CN115595543B - MoAlB ceramic film with MAB phase structure and preparation method thereof - Google Patents
MoAlB ceramic film with MAB phase structure and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000004544 sputter deposition Methods 0.000 claims abstract description 48
- 238000000137 annealing Methods 0.000 claims abstract description 39
- 238000010438 heat treatment Methods 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000000151 deposition Methods 0.000 claims abstract description 23
- 230000008021 deposition Effects 0.000 claims abstract description 21
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 14
- 238000007733 ion plating Methods 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 239000010408 film Substances 0.000 claims description 79
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- 239000013077 target material Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000010409 thin film Substances 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 7
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- 238000004381 surface treatment Methods 0.000 abstract description 2
- 238000005137 deposition process Methods 0.000 description 9
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- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 229910000601 superalloy Inorganic materials 0.000 description 2
- 238000002076 thermal analysis method Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052796 boron Inorganic materials 0.000 description 1
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Classifications
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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
- C23C14/22—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
- C23C14/06—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
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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
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
- C23C14/548—Controlling the composition
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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
- C23C14/58—After-treatment
- C23C14/5806—Thermal treatment
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- 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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention relates to the technical field of surface treatment, in particular to MoAlB ceramic film with a MAB phase structure and a preparation method thereof, which adopts a four-target magnetron sputtering ion plating and annealing heat treatment two-step method for preparation, and comprises the following specific steps: s1, performing sputter deposition on a substrate material by adopting a MoB 2, mo and double Al target four-target system to obtain a deposition state film; s2, annealing heat treatment is carried out on the deposited film, and the crystalline MoAlB ceramic film with the 222 MAB phase structure is obtained. The invention adopts a magnetron sputtering ion plating and annealing heat treatment two-step method to obtain MoAlB ceramic film with MAB phase structure under low temperature condition; meanwhile, the controllable preparation of the film with specific components and the microstructure MoAlB can be realized, the process is stable, and the industrialized production is easy to realize.
Description
Technical Field
The invention relates to the technical field of surface treatment, in particular to MoAlB ceramic film with a MAB phase structure and a preparation method thereof.
Background
With the rapid development of the fields of aviation, aerospace, nuclear power and the like in China, the high-temperature performance of the material is more and more required. The traditional superalloy material is limited by the fact that the melting point of the superalloy material cannot meet the requirement, and ceramic materials with better heat resistance are the only choices. The transition metal carbide/nitride/boride and its composite materials are attracting attention as ultra-high temperature ceramic materials due to their high hardness, high melting point and good corrosion resistance, which are derived from the strong covalent and ionic bonding characteristics. However, intrinsic brittleness and poor oxidation resistance are major bottlenecks in service in high temperature extreme environments, and are a challenge to be overcome by the current scientific community. Therefore, it is important to develop a material having both ceramic and metal characteristics.
Inspired by the abbreviation of MAX phase material (M n+1AXn, where M is a transition group metal element, a is a group iiia or iva element, X is carbon or nitrogen, n is 1, 2, and 3), insertion of single or double layer main group atoms (typically Al atoms) in the binary boride may also form a ternary layered transition metal boride known as the "MAB phase". The MAB phase ((MB) 2 xAly(MB2) z abbreviation, where B stands for boron element, x is 1, 2 …, y is 1, 2, 3 …, z=0, 1, 2 …) material is a series of ternary layered borides, including MAB compounds and MAB solid solutions. MABphaseiscomposedofMBatomiclayer(MBene)andAatomiclayerwhicharealternatelyarrangedtoformalaminatedstructure,M-Blayerisconnectedbystrongcovalentbondandionicbond,M-Alayerisconnectedbyweakermetalbond; the layered crystal structure and the weak interlayer combination combine the excellent characteristics of metal and ceramic, such as high fracture toughness, high damage tolerance, excellent machinability, good high-temperature oxidation resistance and ablation resistance.
MoAlB as one of the MAB phases of interest, the bilayer "Al-rich" layer has a "reservoir" effect, providing enough Al to form a continuous Al 2O3 protective film during oxidation, and is expected to be a candidate for high temperature structural components and high temperature coatings. Meanwhile, the composite material has good electric conduction/thermal performance and neutron shielding performance, the material has great application potential in the fields of heating elements, electrode materials, electrical contacts, nuclear material coating layers and the like.
