CN110983255A - A food containing L12Preparation method of Ni-based multilayer film of ordered phase - Google Patents

A food containing L12Preparation method of Ni-based multilayer film of ordered phase Download PDF

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CN110983255A
CN110983255A CN201911317464.4A CN201911317464A CN110983255A CN 110983255 A CN110983255 A CN 110983255A CN 201911317464 A CN201911317464 A CN 201911317464A CN 110983255 A CN110983255 A CN 110983255A
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sputtering
multilayer film
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film
layer
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CN110983255B (en
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张超
张保森
毛向阳
马晨
刘释轩
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Nanjing Institute of 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
    • 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
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates 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
    • 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
    • C23C14/14—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
    • 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
    • C23C14/3435—Applying energy to the substrate during sputtering
    • C23C14/345—Applying energy to the substrate during sputtering using substrate bias
    • 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

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Abstract

The invention discloses a composition containing L12A method for preparing an ordered phase Ni-based multilayer film comprising the steps of: step (1): selecting SiO with thickness of 0.5mm and surface attached with 500nm2The monocrystalline silicon wafer is used as a substrate, and after cleaning and blow-drying, a film is prepared. Step (2): applying bias voltage of-60 to-100V on the substrate by adopting a direct current magnetron sputtering method, pre-sputtering for 20 to 30min, and cleaning the substrate. The invention provides a compound containing L12The preparation method of the Ni-based multilayer film with the ordered phase solves the problem that the Ni-based metal film has insufficient strength at the temperature of 600 ℃ or after annealing treatment at the temperature, has simple operation, easily controlled conditions and good repeatability, and can be used for practical applicationThe application also provides a guiding function for researching the improvement of the high-temperature mechanical property of other metal multilayer films.

Description

A food containing L12Preparation method of Ni-based multilayer film of ordered phase
Technical Field
The invention relates to a preparation method of a Ni-based multi-layer film, belonging to the technical field of materials
Background
With the continued forward development of the MEMS industry, MEMS device structures and functions become more and more complex. Currently, MEMS devices are mostly made of silicon-based materials and are increasingly used in various devices such as movable components, pressure sensors, accelerometers, gyroscopes, etc., and consumer electronics. So far, in the conventional MEMS fabrication process based on IC technology, it is common to adopt a method of reducing the number of defects in the Si-based material to avoid damage to the Si-based material due to its intrinsic brittleness, and to fabricate two-dimensional sensors of the type such as accelerometers and gyroscopes by depositing a polycrystalline silicon thin film. However, polysilicon is often limited to a few tens of microns in thickness due to the large internal stress of the film after its deposition. The next generation of MEMS sensors and actuators are required to be able to operate at temperatures above 150 ℃, with 10 times higher sensitivity, minimal potential drift, and good thermal stability. In contrast, metallic materials have higher strength and toughness and are relatively easy to manufacture. On a microscopic scale, metal alloys are easy to manufacture and shape, and the properties of the material are controllable. Therefore, under the conditions of extreme environment and high temperature, the metal material can be developed to realize the application in the MEMS. Among them, the Ni-based thin film material has been widely used for structural members such as micro springs, micro gears, and micro cantilevers because of its excellent toughness and high-temperature oxidation resistance, and its relative ease of fabrication and formation.
For Ni-based films, the hardness of the pure Ni film is remarkably reduced due to rapid growth of internal crystal grains at the temperature of more than 300 ℃, and the pure Ni film presents a high-temperature softening phenomenon, thereby severely restricting the application of the pure Ni film in a high-temperature environment. Among them, Ni having a superlattice as the most common high-temperature strengthening phase in Ni-based superalloy3L1 typified by Al phase2A phase of a type ordered compound having high strength, high melting point, oxidation resistance, corrosion resistance and strength which is abnormally increased with temperature in a certain temperature rangeBut is increased. The composite material is an ideal novel structural material and is widely applied to the fields of aviation, power, machinery, electronics and the like. The composite multilayer film formed by pure Ni and other components prepared by the magnetron sputtering method has good application prospect in a high-density metal wiring structure of a very large scale integrated circuit (VSLI) and a micro film-based device of a Micro Electro Mechanical System (MEMS). Thus, Ni/Ni can be prepared by magnetron sputtering3Al multilayer film to obtain high-strength Ni-based thin film material for high temperature MEMS. However, non-equilibrium Ni/Ni prepared by magnetron sputtering3It is difficult to obtain L1 having a superlattice in Al multilayer film2Ordered compound phase, such multilayer films have difficulty in achieving the desired strength at high temperatures.
