CN116445998A - Double-crystal copper-nickel alloy metal layer and preparation method thereof - Google Patents
Double-crystal copper-nickel alloy metal layer and preparation method thereof Download PDFInfo
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- CN116445998A CN116445998A CN202210020528.XA CN202210020528A CN116445998A CN 116445998 A CN116445998 A CN 116445998A CN 202210020528 A CN202210020528 A CN 202210020528A CN 116445998 A CN116445998 A CN 116445998A
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- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 229910000570 Cupronickel Inorganic materials 0.000 title claims abstract description 139
- 229910002065 alloy metal Inorganic materials 0.000 title claims abstract description 137
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000013078 crystal Substances 0.000 title claims description 133
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 238000007747 plating Methods 0.000 claims description 36
- 238000000137 annealing Methods 0.000 claims description 32
- 238000009713 electroplating Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 13
- 150000002815 nickel Chemical class 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 150000001879 copper Chemical class 0.000 claims description 4
- 239000010410 layer Substances 0.000 description 74
- 238000012360 testing method Methods 0.000 description 62
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 42
- 230000000052 comparative effect Effects 0.000 description 42
- 229910052802 copper Inorganic materials 0.000 description 39
- 239000010949 copper Substances 0.000 description 39
- 229910052751 metal Inorganic materials 0.000 description 33
- 239000002184 metal Substances 0.000 description 32
- 239000000758 substrate Substances 0.000 description 24
- 238000010884 ion-beam technique Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000005498 polishing Methods 0.000 description 5
- 241000080590 Niso Species 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 3
- 238000001887 electron backscatter diffraction Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- BSXVKCJAIJZTAV-UHFFFAOYSA-L copper;methanesulfonate Chemical compound [Cu+2].CS([O-])(=O)=O.CS([O-])(=O)=O BSXVKCJAIJZTAV-UHFFFAOYSA-L 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- CXIHYTLHIDQMGN-UHFFFAOYSA-L methanesulfonate;nickel(2+) Chemical compound [Ni+2].CS([O-])(=O)=O.CS([O-])(=O)=O CXIHYTLHIDQMGN-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/615—Microstructure of the layers, e.g. mixed structure
- C25D5/617—Crystalline layers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Thermal Sciences (AREA)
- Mechanical Engineering (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention provides a bicrystal copper-nickel alloy metal layer, wherein more than 50% of the volume of the bicrystal copper-nickel alloy metal layer comprises a plurality of bicrystal grains, the plurality of bicrystal grains comprise a plurality of columnar bicrystal grains, and the nickel content in the bicrystal copper-nickel alloy metal layer is between 0.05at% and 20at%. In addition, the invention also provides a preparation method of the bicrystal copper-nickel alloy metal layer.
Description
Technical Field
The invention provides a double-crystal copper-nickel alloy metal layer and a preparation method thereof, in particular to a double-crystal copper-nickel alloy metal layer with high hardness and a preparation method thereof.
Background
The prior art has been rolled (rolling), or doped with other metals such as: titanium (Ti), nickel (Ni), zinc (Zn) to strengthen the mechanical properties of copper, however, this known technique has the following drawbacks.
If the copper foil containing copper grains is reinforced by rolling, the grains of pure copper are deformed, so that the mechanical properties are improved but the electric resistance and the heat conduction are improved. In addition, if other metals are doped into the copper film, the resulting alloy will have an increased resistance and a decreased conductivity. Furthermore, the strength of the nano-bicrystal structured copper film itself has been high, and if the nano-bicrystal copper foil is reinforced in a grain refinement manner, the nano-bicrystal copper foil may be poor in thermal stability.
In view of the foregoing, there is a need to develop a novel nano-twinned copper metal layer that can maintain the characteristics of nano-twinned copper metal layer in addition to improved strength for use in various electronic devices.
Disclosure of Invention
An object of the present invention is to provide a double-crystal copper-nickel alloy metal layer which can simultaneously have an excellent hardness value while maintaining the conductive characteristics (high conductivity and low resistance) of double-crystal copper.
In the bicrystal copper-nickel alloy metal layer, more than 50% of the volume of the bicrystal copper-nickel alloy metal layer comprises a plurality of bicrystal grains, the plurality of bicrystal grains comprise a plurality of columnar bicrystal grains, and the nickel content in the bicrystal copper-nickel alloy metal layer is between 0.05at% and 20at%. The volume percentage of the plurality of bicrystal grains can be observed or measured by any section of the bicrystal copper-nickel alloy metal layer. In addition, the content of the elements may be obtained by, for example, chemical analysis or field emission high-resolution electron microprobe (EPMA) analysis.
In addition, the invention also provides a substrate containing the bicrystal copper-nickel alloy metal layer, which comprises the following components: a substrate; and a bicrystal copper-nickel alloy metal layer as described above, which is arranged on the substrate or embedded in the substrate.
Furthermore, the invention also provides a preparation method of the bicrystal copper-nickel alloy metal layer, which comprises the following steps: providing an electroplating device, comprising an anode, a cathode, an electroplating solution and an electric power supply source, wherein the electric power supply source is respectively connected with the anode and the cathode, and the anode and the cathode are immersed in the electroplating solution; and electroplating by using the power supply source to provide power, and growing the double-crystal copper-nickel alloy metal layer on one surface of the cathode. Wherein, the electroplating solution can comprise a copper salt, an acid and a nickel salt.