Up to now, the research on MoAlB materials is mainly focused on theoretical calculation, blocks and powder materials, and the patent with application number 201911300427.2 discloses a preparation method of a compact MoAlB ceramic material, a product thereof and a preparation method of high-purity MoAlB ceramic powder, wherein a plasma sintering method is adopted to prepare a compact and high-purity MoAlB block material at the temperature of 800-1200 ℃ and the pressure of 50-100 MPa, and then the compact and high-purity MoAlB block material is crushed to obtain the powder material. However, the preparation process requires excessive Al and higher temperature, and the preparation of the bulk MoAlB material is difficult to realize, so that the process energy consumption is high, and practical application is further limited.
MoAlB film materials can be prepared in a large area under the condition of meeting the performance requirements, and the process temperature is low (< 700 ℃) and the dependence on the substrate is low, so that the MoAlB film materials become one of effective ways for replacing bulk materials. Evertz et al utilize MoAlB composite targets, and adopt a magnetron sputtering method to heat a substrate to prepare a MoAlB film under a low-temperature condition, but the prepared film has poor crystallinity and low purity, and the preparation process has high requirements on equipment and is difficult to regulate and control film components and microstructures. Therefore, the preparation of the high-purity compact MoAlB film with controllable components and structure is a technical key for promoting the popularization and application of the MoAlB film.
Disclosure of Invention
Aiming at the problem that film components and microstructure are not easy to regulate and control in the prior art, the invention provides a MoAlB ceramic film with an MAB phase structure and a preparation method thereof.
The invention is realized by the following technical scheme:
A preparation method of MoAlB ceramic film with MAB phase structure adopts a two-step method of four-target magnetron sputtering ion plating and annealing heat treatment, and comprises the following specific steps:
S1, performing sputter deposition on a substrate material by adopting a MoB 2, mo and double Al target four-target system to obtain a deposition state film;
s2, annealing heat treatment is carried out on the deposited film, and the crystalline MoAlB ceramic film with the 222 MAB phase structure is obtained.
Preferably, in S1, the deposited film is prepared as follows:
S11, selecting and cleaning target materials and substrate materials;
S12, performing sputter deposition on a substrate material under the vacuum degree condition to obtain a deposited film; during sputtering deposition, the targets are combined in a manner of double Al targets being opposite, and MoB 2 and Mo targets are opposite.
Preferably, in S11, the substrate material is single-sided polished single crystal Al 2O3, and is sequentially ultrasonically cleaned in an acetone solution and an absolute ethanol solution.
Preferably, in S11, ion cleaning is adopted for target cleaning, and when the vacuum degree of the chamber is less than 7.33X10 -3 Pa, inert gas is introduced, and the negative bias of the substrate is adjusted to 300V-350V for 10 min-20 min.
Preferably, in S12, during sputter deposition, the sputtering power of the MoB 2 target is 700-750W, the sputtering power of the Mo target is 150-200W, the sputtering power of the Al target is 300-350W, the negative bias voltage of the substrate is 50-90V, the rotating speed of the workpiece frame is 3-5 rpm, the working air pressure in the chamber is about 6.67-12.50X10 -2 Pa, and when the vacuum degree in the chamber is less than 7.33X10 -3 Pa, inert gas is introduced into the chamber; the deposition time is 0.5 h-3 h, and the temperature in the chamber is 25-100 ℃.
Preferably, in S1, mo in the as-deposited film: al: the stoichiometric ratio of B is 1:1:1.
Preferably, in S2, the temperature range is 500-800 ℃, the heat preservation time is 0.5-1 h, and the heating rate is less than 5 ℃/min during the annealing heat treatment.
Preferably, in S2, a protective atmosphere is introduced during the annealing heat treatment.
Preferably, in S2, the cooling mode is furnace-following cooling.
A crystalline MoAlB ceramic film with MAB phase structure is prepared by adopting a MoAlB ceramic film preparation method with MAB phase structure.
