CN118047545A - Glass substrate plated with high-bonding-strength copper layer and preparation method thereof - Google Patents
Glass substrate plated with high-bonding-strength copper layer and preparation method thereof Download PDFInfo
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- CN118047545A CN118047545A CN202410165282.4A CN202410165282A CN118047545A CN 118047545 A CN118047545 A CN 118047545A CN 202410165282 A CN202410165282 A CN 202410165282A CN 118047545 A CN118047545 A CN 118047545A
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- 239000011521 glass Substances 0.000 title claims abstract description 100
- 239000010949 copper Substances 0.000 title claims abstract description 98
- 239000000758 substrate Substances 0.000 title claims abstract description 86
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 52
- 230000007704 transition Effects 0.000 claims abstract description 39
- 238000004544 sputter deposition Methods 0.000 claims description 115
- 238000000151 deposition Methods 0.000 claims description 57
- 230000008021 deposition Effects 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 27
- 238000004140 cleaning Methods 0.000 claims description 17
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000013077 target material Substances 0.000 claims description 6
- 230000004888 barrier function Effects 0.000 claims 2
- 239000007789 gas Substances 0.000 description 65
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 244000137852 Petrea volubilis Species 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 238000004506 ultrasonic cleaning Methods 0.000 description 7
- 239000002390 adhesive tape Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052774 Proactinium Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005546 reactive sputtering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/001—General methods for coating; Devices therefor
- C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3615—Coatings of the type glass/metal/other inorganic layers, at least one layer being non-metallic
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3626—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a nitride, oxynitride, boronitride or carbonitride
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3639—Multilayers containing at least two functional metal layers
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
- C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention provides a glass substrate plated with a high-bonding-strength copper layer and a preparation method thereof, wherein the glass substrate comprises a glass substrate, and a gradient transition layer and a copper layer are sequentially laminated on the glass substrate; the gradient transition layer comprises at least one composite layer, and the composite layer consists of a Zr layer and a ZrN layer which are stacked; the Zr layer is positioned on one side close to the glass substrate, and the ZrN layer is positioned on one side close to the copper layer. The copper layer and the glass substrate have strong binding force, are not easy to peel off, and improve the comprehensive performance of the glass substrate.
Description
Technical Field
The invention belongs to the technical field of electronic packaging technology and functional film preparation, and particularly relates to a glass substrate plated with a copper layer with high bonding strength and a preparation method thereof.
Background
The glass substrate (including the printed circuit board) has good electrical insulation and chemical stability, and has similar thermal expansion coefficient with components and parts, and is hopeful to replace the traditional organic substrate as a device packaging substrate material, so the glass substrate has wide application prospect in the fields of PCB, LED, power device packaging and the like. The surface of the glass substrate needs to be metallized before packaging, however, the surface of the glass substrate has high flatness, low surface energy and chemical inertness, and particularly, the inherent thermal expansion coefficient difference between the glass substrate and metal causes larger stress at the interface between the glass substrate and the metal, so that the metal layer has poor adhesive force, low binding force and easy stripping, and further the glass substrate is invalid. In addition, it is very difficult to prepare a continuous and complete film on the surface of the glass substrate, and the bonding strength between the metal film prepared by the traditional preparation methods such as electroplating and electroless plating and the glass substrate is poor, so that the mass production and application of the metal film are limited.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the glass substrate plated with the copper layer with high bonding strength and the preparation method thereof, wherein the copper layer has strong bonding force with the glass substrate, is not easy to peel off, and improves the comprehensive performance of the glass substrate.
The invention is realized by the following technical scheme:
The glass substrate plated with the high-bonding-strength copper layer comprises a glass substrate, wherein a gradient transition layer and a copper layer are sequentially laminated on the glass substrate; the gradient transition layer comprises at least one composite layer, and the composite layer consists of a Zr layer and a ZrN layer which are stacked; the Zr layer is positioned on one side close to the glass substrate, and the ZrN layer is positioned on one side close to the copper layer.
Preferably, the number of layers of the composite layer is 1-5.
Preferably, the thickness of the composite layer is 200-500 nm, and the thickness of the gradient transition layer is 0.2-1.5 mu m.
Preferably, the copper layer has a thickness of 1 to 2 μm.