In the preparation method of the invention, by adding a proper amount of nickel salt into the electroplating solution, a bicrystal copper-nickel alloy metal layer can be formed through a simple co-electroplating process. Compared with the previous double-crystal copper metal layer which does not contain nickel, the double-crystal copper-nickel alloy metal layer prepared by the method has the advantage that the double-crystal structure of the double-crystal copper metal layer which does not contain nickel is reserved, and the hardness value is remarkably improved. Therefore, the double-crystal copper-nickel alloy metal layer provided by the invention has the characteristics of high electric conductivity, high thermal conductivity and the like, and also has high strength, so that the double-crystal copper-nickel alloy metal layer can be applied to various electronic components.
In the present invention, more than 50% of the volume of the twinned copper-nickel alloy metal layer may include a plurality of twinned grains. In an embodiment of the present invention, for example, 50% to 99%, 50% to 95%, 50% to 90%, 55% to 90%, 60% to 90%, or 65% to 95% by volume may include a plurality of bicrystal grains; the invention is not limited thereto.
In the present invention, the plating solution includes a nickel salt in addition to a copper salt, so that a bi-crystal copper-nickel alloy metal layer is formed by co-plating. By adjusting the concentration of nickel salts in the electroplating solution, a double-crystal copper-nickel alloy metal layer with specific proportion of nickel content can be formed by a co-electroplating mode.
In the invention, the nickel content in the bicrystal copper-nickel alloy metal layer can be between 0.05at% and 20at%, and the balance is copper element; the present invention does not exclude the possibility of possibly containing other trace amounts of impurity metal elements. When the bi-crystal copper-nickel alloy metal layer contains nickel element in a specific proportion, the formed bi-crystal copper-nickel alloy metal layer has an increased hardness value. In one embodiment of the present invention, the nickel content may be, for example, 0.1at% to 20at%, 0.1at% to 15at%, 0.1at% to 10at%, 0.1at% to 5at%, 0.1at% to 3at%, or 0.1at% to 1at%; the invention is not limited thereto.
In the present invention, the bicrystal grains in the bicrystal copper-nickel alloy metal layer can be formed by stacking a plurality of nano bicrystals along the direction within + -15 degrees of the [111] crystal axis direction.
In an embodiment of the present invention, the bimorph die may include a plurality of columnar bimorph dies, wherein the columnar bimorph dies may be formed by stacking a plurality of nano bimorphs along a direction within ±15 degrees of a [111] crystal axis direction, and an included angle between a stacking direction of at least a portion of the nano bimorphs and a thickness direction of the bimorph copper-nickel alloy metal layer is between 0 degrees and 20 degrees. When columnar bicrystal grains grow to the surface of the bicrystal copper-nickel alloy metal layer, more than 50% of the area of the surface of the bicrystal copper-nickel alloy metal layer can be exposed to the (111) surface of the nano bicrystal; at this time, the surface of the twin copper-nickel alloy metal layer of the present invention may have a preferred direction of (111). In an embodiment of the present invention, the nano-duplex (111) surface exposed on the surface of the duplex copper-nickel alloy metal layer may occupy the total area of the surface of the duplex copper-nickel alloy metal layer, for example, 50% to 99%, 55% to 99%, 60% to 99%, 65% to 99%, 70% to 99%, 75% to 95%, or 75% to 90%; the invention is not limited thereto. In one embodiment of the present invention, the nano-duplex (111) surface exposed on the surface of the duplex copper-nickel alloy metal layer may account for about 95% to 99% of the total area of the duplex copper-nickel alloy metal layer surface; the invention is not limited thereto. Here, the preferred direction of the nano-bi-crystalline copper metal layer surface can be measured by a back-scattering electron diffractometer (Electron Backscatter Diffraction, EBSD).
In one embodiment of the present invention, when the bicrystal grains of the bicrystal copper-nickel alloy metal layer have a significant bicrystal grain thickness to diameter ratio, for example, the thickness is significantly greater than the diameter, the bicrystal grains are columnar bicrystal grains.
In another embodiment of the present invention, the dual-crystal copper-nickel alloy metal layer may further include a plurality of fine grains having a nano-dual stacking direction not having a preferred direction, in addition to the aforementioned columnar dual-crystal grains stacked along the direction within ±15 degrees of the [111] crystal axis direction, stacked on the columnar dual-crystal grains. The stacking direction (i.e., twinning direction) of the fine-grained nano-twins is not particularly limited, and the nano-twins exposed on the surface of the twinned copper-nickel alloy metal layer may not have a preferred direction; in other words, the surface of the bicrystal copper-nickel alloy metal layer does not have a preferred direction. Wherein the fine grains may not have a significant ratio of the thickness and diameter of the bicrystal grains, and the bicrystal grains may also have a smaller diameter and thickness, for example, between 100nm and 500 nm.