Compared with the prior art, the invention has the following beneficial effects:
According to the preparation method of MoAlB ceramic film with MAB phase structure, the MoAlB ceramic film with MAB phase structure can be obtained under low temperature condition by adopting two steps of magnetron sputtering ion plating and annealing heat treatment; meanwhile, the controllable preparation of the film with specific components and the microstructure MoAlB can be realized, the process is stable, and the industrialized production is easy to realize.
The preparation of MAB phase film by magnetron sputtering ion plating technology is an unbalanced state process, and can obtain a dense high-quality film with strong binding force and controllable thickness under the condition of lower than the synthesis temperature of bulk materials. In addition, the heat treatment process can realize the precise regulation and control of the phase composition and microstructure of the film.
Drawings
FIG. 1 is a schematic diagram of a 4-target magnetron sputtering ion plating apparatus used in a preparation method of MoAlB ceramic thin films with MAB phase structures according to the present invention;
FIG. 2 is a TG-DSC spectrum of a sample of as-deposited Mo-Al-B film of comparative example 1 of the present invention;
FIG. 3 is a grazing incidence X-ray diffraction (GIXRD) pattern (PDF # 72-1277) for the films of the comparative and example embodiments of the invention;
FIG. 4 is a surface and cross-sectional morphology of the as-deposited Mo-Al-B film of comparative example 1 of this invention;
FIG. 5 is a surface and cross-sectional morphology of the crystalline MoAlB film of example 2 of the present invention;
FIG. 6 is a surface and cross-sectional morphology of the crystalline MoAlB film of example 3 of the present invention.
Detailed Description
The invention will now be described in further detail with reference to specific examples, which are intended to illustrate, but not to limit, the invention.
The invention discloses a preparation method of MoAlB ceramic film with MAB phase structure, which adopts a four-target magnetron sputtering ion plating and annealing heat treatment two-step method to prepare, and comprises the following specific steps:
S1, performing sputter deposition on a substrate material by using MoB 2, mo and a double Al target four-target system (using equipment shown in FIG. 1), and obtaining Mo: al: the stoichiometric ratio of B is 1:1:1, the specific preparation process is as follows:
S11, selecting and cleaning target materials and substrate materials;
single-sided polished monocrystalline Al 2O3 (0001 crystal orientation) is selected as a substrate material, the size of the substrate material is 10mm multiplied by 10mm, the thickness of the substrate material is 430 mu m plus or minus 20 mu m, and the substrate material is sequentially ultrasonically cleaned in an acetone solution and an absolute ethanol solution for 10-20 min.
The method comprises the steps of adopting ion cleaning when a target material is cleaned, placing a glass slide on a double-shaft workpiece frame in a cavity before an experiment, connecting a power supply to perform pre-sputtering, and introducing inert gas Ar (purity is 99.99%) when the vacuum degree of the cavity is less than 7.33 multiplied by 10 -3 Pa, wherein the flow rate of the inert gas is 15-20 Sccm, adjusting the negative bias voltage of a matrix to 300-350V for 10-20 min, so as to clean oxide and impurities on the surface of the target material.
S12, performing sputter deposition on a substrate material under the vacuum degree condition to obtain a deposited film; during sputtering deposition, the target material combination mode is double Al target opposition, moB 2 and Mo targets opposition, and the specific operation steps are as follows: during sputtering deposition, loading a pre-ultrasonically cleaned monocrystalline Al 2O3 substrate into a chamber, and when the vacuum degree of the chamber is less than 7.33X10 -3 Pa, introducing inert gas Ar, adjusting the sputtering power value of a target material, and depositing the monocrystalline Al 2O3 substrate to obtain Mo with the thickness of about 0.75-4.5 μm: al: the stoichiometric ratio of B satisfies 1:1:1, namely a Mo-Al-B amorphous film.
The target material combination mode is double Al target opposition, moB 2 is opposite to Mo target, moB 2 target sputtering power is 700W-750W, mo target sputtering power is 150W-200W, al target sputtering power is 300W-350W, base body negative bias is 50V-90V, the rotating speed of a workpiece frame is 3 rpm-5 rpm, working air pressure in a cavity is about 6.67-12.50X10 -2 Pa, deposition time is 0.5 h-3 h, and temperature in the cavity is 25-100 ℃.