The preparation method of the glass substrate plated with the high-bonding-strength copper layer comprises the following steps:
S1, sequentially depositing a Zr layer and a ZrN layer on a glass substrate in a magnetron sputtering mode, and repeating the process until a composite layer with the required number of layers is obtained to form a gradient transition layer;
S2, depositing a copper layer on the gradient transition layer in a magnetron sputtering mode to obtain the glass substrate plated with the copper layer with high bonding strength.
Preferably, S1 is specifically: a Zr target is used as a target material, and a Zr layer is deposited on the glass substrate in a magnetron sputtering mode under the condition of introducing Ar gas; then stopping sputtering, introducing Ar gas and N 2 gas, and depositing a ZrN layer on the Zr layer in a magnetron sputtering mode; and repeating the process until the composite layer with the required number of layers is obtained, and forming the gradient transition layer.
Further, during the deposition of the Zr layer, the process parameters are: the working air pressure is 0.30-1.00 Pa, the direct-current sputtering power is 50-80W, and the deposition time is 30-60 min; when the ZrN layer is deposited, the process parameters are as follows: the flow rate of N 2 gas is 2-10 sccm, the working air pressure is 0.30-1.00 Pa, the direct current sputtering power is 80W, and the deposition time is 60-120 min.
Further, in S1, when the number of layers of the deposited composite layer exceeds one, before the Zr layers in the other composite layers except the first composite layer are deposited, the target baffle is closed, the target is sputter cleaned, and after the cleaning is completed, the target baffle is opened, and the Zr layer is sputter deposited.
Preferably, S2 is specifically: and adopting a Cu target as a target material, and depositing a copper layer on the gradient transition layer in a magnetron sputtering mode under the condition of introducing Ar gas.
Further, when depositing the copper layer, the process parameters are as follows: the DC sputtering power is 80-120W, the working air pressure is 0.5-1 Pa, and the sputtering deposition time is 1-2 h.
Compared with the prior art, the invention has the following beneficial effects:
According to the glass substrate, the (ZrN/Zr) x (x is a positive integer) gradient transition layer is arranged between the glass substrate and the copper layer, the gradient transition layer is formed by alternately laminating the Zr layer and the ZrN layer, the thermal expansion coefficients of the Zr layer and the ZrN layer are both between the glass substrate and the copper layer, the problem of poor thermal expansion coefficient exists only in the Zr layer or the ZrN layer, the interface stress cannot be relieved, the Zr layer and the ZrN layer are combined, the problem of mismatching of the thermal expansion coefficients between the glass substrate and the copper layer can be solved, the interface compatibility is further enhanced, and the interface bonding strength is improved. The surface of the glass substrate plated with the copper layer with high bonding strength is compact and flat, is in a uniform particle state and has excellent electrical performance.
Furthermore, according to the glass substrate disclosed by the invention, the interface structure of the glass substrate and the copper layer can be optimized by adjusting the thickness of the gradient transition layer, and the interface bonding strength of the copper layer/glass substrate is gradually improved along with the increase of the number of the composite layers, so that the interface bonding strength of the copper layer/glass substrate can be adjusted by adjusting the number of the composite layers, and the interface bonding performance of the copper layer/glass substrate is improved.
The method adopts the magnetron sputtering technology to deposit the Zr layer, the ZrN layer and the copper layer on the glass substrate, has simple preparation method and strong controllability, and is easy to prepare in large scale.
Further, the size of each particle in the Zr layer and the ZrN layer can be regulated by regulating the working air pressure of the sputtering of the zirconium target, and the microstructure of the Zr layer and the ZrN layer can be regulated.
Drawings
FIG. 1 is a surface topography image of the (ZrN/Zr) x gradient transition layers of examples 1-3 of the present invention; (a) And (b) is the (ZrN/Zr) 1 gradient transition layer of example 1; (c) And (d) is the (ZrN/Zr) 2 gradient transition layer of example 2; (e) And (f) is the (ZrN/Zr) 3 gradient transition layer of example 3.
FIG. 2 is a cross-sectional morphology of Cu/(ZrN/Zr) x/glass composite structures in examples 1-3 of the present invention.
