CN106567049A - MAX phase ceramic coating and preparation method and device thereof - Google Patents

MAX phase ceramic coating and preparation method and device thereof Download PDF

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Publication number
CN106567049A
CN106567049A CN201610882869.2A CN201610882869A CN106567049A CN 106567049 A CN106567049 A CN 106567049A CN 201610882869 A CN201610882869 A CN 201610882869A CN 106567049 A CN106567049 A CN 106567049A
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coating
max phase
target
matrix
preparation
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CN106567049B (en
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黄峰
舒瑞
黄庆
李朋
孟凡平
葛芳芳
朱萍
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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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
    • C23C14/0688—Cermets, e.g. mixtures of metal and one or more of carbides, nitrides, oxides or borides

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention discloses a MAX phase ceramic coating. The composition of the coating is V<2>Al<x>C<2-x>, wherein x equals 0.7-1.5. The coating is of a columnar crystal growing structure. Each columnar crystal is formed by arranging an Al atom layer and two V atom layers alternately, a C atom layer is located between the two V atom layers, and the coating density is 4.5-5.2 g/cm3. The invention further discloses a preparation method of the MAX phase ceramic coating. By means of a dual-target magnetron sputtering method assisted by a radio frequency and intermediate frequency combined power supply applying method, the MAX phase ceramic coating is grown on an amorphous matrix in a nonepitaxial mode at the preparation temperature of 550-650 DEG C. Under the preparation conditions, the purity of the obtained V<2>Al<x>C<2-x> coating reaches up to 99.9%, and the hardness of the coating reaches up to 13-16 GPa. The method has the advantages that one-step synthesis is realized; the cost is low; the controllability is high; low-temperature preparation of the MAX phase coating is facilitated; and the method can be applied to multiple fields.

Description

A kind of MAX phase ceramics coating and preparation method thereof and preparation facilitiess
Technical field
The invention belongs to metal-cermic coating field, and in particular to a kind of MAX phase ceramics coating and preparation method thereof and system Standby device.
Background technology
MAX is Mn+1AXnAbbreviation (n=1～3, according to value difference, MAX phases can be divided into 211,312,413 phases Deng), wherein M represents a class early stage transition metal, such as Ti, V, Cr, Zr, Nb, Mo, Sc, Hf and Ta etc.；A represents the 3rd Or the 4th major element, such as Al, Si, P, S, Ga, Ge, As, In, Sn, Ti and Pb etc.；X is C or N.
MAX phases have had some premium properties of metal and ceramics concurrently as a kind of ternary layered structural material.Such as inherit The excellent heat conductivity of metal material, electric conductivity, thermal shock resistance, damage tolerance and preferable machinability；Inherit ceramics The advantages of elasticity modulus of materials height, high temperature resistant, antioxidation and decay resistance.Many excellent performances cause the material in height Good application prospect is suffered under numerous severe rugged environments such as temperature, oxidation or corrosion.Particularly in core application aspect, MAX phases Material is used as resistance to radiation protection coating, cladding nuclear fuels material etc. and austenitic stainless steel, ferrite, martensitic stain less steel, vanadium Alloy and SiCfThe more ripe nuclear power structure material such as/SiC ceramic matrix composite material is used in combination, it will significantly promote nuclear material Improve and reform, wherein the research to neutron void swelling effect has been achieved with good result.
It is the key technology for enabling the material to apply in terms of nuclear defence that vapour deposition prepares MAX phase coating technologies.Mesh Before, Ti has successfully been prepared using physical gas phase deposition technology3SiC2、V2GeC、Nb2AlC、Zr2The MAX phase coatings such as AlC.But make Standby process still suffers from larger problem, makes a concrete analysis of as follows：
First, high temperature is needed to prepare.MAX phase materials generally have larger c-axis value, this labyrinth with big structure cell Generally require to obtain high kinetics energy under the high temperature conditions and the atom of diffusivity can be formed.With three major types MAX phase structures：211 phases312 phases413 phasesUnit cell dimension increase successively Greatly, preparation temperature is also raised successively.In M2In AlC material systems, magnetron sputtering technology of preparing is compared to block sintering technology, most Pipe can reduce about 400 DEG C of its preparation temperature, but its preparation temperature is still needed at 800～1200 DEG C or so.With preparation temperature Reduction, the content of the MAX phases in coating is also lower.
