CN114086122A - Ceramic-based gradient plating layer based on high film-substrate binding force on copper substrate and preparation method thereof - Google Patents

Ceramic-based gradient plating layer based on high film-substrate binding force on copper substrate and preparation method thereof Download PDF

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CN114086122A
CN114086122A CN202111422457.8A CN202111422457A CN114086122A CN 114086122 A CN114086122 A CN 114086122A CN 202111422457 A CN202111422457 A CN 202111422457A CN 114086122 A CN114086122 A CN 114086122A
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film
target
multilayer film
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substrate
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CN114086122B (en
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鞠洪博
汪然
喻利花
许俊华
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Jiangsu University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/06—Surface hardening
    • C21D1/09—Surface hardening by direct application of electrical or wave energy; by particle radiation
    • C21D1/10—Surface hardening by direct application of electrical or wave energy; by particle radiation by electric induction
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/62—Quenching devices
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/32—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for gear wheels, worm wheels, or the like
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E30/00—Energy generation of nuclear origin
    • Y02E30/30—Nuclear fission reactors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Abstract

The invention discloses a ceramic-based gradient coating based on high film-substrate binding force on a copper substrate, which is characterized in that a Ti-Cr film, a Ti-Cr-Zr film, a Ti-Zr film and a TiN + ZrN film are sequentially deposited in order of decreasing thermal expansion coefficient of the films to form a nano-structure multilayer film material as a coating, wherein the thickness of the film is 2.5-10 mu m. Also discloses a preparation method of the multilayer film structure plating layer. The Ti-Cr/Ti-Cr-Zr/Ti-Zr/TiN + ZrN gradient coating has high bonding force with a copper substrate, has the advantages of simple process flow and high production efficiency, and can be applied to the modification of the mechanics, wear resistance and insulating property of the surface of a copper device; the problem of strike sparks between a sensor and an opposite workpiece caused by collision in the current industrial application process is solved.

Description

Ceramic-based gradient plating layer based on high film-substrate binding force on copper substrate and preparation method thereof
Technical Field
The invention relates to the field of composite multilayer films, in particular to a ceramic-based gradient plating layer based on high film-substrate binding force on a copper substrate and a preparation method thereof.
Background
In recent years, induction quenching plays an important role in metal hot working process with the advantages of high efficiency, environmental protection, reliability and the like which are difficult to compare with other heat treatment processes, and the industrial application of the double-frequency induction quenching technology in the field of heavy-duty gear surface strengthening greatly promotes the development of high-performance mechanical power equipment in the last two decades.
The terminal of the double-frequency induction heating quenching equipment is a copper quenching inductor which induces induction current on the surface of the opposite gear based on the electromagnetic induction principle to generate skin effect, so that the temperature is rapidly increased to realize induction quenching. In order to avoid damage to the sensor caused by fire striking, a longer distance is required between the sensor and the opposite workpiece, and the thermal efficiency of the skin effect is inversely proportional to the distance.
Therefore, how to use the surface technology to design and prepare an insulating film material on the surface of the copper quenching sensor so as to solve the problem of sparking caused by collision between the sensor and an opposite workpiece due to the workpiece precision and improve the double-frequency induction heating quenching efficiency has very important scientific research value and industrial application significance.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the defects of the prior art, the invention provides a ceramic-based gradient coating based on high film-substrate binding force on a copper substrate, and the Ti-Cr/Ti-Cr-Zr/Ti-Zr/TiN + ZrN gradient coating has high binding force with the copper substrate, has the advantages of simple process flow and high production efficiency, and can be applied to the modification of the mechanical property, the wear resistance and the insulating property of the surface of a copper device; the problem of strike sparks between a sensor and an opposite workpiece caused by collision in the current industrial application process is solved.
The technical scheme is as follows: the ceramic-based gradient plating layer based on the high film-substrate binding force on the copper substrate is characterized in that: sequentially depositing a Ti-Cr film, a Ti-Cr-Zr film, a Ti-Zr film and a TiN + ZrN film by taking the descending of the thermal expansion coefficient of the films as a sequence to form a nano-structure multilayer film material as a coating, wherein the thickness of the film is 2.5-10 mu m.
Wherein, the Ti-Cr film is a composite film structure, the Ti-Cr composite film comprises an hcp-Ti and bcc-Cr two-phase structure, and the atomic percentage content of Ti and Cr elements is respectively 62.5 percent and 37.5 percent; the Ti-Cr composite film induces the diffusion between the Ti-Cr layer and the substrate after being subjected to the vacuum annealing treatment at the temperature of 600-700 ℃, and forms Cu in/between the Ti-Cr layer and the substrate4Ti3、Cr2A Ti phase.