Detailed Description
For a further understanding of the present invention, the present invention is described below in conjunction with the following examples, which are provided to further illustrate the features and advantages of the present invention and are not intended to limit the claims of the present invention.
The glass substrate plated with the high-bonding-strength copper layer comprises a glass substrate, wherein a gradient transition layer and a copper layer are sequentially laminated on the glass substrate; the gradient transition layer comprises at least one composite layer, and the composite layer consists of a Zr layer and a ZrN layer which are stacked; the Zr layer is positioned on one side close to the glass substrate, and the ZrN layer is positioned on one side close to the copper layer.
In a specific embodiment of the present invention, the number of layers of the composite layer is 1-5, for example, the composite layer may be 1 layer, 2 layers, or 3 layers. The thickness of the composite layer is 200-500 nm, more preferably 400-500 nm; the thickness of the gradient transition layer is 0.2-1.5 μm, more preferably 0.4-1.2 μm; the thickness of the copper layer is 1 to 2. Mu.m, more preferably 0.9 to 1.1. Mu.m.
The preparation method of the glass substrate plated with the high-bonding-strength copper layer comprises the following steps:
S1, sequentially depositing a Zr layer and a ZrN layer on a glass substrate in a magnetron sputtering mode, and repeating the process until a composite layer with the required number of layers is obtained to form a gradient transition layer;
S2, depositing a copper layer on the gradient transition layer in a magnetron sputtering mode to obtain the glass substrate plated with the copper layer with high bonding strength.
In a specific embodiment of the present invention, before S1, the glass substrate is subjected to a cleaning pretreatment: and sequentially placing the glass substrate in acetone and ethanol for ultrasonic cleaning respectively, and then drying and placing in a vacuum chamber for standby.
In the embodiment of the invention, the S1 is specifically: a Zr target is used as a target material, and a Zr layer is deposited on the glass substrate in a magnetron sputtering mode under the condition of introducing Ar gas; then stopping magnetron sputtering, introducing Ar gas and N 2 gas, and depositing a ZrN layer on the Zr layer in a magnetron sputtering mode; and repeating the process until the composite layer with the required number of layers is obtained, and forming the gradient transition layer. Ar gas is used as sputtering gas, N 2 gas is used as reaction gas for depositing ZrN, and ZrN layer in the gradient transition layer is needed to be realized by reactive sputtering.
In the specific embodiment of the invention, when the Zr layer is deposited, the process parameters are as follows: the flow rate of Ar gas is 20sccm, the working air pressure is 0.30-1.00 Pa, the direct current sputtering power is 50-80W, and the deposition time is 30-60 min. When the ZrN layer is deposited, the process parameters are as follows: the flow rate of Ar gas is 20sccm, the flow rate of N 2 gas is 2-10 sccm, the working air pressure is 0.30-1.00 Pa, the direct current sputtering power is 80W, and the deposition time is 60-120 min.
In the specific embodiment of the invention, when the number of deposited composite layers exceeds one, before the Zr layers in other composite layers except the first composite layer are deposited, the target baffle is closed, the target is subjected to sputtering cleaning, zrN remained on the surface of the target during the sputtering deposition of the previous ZrN layer is fully sputtered on the target baffle, then the target baffle is opened, and the pure Zr layer is sputtered and deposited.
In the embodiment of the invention, the S2 is specifically: and adopting a Cu target as a target material, and depositing a copper layer on the gradient transition layer in a magnetron sputtering mode under the condition of introducing Ar gas.
In the embodiment of the invention, when a copper layer is deposited, the process parameters are as follows: the DC sputtering power is 80-120W, the Ar gas flow is 20sccm, the working air pressure is 0.5-1 Pa, and the sputtering deposition time is 1-2 h.
In the invention, the sputtering deposition is carried out at room temperature.
Example 1
The preparation method of the glass substrate plated with the high-bonding-strength copper layer comprises the following steps:
And 1) sequentially placing the glass substrate (2 cm multiplied by 2 cm) into acetone and absolute ethyl alcohol, ultrasonically cleaning for 10min, taking out, drying by a blower, and horizontally fixing on a sample tray by adopting a high-temperature-resistant double-sided adhesive tape. Zr target (phi 50mm multiplied by 5mm, purity 99.95%) is surface polished with 600 mesh water sand paper, put into acetone for ultrasonic cleaning for 10min, and then mounted on the target position of sputtering chamber.