2nd, there is dependency to substrate or cushion.MAX phase coatings are required in single crystal substrates or have good knot mostly Prepared by the transition zone Epitaxial growth of crystalline substance, particularly the MAX phases of As-deposited state.The structure type of general epitaxy single-crystal substrate is Emission in Cubic or the Al such as MgO (110), TiC (111), VC (111)2O3(0001)/(1120) hexagonal phase.For example：Palmquist grinds Study carefully group (Magnetron sputtered epitaxial single-phase Ti3SiC2 thin films,Applied physics letters,2002,81(5):835) in MgO (111) substrate with TiC (111) cushion, using Ti, Tri- independent targets of Si, C obtain monocrystalline Ti at 900 DEG C3SiC2Epitaxial film.But be difficult to obtain brilliant in amorphous substrate State MAX phase coating, is typically prepared the coating for obtaining and is mostly binary, double carbide or non crystalline structure.
Above-mentioned these problems significantly limit MAX phases coating material in terms of the industrialization such as nuclear defence, extraordinary corrosion Using.Therefore, although the successful preparation of MAX phase thin film is received significant attention, but as synthesis temperature is high, there is impurities phase, And there is the deficiencies such as dependency to substrate, limit its application.
In sum, this area still lacks a kind of energy low temperature preparation (≤650 DEG C), the MAX phase coating little to matrix dependency And preparation method thereof.
The content of the invention
It is an object of the invention to provide a kind of MAX phase ceramics coating and preparation method thereof.The MAX phase ceramics coating exists It is not required to remain to obtain the MAX phases of high-purity (99.9%) crystalline state in the case of prepared by high temperature (650 DEG C of ＜), and to matrix Dependency is low, be not required to epitaxial growth.
What the purpose of the present invention was achieved through the following technical solutions：
A kind of MAX phase ceramics coating, the MAX phase ceramics coating into being grouped into V2AlxC2-x, x=0.7～1.5, its Middle x is atom ratio, and coating is crystalline state, is in the form of a column crystals growth structure, and each column crystal is by one layer of Al atomic layer and two-layer V Atomic layer is alternately arranged to be formed, and C atomic layers are located between two-layer V atomic layer, and coating density is 4.5～5.2g/cm3.Each The width of column crystal is 80～150nm, and length-width ratio is 6.5～8.
Using X-ray diffractometer (XRD) in MAX phase ceramics coatings described in 2 θ=10～90 ° scope build-in tests, exist respectively 35.55 °, 41.27 °, 63.85 °, occur in that V respectively at 78.86 °2AlxC2-x(100), (103), (110), (116) diffraction Peak.
The MAX phase ceramics coating is presented V2AlC (110) crystal face preferential growth.
The thickness of the MAX phase ceramics coating is 0.5～2 μm.
The hardness of the MAX phase ceramics coating is 13～16GPa.
Present invention also offers a kind of preparation method of MAX phase ceramics coating, is deposited using physical vapor method, preferably magnetic Control sputtering method deposition.
A kind of preparation method of above-mentioned MAX phase ceramics coating, is prepared using double target magnetic control sputtering methods, concrete steps bag Include：
(1) matrix cleaning；
(2) target is installed and power supply connects：By VnAl1-nTarget is connected with the intermediate frequency power supply of RF-assisted, VmC1-mTarget and intermediate frequency Power supply is connected, wherein n=0.4～0.6, m=0.4～0.6, and both at atom ratio, and the purity of two targets is both greater than 99.99%；The target is prepared using prior art；
(3) coating deposition：Matrix after cleaning is loaded in vacuum chamber, when Chamber vacuum degree is 1 × 10-5～5 × 10- 5During Pa, it is 0.5～0.8Pa to be passed through argon and control sputtering pressure, and the Sputtering power density for adjusting target is 3.2～7.0W/ cm2, allow VnAl1-nAnd VmC1-mTwo targets are while build-up of luminance, opens sample baffle plate afterwards, matrix is deposited, crystalline state is obtained MAX phase ceramics coatings, i.e. V2AlxC2-xCoating.