Thus, how to prepare L1 having a superlattice with high strength at high temperature2The Ni-based multilayer film of the type ordered compound phase is a problem to be solved urgently at present.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a preparation method of a Ni-based multilayer film applicable to high-temperature MEMS, the process is simple to operate, the conditions are easy to control, the repeatability is good, the prepared multilayer film has clear layer boundary and smooth and flat surface, and the prepared multilayer film contains ordered L12Ordered phase with excellent high temperature mechanical performance.
The inventor researches and discovers that for the Ni-based nano-metal multilayer film, the high-temperature strengthening mechanism of the Ni-based nano-metal multilayer film can sensitively depend on a large number of grain boundaries, interlayer interfaces and synergistic effects thereof in the multilayer film, and the specific ordering transformation of the film layer containing the L12 ordering compound (gamma' -phase) can also increase the high-temperature strength of the multilayer film, so that the high-temperature mechanical behavior of the Ni-based nano-metal multilayer film is greatly different from that of a Ni-based alloy block material, and therefore, the modulation period of the Ni-based multilayer film structure has a relatively obvious influence on the mechanical behavior at high temperature. The inventors selected pure Ni and L12Type-ordered compound phases, e.g. Ni3Al，Ni3The (Al, Ti) ordered compound phase is taken as a research object, a modulated nano Ni-based multilayer film is prepared by alternate deposition by adopting a direct current magnetron sputtering technology,by controlling technological parameters such as sputtering time, sputtering power and the like of each target, a periodic structure formed by pure Ni phases and Ni-based solid solution in a deposition state in an alternating mode is obtained, wherein the content of Al or the sum of the content of Al and Ti in the Ni-based solid solution is 20 at.% to 30 at.%, and then vacuum annealing heat treatment is carried out on the nano Ni-based multilayer film in the deposition state at a certain temperature to convert the nano Ni-based multilayer film into L12Type-ordered compound phases, e.g. Ni3Al，Ni3(Al, Ti) are equal due to the class L12The type ordered compound phase is used as an important strengthening phase in the Ni-based high-temperature alloy, the high-temperature strength of the type ordered compound phase does not decrease and inversely increases along with the increase of the temperature at about 650 ℃, so that compared with a pure Ni film, the strength of a multilayer film structure formed by the alternation of two phases is obviously improved at high temperature, and the interface between the two phases can block the movement of dislocation, so that the type ordered compound phase has higher hardness. In addition, due to pure L12The intrinsic brittleness of the ordered compound phase film is larger, and the toughness of the ordered compound phase film can be obviously improved by compounding the ordered compound phase film with a pure Ni film. The specific scheme is as follows:
a food containing L12The preparation method of the Ni-based multilayer film of the ordered phase is carried out according to the following steps:
step (1) attaching SiO with the thickness of 0.5mm and the surface of 500nm2The monocrystalline silicon wafer substrate is sequentially ultrasonically cleaned by acetone and ethanol, dried and then placed on a substrate table of ultrahigh vacuum magnetron sputtering equipment to prepare for coating;
step (2) adopts a direct current magnetron sputtering method, and the metal target material is placed on a target platform of a vacuum chamber with the vacuum degree of 1.0 multiplied by 10-5～6.0×10-5Introducing argon gas under the Torr condition, controlling the flow to be 70-90 sccm, and controlling the cavity pressure during sputtering to be 2.0 multiplied by 10-3～5.0×10-3Torr, applying a bias voltage of-60 to-100V on a substrate, wherein the power of a Ni target is 90 to 110W, and pre-sputtering for 20 to 30min to clean residual impurities on the substrate;