Step 2), the background vacuum degree of the sputtering chamber is 5.0 multiplied by 10 -4 Pa, ar gas (purity is 99.99%) is introduced, the flow rate of the Ar gas is set to 20sccm, the working air pressure is 0.5Pa, a direct current power supply is turned on, the sputtering power of the Zr target is adjusted to 80W, and the sputtering deposition of the Zr layer is started, wherein the sputtering time is 60min; after the sputtering deposition of the Zr layer is finished, a sputtering power supply is turned off, N 2 gas is introduced, the flow rate of N 2 gas is 6sccm, ar gas and N 2 gas in a sputtering chamber are fully mixed, then the direct current sputtering power is adjusted to 80W, the sputtering starts, the sputtering deposition time is 60 minutes, and the (ZrN/Zr) 1/glass for depositing a layer of composite layer is obtained;
Step 3), preparing a copper layer on the basis of the step 2), and specifically, the method comprises the following steps:
The Cu target (phi 50mm multiplied by 5mm, purity 99.95%) was surface polished with 600 mesh water sand paper, placed in acetone for ultrasonic cleaning for 10min, and then mounted on the sputtering chamber target.
The technological parameters are as follows: the background vacuum degree of the sputtering chamber was 5.0X10 -4 Pa, the DC sputtering power was 100W, the flow rate of Ar gas was 20sccm, the working pressure was 0.5Pa, and sputtering deposition was performed for 1h to obtain Cu/(ZrN/Zr) 1/glass (note: 1 #).
Example 2
The preparation method of the glass substrate plated with the high-bonding-strength copper layer comprises the following steps:
And 1) sequentially placing the glass substrate (2 cm multiplied by 2 cm) into acetone and absolute ethyl alcohol, ultrasonically cleaning for 10min, taking out, drying by a blower, and horizontally fixing on a sample tray by adopting a high-temperature-resistant double-sided adhesive tape. Zr target (phi 50mm multiplied by 5mm, purity 99.95%) is surface polished with 600 mesh water sand paper, put into acetone for ultrasonic cleaning for 10min, and then mounted on the target position of sputtering chamber.
Step 2), the background vacuum degree of the sputtering chamber is 5.0 multiplied by 10 -4 Pa, ar gas (purity is 99.99%) is introduced, the flow rate of the Ar gas is set to 20sccm, the working air pressure is 0.5Pa, a direct current power supply is turned on, the sputtering power of the Zr target is adjusted to 80W, and the sputtering deposition of the Zr layer is started, wherein the sputtering time is 60min; after the sputtering deposition of the Zr layer is finished, a sputtering power supply is turned off, N 2 gas is introduced, the flow rate of N 2 gas is 6sccm, ar gas and N 2 gas in a sputtering chamber are fully mixed, then the direct current sputtering power is adjusted to 80W, the sputtering starts, the sputtering deposition time is 60min, and the deposition of the first composite layer is finished; stopping introducing N 2 gas, closing a target baffle, performing target sputtering cleaning, opening the target baffle after cleaning, sputtering and depositing a Zr layer, closing a sputtering power supply after the sputtering and depositing of the Zr layer are finished, introducing N 2 gas, wherein the flow of N 2 gas is 6sccm, fully mixing Ar gas and N 2 gas in a sputtering chamber, adjusting the direct current sputtering power to 80W, starting sputtering, and completing the deposition of a second composite layer for 60 minutes to obtain (ZrN/Zr) 2/glass for depositing two composite layers;
Step 3), preparing a copper layer on the basis of the step 2), and specifically, the method comprises the following steps:
The Cu target (phi 50mm multiplied by 5mm, purity 99.95%) was surface polished with 600 mesh water sand paper, placed in acetone for ultrasonic cleaning for 10min, and then mounted on the sputtering chamber target.
The technological parameters are as follows: the background vacuum degree of the sputtering chamber was 5.0X10 -4 Pa, the DC sputtering power was 100W, the flow rate of Ar gas was 20sccm, the working pressure was 0.5Pa, and sputtering deposition was performed for 1 hour to obtain Cu/(ZrN/Zr) 2/glass (note: 2 #).