In still another embodiment of the present invention, the dual-crystal copper-nickel alloy metal layer may further include a plurality of inclined dual-crystal grains stacked on the columnar dual-crystal grains in addition to the columnar dual-crystal grains stacked in the direction within ±15 degrees of the [111] crystal axis direction. The inclined bicrystal grains can be formed by stacking nano bicrystals along the direction within +/-15 degrees of the [111] crystal axis direction, and the included angle between the stacking direction of at least part of the nano bicrystals in the inclined bicrystal grains and the thickness direction of the bicrystal copper-nickel alloy metal layer can be between 10 and 60 degrees. Since the oblique bicrystal grains are grains intersecting the thickness direction of the bicrystal copper-nickel alloy metal layer at an angle as described above, the nano bicrystal exposed on the surface of the bicrystal copper-nickel alloy metal layer may not have a preferred direction; in other words, the surface of the bicrystal copper-nickel alloy metal layer does not have a preferred direction.
In the present invention, at least a part of the bicrystal grains, whether the aforementioned columnar bicrystal grains, fine grains or oblique bicrystal grains, may be connected to each other, for example, 50%, 60%, 70%, 80%, 90% or 95% or more of the bicrystal grains may be connected to each other.
In the invention, the thickness of the bicrystal copper-nickel alloy metal layer can be adjusted according to the requirement. In one embodiment of the present invention, the thickness of the bi-crystalline copper-nickel alloy metal layer may be, for example, between 0.1 μm and 500 μm, 0.1 μm and 400 μm, 0.1 μm and 300 μm, 0.1 μm and 200 μm, 0.1 μm and 100 μm, 0.1 μm and 80 μm, 0.1 μm and 50 μm, 1 μm and 50 μm, 2 μm and 50 μm, 3 μm and 50 μm, 4 μm and 50 μm, 5 μm and 40 μm, 5 μm and 35 μm, 5 μm and 30 μm or 5 μm and 25 μm; the invention is not limited thereto.
In the present invention, the columnar bimorph grains or the oblique bimorph grains may have a diameter of 0.1 μm to 50 μm, respectively. In one embodiment of the present invention, the diameter of the columnar or oblique bicrystal grains may be, for example, between 0.1 μm and 45 μm, 0.1 μm and 40 μm, 0.1 μm and 35 μm, 0.5 μm and 30 μm, 1 μm and 25 μm, 1 μm and 20 μm, 1 μm and 15 μm or 1 μm and 10 μm; the invention is not limited thereto. In the present invention, the diameter of the columnar bimorph grains or the oblique bimorph grains may be a length measured in a direction substantially perpendicular to the bimorph direction of the bimorph grains; in further detail, the diameter of the columnar bimorph grains or the oblique bimorph grains may be a length (e.g., a maximum length) measured in a direction substantially perpendicular to a stacking direction of the bimorph faces of the bimorph grains (i.e., a bimorph face extending direction).
In the present invention, the thickness of the columnar bimorph grains or the oblique bimorph grains may be between 0.1 μm and 500 μm, respectively. In one embodiment of the present invention, the thickness of the columnar or oblique bicrystal grains may be, for example, between 0.1 μm and 500 μm, 0.1 μm and 400 μm, 0.1 μm and 300 μm, 0.1 μm and 200 μm, 0.1 μm and 100 μm, 0.1 μm and 80 μm, 0.1 μm and 50 μm, 1 μm and 50 μm, 2 μm and 50 μm, 3 μm and 50 μm, 4 μm and 50 μm, 5 μm and 40 μm, 5 μm and 35 μm, 5 μm and 30 μm or 5 μm and 25 μm. In the present invention, the thickness of the columnar bimorph grain or the oblique bimorph grain may be a thickness measured in a direction of a bimorph direction of the bimorph grain; in further detail, the thickness of the columnar bimorph or the oblique bimorph may be a thickness (e.g., maximum thickness) measured in a stacking direction of the bimorph faces of the bimorph.
In the present invention, the "bimorph direction of the bimorph grains" means a stacking direction of the bimorph faces in the bimorph grains. Wherein the double crystal planes of the double crystal grains may be substantially perpendicular to the stacking direction of the double crystal planes.
In the invention, the included angle between the bicrystal direction of the bicrystal crystal grain and the thickness direction of the bicrystal copper-nickel alloy metal layer can be measured by one section of the bicrystal copper-nickel alloy metal layer. Similarly, a cross section of the dual-crystal copper-nickel alloy metal layer can be used to measure the thickness of the dual-crystal copper-nickel alloy metal layer, the diameter and thickness of the dual-crystal grain, and other characteristics. Alternatively, the diameter, thickness, etc. of the bicrystal grains may be measured on the surface of the bicrystal copper-nickel alloy metal layer. In the present invention, the measuring method is not particularly limited, and may be a scanning electron microscope (Scanning electron microscope, SEM), a transmission electron microscope (Transmission electron microscope, TEM), a Focused Ion Beam (FIB), or other suitable means.
In the present invention, the bicrystal copper-nickel alloy metal layer of the present invention may be formed by a co-plating method. The cathode in the electroplating device can be used as a substrate, and the formed bicrystal copper-nickel alloy metal layer can be arranged on the substrate or embedded in the substrate. The cathode may be a substrate having a metal layer on a surface thereof, or a metal substrate. Wherein, the substrate can be a silicon substrate, a glass substrate, a quartz substrate, a metal substrate, a plastic substrate, a printed circuit board, a III-V material substrate or a laminated substrate thereof; and the substrate may have a single-layer or multi-layer structure.