after the pre-sputtering in the step (3), adjusting the bias voltage to-20 to-30V, performing film plating, plating a pure Ni layer with the power of 90-110W, and then plating a Ni-20 at.% to 30 at.% Al or a Ni-20 at.% to 30 at.% Al (Ti) layer by adopting a Ni/Al or Ni/Al-Ti double-target co-sputtering mode, wherein the power of a Ni target is 100W, and the power of an Al or Al-Ti alloy target is 30-50W; the deposition rate of the Ni layer is 0.20-0.25 nm, the deposition rate of the Ni-20 at.% to 30 at.% Al or the deposition rate of the Ni-20 at.% to 30 at.% (Al, Ti) layer is 0.33-0.41 nm, and the time ratio of the deposition sputtering of the Ni target to the Al or Al-Ti alloy target is controlled to be about 8: 5 to ensure that the Ni monolayer is the same as a Ni-20 at.% to 30 at.% Al or Ni-20 at.% to 30 at.% (Al, Ti) monolayer; the time for sputtering the Ni monolayer is 175-700 s, the time for sputtering the Ni-20 at.% to 30 at.% Al or the Ni-20 at.% to 30 at.% (Al, Ti) monolayer is 100-490 s, the thickness of the obtained Ni monolayer/Ni-20 at.% to 30 at.% Al or the Ni-20 at.% to 30 at.% (Al, Ti) monolayer is 40-160 nm, the Ni-20 at.% to 30 at.% Al or the Ni-20 at.% to 30 at.% Al, Ti layers are sequentially and alternately deposited according to the sequence of firstly plating the Ni layer and then plating the Ni-20 at.% to 30 at.% Al or the Ni-20 at.% to 30 at.% to obtain a deposited multilayer film, and the total time of sputtering is 1-1.5 h;
step (4) carrying out vacuum annealing treatment on the deposited Ni/Ni-20 at.% to 30 at.% Al or Ni-20 at.% to 30 at.% (Al, Ti) multilayer film at 600 ℃, wherein the heating rate is 20-30 ℃/min, the heat preservation time is 1h, the cooling rate is 40-50 ℃/min, and the vacuum degree is 5 multiplied by 10-7～1.0×10-6Torr; after cooling to room temperature, the vacuum was turned on and the sample was taken out, and 500nm SiO was attached to the surface2The surface of the single crystal silicon wafer substrate is provided with L12Ni-based multilayer films of ordered phase.
Further, in the step (1), the thickness is 0.5mm and 500nm of SiO is attached to the surface2The monocrystalline silicon wafer substrate is cleaned by acetone and ethanol for 20-30 min.
Further, in steps (2) and (3), the Ni target purity was 99.999 wt.%.
Further, in the steps (2) and (3), the purity of the Ni target is 99.999 wt.%, the purity of the Al target is 99.999 wt.% or the mass fraction of Al in the Al-Ti alloy target is 40-60 at.%, and the mass fraction of Ti is 40-60 at.%.
Further, in the step (3), the thickness of the single-layer film Ni is 40-320 nm, and the thickness of the single-layer film Ni-20 at.% to 30 at.% Al or the thickness of the single-layer film Ni-20 at.% to 30 at.% (Al, Ti) is 40-320 nm.
Further, in the step (3), the catalyst contains L12The thickness of the Ni-based multilayer film of the ordered phase was 1300 nm.
Further, in the step (3), when the Ni-20 at.% to 30 at.% Al layer is plated, the Ni target is 100W, the Al power is 40W, so as to obtain a Ni-25 at.% Al layer, and the deposition rate is 0.37 nm/s.
Further, in the step (3), when the Ni-20 at.% to 30 at.% (Al, Ti) layer is plated, the power of the Ni target is 100W, the power of the Al-Ti alloy target is 42W, so that a Ni-25 at.% (Al, Ti) layer is obtained, and the deposition rate is 0.38 nm/s.
Further, in step (4), the Ni-25 at.% Al single or multilayer is subjected to a 600 ℃ vacuum heat treatment to obtain ordered L12Phase Ni3Al monolayer or multilayer.
Further, in step (4), the single layer or the multiple layers of Ni-25 at% (Al, Ti) are subjected to vacuum heat treatment at 600 ℃ to obtain ordered L12Phase Ni3(Al, Ti) single layer or multilayer.
Compared with the traditional preparation method of the Ni-based multilayer film, the preparation method has the following advantages that: the product of the invention contains L12The Ni-based multilayer film of the ordered phase has the highest nano-hardness of 5.1GPa after annealing heat treatment at 600 ℃, is far more than the average nano-hardness of 1.1GPa of a pure Ni film after annealing at 600 ℃, and contains L12The Ni-based multilayer film of the ordered phase still maintains higher strength at a high temperature of 600 ℃.