The Ti-Cr film and the Ti-Cr-Zr film form a multilayer film structure, the Ti-Cr/Ti-Cr-Zr multilayer film comprises three-phase structures of hcp-Ti, bcc-Cr and hcp-Zr, and the atomic percentage content of Ti, Cr and Zr elements is 38.5%, 23.9% and 37.6% in sequence; the Ti-Cr/Ti-Cr-Zr multilayer film induces the diffusion of the Ti-Cr layer and the Ti-Cr-Zr layer after being subjected to the vacuum annealing treatment at the temperature of 600-700 ℃, and forms Cu in/between the layers4Ti3、Cu4Ti、Cr2A Ti phase.
The Ti-Cr film, the Ti-Cr-Zr film and the Ti-Zr film form a multilayer film structure, the Ti-Cr/Ti-Cr-Zr/Ti-Zr multilayer film comprises three-phase structures of hcp-Ti, bcc-Cr and hcp-Zr, and the atomic percentage content of Ti, Cr and Zr elements is 36.3%, 14.4% and 48.3% in sequence; the Ti-Cr/Ti-Cr-Zr/Ti-Zr multilayer film induces interlayer diffusion after being subjected to vacuum annealing treatment at 700-800 ℃, and forms Cu in/between layers4Ti3、Cr2Ti、Cu51Zr24、Cu4Ti、Cu3Ti、Cr0.62Cu0.38And (4) phase(s).
The Ti-Cr film, the Ti-Cr-Zr film, the Ti-Zr film and the TiN + ZrN film form a multilayer film structure, the Ti-Cr/Ti-Cr-Zr/Ti-Zr/TiN + ZrN multilayer film comprises five-phase structures of hcp-Ti, bcc-Cr, hcp-Zr, fcc-TiN and fcc-ZrN, and the atomic percentage contents of Ti, Cr, Zr and N are 32.8%, 9.84%, 49.2% and 8.16% in sequence; the Ti-Cr/Ti-Cr-Zr/Ti-Zr/TiN + ZrN multilayer film induces interlayer diffusion after being subjected to vacuum annealing treatment at 800-900 ℃, and forms Cu in/between layers4Ti3、Cr2Ti、Cu51Zr24、Cu4Ti、Cu3Ti、Cr0.62Cu0.38And (4) phase(s).
After the high vacuum annealing treatment, the film-base binding force of the film is improved to more than 20N after annealing from 2.544N before annealing.
The preparation method of the ceramic-based gradient plating layer based on the high film-substrate binding force on the copper substrate comprises the following steps:
1) preparing Ti-Cr composite films with different Ti contents by utilizing multi-target confocal unbalanced magnetron sputtering to obtain the sputtering power of a Ti-Cr film material and a Ti target; fixing the power of Ti and Cr targets on the basis of the Ti-Cr film, changing the power of the Zr target, preparing a Ti-Cr/Ti-Cr-Zr multilayer film, and obtaining the sputtering power of the Ti-Cr/Ti-Zr multilayer film material and the Zr target in the second layer of Ti-Cr-Zr film; closing the Cr target baffle on the basis of the Ti-Cr/Ti-Cr-Zr multilayer film to prepare a Ti-Cr/Ti-Cr-Zr/Ti-Zr multilayer film; finally, closing the Cr target baffle, keeping the power of the Ti and Zr unchanged, and preparing a Ti-Cr/Ti-Cr-Zr/Ti-Zr/TiN + ZrN multilayer film on the Ti-Cr/Ti-Cr-Zr/Ti-Zr multilayer film in an argon-nitrogen ratio of 10: 3;
2) ultrasonically cleaning a substrate Cu for 5-10 min by water, acetone and absolute ethyl alcohol in sequence, drying and fixing the substrate Cu on a rotatable substrate table of a sputtering chamber, closing a sample baffle, and respectively fixing a Ti target, a Cr target and a Zr target with the purity of 99.9% on three radio frequency guns of a magnetron sputtering instrument;
3) the pressure in the sputtering chamber was evacuated to 6.0X 10-4Introducing argon with the purity of 99.999 percent below Pa, controlling the flow to be 10sccm, and keeping the gas pressure of the sputtering chamber at 0.25 Pa;
4) closing the sample baffle, adjusting the power of the Ti target, the Cr target and the Zr target to be 50W, and sputtering for 5-10 min to clean various impurities on the surface of the target material;
5) introducing argon to keep the air pressure of the sputtering chamber at 0.3Pa, adjusting the power of the Cr target to 60W, closing the Zr target baffle, opening the sample baffle, keeping the rotating speed of the sample at 6r/min, adjusting the power of the Ti target to the sputtering power obtained in the step (1), and depositing the Ti-Cr composite film for 2 hours; after the deposition is finished, fixing the power of Ti and Cr targets, opening a Zr target baffle, adjusting the power of the Zr target to be the sputtering power obtained in the step (1), and continuously depositing the Ti-Cr-Zr film on the Ti-Cr film for 2 hours; after the deposition is finished, closing the Cr target baffle, keeping the power of the Ti and Zr targets unchanged, and continuously depositing a Ti-Zr film on the Ti-Cr/Ti-Cr-Zr multilayer film; finally, closing the Cr target baffle, introducing nitrogen with the purity of 99.999 percent, controlling the flow to be 3sccm, keeping the pressure of a sputtering chamber at 0.3Pa, controlling the flow ratio of argon to nitrogen to be 10:3, opening the sample baffle, and continuously depositing the TiN + ZrN film on the Ti-Cr/Ti-Cr-Zr/Ti-Zr/multilayer film for 2 hours; obtaining the Ti-Cr/Ti-Cr-Zr/Ti-Zr/TiN + ZrN multilayer film material coating.
