zones, the temperature difference between adjacent temperature zones in the annealing furnace with the multiple temperature zones is 5-50 ℃, the temperature of the multiple temperature zones is 800-1080 ℃, and the temperature of at least one temperature zone is above 900 ℃; the gas atmosphere in the annealing process is one or more of hydrogen, argon and helium, and the annealing time is more than 5 minutes.
2. The method of claim 1, wherein the temperature of at least one of said temperature zones is above 980 ℃.
3. The method of claim 1 or 2, wherein the plurality of temperature zones comprises a first temperature zone, a second temperature zone, and a third temperature zone.
4. The method according to claim 3, wherein the temperature of the first temperature zone is 980-1040 ℃, the temperature of the second temperature zone is 950-1020 ℃, and the temperature of the third temperature zone is 850-1000 ℃.
5. The method of claim 3, further comprising a fourth temperature zone and a fifth temperature zone.
6. The method according to claim 5, wherein the temperature of the first temperature zone is 1000 to 1040 ℃, the temperature of the second temperature zone is 980 to 1030 ℃, the temperature of the third temperature zone is 950 to 1020 ℃, the temperature of the fourth temperature zone is 900 to 1010 ℃, and the temperature of the fifth temperature zone is 850 to 1000 ℃.
7. The method according to claim 1 or 2, wherein the temperature difference between the adjacent temperature zones is 10-30 ℃.
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| CN107904654A (en) * | 2017-01-12 | 2018-04-13 | 北京大学 | A kind of preparation method of large size single crystal copper foil |
| CN108728813A (en) * | 2017-04-25 | 2018-11-02 | 北京大学 | A kind of method and device quickly continuously preparing oversized single crystal film |
| 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 |
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