In the present invention, the plating solution may include a copper salt, an acid, and a nickel salt. Examples of salts of copper in the plating solution may include, but are not limited to, copper sulfate, copper methylsulfonate, or combinations thereof; examples of acids in the plating solution may include, but are not limited to, hydrochloric acid, sulfuric acid, methylsulfonic acid, or combinations thereof; examples of salts of nickel in the plating solution may include, but are not limited to, nickel sulfate, nickel methylsulfonate, or combinations thereof. In addition, the plating solution may also include an additive, such as gelatin, a surfactant, a lattice modifier, or a combination thereof.
In the present invention, direct current plating, pulse plating, or both direct current plating and pulse plating may be used alternately to form the bi-crystal copper-nickel alloy metal layer.
In one embodiment of the present invention, direct current plating is used to prepare the bi-crystal copper-nickel alloy metal layer. The current density of the direct current plating may be, for example, 0.5ASD to 30ASD, 1ASD to 30ASD, 2ASD to 25ASD, 2ASD to 20ASD, 2ASD to 15ASD, or 2ASD to 10ASD; the invention is not limited thereto.
In another embodiment of the present invention, pulse plating is used to produce a bi-crystal copper-nickel alloy metal layer. The forward current density of the pulse plating may be, for example, 0.5ASD to 30ASD, 1ASD to 30ASD, 2ASD to 25ASD, 2ASD to 20ASD, 2ASD to 15ASD, or 2ASD to 10ASD; while the negative current density may be, for example, 0.1ASD to 10ASD, 0.1ASD to 8ASD, 0.1ASD to 5ASD, 0.1ASD to 3ASD, 0.3ASD to 3ASD, or 0.3ASD to 1ASD; the invention is not limited thereto. When pulse plating is used to prepare the bicrystal copper-nickel alloy metal layer, in one embodiment of the invention, the bicrystal grains in the prepared bicrystal copper-nickel alloy metal layer may comprise columnar bicrystal grains; in another embodiment of the present invention, when the thickness of the electroplated bicrystal copper-nickel alloy metal layer is increased, the bicrystal grains in the obtained bicrystal copper-nickel alloy metal layer can optionally include fine grains, oblique bicrystal grains or a combination thereof, besides columnar bicrystal grains, stacked on the columnar bicrystal grains.
In one embodiment of the present invention, after growing the bicrystal copper-nickel alloy metal layer on the surface of the cathode, the bicrystal copper-nickel alloy metal layer may be selectively annealed. Therefore, the hardness of the bicrystal copper-nickel alloy metal layer can be further improved. Here, the temperature of the annealing treatment may be between 50 ℃ and 250 ℃. When the temperature of the annealing treatment exceeds this range, the bimorph structure in the bimorph copper-nickel alloy metal layer may be reduced or vanished. In an embodiment of the present invention, the temperature of the annealing treatment may be between 50 ℃ to 250 ℃, 75 ℃ to 200 ℃, 100 ℃ to 175 ℃, or 100 ℃ to 150 ℃; the invention is not limited thereto. In addition, in the present invention, the time of the annealing treatment is not particularly limited, and for example, may be between 30 minutes to 10 hours, 30 minutes to 8 hours, 30 minutes to 5 hours, or 1 hour to 5 hours; the invention is not limited thereto.
The shape of the double-crystal copper-nickel alloy metal layer provided by the invention is not particularly limited, and can be foil, film, wire or block; the invention is not limited thereto. In addition, the double-crystal copper-nickel alloy metal layer provided by the invention can have a single-layer or multi-layer structure. Furthermore, the double-crystal copper-nickel alloy metal layer provided by the invention can be combined with other materials to form a multi-layer composite structure.
The double-crystal copper-nickel alloy metal layer provided by the invention can be applied to various electronic products, such as through silicon crystal perforation of a three-dimensional integrated circuit (3D-IC), pin through holes of a packaging substrate, various metal wires, substrate lines, connectors and the like; the invention is not limited thereto.
Drawings
The features of the present invention will become more apparent from the detailed description set forth below when taken in conjunction with the drawings.
FIG. 1 is a diffraction pattern of a back-scattering electron diffractometer of a dual-crystal copper metal coupon of comparative example 1 of the present invention.
FIG. 2 is a diffraction pattern of a back-scattered electron diffractometer for a bi-crystal copper-nickel alloy metal coupon according to example 1 of the present invention.
FIG. 3 is a focused ion beam image of a dual-crystal copper-nickel alloy metal coupon according to example 1 of the present invention.
FIG. 4 is a graph showing the hardness comparison of the test pieces of example 1 and comparative example 1 of the present invention before annealing and after annealing at different temperatures for one hour.
FIG. 5 is a graph showing the hardness comparison of test pieces of example 1 and comparative example 1 according to the present invention annealed at 100℃for one hour and five hours.
FIG. 6 is a graph showing the hardness comparison of test pieces of example 1 and comparative example 1 according to the present invention annealed at 200℃for one hour and five hours.
FIG. 7 is a diffraction pattern of a back-scattering electron diffractometer of the dual-crystal copper metal coupon of comparative example 2 of the present invention.
FIG. 8 is a diffraction pattern of a back-scattered electron diffractometer for a bi-crystal copper-nickel alloy metal coupon according to example 2 of the present invention.