The technical principle is as follows: by utilizing a multi-target confocal unbalanced magnetron sputtering method, the difference of thermal expansion coefficients between a surface ceramic coating and a Cu substrate is shortened by adding an intermediate transition layer as a design criterion, after vacuum annealing treatment, chemical reaction or diffusion is carried out in a modulation layer or between modulation layer interfaces, intermetallic compounds not only have metal bonds but also covalent bonds, the bonding force among atoms is enhanced by the occurrence of the covalent bonds, the chemical bonds tend to be stable, and the material is endowed with the characteristics of high melting point, high hardness and higher bonding force, so that the bonding force of the nano multilayer film material is improved, and finally the Ti-Cr/Ti-Cr-Zr/Ti-Zr/TiN + ZrN nano multilayer film material with high film-substrate bonding force is obtained.
Annealing process: background vacuum degree of 6.0 × 10-4Pa, and heating rate of 10 deg.C/min; when annealing is carried out at 600 ℃, the temperature is kept at 300 ℃ for 30min, and then the annealing furnace is cooled to room temperature after the temperature is kept at 600 ℃ for 60 min; when annealing is carried out at 700 ℃, the temperature is kept at 350 ℃ for 30min, and after the temperature is kept at 700 ℃ for 60min, the annealing furnace is cooled to room temperature; when annealing is carried out at 800 ℃, the temperature is kept at 400 ℃ for 30min, and the annealing furnace is cooled to room temperature after the temperature is kept at 800 ℃ for 60 min.
After the film material is subjected to high vacuum annealing treatment, chemical reactions occur in a single modulation layer and between modulation layer interfaces to generate intermetallic compounds and diffusion, the intermetallic compounds have metal bonds and covalent bonds, the bonding force between atoms is enhanced due to the covalent bonds, the chemical bonds tend to be stable, and the characteristics of high melting point, high hardness and high bonding force are endowed to the material.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: the invention utilizes the multi-target confocal unbalanced magnetron sputtering technology, and improves the film-substrate binding force by combining the decreasing of the thermal expansion coefficient and the interlayer metallurgy as a design principle, thereby having more application value.
The Ti-Cr/Ti-Cr-Zr/Ti-Zr/TiN + ZrN gradient coating has high bonding force with a copper substrate, has the advantages of simple process flow and high production efficiency, and can be applied to the modification of mechanics, wear resistance and insulating property of the surface of a copper device (such as a quenching sensor).
The preparation method is simple and has high production efficiency; the film material can be applied to the terminal of double-frequency induction quenching equipment, greatly promotes the industrial application of the induction quenching technology in the field of heavy-duty gear surface strengthening, and accelerates the development of high-performance mechanical power equipment.
Drawings
FIG. 1 is a film-substrate bonding diagram of a Ti-Cr/Ti-Cr-Zr/Ti-Zr/TiN + ZrN nano-multilayer film at room temperature;
FIG. 2 is a film-substrate bonding force diagram of the Ti-Cr composite film material after vacuum annealing at 600-700 deg.C;
FIG. 3 is a film-substrate bonding force diagram of the Ti-Cr/Ti-Cr-Zr nano multi-layer film material after vacuum annealing at 600-700 ℃;
FIG. 4 is a film-substrate bonding force diagram of the Ti-Cr/Ti-Cr-Zr/Ti-Zr nano multi-layer film material after vacuum annealing at 700-800 deg.C;
FIG. 5 is a film-substrate bonding force diagram of Ti-Cr/Ti-Cr-Zr/Ti-Zr/TiN + ZrN nano-multilayer film after vacuum annealing at 800-900 ℃;
FIG. 6 is an XRD diagram of a Ti-Cr/Ti-Cr-Zr/Ti-Zr/TiN + ZrN nano-multilayer film after vacuum annealing at 800-900 ℃;
FIG. 7 is a schematic structural diagram of a Ti-Cr/Ti-Cr-Zr/Ti-Zr/TiN + ZrN nano-multilayer film.