Example 3
The preparation method of the glass substrate plated with the high-bonding-strength copper layer comprises the following steps:
And 1) sequentially placing the glass substrate (2 cm multiplied by 2 cm) into acetone and absolute ethyl alcohol, ultrasonically cleaning for 10min, taking out, drying by a blower, and horizontally fixing on a sample tray by adopting a high-temperature-resistant double-sided adhesive tape. Zr target (phi 50mm multiplied by 5mm, purity 99.95%) is surface polished with 600 mesh water sand paper, put into acetone for ultrasonic cleaning for 10min, and then mounted on the target position of sputtering chamber.
Step 2), the background vacuum degree of the sputtering chamber is 5.0 multiplied by 10 -4 Pa, ar gas (purity is 99.99%) is introduced, the flow rate of the Ar gas is set to 20sccm, the working air pressure is 0.5Pa, a direct current power supply is turned on, the sputtering power of the Zr target is adjusted to 80W, and the sputtering deposition of the Zr layer is started, wherein the sputtering time is 60min; after the sputtering deposition of the Zr layer is finished, a sputtering power supply is turned off, N 2 gas is introduced, the flow rate of N 2 gas is 6sccm, ar gas and N 2 gas in a sputtering chamber are fully mixed, then the direct current sputtering power is adjusted to 80W, the sputtering starts, the sputtering deposition time is 60min, and the deposition of the first composite layer is finished; stopping introducing N 2 gas, closing a target baffle, performing target sputtering cleaning, opening the target baffle after cleaning, sputtering and depositing a Zr layer, closing a sputtering power supply after the sputtering and depositing of the Zr layer are finished, introducing N 2 gas, wherein the flow of N 2 gas is 6sccm, fully mixing Ar gas and N 2 gas in a sputtering chamber, adjusting the direct current sputtering power to 80W, starting sputtering, and depositing for 60min, wherein the depositing of a second composite layer is finished; stopping introducing N 2 gas, closing a target baffle, performing target sputtering cleaning, opening the target baffle after cleaning, sputtering and depositing a Zr layer, closing a sputtering power supply after the sputtering and depositing of the Zr layer are finished, introducing N 2 gas, wherein the flow of N 2 gas is 6sccm, fully mixing Ar gas and N 2 gas in a sputtering chamber, adjusting the direct current sputtering power to 80W, starting sputtering, and completing the deposition of a third composite layer, thereby obtaining (ZrN/Zr) 3/glass for depositing three composite layers;
Step 3), preparing a copper layer on the basis of the step 2), and specifically, the method comprises the following steps:
The Cu target (phi 50mm multiplied by 5mm, purity 99.95%) was surface polished with 600 mesh water sand paper, placed in acetone for ultrasonic cleaning for 10min, and then mounted on the sputtering chamber target.
The technological parameters are as follows: the background vacuum degree of the sputtering chamber was 5.0X10 -4 Pa, the DC sputtering power was 100W, the flow rate of Ar gas was 20sccm, the working pressure was 0.5Pa, and sputtering deposition was performed for 1h to obtain Cu/(ZrN/Zr) 3/glass (note: 3 #).
Comparative example 1
The method for producing a glass substrate plated with a copper layer of this comparative example comprises:
And 1) sequentially placing the glass substrate (2 cm multiplied by 2 cm) into acetone and absolute ethyl alcohol, ultrasonically cleaning for 10min, taking out, drying by a blower, and horizontally fixing on a sample tray by adopting a high-temperature-resistant double-sided adhesive tape.
And 2) polishing the surface of a Cu target (phi 50mm multiplied by 5mm, purity 99.95%) by using 600-mesh water sand paper, putting the Cu target into acetone, ultrasonically cleaning the Cu target for 10min, and then mounting the Cu target on a target position of a sputtering chamber.
The sputtering process parameters are as follows: the background vacuum degree of the sputtering chamber is 5.0 multiplied by 10 -4 Pa, a direct current sputtering Cu target is adopted, the sputtering power is 100W, the flow of Ar gas is 20sccm, the working air pressure is 0.5Pa, the sputtering deposition of a Cu layer is carried out, and the sputtering time is 60min, so that the Cu/glass is obtained.