In step (1), described matrix cleaning includes at least one in Chemical cleaning and plasma glow etch cleaner. Wherein, Chemical cleaning step is：Matrix is sequentially placed into into concentration for 60% decontamination amidin, saturation Na2CO3Aqueous solution, third It is each in ketone, dehydrated alcohol, deionized water to be cleaned by ultrasonic 10min, the then forced air drying in the drying baker that temperature is 100 DEG C 1.5h, or adopt purity and dry up for 99.99% high pure nitrogen.Plasma glow etch cleaner step is：Matrix is hung In vacuum chamber, when vacuum is less than 1 × 10-3After Pa, it is passed through argon and maintains air pressure to be 0.3～2.0Pa, be then turned on penetrating Frequency power simultaneously applies back bias voltage to substrate simultaneously, etches 10～20min, Jing to substrate using the plasma glow body that argon is produced After plasma glow etch cleaner, hydrone, gas molecule or the dust particale that matrix surface adheres to is fallen by bombardment completely.
In step (2), by VnAl1-nTarget and VmC1-mTarget is connected with the intermediate frequency power supply of RF-assisted and intermediate frequency power supply phase respectively Even, the target mounting means increases substantially can film forming atomic quantity, energy, and aids in low-energy ion bombardment, keeping Preferable quality of forming film is can control while suitable rate of film build, the coating of preparation is fine and close, and penetrability hole is few.
In step (3) coating deposition process, back bias voltage is applied with to matrix, is biased as 0～-50V.
In step (3) coating deposition process, matrix is heated, heating-up temperature is 550～650 DEG C.
In step (3) coating deposition process, sedimentation rate is 10～20nm/min.
Described matrix is amorphous glass substrate, Si matrixes or stainless steel base.The surface of the Si matrixes has 1～3nm's Natural oxidation silicon.
Present invention also offers a kind of preparation facilitiess of above-mentioned MAX phase ceramics coating, including the sample stage 1 equipped with matrix, It is connected with the intermediate frequency power supply of RF-assisted and V is installednAl1-nFirst magnetic control target head 2 of target, is connected with intermediate frequency power supply and is installed VmC1-mSecond magnetic control target head 3 of target, and baffle plate is installed on sample stage and two target heads.Wherein, in two magnetic control target heads The line at the heart and sample stage center constitutes a triangle, and the distance at two magnetic control target head center to sample stage centers is equal, magnetic The angle of the line of control target head and sample stage and two magnetic control target head line of centres formation is inclination alpha, sample stage center to two The distance of the magnetic control target head line of centres is height h, and the inclination alpha is 45～60 °, and height h is 8～15cm.
The coating that magnetic control target head is obtained to the position of sample stage, position difference is adjusted by adjustable inclination α and height h Composition is different.Using two target heads of plasma sputtering so that the atom in correspondence target is sputtered out in substrate deposit, shape Core and growth, ultimately form MAX phase ceramics coating of the present invention.
Compared with prior art, the invention has the advantages that：
(1) condition that MAX phases are formed weakens, and amorphous substrate allows the random forming core of crystalline state MAX phase, and the present invention is by electricity Source control in addition low energy ion auxiliary, is more beneficial for MAX phase structure long-range repeated arrangement；
(2) as the formation of MAX phases requires harsh, substrate and target in the preparation process by regulation of the invention to elemental composition The distance of material finds most suitable into phase window.
The invention provides a kind of MAX phase ceramics coating, consists of V2AlxC2-x, x=0.7～1.5, using double target magnetic controls Prepared by sputtering method, the MAX phase ceramics coating is low to the dependency of matrix, without the need for epitaxial growth, can obtain at 550～650 DEG C MAX phases, and the MAX phases high purity 99.9% for obtaining, process is simple are expected in special high temperature-resistant, resistant material, resistance to irradiation The aspect such as protective coating and cladding nuclear fuels material is applied.
Description of the drawings
Fig. 1 is the schematic device that the present invention prepares MAX phase ceramics coatings；
Fig. 2 is the SEM microstructure figures that the present invention prepares MAX phase ceramics coatings, wherein (a-1) is respectively right with (a-2) The surface of ratio 1 and Cross Section Morphology, (b-1) are respectively surface and the Cross Section Morphology of comparative example 2, (c-1) with (c-2) with (b-2) The respectively surface of embodiment 1 and Cross Section Morphology；
Fig. 3 be the present invention prepare MAX phase ceramics coatings (a) XRD spectra, (b) Raman collection of illustrative plates；
Fig. 4 is the TEM microstructure figures that the present invention prepares MAX phase ceramics coatings prepared by embodiment 1, wherein (a) light field Picture, (b) full resolution pricture, (c) the Fourier transformation image at square frame A, (d) cell configuration.