FIG. 9 is a focused ion beam image of a dual-crystal copper-nickel alloy metal coupon according to example 2 of the present invention.
FIG. 10 is a graph showing the hardness comparison of the test pieces of example 2 and comparative example 2 of the present invention before annealing and after annealing at different temperatures for one hour.
FIG. 11 is a graph showing the hardness comparison of test pieces of example 2 and comparative example 2 according to the present invention annealed at 100℃for one hour and five hours.
FIG. 12 is a graph showing the hardness comparison of test pieces of example 2 and comparative example 2 according to the present invention annealed at 200℃for one hour and five hours.
Fig. 13 is a phase diagram of a copper nickel alloy.
Detailed Description
Different embodiments of the present invention are provided below. These examples are given to illustrate the technical content of the present invention, and are not intended to limit the scope of the claims of the present invention. A feature of one embodiment may be applied to other embodiments by suitable modifications, substitutions, combinations, and separations.
It should be noted that in this context, having "a" component is not limited to having a single component, but may have one or more components unless specifically indicated.
In this context, unless otherwise indicated, the so-called feature a "or" and/or "feature b" refers to the presence of a finger alone, the presence of b alone, or both a and b; the feature A and or and feature B are the simultaneous presence of the nail and B; the terms "comprising," "including," "having," "containing," and "containing" are intended to be inclusive and not limited to.
Furthermore, unless specifically indicated otherwise, the word "a" or "an" on another element does not necessarily mean that the element contacts the other element.
Furthermore, in this context, a numerical value may cover a range of + -10% of the numerical value, and in particular a range of + -5% of the numerical value, unless otherwise indicated. Unless otherwise indicated, a numerical range is made up of a number of sub-ranges defined by a smaller number of endpoints, a smaller number of quartiles, a median, a larger number of quartiles, and a larger number of endpoints.
Example 1-bicrystal copper-nickel alloy Metal coupon
In this example, a 12 inch silicon wafer plated with 100nm titanium/200 nm copper was broken into 2cm 3cm pieces (as cathodes), the surface of the pieces was cleaned with citric acid to remove oxides, and the areas to be plated were defined with acid and alkali resistant tape. The total plating area was 2cm x 2cm.
The plating solution used in this example was prepared from copper sulfate pentahydrate crystals. Copper sulfate pentahydrate (copper ion-containing 50 g/L) was used in total of 196.54g, and 4.5ml of an additive was added, 100g of sulfuric acid (96%) was added, and hydrochloric acid (12N) was added in 0.1ml to the plating solution, and stirred with magnetite until copper sulfate pentahydrate was uniformly mixed in 1 liter of the solution. Finally, dividing the electroplating solution into two tanks, wherein one tank is added with NiSO 4 (0.1M) 10ml as the plating solution of the example; while another tank is not added with NiSO 4 The plating solution of (2) was used as a plating solution of comparative example. The magnet at the bottom of the plating tank was rotated 1200 rpm to maintain uniformity of ion concentration, and the plating was performed at room temperature under one atmosphere. Wherein, the hydrochloric acid added in the electroplating solution can make the copper target (serving as an anode) in the electroplating bath normally dissolved so as to balance the concentration of copper ions in the electroplating solution. Here, the power supply (Keithley 2400) was computer controlled and the forward current density was set to 6 (A/dm) using DC plating 2 ASD), after about 20 minutes of electroplating, a bi-crystalline copper-nickel alloy metal coupon having a thickness of about 20 μm was obtained. In other embodiments of the present invention, a bi-crystal copper-nickel alloy metal coupon having a desired thickness may be plated by controlling the plating current.
When the test piece is finished, the test piece is subjected to electrolytic polishing, and the electrolytic polishing solution comprises 100ml of phosphoric acid, 1ml of acetic acid and 1ml of glycerin. At this time, the test piece to be electropolished is clamped to the anode, and a voltage of 1.75V is applied for 10 minutes to achieve the electropolishing effect. The thickness of the test piece after electropolishing was about 19. Mu.m. The surface of the double-crystal copper-nickel alloy metal test piece can be leveled by electrolytic polishing, and the subsequent hardness test result can be more accurate.
Comparative example 1-double-crystal copper Metal test piece
The preparation method of the double-crystal copper metal test piece of this comparative example is similar to that of the double-crystal copper-nickel alloy metal test piece of example 1, except that this comparative example usesNo NiSO was added as described in example 1 4 Is plated by the plating solution.
The electropolished test pieces of example 1 and comparative example 1 were subjected to a back scattering electron diffraction (EBSD) and Focused Ion Beam (FIB) to analyze the surface preference direction and the microstructure of the test pieces, respectively.
FIGS. 1 and 2 are diffraction patterns of a back-scattering electron diffractometer of the dual-crystal copper metal coupon of comparative example 1 and the dual-crystal copper-nickel alloy metal coupon of example 1, respectively, according to the present invention. FIG. 3 is a focused ion beam image of a dual-crystal copper-nickel alloy metal coupon according to example 1 of the present invention.