Comparative example 2
The method for producing a glass substrate plated with a copper layer of this comparative example comprises:
And 1) sequentially placing the glass substrate (2 cm multiplied by 2 cm) into acetone and absolute ethyl alcohol, ultrasonically cleaning for 10min, taking out, drying by a blower, and horizontally fixing on a sample tray by adopting a high-temperature-resistant double-sided adhesive tape. Zr target (phi 50mm multiplied by 5mm, purity 99.95%) and Cu target (phi 50mm multiplied by 5mm, purity 99.95%) were respectively surface polished with 600 mesh water sand paper, put into acetone, ultrasonically cleaned for 10min, and then mounted on the sputtering chamber target.
Step 2), when the background vacuum degree of the sputtering chamber is 5.0X10 -4 Pa, introducing Ar gas (purity is 99.99%), setting Ar gas flow to 20sccm, operating air pressure to 0.5Pa, switching on a direct current power supply, adjusting the sputtering power of the Zr target to 80W, starting sputtering to deposit a Zr layer, and sputtering for 60min to obtain Zr/glass;
Step 3), preparing a copper layer on the basis of the step 2), and specifically, the method comprises the following steps:
The sputtering process parameters are as follows: the background vacuum degree of the sputtering chamber is 5.0 multiplied by 10 -4 Pa, a direct current sputtering Cu target is adopted, the sputtering power is 100W, the Ar gas flow is 20sccm, the working gas pressure is 0.5Pa, the sputtering deposition of a Cu layer is carried out, and the sputtering time is 60min, so that the Cu/Zr/glass is obtained.
Comparative example 3
The method for producing a glass substrate plated with a copper layer of this comparative example comprises:
And 1) sequentially placing the glass substrate (2 cm multiplied by 2 cm) into acetone and absolute ethyl alcohol, ultrasonically cleaning for 10min, taking out, drying by a blower, and horizontally fixing on a sample tray by adopting a high-temperature-resistant double-sided adhesive tape. Zr target (phi 50mm multiplied by 5mm, purity 99.95%) and Cu target (phi 50mm multiplied by 5mm, purity 99.95%) were respectively surface polished with 600 mesh water sand paper, put into acetone, ultrasonically cleaned for 10min, and then mounted on the sputtering chamber target.
Step 2), when the background vacuum degree of the sputtering chamber is 5.0X10 -4 Pa, introducing Ar gas and N 2 gas, wherein the Ar gas flow is 20sccm, the N 2 gas flow is 6sccm, turning on a direct current power supply after the Ar gas and the N 2 gas in the sputtering chamber are fully mixed, adjusting the sputtering power of the Zr target to 80W, starting reactive sputtering to deposit a ZrN layer, and sputtering for 60min to obtain ZrN/glass;
Step 3), preparing a copper layer on the basis of the step 2), and specifically, the method comprises the following steps:
The sputtering process parameters are as follows: the background vacuum degree of the sputtering chamber is 5.0 multiplied by 10 -4 Pa, a direct current sputtering Cu target is adopted, the sputtering power is 100W, the Ar gas flow is 20sccm, the working gas pressure is 0.5Pa, the sputtering deposition of a Cu layer is carried out, and the sputtering time is 60min, so that the Cu/ZrN/glass is obtained.
FIG. 1 is a surface morphology image of (ZrN/Zr) x gradient transition layers with different numbers of composite layers in examples 1-3, and it can be seen from the graph that the surface of the gradient transition layer presents uniform, dense, flat and obvious crystallization characteristics, and the particle size becomes larger as the number of composite layers increases.
FIG. 2 is a cross-sectional morphology of Cu/(ZrN/Zr) x/glass in examples 1-3 of the present invention, and it can be seen from the graph that good interfacial bonding relations are formed between the composite layers, between the gradient transition layer and the adjacent copper layer and glass substrate during the sputter deposition process, and the copper layer has a flat surface and a uniform thickness. The copper layer has a columnar crystal structure and a thickness of approximately 1 μm.