Specific embodiment
What the present invention prepared MAX phase ceramics coatings equips schematic diagram as shown in figure 1, including the sample stage 1 equipped with matrix, with The intermediate frequency power supply of RF-assisted is connected and installs VnAl1-nFirst magnetic control target head 2 of target, is connected with intermediate frequency power supply and is installed VmC1-mSecond magnetic control target head 3 of target, and baffle plate is installed on sample stage and two target heads.Wherein, in two magnetic control target heads The line at the heart and sample stage center constitutes a triangle, and the distance at two magnetic control target head center to sample stage centers is equal, magnetic The angle of the line of control target head and sample stage and two magnetic control target head line of centres formation is inclination alpha, sample stage center to two The distance of the magnetic control target head line of centres is height h, and target head is adjusted by adjustable inclination α and height h to the position of sample stage, position The composition for putting the coating that difference is obtained is different.Using two magnetic control target heads of plasma sputtering so that the atom in correspondence target It is sputtered out in substrate deposit, forming core and growth, ultimately forms MAX phase ceramics coating of the present invention.The MAX phases for obtaining Ceramic coating determines coating composition, coating density, coating crystal structure, coating morphology, coating hardness using following methods：
1st, coating composition
Using Peanut embryo measure coating into being grouped into, it is concrete to arrange as follows：4He+Beam energy 2MeV, 20 ° of the angle of emergence, 160 ° of angle of scattering.Energy calibration is done using Au and V during elementary analysiss, with SIMNAR softwares to surveying Examination data are fitted analysis.
2nd, coating density
In the coating of 0.5～2.0 μ m-thick of substrate deposit of rule, by calculating the volume of coating and weighing the matter of coating Amount, calculates according to density computing formula and obtains, and density computing formula is as follows：
Density=mass/volume.
3rd, coating crystal structure
Using German Bruker D8 Advance X-ray diffractometers (XRD), using Cu KαRay is incident, θ/θ patterns, X-ray tube is controlled in 40kV and 40mA, filters out K using nickel filterβRay, it is 20～80 ° to arrange 2 θ of search angle, step-length It is set as 0.01 ° to be measured.
4th, coating morphology
Using Hitachi's S-4800 scanning electron microscopies (SEM, ejecting gun voltage 8KV), the surface, Cross Section Morphology feature to coating is entered Row observation；Using FEI Tecnai transmission electron microscopes (TEM) lower microcosmic Cross Section Morphology of the yardstick to the coating Feature carries out high-resolution observation.
5th, coating hardness
Using MTS NANO G200 nano-hardness testers, Berkovich diamond penetrators, in order to eliminate substrate effect and table The impact of surface roughness, maximum compression distance are set to 100nm, and each sample is averaged after measuring 10 test points.
Comparative example 1
(1) matrix cleaning
Chemical cleaning：From MgO (111) as matrix, which is cleaned, matrix is sequentially placed into into concentration and is gone for 60% Dirty amidin, saturation Na2CO3It is each in aqueous solution, acetone, dehydrated alcohol, deionized water to be cleaned by ultrasonic 10min, then in temperature For forced air drying 1.5h in 100 DEG C of drying baker.And by the good matrix of Chemical cleaning, be suspended in vacuum chamber, work as vacuum Less than 1 × 10-3After Pa, it is passed through argon and maintains air pressure to be 0.5Pa.Afterwards, open radio-frequency power supply, while to matrix apply- 200V is biased, using the plasma glow of argon generation to its etch cleaner 10min.
(2) target is installed and power supply connects：By V0.5Al0.5Target and V0.5C0.5Target is connected with DC source respectively, and is adjusted Inclination alpha=45 ° and height h=9.2cm.
(3) coating deposition
Cleaned MgO (111) matrix is loaded on sample stage, heating base reservoir temperature is to 600 DEG C, and is incubated 30min.When Chamber vacuum degree is less than 2.2 × 10-5Pa, is passed through argon, controls sputtering pressure for 0.5Pa, adjustment V0.5Al0.5The sputtering power of target Density is 7.0W/cm2, V0.5C0.5The Sputtering power density of target is 5.0W/cm2, matrix is applied -40V bias and 750 DEG C Temperature, opens sample baffle plate, and it is 18nm/min to control sedimentation rate, carries out non-epitaxial life on the silicon substrate surface with oxide layer It is long, obtain V2AlxC2-xCoating, wherein x=0.9, coating layer thickness are 2 μm.