S2, annealing heat treatment is carried out on the deposited film at 500-800 ℃, protective atmosphere is introduced in the annealing heat treatment process, the heat preservation time is 0.5-1 h, the heating rate is less than 5 ℃/min, and the cooling mode is cooling along with the furnace, so that the crystalline MoAlB ceramic film with the 222-type MAB phase structure is obtained.
Comparative example 1
The method is characterized in that a magnetron sputtering ion plating technology is adopted to prepare a Mo-Al-B amorphous film, a 4-target system is used for sputtering deposition in the process, moB 2, mo and Al targets are used as sputtering targets, and the targets are combined in a mode of double Al targets being opposite, and MoB 2 and Mo targets are opposite.
S11, ion cleaning, wherein the specific process parameters are as follows: vacuum pumping the chamber to < 7.33X10 -3 Pa by using a mechanical pump and a molecular pump, then introducing inert gas Ar (purity is 99.99%), adjusting the negative bias of a matrix to 350V, enabling the sputtering power of a MoB 2 target to 750W, enabling the sputtering power of a Mo target to be 200W, enabling the sputtering power of an Al target to be 350W, enabling the rotating speed of a workpiece frame to be 5rpm, enabling the working air pressure in the chamber to be about 1.1112X10 -1 Pa, enabling the temperature in the chamber to be 25-55 ℃ in the cleaning process, and enabling the working time to be 20min, wherein the purpose is to remove oxides and impurities on the surface of the target;
the substrate material is single-sided polished monocrystalline Al 2O3 (0001 crystal orientation) (size 10mm×10mm, thickness 430+ -20 μm), and is respectively placed in acetone and absolute ethanol for ultrasonic cleaning for 15min before deposition.
S12, loading the ultrasonically cleaned monocrystalline Al 2O3 substrate into a chamber, introducing inert gas Ar when the vacuum degree of the chamber is less than 7.33 multiplied by 10 -3 Pa, adjusting the sputtering power value of the target, and depositing a Mo-Al-B amorphous film on the surface of the monocrystalline Al 2O3 substrate; the specific parameters are as follows: the MoB 2 target sputtering power is 428W, the Mo target sputtering power is 175W, the Al target sputtering power is 312W, the Ar flow is 18Sccm, the base body negative bias is 65V, the rotating speed of a workpiece frame is 5rpm, the working air pressure in a chamber is about 1.12 multiplied by 10 -1 Pa, the deposition time is 40min, the temperature in the chamber is 25-100 ℃ in the film deposition process, and the thickness of the obtained film is about 1 mu m.
And after the S12 process is finished, taking out the sample for phase structure and section morphology characterization when the temperature in the chamber is reduced to below 50 ℃. The results of thermal analysis (TG-DSC) are shown in FIG. 2, and two crystallization exothermic peaks at 594.97 ℃ and 661.04 ℃ can be observed in the spectrum. As shown in figure 3, the XRD pattern of the deposited film shows a broad steamed bread peak, which indicates that the prepared Mo-Al-B film has a typical amorphous structure, the components are adjusted by utilizing multiple targets, and the purity of the prepared film phase is higher. With reference to the cross-sectional morphology in the upper right hand corner of fig. 4, it can be observed that the film surface is flat and dense, and bonds well to the substrate.
Comparative example 2
A4-target magnetron sputtering ion plating technology is adopted to prepare the Mo-Al-B amorphous film, single crystal Al 2O3 is selected as a substrate material in S12, and the amorphous film is respectively placed in acetone and absolute ethyl alcohol for ultrasonic cleaning for 15min before deposition. In the sputtering deposition process, the sputtering power of the MoB 2 target is 428W, the sputtering power of the Mo target is 175W, the sputtering power of the Al target is 312W, the Ar flow is 18Sccm, the negative bias of the matrix is 65V, the rotating speed of the workpiece frame is 5rpm, the working air pressure in the chamber is about 1.12 multiplied by 10 -1 Pa, the deposition time is 40min, and the temperature in the chamber is 25-100 ℃ in the film deposition process.