Table 1 shows the resistance and interfacial bonding strength of various Cu/(ZrN/Zr) x/glass composites. As can be seen from the table, when the pure Zr layer or the pure ZrN layer is used as the transition layer between the copper layer and the glass substrate, the resistance value is lower, but the interface bonding strength is lower than that of the composite structure with the ZrN/Zr composite layer as the transition layer. For the ZrN/Zr gradient transition layer, the resistance value of the composite structure is slightly increased, but the interface bonding strength of Cu/(ZrN/Zr) x/glass is increased along with the increase of the number of composite layers.
TABLE 1 electrical properties and interfacial bonding strength of Cu/(ZrN/Zr) x/glass composite Structure
The glass substrate plated with the high-bonding-strength copper layer has the advantages that the gradient transition layer is of a polycrystalline or amorphous structure, the compressive stress of a material interface can be relieved, the bonding strength is improved, the glass substrates with different layers of composite layers have excellent electrical performance and interface bonding performance, and the bonding strength of the copper layer/glass substrate interface is further improved along with the increase of the layers of the composite layers. In conclusion, the interface bonding strength of the glass substrate and the copper layer can be improved by adding a Zr-based gradient transition layer between the two layers.
Claims (10)
1. The glass substrate plated with the high-bonding-strength copper layer is characterized by comprising a glass substrate, wherein a gradient transition layer and a copper layer are sequentially laminated on the glass substrate; the gradient transition layer comprises at least one composite layer, and the composite layer consists of a Zr layer and a ZrN layer which are stacked; the Zr layer is positioned on one side close to the glass substrate, and the ZrN layer is positioned on one side close to the copper layer.
2. The high bond strength copper layer coated glass substrate according to claim 1, wherein the number of layers of the composite layer is 1 to 5.
3. The high bond strength copper coated glass substrate of claim 1, wherein the composite layer has a thickness of 200-500 nm and the graded transition layer has a thickness of 0.2-1.5 μm.
4. The high bond strength copper layer plated glass substrate according to claim 1, wherein the copper layer has a thickness of 1 to 2 μm.
5. The method for producing a glass substrate plated with a copper layer having high bonding strength according to any one of claims 1 to 4, comprising:
S1, sequentially depositing a Zr layer and a ZrN layer on a glass substrate in a magnetron sputtering mode, and repeating the process until a composite layer with the required number of layers is obtained to form a gradient transition layer;
S2, depositing a copper layer on the gradient transition layer in a magnetron sputtering mode to obtain the glass substrate plated with the copper layer with high bonding strength.
6. The method for producing a glass substrate plated with a copper layer having high bonding strength according to claim 5, wherein S1 is specifically: a Zr target is used as a target material, and a Zr layer is deposited on the glass substrate in a magnetron sputtering mode under the condition of introducing Ar gas; then stopping sputtering, introducing Ar gas and N 2 gas, and depositing a ZrN layer on the Zr layer in a magnetron sputtering mode; and repeating the process until the composite layer with the required number of layers is obtained, and forming the gradient transition layer.
7. The method for producing a glass substrate plated with a copper layer having high bonding strength according to claim 6, wherein the process parameters at the time of depositing the Zr layer are: the working air pressure is 0.30-1.00 Pa, the direct-current sputtering power is 50-80W, and the deposition time is 30-60 min; when the ZrN layer is deposited, the process parameters are as follows: the flow rate of N 2 gas is 2-10 sccm, the working air pressure is 0.30-1.00 Pa, the direct current sputtering power is 80W, and the deposition time is 60-120 min.
8. The method according to claim 6, wherein in S1, when the number of layers of the deposited composite layer exceeds one, before the Zr layers in the other composite layers except the first composite layer are deposited, the target barrier is closed, the target is sputter cleaned, and after the cleaning, the target barrier is opened, and the Zr layer is sputter deposited.
9. The method for producing a glass substrate plated with a copper layer having high bonding strength according to claim 5, wherein S2 is specifically: and adopting a Cu target as a target material, and depositing a copper layer on the gradient transition layer in a magnetron sputtering mode under the condition of introducing Ar gas.
10. The method for preparing a glass substrate coated with a copper layer with high bonding strength according to claim 9, wherein the process parameters are as follows: the DC sputtering power is 80-120W, the working air pressure is 0.5-1 Pa, and the sputtering deposition time is 1-2 h.
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