Detailed Description
The technical solution of the present invention is further described with reference to the accompanying drawings and the detailed description.
The invention firstly utilizes multi-target confocal unbalanced magnetron sputtering to prepare Ti-Cr composite films with different Ti powers, determines the power of a Ti target in a Ti-Cr film material with the highest film-substrate binding force, and carries out vacuum annealing treatment at 600-700 ℃, and concretely comprises the following steps:
adopting Ti target and Cr target with purity of 99.9% as source material, introducing reaction argon with purity of 99.999%, argon gas flow of 10sccm, vacuum degree lower than 6.0 × 10-4And (3) sputtering at Pa for 2h, wherein the working air pressure is 0.3Pa, the sputtering power of the Cr target is 60W, and the Ti target sputtering power is adjusted to prepare the Ti-Cr film material on the Cu substrate by sputtering by a double-target confocal radio frequency reaction magnetron sputtering method at room temperature.
When the power of the Ti target is adjusted to be 50W, the atomic percentage contents of Ti and Cr elements in the film are 45.4 percent and 54.6 percent in sequence, the film is of a hcp-Ti and bcc-Cr two-phase structure, and the film-substrate binding force of the Ti-Cr film is 2.567N;
when the power of the Ti target is adjusted to be 80W, the atomic percentage contents of Ti and Cr elements in the film are 57.1 percent and 42.9 percent in sequence, the film is of a hcp-Ti and bcc-Cr two-phase structure, and the film-substrate binding force of the Ti-Cr film is 3.046N;
when the power of the Ti target is adjusted to be 100W, the atomic percentage contents of Ti and Cr elements in the film are respectively 62.5 percent and 37.5 percent, the film is of a hcp-Ti and bcc-Cr two-phase structure, and the film-substrate binding force of the Ti-Cr film is 3.573N;
when the power of the Ti target is adjusted to be 150W, the atomic percentage contents of Ti and Cr elements in the film are 71.4 percent and 28.6 percent in sequence, the film is of a hcp-Ti and bcc-Cr two-phase structure, and the film-substrate binding force of the Ti-Cr film is 1.139N;
when the power of the Ti target is adjusted to be 180W, the atomic percentage contents of Ti and Cr elements in the film are 75.2 percent and 24.8 percent in sequence, the film is of a hcp-Ti and bcc-Cr two-phase structure, and the film-substrate binding force of the Ti-Cr film is 1.339N;
from the above experiment, the optimum sputtering power of the Ti target was determined to be 100W.
The power of the Ti target and the Cr target is fixed to be unchanged, the Ti-Cr/Ti-Cr-Zr multi-layer film material is prepared, and the vacuum annealing treatment at the temperature of 600-700 ℃ is carried out.
Firstly, fixing the Ti target power to be 100W and the Cr target to be 60W, preparing a Ti-Cr composite film with the highest film-substrate binding force by utilizing multi-target confocal unbalanced magnetron sputtering, then preparing Ti-Cr-Zr films with different Zr contents on the Ti-Cr films, and obtaining a Ti-Cr/Ti-Cr-Zr multi-layer film material with the highest film-substrate binding force, wherein in order to ensure that the growth environment of the film is not changed, the Ti and Cr target powers of the Ti-Cr-Zr layers are the same as that described above, and the specific method is as follows:
adopting Ti target, Cr target and Zr target with the purity of 99.9% as source materials, introducing reaction nitrogen with the purity of 99.999%, wherein the flow rate of argon gas is 10sccm, and the vacuum degree is lower than 6.0 multiplied by 10-4And (3) sputtering at Pa, wherein the working pressure is 0.3Pa, the sputtering power of the Ti target is 100W, the sputtering power of the Cr target is 60W, and sputtering on a Cu substrate at room temperature by adopting a double-target confocal radio frequency reaction magnetron sputtering method to prepare the Ti-Cr film material for 2 hours. Fixing the Ti and Cr targets with constant power after the sputtering is finished, and continuously depositing Ti-Cr-Zr films with different Zr contents for 2 hours on the Ti-Cr films to obtain the Ti-Cr/Ti-Cr-Zr multilayer film material.