Gained V2AlxC2-xShown in the surface topography of coating such as Fig. 2 (a-1), coating surface tight, even particle distribution, Particle size is 50～70nm.Cross Section Morphology figure shows the coating without column crystal, and coating is relatively compact.Gained V2AlxC2-xCoating XRD test results, show that crystallised component is V in the coating2C。
By nano-indenter test, the hardness of the coating is 23.0GPa, and Young's moduluss are 320GPa.
Comparative example 2
(1) matrix cleaning
Chemical cleaning：From MgO (111) as matrix, which is cleaned, matrix is sequentially placed into into concentration and is gone for 60% Dirty amidin, saturation Na2CO3It is each in aqueous solution, acetone, dehydrated alcohol, deionized water to be cleaned by ultrasonic 10min, adopt purity for 99.99% high pure nitrogen is dried up.And Chemical cleaning good matrix is suspended in vacuum chamber, when vacuum less than 1 × 10-3After Pa, it is passed through argon and maintains air pressure to be 1.0Pa.Afterwards, radio-frequency power supply is opened, while apply -200V biass to matrix, Using the plasma glow of argon generation to its etch cleaner 15min.
(2) target is installed and power supply connects：By V0.4Al0.6Target is connected with the intermediate frequency power supply of RF-assisted, V0.6C0.4Target with Intermediate frequency power supply is connected, and adjustable inclination α=40 ° and height h=9.2cm.
(3) coating deposition
Cleaned MgO (111) matrix is loaded on sample stage, heating base reservoir temperature is to 600 DEG C, and is incubated 30min.When Chamber vacuum degree is less than 2.2 × 10-5Pa, is passed through argon, controls sputtering pressure for 0.5Pa, adjustment V0.4Al0.6The sputtering power of target Density is 7.0W/cm2, V0.6C0.4The Sputtering power density of target is 5.0W/cm2, matrix is applied -40V bias and 600 DEG C Temperature, opens sample baffle plate, and it is 20nm/min to control sedimentation rate, carries out epitaxial growth to the surface of MgO (111) matrix, obtains To V2AlxC2-xCoating, wherein x=0.5.
Gained V2AlxC2-xShown in the surface topography of coating such as Fig. 2 (b-1), coating surface distribution of particles is uneven, granule chi Very little is 80～150nm.Fig. 2 (b-2) Cross Section Morphology figure shows that the coating has column crystal, and coating is relatively compact.Gained V2AlxC2-xApply Shown in XRD test results such as Fig. 3 (a) of layer, shown in measurement result such as Fig. 3 (b) of Raman spectrum, the coating contains VAl3Metal Between compound, nodeless mesh state V2AlC is generated.
By nano-indenter test, the hardness of the coating is 17.8GPa, and Young's moduluss are 305GPa.
Comparative example 3
(1) matrix cleaning
Chemical cleaning：From MgO (111) as matrix, which is cleaned, matrix is sequentially placed into into concentration and is gone for 60% Dirty amidin, saturation Na2CO3It is each in aqueous solution, acetone, dehydrated alcohol, deionized water to be cleaned by ultrasonic 10min, adopt purity for 99.99% high pure nitrogen is dried up.And Chemical cleaning good matrix is suspended in vacuum chamber, when vacuum less than 1 × 10-3After Pa, it is passed through argon and maintains air pressure to be 1.0Pa.Afterwards, radio-frequency power supply is opened, while apply -200V biass to matrix, Using the plasma glow of argon generation to its etch cleaner 15min.
(2) target is installed and power supply connects：By V0.5Al0.5Target is connected with the intermediate frequency power supply of RF-assisted, V0.5C0.5Target with Intermediate frequency power supply is connected, and adjustable inclination α=45 ° and height h=9.2cm.