As shown in fig. 1 and 2, the measurement results of the back-scattering electron diffractometer revealed that the twin copper metal coupon of comparative example 1 and the twin copper-nickel alloy metal coupon of example 1 were columnar twin grains connected to each other in almost all volumes (95% or more volumes) and the diameters of the columnar twin grains were in the range of about 0.5 μm to 3 μm. In addition, the bimorph grains were stacked with the nano bimorph grains along the [111] crystal axis direction, and the bimorph faces of the nano bimorph grains were substantially parallel to the cathode surface (i.e., the stacking direction of the nano bimorph grains was substantially parallel to the thickness direction of the test piece), so almost all the surface (95% or more area) of the test piece was exposed to the (111) face of the nano bimorph grains, representing that the bimorph copper metal test piece of comparative example 1 and the bimorph copper-nickel alloy metal test piece of example 1 had the preferred direction of (111).
As shown in fig. 3, the measurement results of the focused ion beam showed that most of the grains in the dual-crystal copper-nickel alloy metal coupon of example 1 had very dense dual crystals. More than 95% of the volume of the bi-crystal copper-nickel alloy metal coupon comprises bi-crystal grains. The included angle between the bicrystal direction of more than 95% of bicrystal grains and the thickness direction of the bicrystal copper-nickel alloy metal test piece is about 0 degrees, and the included angle between the bicrystal direction of more than 95% of bicrystal grains and the surface of the substrate is about 90 degrees, which means that the bicrystal faces of the bicrystal grains are substantially parallel to the surface of the substrate. In addition, more than 95% of the bicrystal grains in the bicrystal copper-nickel alloy metal test piece have a thickness of about 1 μm to 20 μm.
Hardness test
The product of example 1 and comparative example 1The obtained electrolytic polished test piece was cleaned with a citric acid solution, and then water drops on the surface of the test piece were removed with a nitrogen spray gun. Then, the dual-crystal copper metal test piece of comparative example 1 and the dual-crystal copper-nickel alloy metal test piece of example 1 were placed in a furnace tube for annealing, respectively, and the vacuum pressure environment was 10 -3 torr, annealing temperature is 100 ℃, 150 ℃ and 200 ℃, and annealing time is one hour and five hours respectively. The test pieces of example 1 and comparative example 1 before and after annealing were tested by a Vickers hardness tester, which had a diamond hole formed in the test piece, and the hardness of the test piece before and after annealing was calculated by computer operation.
FIG. 4 is a graph showing the hardness comparison of the test pieces of example 1 and comparative example 1 of the present invention before annealing and after annealing at different temperatures for one hour. Table 1 below shows the results of comparing the total degree of reinforcement of the test pieces of example 1 and comparative example 1, wherein the comparative object of the total degree of reinforcement is the unannealed hardness value of the test piece of comparative example 1, as indicated by the rectangle in FIG. 4.
TABLE 1
| Annealing temperature/time | Total degree of enhancement (%) |
| Normal temperature (before annealing) | 29.74 |
| 100 ℃/hour | 30.28 |
| 150 ℃/hour | 11.45 |
| 200 ℃/hour | 14.46 |
As shown in the results of fig. 4 and table 1, the hardness of the twin copper-nickel alloy metal coupon of example 1 was higher than that of the twin copper metal coupon of comparative example 1 before the annealing treatment; the hardness of the double-crystal copper metal test piece can be effectively improved by adding a proper amount of nickel. In addition, the hardness of the double-crystal copper-nickel alloy metal test piece of the embodiment 1 can reach 191HV after being annealed at 100 ℃ for 1 hour; the hardness of the dual-crystal copper-nickel alloy metal coupon of example 1 was enhanced by 30.28% as compared to the dual-crystal copper metal coupon of comparative example 1, which was not annealed. This result shows that the hardness of the dual-crystal copper-nickel alloy metal coupon of example 1 can be further improved after the annealing treatment at low temperature.
FIGS. 5 and 6 are graphs showing hardness comparisons of test pieces of example 1 and comparative example 1 of the present invention annealed at 100℃and 200℃for one hour and five hours, respectively. The results show that the hardness value of the dual-crystal copper-nickel alloy metal coupon of example 1 was not significantly reduced even after long-term annealing treatment, indicating that it has good thermal stability.
Example 2-bicrystal copper-nickel alloy Metal coupon
The preparation method of the double-crystal copper-nickel alloy metal coupon of this example was similar to that of example 1, except that pulse plating was used in this example, the positive current was 8ASD, the negative current was 0.7ASD, the plating time was about 24 minutes, and the thickness of the resulting coupon was about 23 μm. When the test piece was completed, the electrolytic polishing was performed in a similar manner to example 1, and the thickness of the test piece after the electrolytic polishing was about 22. Mu.m.
Comparative example 2-double-crystal copper Metal test piece
The preparation method of the double-crystal copper metal test piece of this comparative example is similar to that of the double-crystal copper-nickel alloy metal test piece of example 2, except that no NiSO was added in this comparative example 4 Is plated by the plating solution.
The electropolished test pieces of example 2 and comparative example 2 were subjected to a back-scattering electron diffractometer and a focused ion beam to analyze the preferred directions of the surfaces and the microstructure of the test pieces, respectively.
Fig. 7 and 8 are diffraction patterns of a back scattering electron diffractometer of the dual-crystal copper metal coupon of comparative example 2 and the dual-crystal copper-nickel alloy metal coupon of example 2, respectively, of the present invention. FIG. 9 is a focused ion beam image of a dual-crystal copper-nickel alloy metal coupon according to example 2 of the present invention.