When the Zr target power is adjusted to be 30W, the atomic percentage content of Ti, Cr and Zr in the film is 57.1 percent, 34.3 percent and 8.6 percent in sequence, the film is of a three-phase structure of hcp-Ti, bcc-Cr and hcp-Zr, and the film-substrate binding force of the Ti-Cr/Ti-Cr-Zr multilayer film is 1.132N;
when the Zr target power is adjusted to be 60W, the atomic percentage content of Ti, Cr and Zr in the film is 52.6 percent, 31.6 percent and 15.8 percent in sequence, the film is of a three-phase structure of hcp-Ti, bcc-Cr and hcp-Zr, and the film-substrate binding force of the Ti-Cr/Ti-Cr-Zr multilayer film is 1.654N;
when the Zr target power is adjusted to be 100W, the atomic percentage content of Ti, Cr and Zr in the film is 47.6 percent, 28.6 percent and 23.8 percent in sequence, the film is of a three-phase structure of hcp-Ti, bcc-Cr and hcp-Zr, and the film-substrate binding force of the Ti-Cr/Ti-Cr-Zr multilayer film is 2.521N;
when the Zr target power is adjusted to be 150W, the atomic percentage content of Ti, Cr and Zr in the film is 42.6 percent, 25.5 percent and 31.9 percent in sequence, the film is of a three-phase structure of hcp-Ti, bcc-Cr and hcp-Zr, and the film-substrate binding force of the Ti-Cr/Ti-Cr-Zr multilayer film is 4.18N;
when the Zr target power is adjusted to be 200W, the atomic percentage content of Ti, Cr and Zr in the film is 38.5 percent, 23.9 percent and 37.6 percent in sequence, the film is of a three-phase structure of hcp-Ti, bcc-Cr and hcp-Zr, and the film-substrate binding force of the Ti-Cr/Ti-Cr-Zr multilayer film is 4.192N;
from the above experiment, the optimum sputtering power of the Zr target was determined to be 200W.
The optimal power of the Ti, Cr and Zr targets is fixed to be unchanged, the Ti-Cr/Ti-Cr-Zr/Ti-Zr multilayer film material is prepared for 2 hours, and the vacuum annealing treatment at 800 ℃ of 700-.
The Ti-Cr/Ti-Cr-Zr/Ti-Zr multilayer film materials all adopt Ti targets, Cr targets and Zr targets with the purity of 99.9 percent as source materials, reaction argon with the purity of 99.999 percent is introduced, and the vacuum degree is lower than 6.0 multiplied by 10-4Sputtering at Pa, wherein the working pressure is 0.3Pa, and alternately sputtering on the substrate at room temperature by adopting a three-target confocal radio frequency reaction magnetron sputtering method.
The method specifically comprises the following steps:
(1) ultrasonically cleaning a Cu substrate for 5-10 min by water, acetone and absolute ethyl alcohol in sequence, drying the Cu substrate, fixing the Cu substrate on a rotatable substrate table in a sputtering chamber, and closing a sample baffle;
(2) respectively fixing a Ti target, a Cr target and a Zr target with the purity of 99.9 percent on three radio frequency guns;
(3) the pressure in the sputtering chamber was evacuated to 6.0X 10-4Pa below;
(4) argon with the purity of 99.999 percent is introduced, the flow is controlled to be 10sccm, and the pressure of a sputtering chamber is kept at 0.25 Pa;
(5) adjusting the power of the Ti target, the Cr target and the Zr target to be 50W, and sputtering for 5-10 min to clean various impurities on the surface of the target material;
(6) introducing argon to keep the air pressure of a sputtering chamber at 0.3Pa, adjusting the power of a Ti target to be 100W and the power of a Cr target to be 60W, closing a Zr target baffle, opening a sample baffle, keeping the rotating speed of the sample at 6r/min, and depositing a Ti-Cr composite film for 2 h; after the deposition is finished, fixing the power of the Ti target and the Cr target unchanged, adjusting the power of the Zr target to 200W, and continuously depositing the Ti-Cr-Zr film on the Ti-Cr film for 2 h; and after the deposition is finished, closing the Cr target baffle, keeping the power of the Ti and Zr targets unchanged, and continuously depositing the Ti-Zr film on the Ti-Cr/Ti-Cr-Zr multilayer film for 2 hours to prepare the Ti-Cr/Ti-Cr-Zr/Ti-Zr multilayer film material.
Then preparing Ti-Cr/Ti-Cr-Zr/Ti-Zr/TiN + ZrN multilayer film material, and carrying out vacuum annealing treatment at 800-900 ℃.
The Ti-Cr/Ti-Cr-Zr/Ti-Zr multilayer thin film materials all adopt a Ti target with the purity of 99.9 percent, a Cr target and a Zr target as source materials, reaction argon and nitrogen with the purity of 99.999 percent are introduced, the flow ratio of the argon to the nitrogen is 10sccm to 3sccm, the vacuum degree is lower than 6.0 multiplied by 10-4Sputtering at Pa, wherein the working pressure is 0.3Pa, and alternately sputtering on the substrate at room temperature by adopting a three-target confocal radio frequency reaction magnetron sputtering method.