(3) coating deposition
Cleaned MgO (111) matrix is loaded on sample stage, heating base reservoir temperature is to 500 DEG C, and is incubated 30min.When Chamber vacuum degree is less than 5.0 × 10-5Pa, is passed through argon, controls sputtering pressure for 0.5Pa, adjustment V0.5Al0.5The sputtering work(of target Rate density is 7.0W/cm2, V0.5C0.5The Sputtering power density of target is 5.0W/cm2, to matrix apply -40V bias and 500 DEG C Temperature, open sample baffle plate, control sedimentation rate be 20nm/min, epitaxial growth is carried out to the surface of MgO (111) matrix, Obtain V2AlxC2-xCoating, wherein x=1.4.
SEM testing results show the uniform bright and clean column crystal of the coating surface, and coating is relatively compact.The Jing XRD determining coating Containing V2C and VAl3Two kinds of compounds, nodeless mesh state V2AlC is generated.
By nano-indenter test, the hardness of the coating is 18.5GPa, and Young's moduluss are 293GPa.
Embodiment 1
(1) matrix cleaning
Chemical cleaning：From SiO2/ Si pieces do matrix, and which is cleaned, and matrix is sequentially placed into concentration and is gone for 60% Dirty amidin, saturation Na2CO3It is each in aqueous solution, acetone, dehydrated alcohol, deionized water to be cleaned by ultrasonic 10min, adopt purity for 99.99% high pure nitrogen is dried up.And Chemical cleaning good matrix is suspended in vacuum chamber, when vacuum less than 1 × 10-3After Pa, it is passed through argon and maintains air pressure to be 1.0Pa.Afterwards, radio-frequency power supply is opened, while apply -200V biass to matrix, Using the plasma glow of argon generation to its etch cleaner 15min.
(2) target is installed and power supply connects：By V0.5Al0.5Target is connected with the intermediate frequency power supply of RF-assisted, V0.5C0.5Target with Intermediate frequency power supply is connected, and adjustable inclination α=45 ° and height h=9.2cm.
(3) coating deposition
By cleaned SiO2/ Si sheet matrixes load on sample stage, when Chamber vacuum degree is less than 2.2 × 10-5Pa, is passed through argon Gas, controls sputtering pressure for 0.5Pa, adjustment V0.5Al0.5The Sputtering power density of target is 7.0W/cm2, V0.5C0.5The sputtering work(of target Rate density is 5.0W/cm2, apply the bias of -10V and 600 DEG C of temperature to matrix, open sample baffle plate, control sedimentation rate For 15nm/min, Si sheet matrixes are deposited, V is obtained2AlxC2-xCoating, wherein x=0.9.
Gained V2AlxC2-xShown in the surface topography of coating such as Fig. 2 (c-1), surface topography rises and falls, and grain shape is irregular, Particle size is 80～150nm.Fig. 2 (c-2) Cross Section Morphology figure shows the coating for obvious columnar crystal structure, column crystal width For 150nm, length-width ratio is 8, and coating is relatively compact, and the coating density is 4.6g/cm3, coating layer thickness is 0.5 μm.Gained V2AlxC2-xShown in XRD test results such as Fig. 3 (a) of coating, shown in measurement result such as Fig. 3 (b) of Raman spectrum, the present embodiment Gained V2AlxC2-xThe XRD spectra of coating shows that 78.86 ° occur in that V respectively at 35.55 °, 41.27 °, 63.85 °2AlC (100), (103), (110), (116) diffraction maximum, are not difficult to find out do not have the generation of other impurities phase, crystalline state V2The content of AlC Almost 100%.And 100～500cm in Raman spectral peaks-1In the range of there is 258cm-1, 360cm-1Two characteristic peaks, It is belonging to V2The Raman vibration of corresponding keys in AlC phases.Illustrate that the V-Al-C coating structures for preparing are crystalline state V2AlC, V2AlC has There is (110) preferred orientation.
To V obtained by the present embodiment2AlxC2-xCoating cross sections sample carries out thinning its light field being observed under transmission electron microscope Picture, as a result as shown in Fig. 4 (a), the compact structure of coating；The growth structure after coating preferred orientation is observed under high-resolution such as Shown in Fig. 4 (b), and subregion carries out Fourier transformation in selection figure, as a result as shown in Fig. 4 (c), larger original in Fig. 4 (c) Sub- Al atomic layers and two-layer V atomic layer are alternately arranged to form the unique nanometer laminated structure of MAX phase materials, and it is former that C atoms are distributed in V In the middle of sub；Fig. 4 (d) is expressed as V2In the crystal structure of the AlC cell configuration figure formed by three kinds of Atomic Arrangements.