And S2, carrying out 500 ℃ annealing heat treatment on the deposited film by adopting a high-temperature tube furnace. Before annealing, inert Ar gas is introduced in advance, so that oxygen in a pipeline is removed, and the introduction time is 10min. Specific parameters of annealing heat treatment are as follows: the heating rate is less than 5 ℃/min, the annealing temperature is 500 ℃, the heat preservation time is 1h, and the cooling mode is furnace cooling. Meanwhile, protective atmosphere Ar is continuously introduced in the annealing heat treatment process to prevent the film from oxidizing, and compared with vacuum annealing heat treatment, the annealing heat treatment is carried out in inert atmosphere, so that the evaporation of Al element in the film can be effectively prevented. The phase structure is shown in figure 3, and after annealing heat treatment at 500 ℃, the film is still in an amorphous structure.
Example 1
A4-target magnetron sputtering ion plating technology is adopted to prepare the Mo-Al-B amorphous film, single crystal Al 2O3 is selected as a substrate material in S12, and the amorphous film is respectively placed in acetone and absolute ethyl alcohol for ultrasonic cleaning for 15min before deposition. In the sputtering deposition process, the sputtering power of the MoB 2 target is 428W, the sputtering power of the Mo target is 175W, the sputtering power of the Al target is 312W, the Ar flow is 18Sccm, the negative bias of the matrix is 65V, the rotating speed of the workpiece frame is 5rpm, the working air pressure in the chamber is about 1.12 multiplied by 10 -1 Pa, the deposition time is 40min, and the temperature in the chamber is 25-100 ℃ in the film deposition process.
And S2, carrying out 600 ℃ annealing heat treatment on the deposited film by adopting a high-temperature tube furnace. Before annealing, inert Ar gas is introduced in advance for 10min. Specific parameters of annealing heat treatment are as follows: the heating rate is less than 5 ℃/min, the annealing temperature is 600 ℃, the heat preservation time is 1h, and the cooling mode is furnace cooling. The phase structure is shown in figure 3, after annealing heat treatment at 600 ℃, crystallization transformation is carried out on the film, 222-type MAB phase characteristic diffraction peaks appear in spectral lines, the deposited Mo-Al-B amorphous film is transformed into a crystalline MoAlB ceramic film with the MAB phase structure, and the result is consistent with the crystallization exothermic peak appearing at 594.97 ℃ in the thermal analysis map.
Example 2
A4-target magnetron sputtering ion plating technology is adopted to prepare the Mo-Al-B amorphous film, single crystal Al 2O3 is selected as a substrate material in S12, and the amorphous film is respectively placed in acetone and absolute ethyl alcohol for ultrasonic cleaning for 15min before deposition. In the sputtering deposition process, the sputtering power of the MoB 2 target is 428W, the sputtering power of the Mo target is 175W, the sputtering power of the Al target is 312W, the Ar flow is 18Sccm, the negative bias of the matrix is 65V, the rotating speed of the workpiece frame is 5rpm, the working air pressure in the chamber is about 1.12 multiplied by 10 -1 Pa, the deposition time is 40min, and the temperature in the chamber is 25-100 ℃ in the film deposition process.
And S2, carrying out 700 ℃ annealing heat treatment on the deposited film by adopting a high-temperature tube furnace. Before annealing, inert Ar gas is introduced in advance for 10min. Specific parameters of annealing heat treatment are as follows: the heating rate is less than 5 ℃/min, the annealing temperature is 700 ℃, the heat preservation time is 1h, and the cooling mode is furnace cooling. Referring to fig. 3, moAlB thin films after 700 c annealing have higher crystallinity. Referring to fig. 5, the film is uniform, flat and dense.
Example 3
A4-target magnetron sputtering ion plating technology is adopted to prepare the Mo-Al-B amorphous film, single crystal Al 2O3 is selected as a substrate material in S12, and the amorphous film is respectively placed in acetone and absolute ethyl alcohol for ultrasonic cleaning for 15min before deposition. In the sputtering deposition process, the sputtering power of the MoB 2 target is 428W, the sputtering power of the Mo target is 175W, the sputtering power of the Al target is 312W, the Ar flow is 18Sccm, the negative bias of the matrix is 65V, the rotating speed of the workpiece frame is 5rpm, the working air pressure in the chamber is about 1.12 multiplied by 10 -1 Pa, the deposition time is 40min, and the temperature in the chamber is 25-100 ℃ in the film deposition process.