The method specifically comprises the following steps:
(1) ultrasonically cleaning a Cu substrate for 5-10 min by water, acetone and absolute ethyl alcohol in sequence, drying the Cu substrate, fixing the Cu substrate on a rotatable substrate table in a sputtering chamber, and closing a sample baffle;
(2) respectively fixing a Ti target, a Cr target and a Zr target with the purity of 99.9 percent on three radio frequency guns;
(3) the pressure in the sputtering chamber was evacuated to 6.0X 10-4Pa below;
(4) argon with the purity of 99.999 percent is introduced, the flow is controlled to be 10sccm, and the pressure of a sputtering chamber is kept at 0.25 Pa;
(5) adjusting the power of the Ti target, the Cr target and the Zr target to be 50W, and sputtering for 5-10 min to clean various impurities on the surface of the target material;
(6) increasing the flow of argon gas, keeping the air pressure of a sputtering chamber at 0.3Pa, adjusting the power of a Ti target to be 100W and the power of a Cr target to be 60W, closing a Zr target baffle, opening a sample baffle, keeping the rotating speed of the sample at 6r/min, and depositing a Ti-Cr composite film for 2 h; after the deposition is finished, fixing the power of the Ti target and the Cr target unchanged, adjusting the power of the Zr target to 200W, and continuously depositing the Ti-Cr-Zr film on the Ti-Cr film for 2 h; and after the deposition is finished, closing the Cr target baffle, keeping the power of the Ti and Zr targets unchanged, and continuously depositing the Ti-Zr film on the Ti-Cr/Ti-Cr-Zr multilayer film for 2 hours. After the deposition is finished, closing the sample baffle, introducing nitrogen with the purity of 99.999 percent, controlling the flow to be 3sccm, keeping the pressure of a sputtering chamber at 0.3Pa and the argon-nitrogen ratio to be 10:3, opening the sample baffle, continuously depositing the TiN + ZrN thin film on the Ti-Cr/Ti-Cr-Zr/Ti-Zr multilayer film for 2 hours, and preparing the Ti-Cr/Ti-Cr-Zr/Ti-Zr/TiN + ZrN multilayer thin film material.
Annealing treatment of the nano multilayer thin film material at different temperatures is carried out as follows:
(1) at room temperature, the atomic percentage content of Ti, Cr, Zr and N in the Ti-Cr/Ti-Cr-Zr/Ti-Zr/TiN + ZrN multilayer film material is 32.8%, 9.84%, 49.2% and 8.16% in sequence, the film material is of five-phase structures of hcp-Ti, bcc-Cr, hcp-Zr, fcc-TiN and fcc-ZrN, and the film-substrate binding force of the Ti-Cr/Ti-CrZ-r/Ti-Zr/TiN + ZrN multilayer film is 2.544N;
(2) performing 600-700 deg.C vacuum annealing treatment on the Ti-Cr composite film to induce diffusion between the Ti-Cr layer and the substrate and form Cu in/between the Ti-Cr layer4Ti3、Cr2The film-substrate binding force of the Ti-Cr composite film is 10.815N, the formation of intermetallic compounds is accompanied with the formation of metal bonds and covalent bonds, the formation of the covalent bonds enhances the binding force between atoms, the chemical bonds tend to be stable, and the material is endowed with the characteristics of high melting point, high hardness and high binding force;
(3) subjecting the Ti-Cr/Ti-Cr-Zr multilayer film to a 600-700 ℃ vacuum annealing treatment to induce diffusion of the Ti-Cr layer and the Ti-Cr-Zr layer and form Cu in/between the layers4Ti3、Cu4Ti、Cr2The film-substrate binding force of the Ti-Cr/Ti-Cr-Zr multilayer film is 15.724N, the formation of intermetallic compounds is accompanied with the formation of metal bonds and covalent bonds, the formation of the covalent bonds strengthens the binding force between atoms, the chemical bonds tend to be stable, and the material is endowed with the characteristics of high melting point, high hardness and high binding force;
(4) subjecting the Ti-Cr/Ti-Cr-Zr/Ti-Zr multilayer film to a vacuum annealing treatment at 700 ℃ to 800 ℃ to induce interlayer diffusion and form Cu in/between the layers4Ti3、Cr2Ti、Cu51Zr24、Cu4Ti、Cu3Ti、Cr0.62Cu0.38The film-substrate binding force of the Ti-Cr/Ti-Cr-Zr/Ti-Zr multilayer film is more than 20N, the formation of intermetallic compounds is accompanied with the formation of metallic bonds and covalent bonds, the bonding force between atoms is enhanced due to the covalent bonds, the chemical bonds tend to be stable, and the characteristics of high melting point, high hardness and high binding force are endowed to the material.