The present invention contains L12After the Ni-based multilayer film of the ordered phase is annealed at 600 ℃, the nano-hardness increases along with the reduction of the thickness of the single layer and reaches the maximum value when the thickness of the single layer is 40nm, which is mainly caused by the ordered L12The formation of the high-temperature strengthening phase results in an increase in hardness. Meanwhile, along with the reduction of the thickness of the single layer, the nanometer hardness of the multilayer film is increased due to the blocking effect of a large number of interlayer interfaces in the multilayer film on the grain growth and dislocation movement, the thickness of the single layer is continuously reduced to 40nm, at the moment, the dislocation is bound between the interlayer interfaces in a bending shape due to the fact that the length of a dislocation line is larger than the thickness of the single layer, the nanometer hardness is continuously increased, and the nanometer hardness is orderly arranged at L12The method has the advantages of simple operation, easily controlled conditions and good repeatability, and can be used for solving the problem of insufficient strength of the Ni-based metal film at the temperature of 600 ℃ or after annealing treatment at the temperatureIn practical application, the method also provides a guiding function for researching the improvement of the high-temperature mechanical property of other metal multilayer films.
Drawings
FIG. 1 shows the L1-containing polymer prepared in examples 1 to 42Multilayer film XRD patterns of the ordered phase;
FIG. 2 shows the composition prepared in example 1 and containing L12Ni/Ni of ordered phase with 160nm of single-layer film thickness3An SEM (scanning electron microscope) appearance diagram of the cross section of the Al multilayer film;
FIG. 3 shows the product of example 4 containing L12Single layer of ordered phase Ni/Ni with film thickness of 40nm3BF-TEM photograph of multi-layer film of (Al, Ti);
FIG. 4 shows the product of example 4 containing L12Single layer of ordered phase Ni/Ni with film thickness of 40nm3And (Al, Ti) multilayer film main element line scanning pattern.
Detailed Description
The present invention will be further described with reference to the accompanying drawings.
Example 1:
as shown in fig. 1-4, a composition containing L12A method for preparing an ordered phase Ni-based multilayer film comprising the steps of:
step (1) attaching SiO with the thickness of 0.5mm and the surface of 500nm2The monocrystalline silicon wafer substrate is sequentially cleaned by acetone and ethanol in an ultrasonic mode, dried, placed on a substrate table of ultrahigh vacuum magnetron sputtering equipment, and prepared for coating.
Step (2) adopts a direct current magnetron sputtering method, a metal target material is placed on a target platform of a vacuum chamber, and the background vacuum degree is 1.0 multiplied by 10-5Under the condition of Torr, argon gas is introduced, the flow is controlled to be 75sccm, and the cavity pressure during sputtering is 2 multiplied by 10- 3And Torr, applying a bias of-60V on the substrate, wherein the power of the Ni target is 100W, and pre-sputtering for 20-30 min to clean the impurities remained on the substrate.
After the pre-sputtering in the step (3), adjusting the bias voltage to-20V, performing film coating, firstly plating a pure Ni layer with the power of 100W, and then plating a Ni-25 at.% Al layer by adopting a Ni and Al double-target co-sputtering mode, wherein the Ni target power is 100W, and the Al alloy target power is 40W. The deposition rate of the Ni layer is 0.23nm, the deposition rate of the Ni-25 at.% Al layer is 0.37nm, the time for sputtering the Ni monolayer is 695s, the time for sputtering the Ni-25 at.% Al monolayer is 432s, the thickness of the obtained Ni monolayer film/Ni-25 at.% Al monolayer film is 160nm, the Ni layer is plated firstly and then the Ni-25 at.% Al layer is plated in sequence and alternately deposited, and the total sputtering time is 1h, so that the deposited multilayer film is obtained.
Step (4) vacuum annealing treatment is carried out on the Ni/Ni-25 at.% Al multilayer film in a deposition state at 600 ℃, the heating rate is 20-30 ℃/min, the heat preservation time is 1h, the cooling rate is 40 ℃/min, and the vacuum degree is 1.0 x 10-6And (5) Torr. After cooling to room temperature, the vacuum was turned on and the sample was taken out, and 500nm SiO was attached to the surface2The surface of the single crystal silicon wafer substrate is provided with L12Ni/Ni of ordered phase with 160nm of single-layer film thickness3An Al multilayer film.