By nano-indenter test, V obtained by the present embodiment2AlxC2-xThe hardness of coating is 13.9GPa, and Young's moduluss are 270GPa。
Embodiment 2
Compared with Example 1, other conditions are constant, and the heating-up temperature of matrix is changed to 550 DEG C only, remain to obtain crystalline state V2AlC。
By nano-indenter test, V obtained by the present embodiment2AlxC2-xThe hardness of coating is 12.5GPa；Young's moduluss are 250GPa。
Embodiment 3
(1) matrix cleaning
Chemical cleaning：From amorphous glass as matrix, which is cleaned, matrix is sequentially placed into into concentration and is gone for 60% Dirty amidin, saturation Na2CO3It is each in aqueous solution, acetone, dehydrated alcohol, deionized water to be cleaned by ultrasonic 10min, adopt purity for 99.99% high pure nitrogen is dried up.And Chemical cleaning good matrix is suspended in vacuum chamber, when vacuum less than 1 × 10-3After Pa, it is passed through argon and maintains air pressure to be 1.0Pa.Afterwards, radio-frequency power supply is opened, while apply -200V biass to matrix, Using the plasma glow of argon generation to its etch cleaner 15min.
(2) target is installed and power supply connects：By V0.5Al0.5Target is connected with the intermediate frequency power supply of RF-assisted, V0.5C0.5Target with Intermediate frequency power supply is connected, and adjustable inclination α=60 ° and height h=13.5cm.
(3) coating deposition
Cleaned glass basis is loaded on sample stage, when Chamber vacuum degree is less than 1.0 × 10-5Pa, is passed through argon, control Sputtering pressure processed is 0.7Pa, adjusts V0.5Al0.5The Sputtering power density of target is 7.0W/cm2, V0.5C0.5The sputtering power of target is close Spend for 5.0W/cm2, apply the bias of -10V and 600 DEG C of temperature to matrix, open sample baffle plate, controlling sedimentation rate is 15nm/min, deposits to glass basis, obtains V2AlxC2-xCoating, wherein x=1.15.
V obtained by the present embodiment2AlxC2-xCoating is obvious columnar crystal structure, and column crystal width is 100nm, and length-width ratio is 6.5, coating is relatively compact, and the coating density is 4.6g/cm3, coating layer thickness is 1.5 μm.Gained V2AlxC2-xThe XRD of coating is surveyed Shown in test result such as Fig. 3 (a), shown in measurement result such as Fig. 3 (b) of Raman spectrum, V obtained by the present embodiment2AlxC2-xCoating XRD spectra shows that 78.86 ° occur in that V respectively at 35.55 °, 41.27 °, 63.85 °2AlC(100)、(103)、(110)、 (116) diffraction maximum, is also not difficult to find out do not have the generation of other impurities phase, crystalline state V2The content of AlC is almost 100%.And 100～500cm in Raman spectral peaks-1In the range of there is 258cm-1, 360cm-1Two characteristic peaks, belong to V2In AlC phases The Raman vibration of corresponding keys.Illustrate that the V-Al-C coating structures for preparing are crystalline state V2AlC, K=0.65, illustrate crystalline state V2AlC has There is (110) preferred orientation.
By nano-indenter test, V obtained by the present embodiment2AlxC2-xThe hardness of coating is 15.0GPa；Young's moduluss are 285GPa。
Embodiment 4
Compared with Example 3, other conditions are constant, and the heating-up temperature of matrix is changed to 550 DEG C only, remain to obtain crystalline state V2AlC。
By nano-indenter test, V obtained by the present embodiment2AlxC2-xThe hardness of coating is 13.5GPa；Young's moduluss are 260GPa。
Embodiment 5
(1) matrix cleaning
Chemical cleaning：From rustless steel as matrix, which is cleaned, matrix is sequentially placed into into concentration for 60% decontamination Amidin, saturation Na2CO3It is each in aqueous solution, acetone, dehydrated alcohol, deionized water to be cleaned by ultrasonic 10min, adopt purity for 99.99% high pure nitrogen is dried up.And Chemical cleaning good matrix is suspended in vacuum chamber, when vacuum less than 1 × 10-3After Pa, it is passed through argon and maintains air pressure to be 1.0Pa.Afterwards, radio-frequency power supply is opened, while apply -200V biass to matrix, Using the plasma glow of argon generation to its etch cleaner 15min.