(5) Carrying out vacuum annealing treatment at 800-900 ℃ on the Ti-Cr/Ti-Cr-Zr/Ti-Zr/TiN + ZrN multilayer film to induce interlayer diffusion and form Cu in/between the layers4Ti3、Cr2Ti、Cu51Zr24、Cu4Ti、Cu3Ti、Cr0.62Cu0.38The film-substrate binding force of the Ti-Cr/Ti-Cr-Zr/Ti-Zr/TiN + ZrN multilayer film is more than 20N, the formation of intermetallic compounds is accompanied with the formation of metal bonds and covalent bonds, the inter-atomic binding force is enhanced due to the formation of the covalent bonds, the chemical bonds tend to be stable, and the characteristics of high melting point, high hardness and high binding force are endowed to the material.

Claims (7)

1. The ceramic-based gradient plating layer based on the high film-substrate binding force on the copper substrate is characterized in that: sequentially depositing a Ti-Cr film, a Ti-Cr-Zr film, a Ti-Zr film and a TiN + ZrN film by taking the descending of the thermal expansion coefficient of the films as a sequence to form a nano-structure multilayer film material as a coating, wherein the thickness of the film is 2.5-10 mu m.
2. The ceramic-based gradient plating layer based on high film-based bonding force on copper substrate according to claim 1, wherein: the Ti-Cr film is of a composite film structure, the Ti-Cr composite film comprises hcp-Ti and bcc-Cr two-phase structures, and the atomic percentage content of Ti and Cr elements is respectively 62.5 percent and 37.5 percent; the Ti-Cr composite film induces the diffusion between the Ti-Cr layer and the substrate after being subjected to the vacuum annealing treatment at the temperature of 600-700 ℃, and forms Cu in/between the Ti-Cr layer and the substrate4Ti3、Cr2A Ti phase.
3. The ceramic-based gradient plating layer based on high film-based bonding force on copper substrate according to claim 1, wherein: the Ti-Cr film and the Ti-Cr-Zr film form a multilayer film structure, the Ti-Cr/Ti-Cr-Zr multilayer film comprises three-phase structures of hcp-Ti, bcc-Cr and hcp-Zr, and the atomic percentage content of Ti, Cr and Zr is 38.5%, 23.9% and 37.6% in sequence; the Ti-Cr/Ti-Cr-Zr multilayer film induces the diffusion of the Ti-Cr layer and the Ti-Cr-Zr layer after being subjected to the vacuum annealing treatment at the temperature of 600-700 ℃, and forms Cu in/between the layers4Ti3、Cu4Ti、Cr2A Ti phase.
4. High on copper-based substrate according to claim 1The ceramic-based gradient plating with film-substrate binding force is characterized in that: the Ti-Cr film, the Ti-Cr-Zr film and the Ti-Zr film form a multilayer film structure, the Ti-Cr/Ti-Cr-Zr/Ti-Zr multilayer film comprises three-phase structures of hcp-Ti, bcc-Cr and hcp-Zr, and the atomic percentage content of Ti, Cr and Zr elements is 36.3%, 14.4% and 48.3% in sequence; the Ti-Cr/Ti-Cr-Zr/Ti-Zr multilayer film induces interlayer diffusion after being subjected to vacuum annealing treatment at 700-800 ℃, and forms Cu in/between layers4Ti3、Cr2Ti、Cu51Zr24、Cu4Ti、Cu3Ti、Cr0.62Cu0.38And (4) phase(s).
5. The ceramic-based gradient plating layer based on high film-based bonding force on copper substrate according to claim 1, wherein: the Ti-Cr film, the Ti-Cr-Zr film, the Ti-Zr film and the TiN + ZrN film form a multilayer film structure, the Ti-Cr/Ti-Cr-Zr/Ti-Zr/TiN + ZrN multilayer film comprises five-phase structures of hcp-Ti, bcc-Cr, hcp-Zr, fcc-TiN and fcc-ZrN, and the atomic percentage content of Ti, Cr, Zr and N elements is 32.8%, 9.84%, 49.2% and 8.16% in sequence; the Ti-Cr/Ti-Cr-Zr/Ti-Zr/TiN + ZrN multilayer film induces interlayer diffusion after being subjected to vacuum annealing treatment at 800-900 ℃, and forms Cu in/between layers4Ti3、Cr2Ti、Cu51Zr24、Cu4Ti、Cu3Ti、Cr0.62Cu0.38And (4) phase(s).
6. The ceramic-based gradient plating layer based on high film-based bonding force on copper substrate according to claim 1, wherein: after the high vacuum annealing treatment is carried out on the coating film material, the film-substrate binding force of the film is improved to more than 20N after annealing from 2.544N before annealing.