Example 2:
a food containing L12A method for preparing an ordered phase Ni-based multilayer film comprising the steps of:
step (1) attaching SiO with the thickness of 0.5mm and the surface of 500nm2The monocrystalline silicon wafer substrate is sequentially cleaned by acetone and ethanol in an ultrasonic mode, dried, placed on a substrate table of ultrahigh vacuum magnetron sputtering equipment, and prepared for coating.
Step (2) adopts a direct current magnetron sputtering method, a metal target material is placed on a target platform of a vacuum chamber, and the background vacuum degree is 1.0 multiplied by 10-5Under the condition of Torr, argon gas is introduced, the flow is controlled to be 75sccm, and the cavity pressure during sputtering is 2 multiplied by 10- 3And Torr, applying a bias of-60V on the substrate, wherein the power of the Ni target is 100W, and pre-sputtering for 20-30 min to clean the impurities remained on the substrate.
After the pre-sputtering in the step (3), adjusting the bias voltage to-20V, performing film coating, firstly plating a pure Ni layer with the power of 100W, and then plating a Ni-25 at.% Al layer by adopting a Ni and Al double-target co-sputtering mode, wherein the Ni target power is 100W, and the Al alloy target power is 40W. The deposition rate of the Ni layer is 0.23nm, the deposition rate of the Ni-25 at.% Al layer is 0.37nm, the thickness of the obtained Ni single-layer film/the Ni-25 at.% Al single-layer film is 40nm by controlling the time for sputtering the Ni single layer to be 174s and the time for sputtering the Ni-25 at.% Al single layer to be 110s, the Ni single-layer film/the Ni-25 at.% Al single-layer film are alternately deposited in sequence according to the sequence of firstly plating the Ni layer and then plating the Ni-25 at.% Al layer, and the total sputtering time is 1h, so that the deposited multilayer film is obtained.
Step (4) vacuum annealing treatment is carried out on the Ni/Ni-25 at.% Al multilayer film in a deposition state at 600 ℃, the heating rate is 20-30 ℃/min, the heat preservation time is 1h, the cooling rate is 40 ℃/min, and the vacuum degree is 1.0 x 10-6And (5) Torr. After cooling to room temperature, the vacuum was turned on and the sample was taken out, and 500nm SiO was attached to the surface2The surface of the single crystal silicon wafer substrate is provided with L12Single layer of ordered phase Ni/Ni with film thickness of 40nm3An Al multilayer film.
Example 3:
a food containing L12A method for preparing an ordered phase Ni-based multilayer film comprising the steps of:
step (1) attaching SiO with the thickness of 0.5mm and the surface of 500nm2The monocrystalline silicon wafer substrate is sequentially cleaned by acetone and ethanol in an ultrasonic mode, dried, placed on a substrate table of ultrahigh vacuum magnetron sputtering equipment, and prepared for coating.
Step (2) adopts a direct current magnetron sputtering method, a metal target material is placed on a target platform of a vacuum chamber, and the background vacuum degree is 1.0 multiplied by 10-5Under the condition of Torr, argon gas is introduced, the flow is controlled to be 75sccm, and the cavity pressure during sputtering is 2 multiplied by 10- 3And Torr, applying a bias of-60V on the substrate, wherein the power of the Ni target is 100W, and pre-sputtering for 20-30 min to clean the impurities remained on the substrate.
After the pre-sputtering in the step (3), adjusting the bias voltage to-20V, performing film coating, firstly plating a pure Ni layer with the power of 100W, and then plating a Ni-25 at.% (Al, Ti) layer by adopting a co-sputtering mode of a pure Ni target and an Al-Ti alloy target, wherein the power of the Ni target is 100W, and the power of the Al alloy target is 40W. The deposition rate of the Ni layer is 0.23nm, the deposition rate of the Ni-25 at.% (Al, Ti) layer is 0.40nm, the time for sputtering the Ni monolayer is 695s, and the time for sputtering the Ni-25 at.% (Al, Ti) monolayer is 400s, the thickness of the obtained Ni film/Ni-25 at.% (Al, Ti) monolayer film is 160nm, the Ni layer is plated firstly and then the Ni-25 at.% (Al, Ti) layer is plated in sequence and alternately deposited, and the total sputtering time is 1h, so that the deposited multilayer film is obtained.