As shown in fig. 9, the bicrystal grains in the bicrystal copper-nickel alloy metal coupon of example 2 were columnar bicrystal grains within a range of about 5 μm from the substrate surface. The bicrystal grains in the bicrystal copper-nickel alloy metal coupon of example 2, outside the range of about 5 μm from the substrate surface, also include oblique bicrystal grains and fine grains, stacked on the columnar bicrystal grains. Wherein, the included angle between the stacking direction of nano-double crystals of the inclined double crystal grains and the thickness direction of the test piece is between 10 degrees and 60 degrees, and the stacking direction of nano-double crystals of the fine crystal grains does not have the preferential direction. This result verifies the reason why the test piece shown in the diffraction patterns of the backscatter electron diffractometer of fig. 7 and 8 does not have the preferable direction.
The electropolished test pieces obtained in example 2 and comparative example 2 were subjected to hardness test by the same method as described above. FIG. 10 is a graph showing the hardness comparison of the test pieces of example 2 and comparative example 2 of the present invention before annealing and after annealing at different temperatures for one hour. Table 2 below shows the results of comparing the total degree of reinforcement of the test pieces of example 2 and comparative example 2 of the present invention, wherein the comparative object of the total degree of reinforcement is the hardness value of the test piece of comparative example 2 before annealing, as indicated by the rectangle in FIG. 10.
TABLE 2
| Annealing temperature/time | Total degree of enhancement (%) |
| Normal temperature (before annealing) | 37.90 |
| 100 ℃/hour | 39.57 |
| 150 ℃/hour | 35.04 |
| 200 ℃/hour | 35.16 |
As shown in the results of fig. 10 and table 2, the hardness of the twin copper-nickel alloy metal coupon of example 2 was higher than that of the twin copper metal coupon of comparative example 2 before the annealing treatment; the hardness of the double-crystal copper metal test piece can be effectively improved by adding a proper amount of nickel. In addition, the dual-crystal copper-nickel alloy metal coupon of example 2, annealed at 100 ℃ for 1 hour, had a hardness of 234.2HV; the hardness of the dual-crystal copper-nickel alloy metal coupon of example 2 was enhanced by 39.57% compared to the dual-crystal copper metal coupon of comparative example 2, which was not annealed. This result shows that the hardness of the dual-crystal copper-nickel alloy metal coupon of example 2 can be further improved after the annealing treatment at low temperature.
FIGS. 11 and 12 are graphs showing hardness comparisons of test pieces of example 2 and comparative example 2 of the present invention annealed at 100℃and 200℃for one hour and five hours, respectively. The results show that the hardness value of the dual-crystal copper-nickel alloy metal coupon of example 2 was not significantly reduced even after long-term annealing treatment, indicating that it has good thermal stability.
Resistivity test
The electropolished test pieces obtained in example 2 and comparative example 2 were subjected to a resistivity test, and herein, after four-point measurement, the test piece resistivity was converted by the following formula (I).
ρ＝Rs×T＝[C.F.×(V/I)]×T (I)
Wherein ρ is the test piece resistivity (μΩ -cm); rs is sheet resistance (Ω); t is the thickness (cm) of the test piece; c.f. is a correction factor; v is the direct current voltage passing through the voltage probe; and I is the fixed direct current through the current probe.
The measurement results showed that the nickel-free bicrystal copper metal coupon of comparative example 2 had a resistivity of about 2.18 mu omega-cm; the duplex copper-nickel alloy metal coupon of example 2 has a resistivity of about 2.07-3.44 mu Ω -cm, showing that the hardness of nano duplex copper can be enhanced and the high conductivity and low resistance properties of nano duplex copper can be maintained when a proper amount of nickel is added.
In summary, the present invention can simply plate out the bi-crystal copper-nickel alloy regularly arranged (preferred orientation) in the lattice direction (example 1) and randomly arranged (random orientation) (example 2) by co-electroplating, and then selectively perform annealing treatment. In the present invention, the hardness of the resulting highly <111> duplex copper-nickel alloy metal coupon (e.g., example 1) was significantly better than the hardness of the <111> duplex copper metal coupon that did not include nickel (e.g., comparative example 1). In this embodiment, the dual-crystal copper-nickel alloy metal coupon (example 2) with extremely high hardness can also be plated by using pulse plating, and the hardness of the coupon can be directly enhanced without additional work hardening.
The nano double-crystal copper with the regular arrangement (preferred orientation) of the lattice directions has good lattice directivity and stronger strength than bulk copper. Since nano-bicrystal copper itself has high strength, it is not easy to increase its strength. Therefore, in the invention, the hardness of the bicrystal copper-nickel alloy metal test piece can be further enhanced by a short-time rapid low-temperature annealing mode. In addition, nickel is a high-strength metal among metals, and as seen from the phase diagram (fig. 13), the nickel-copper alloy of the present invention is mutually fusible and does not generate eutectoid. Furthermore, the bi-crystal copper-nickel alloy metal test piece has less nickel doped, so that the occurrence probability of electromigration effect can be reduced without affecting the electrical property of the component, and the reliability of the component can be effectively improved. In particular, in the double-crystal copper-nickel alloy metal test piece, after nickel is added, the resistivity is not obviously improved, and good high conductivity is still maintained; accordingly, the dual-crystal copper-nickel alloy metal layer provided by the invention is a conductor with high strength, high electrical conductivity and high thermal conductivity, and can be applied to various electronic components.