7. The preparation method of the ceramic-based gradient plating layer based on the high film-substrate binding force on the copper substrate is characterized by comprising the following steps of: the method comprises the following steps:
1) preparing Ti-Cr composite films with different Ti contents by utilizing multi-target confocal unbalanced magnetron sputtering to obtain the sputtering power of a Ti-Cr film material and a Ti target; fixing the power of Ti and Cr targets on the basis of the Ti-Cr film, changing the power of the Zr target, preparing a Ti-Cr/Ti-Cr-Zr multilayer film, and obtaining the sputtering power of the Ti-Cr/Ti-Zr multilayer film material and the Zr target in the second layer of Ti-Cr-Zr film; closing the Cr target baffle on the basis of the Ti-Cr/Ti-Cr-Zr multilayer film to prepare a Ti-Cr/Ti-Cr-Zr/Ti-Zr multilayer film; finally, closing the Cr target baffle, keeping the power of the Ti and Zr unchanged, and preparing a Ti-Cr/Ti-Cr-Zr/Ti-Zr/TiN + ZrN multilayer film on the Ti-Cr/Ti-Cr-Zr/Ti-Zr multilayer film in an argon-nitrogen ratio of 10: 3;
2) ultrasonically cleaning a substrate Cu for 5-10 min by water, acetone and absolute ethyl alcohol in sequence, drying and fixing the substrate Cu on a rotatable substrate table of a sputtering chamber, closing a sample baffle, and respectively fixing a Ti target, a Cr target and a Zr target with the purity of 99.9% on three radio frequency guns of a magnetron sputtering instrument;
3) the pressure in the sputtering chamber was evacuated to 6.0X 10-4Introducing argon with the purity of 99.999 percent below Pa, controlling the flow to be 10sccm, and keeping the gas pressure of the sputtering chamber at 0.25 Pa;
4) closing the sample baffle, adjusting the power of the Ti target, the Cr target and the Zr target to be 50W, and sputtering for 5-10 min to clean various impurities on the surface of the target material;
5) introducing argon to keep the air pressure of the sputtering chamber at 0.3Pa, adjusting the power of the Cr target to 60W, closing the Zr target baffle, opening the sample baffle, keeping the rotating speed of the sample at 6r/min, adjusting the power of the Ti target to the sputtering power obtained in the step (1), and depositing the Ti-Cr composite film for 2 hours; after the deposition is finished, fixing the power of Ti and Cr targets, opening a Zr target baffle, adjusting the power of the Zr target to be the sputtering power obtained in the step (1), and continuously depositing the Ti-Cr-Zr film on the Ti-Cr film for 2 hours; after the deposition is finished, closing the Cr target baffle, keeping the power of the Ti and Zr targets unchanged, and continuously depositing a Ti-Zr film on the Ti-Cr/Ti-Cr-Zr multilayer film; finally, closing the Cr target baffle, introducing nitrogen with the purity of 99.999 percent, controlling the flow to be 3sccm, keeping the pressure of a sputtering chamber at 0.3Pa, controlling the flow ratio of argon to nitrogen to be 10:3, opening the sample baffle, and continuously depositing the TiN + ZrN film on the Ti-Cr/Ti-Cr-Zr/Ti-Zr/multilayer film for 2 hours; obtaining the Ti-Cr/Ti-Cr-Zr/Ti-Zr/TiN + ZrN multilayer film material coating.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115449769A (en) * 2022-10-28 2022-12-09 西安稀有金属材料研究院有限公司 High-temperature-resistant low-diffusion alloy film for copper substrate and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USB433892I5 (en) * 1971-03-11 1976-04-06 Matsushita Electric Ind Co Ltd
JP2004273730A (en) * 2003-03-07 2004-09-30 Nippon Telegr & Teleph Corp <Ntt> Thin-film formation method
CN103805996A (en) * 2014-01-16 2014-05-21 中国科学院金属研究所 Composite treating method for nitriding surface of metal material after coating

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USB433892I5 (en) * 1971-03-11 1976-04-06 Matsushita Electric Ind Co Ltd
JP2004273730A (en) * 2003-03-07 2004-09-30 Nippon Telegr & Teleph Corp <Ntt> Thin-film formation method
CN103805996A (en) * 2014-01-16 2014-05-21 中国科学院金属研究所 Composite treating method for nitriding surface of metal material after coating

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
赵时璐;张震;张钧;王建明;张正贵;: "多弧离子镀TiAlZrCr/(Ti,Al,Zr,Cr)N梯度膜的微观结构与耐磨损性能", 金属学报, no. 06, pages 747 - 754 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115449769A (en) * 2022-10-28 2022-12-09 西安稀有金属材料研究院有限公司 High-temperature-resistant low-diffusion alloy film for copper substrate and preparation method thereof
CN115449769B (en) * 2022-10-28 2023-11-21 西安稀有金属材料研究院有限公司 High-temperature-resistant low-diffusion alloy film for copper matrix and preparation method thereof

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