Step (4) of as-deposited Ni/Ni-25 at%Carrying out vacuum annealing treatment on the (Al, Ti) multilayer film at 600 ℃, wherein the heating rate is 20-30 ℃/min, the heat preservation time is 1h, the cooling rate is 40 ℃/min, and the vacuum degree is 1.0 multiplied by 10-6And (5) Torr. After cooling to room temperature, the vacuum was turned on and the sample was taken out, and 500nm SiO was attached to the surface2The surface of the single crystal silicon wafer substrate is provided with L12Ni/Ni of ordered phase with 160nm of single-layer film thickness3(Al, Ti) multilayer film.
Example 4:
a food containing L12A method for preparing an ordered phase Ni-based multilayer film comprising the steps of:
step (1) attaching SiO with the thickness of 0.5mm and the surface of 500nm2The monocrystalline silicon wafer substrate is sequentially cleaned by acetone and ethanol in an ultrasonic mode, dried, placed on a substrate table of ultrahigh vacuum magnetron sputtering equipment, and prepared for coating.
Step (2) adopts a direct current magnetron sputtering method, a metal target material is placed on a target platform of a vacuum chamber, and the background vacuum degree is 1.0 multiplied by 10-5Under the condition of Torr, argon gas is introduced, the flow is controlled to be 75sccm, and the cavity pressure during sputtering is 2 multiplied by 10- 3And Torr, applying a bias of-60V on the substrate, wherein the power of the Ni target is 100W, and pre-sputtering for 20-30 min to clean the impurities remained on the substrate.
After the pre-sputtering in the step (3), adjusting the bias voltage to-20V, performing film coating, firstly plating a pure Ni layer with the power of 100W, and then plating a Ni-25 at.% (Al, Ti) layer by adopting a co-sputtering mode of a pure Ni target and an Al-Ti alloy target, wherein the power of the Ni target is 100W, and the power of the Al alloy target is 40W. The deposition rate of the Ni layer is 0.23nm, the deposition rate of the Ni-25 at.% (Al, Ti) layer is 0.40nm, the thickness of the obtained Ni film/Ni-25 at.% (Al, Ti) single layer film is 40nm by controlling the time for sputtering the Ni single layer to be 174s and the time for sputtering the Ni-25 at.% (Al, Ti) single layer to be 100s, the Ni film/the Ni-25 at.% (Al, Ti) single layer film is sequentially and alternately deposited according to the sequence of firstly plating the Ni layer and then plating the Ni-25 at.% (Al, Ti) layer, and the total sputtering time is 1h, so that the deposited multilayer film is obtained.
Step (4) vacuum annealing the deposited Ni/Ni-25 at.% (Al, Ti) multilayer film at 600 ℃, wherein the heating rate is 20-30 ℃/min, the heat preservation time is 1h, the cooling rate is 40 ℃/min, and the vacuum degree is 1.0 multiplied by 10-6And (5) Torr. After cooling to room temperature, the vacuum was turned on and the sample was taken out, and 500nm SiO was attached to the surface2The surface of the single crystal silicon wafer substrate is provided with L12Single layer of ordered phase Ni/Ni with film thickness of 40nm3(Al, Ti) multilayer film.
The four examples contain L12The nano-hardness of the Ni-based film of the ordered phase is shown in Table 1.
TABLE 1L 12Ordered phase Ni-based film nano-hardness
Example 1 Example 2 Example 3 Example 4
Nano hardness 4.1GPa 4.9GPa 4.4GPa 5.1GPa
As can be seen from the above table, example 4 obtained Ni/Ni with a 40nm single-layer film thickness3The hardness of the (Al, Ti) multilayer film is the best, and the hardness is greatly improved compared with the hardness of a pure Ni film after annealing at 600 ℃ of 1.02 GPa.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.