And S2, carrying out 800 ℃ annealing heat treatment on the deposited film by adopting a high-temperature tube furnace. Before annealing, inert Ar gas is introduced in advance for 10min. Specific parameters of annealing heat treatment are as follows: the heating rate is less than 5 ℃/min, the annealing temperature is 800 ℃, the heat preservation time is 1h, and the cooling mode is cooling along with the furnace. Meanwhile, protective atmosphere Ar is continuously introduced in the annealing heat treatment process. The phase structure is shown in figure 3, and after annealing heat treatment at 800 ℃, the film is in a crystalline structure and has higher crystallinity.
The invention also discloses a crystalline MoAlB ceramic film with the MAB phase structure, which is prepared by adopting the preparation method of the MoAlB ceramic film with the MAB phase structure.
The foregoing description of the preferred embodiment of the present invention is not intended to limit the technical solution of the present invention in any way, and it should be understood that the technical solution can be modified and replaced in several ways without departing from the spirit and principle of the present invention, and these modifications and substitutions are also included in the protection scope of the claims.
Claims (7)
1. A preparation method of MoAlB ceramic film with MAB phase structure is characterized in that the preparation is carried out by adopting a two-step method of four-target magnetron sputtering ion plating and annealing heat treatment, and the specific steps are as follows:
S1, performing sputter deposition on a substrate material by adopting a MoB 2, mo and double Al target four-target system to obtain a deposition state film;
The preparation method of the deposited film comprises the following steps:
S11, selecting and cleaning target materials and substrate materials;
S12, performing sputter deposition on a substrate material under the vacuum degree condition to obtain a deposited film; during sputtering deposition, the target material combination mode is that double Al targets are opposite, and MoB 2 and Mo targets are opposite;
During sputter deposition, the sputtering power of a MoB 2 target is 700W-750W, the sputtering power of a Mo target is 150W-200W, the sputtering power of an Al target is 300W-350W, the negative bias voltage of a substrate is 50V-90V, the rotating speed of a workpiece frame is 3 rpm-5 rpm, the working air pressure in a chamber is 6.67-12.50X10 -2 Pa, and inert gas is introduced into the chamber when the vacuum degree in the chamber is less than 7.33X10 -3 Pa; the deposition time is 0.5 h-3 h, and the temperature in the chamber is 25-100 ℃;
S2, annealing heat treatment is carried out on the deposited film, and a crystalline MoAlB ceramic film with a 222-type MAB phase structure is obtained; wherein, during annealing heat treatment, the temperature range is 600 ℃ to 800 ℃, the heat preservation time is 0.5h to 1 h, and the heating rate is less than 5 ℃/min.
2. The method for preparing a MoAlB ceramic thin film with a MAB phase structure according to claim 1, wherein in S11, the substrate material is single-sided polished single crystal Al 2O3, and sequentially ultrasonically cleaned in acetone solution and absolute ethanol solution.
3. The method for preparing a MoAlB ceramic thin film with a MAB phase structure according to claim 1, wherein in S11, ion cleaning is adopted for target cleaning, and when the vacuum degree of a chamber is less than 7.33×10 -3 Pa, inert gas is introduced, and the negative bias of a substrate is adjusted to 300V-350V for 10 min-20 min.
4. The method for preparing a MoAlB ceramic thin film having a MAB phase structure according to claim 1, wherein in S1, mo in the as-deposited thin film: al: the stoichiometric ratio of B is 1:1:1.
5. The method for preparing a MoAlB ceramic thin film having a MAB phase structure according to claim 1, wherein in S2, a protective atmosphere is introduced during the annealing heat treatment.
6. The method for preparing a MoAlB ceramic thin film having a MAB phase structure according to claim 1, wherein in S2, the cooling mode is furnace-cooling.
7. A crystalline MoAlB ceramic film having a MAB phase structure prepared by the process for preparing MoAlB ceramic films having a MAB phase structure according to any one of claims 1-6.
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