Claims (20)
1. A bicrystal copper-nickel alloy metal layer, wherein more than 50% of the volume of the bicrystal copper-nickel alloy metal layer comprises a plurality of bicrystal grains, the plurality of bicrystal grains comprise a plurality of columnar bicrystal grains, and the nickel content in the bicrystal copper-nickel alloy metal layer is between 0.05at% and 20at%.
2. The dual-crystal copper-nickel alloy metal layer as recited in claim 1, wherein the plurality of dual-crystal grains are stacked in a direction within ±15 degrees of a [111] crystal axis direction of the plurality of nano-dual crystals.
3. The dual-crystal copper-nickel alloy metal layer as claimed in claim 1, wherein the plurality of columnar dual-crystal grains are formed by stacking a plurality of nano-dual crystals along a direction within + -15 degrees of a [111] crystal axis direction, and an included angle between a stacking direction of at least a part of the plurality of nano-dual crystals and a thickness direction of the dual-crystal copper-nickel alloy metal layer is between 0 degrees and 20 degrees.
4. A bi-crystal copper-nickel alloy metal layer according to claim 3, wherein more than 50% of the surface area of the bi-crystal copper-nickel alloy metal layer reveals nano-bi-crystal (111) planes.
5. The dual-crystal copper-nickel alloy metal layer as recited in claim 1, wherein the plurality of dual-crystal grains further comprises a plurality of fine grains having a nano-dual crystal stacking direction that does not have a preferred direction, stacked on the plurality of columnar dual-crystal grains.
6. The bi-crystal copper-nickel alloy metal layer according to claim 5, wherein the surface of the bi-crystal copper-nickel alloy metal layer does not have a preferred surface.
7. The bi-crystal copper-nickel alloy metal layer according to claim 1, wherein the plurality of bi-crystal grains further comprises a plurality of oblique bi-crystal grains stacked on the plurality of columnar bi-crystal grains.
8. The dual-crystal copper-nickel alloy metal layer as claimed in claim 7, wherein the plurality of oblique dual-crystal grains are formed by stacking a plurality of nano-dual crystals along a direction within + -15 degrees of a [111] crystal axis direction, and an included angle between a stacking direction of at least a part of the plurality of nano-dual crystals and a thickness direction of the dual-crystal copper-nickel alloy metal layer is between 10 degrees and 60 degrees.
9. The bi-crystal copper-nickel alloy metal layer according to claim 8, wherein the surface of the bi-crystal copper-nickel alloy metal layer does not have a preferred surface.
10. The bi-crystal copper-nickel alloy metal layer according to claim 1, wherein the plurality of columnar bi-crystal grains each have a diameter of between 0.1 μm and 50 μm.
11. The dual-crystal copper-nickel alloy metal layer according to claim 1, wherein the thickness of the plurality of columnar dual-crystal grains is between 0.1 μm and 500 μm, respectively.
12. The dual-crystal copper-nickel alloy metal layer according to claim 1, wherein at least a portion of the plurality of columnar dual-crystal grains are interconnected with each other.
13. The preparation method of the bicrystal copper-nickel alloy metal layer is characterized by comprising the following steps of:
providing an electroplating device, comprising an anode, a cathode, an electroplating solution and an electric power supply source, wherein the electric power supply source is respectively connected with the anode and the cathode, and the anode and the cathode are immersed in the electroplating solution; and
electroplating by using the power supply source to form a bicrystal copper-nickel alloy metal layer on one surface of the cathode;
wherein more than 50% of the volume of the bicrystal copper-nickel alloy metal layer comprises a plurality of bicrystal grains, the plurality of bicrystal grains comprise a plurality of columnar bicrystal grains, and the nickel content in the bicrystal copper-nickel alloy metal layer is between 0.05at% and 20at%; and
the electroplating solution comprises a copper salt, an acid and a nickel salt.
14. The method of claim 13, further comprising the step of: and after the bicrystal copper-nickel alloy metal layer grows on the surface of the cathode, annealing the bicrystal copper-nickel alloy metal layer.
15. The method of claim 14, wherein the annealing is performed at a temperature between 50 ℃ and 250 ℃.
16. The method of claim 13, wherein the plating is direct current plating.
17. The method of claim 13, wherein the plating is pulse plating.
18. The method of claim 17, wherein the plurality of bimorph dies further comprises a plurality of fine dies having a nano bimorph stacking direction that does not have a preferred direction stacked on the plurality of columnar bimorph dies.
19. The method of claim 17, wherein the plurality of bicrystal grains further comprises a plurality of oblique bicrystal grains stacked on the plurality of columnar bicrystal grains.
20. The method of claim 19, wherein the plurality of oblique bicrystals are stacked from a plurality of nano bicrystals along a direction within ±15 degrees of a [111] crystal axis direction, and wherein at least a portion of the stacked direction of the plurality of nano bicrystals forms an angle with a thickness direction of the bicrystal copper-nickel alloy metal layer of between 10 degrees and 60 degrees.
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