Claims (4)

1. A food containing L12A method for preparing an ordered-phase Ni-based multilayer film, characterized in that: the method comprises the following steps:
step (1) attaching SiO with the thickness of 0.5mm and the surface of 500nm2The monocrystalline silicon wafer substrate is sequentially ultrasonically cleaned by acetone and ethanol, dried and then placed on a substrate table of ultrahigh vacuum magnetron sputtering equipment to prepare for coating;
step (2) adopts a direct current magnetron sputtering method, and the metal target material is placed on a target platform of a vacuum chamber with the vacuum degree of 1.0 multiplied by 10-5～6.0×10-5Introducing argon gas under the Torr condition, controlling the flow to be 70-90 sccm, and controlling the cavity pressure during sputtering to be 2.0 multiplied by 10-3～5.0×10-3Torr, applying a bias voltage of-60 to-100V on a substrate, wherein the power of a Ni target is 90 to 110W, and pre-sputtering for 20 to 30min to clean residual impurities on the substrate;
after the pre-sputtering in the step (3), adjusting the bias voltage to-20 to-30V, performing film plating, plating a pure Ni layer with the power of 90-110W, and then plating a Ni-20 at.% to 30 at.% Al or a Ni-20 at.% to 30 at.% Al (Ti) layer by adopting a Ni/Al or Ni/Al-Ti double-target co-sputtering mode, wherein the power of a Ni target is 100W, and the power of an Al or Al-Ti alloy target is 30-50W; the deposition rate of the Ni layer is 0.20-0.25 nm, the deposition rate of the Ni-20 at.% to 30 at.% Al or the deposition rate of the Ni-20 at.% to 30 at.% (Al, Ti) layer is 0.33-0.41 nm, and the time ratio of the deposition sputtering of the Ni target to the Al or Al-Ti alloy target is controlled to be about 8: 5 to ensure that the Ni monolayer is the same as a Ni-20 at.% to 30 at.% Al or Ni-20 at.% to 30 at.% (Al, Ti) monolayer; the time for sputtering the Ni monolayer is 175-700 s, the time for sputtering the Ni-20 at.% to 30 at.% Al or the Ni-20 at.% to 30 at.% (Al, Ti) monolayer is 100-490 s, the thickness of the obtained Ni monolayer/Ni-20 at.% to 30 at.% Al or the Ni-20 at.% to 30 at.% (Al, Ti) monolayer is 40-160 nm, the Ni-20 at.% to 30 at.% Al or the Ni-20 at.% to 30 at.% Al, Ti layers are sequentially and alternately deposited according to the sequence of firstly plating the Ni layer and then plating the Ni-20 at.% to 30 at.% Al or the Ni-20 at.% to 30 at.% to obtain a deposited multilayer film, and the total time of sputtering is 1-1.5 h;
step (4) carrying out vacuum annealing treatment on the deposited Ni/Ni-20 at.% to 30 at.% Al or Ni-20 at.% to 30 at.% (Al, Ti) multilayer film at 600 ℃, wherein the heating rate is 20-30 ℃/min, the heat preservation time is 1h, the cooling rate is 40-50 ℃/min, and the vacuum degree is 5 multiplied by 10-7～1.0×10-6Torr; after cooling to room temperature, the vacuum was turned on and the sample was taken out, and 500nm SiO was attached to the surface2The surface of the single crystal silicon wafer substrate is provided with L12Ni-based multilayer films of ordered phase.
2. The pharmaceutical composition of claim 1, comprising L12A method for preparing an ordered-phase Ni-based multilayer film, characterized in that: the plated substrate is 0.5mm thick and 500nm SiO film attached to the surface2The monocrystalline silicon wafer substrate is cleaned by acetone and ethanol for 20-30 min.
3. The pharmaceutical composition of claim 1, comprising L12A method for preparing an ordered-phase Ni-based multilayer film, characterized in that: the purity of the Ni target is 99.999 wt.%, the purity of the Al target is 99.999 wt.% or the mass fraction of Al in the Al-Ti alloy target is 40-60 at.%, and the mass fraction of Ti is 40-60 at.%.
4. The pharmaceutical composition of claim 1, comprising L12A method for preparing an ordered-phase Ni-based multilayer film, characterized in that: the temperature for vacuum annealing treatment of the Ni/Ni-20 at.% to 30 at.% Al or Ni-20 at.% to 30 at.% (Al, Ti) multilayer film in a deposition state is 600 ℃.
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CN108193088A (en) * 2017-12-29 2018-06-22 北京理工大学 A kind of precipitation strength type AlCrFeNiV system high-entropy alloys and preparation method thereof
CN108611603A (en) * 2018-05-09 2018-10-02 南京大学 A kind of preparation method of metallized multilayer film

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CN108193088A (en) * 2017-12-29 2018-06-22 北京理工大学 A kind of precipitation strength type AlCrFeNiV system high-entropy alloys and preparation method thereof
CN108611603A (en) * 2018-05-09 2018-10-02 南京大学 A kind of preparation method of metallized multilayer film

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