(2) target is installed and power supply connects：By V0.5Al0.5The intermediate frequency power supply of target and RF-assisted, V0.5C0.5Target and intermediate frequency Power supply is connected, and adjustable inclination α=45 ° and height h=9.2cm.
(3) coating deposition
Cleaned stainless steel base is loaded on sample stage, when Chamber vacuum degree is less than 1.0 × 10-5Pa, is passed through argon, Sputtering pressure is controlled for 0.9Pa, adjustment V0.5Al0.5The Sputtering power density of target is 7.0W/cm2, V0.5C0.5The sputtering power of target Density is 5.0W/cm2, 600 DEG C of temperature is heated to matrix, sample baffle plate is opened, it is 20nm/min to control sedimentation rate, right Glass basis is deposited, and obtains V2AlxC2-xCoating, wherein x=0.95.
V obtained by the present embodiment2AlxC2-xCoating is obvious columnar crystal structure, and column crystal width is 80nm, and length-width ratio is 6.5, coating is relatively compact, and the coating density is 4.6g/cm3, coating layer thickness is 2 μm.Cross Section Morphology figure shows that the coating is post Shape crystal structure,.Jing XRD and Raman spectrum detection, V obtained by the present embodiment2AlxC2-xThe XRD spectra of coating shows 35.55 °, 41.27 °, 55.50 °, 63.85 °, 78.86 ° occur in that V2AlC (100), (103), (106), (110), (116) are spread out Penetrate peak, and 100～500cm in Raman spectral peaks-1In the range of there is 159cm-1, 258cm-1, 360cm-1Three characteristic peaks, Belong to V2The Raman vibration of corresponding keys in AlC phases.Illustrate that the V-Al-C coating structures for preparing are crystalline state V2AlC。
By nano-indenter test, V obtained by the present embodiment2AlxC2-xThe hardness of coating is 15.5GPa, and Young's moduluss are 297GPa。
Embodiment 6
Compared with Example 5, other conditions are constant, and the heating-up temperature of matrix is changed to 550 DEG C only, remain to obtain crystalline state V2AlC。
By nano-indenter test, V obtained by the present embodiment2AlxC2-xThe hardness of coating is 12.5GPa；Young's moduluss are 268GPa。
In addition, it is to be understood that after the above for having read description of the invention, those skilled in the art can be to this Invention makes various changes or modifications, and the technical scheme of these equivalents equally falls within the model limited by the application appended claims Enclose.

Claims (9)

1. a kind of MAX phase ceramics coating, it is characterised in that the MAX phase ceramics coating into being grouped into V2AlxC2-x, x= 0.7～1.5, wherein x are atom ratio, and coating is crystalline state, is in the form of a column crystals growth structure, and each column crystal is by one layer of Al original Sublayer and two-layer V atomic layer are alternately arranged to be formed, and C atomic layers be located at two-layer V atomic layer between, coating density be 4.5～ 5.2g/cm3。
2. MAX phase ceramics coating according to claim 1, it is characterised in that the width of each column crystal is 80～ 150nm, length-width ratio are 6.5～8.
3. MAX phase ceramics coating according to claim 1, it is characterised in that the thickness of the MAX phase ceramics coating is 0.5～2 μm.
4. a kind of preparation method of the MAX phase ceramics coatings according to any one of claims 1 to 3, it is characterised in that adopt Prepared by double target magnetic control sputtering methods, concrete steps include：
(1) matrix cleaning；
(2) target is installed and power supply connects：By VnAl1-nTarget is connected with the intermediate frequency power supply of RF-assisted, VmC1-mTarget and intermediate frequency power supply It is connected, wherein n=0.4～0.6, m=0.4～0.6, both at atom ratio, and the purity of two targets is both greater than 99.99%；
(3) coating deposition：Matrix after cleaning is loaded in vacuum chamber, when Chamber vacuum degree is 1 × 10-5～5 × 10-5During Pa, It is 0.5～0.8Pa to be passed through argon and control sputtering pressure, and the Sputtering power density for adjusting target is 3.2～7.0W/cm2, allow VnAl1-nAnd VmC1-mTwo targets are while build-up of luminance, opens sample baffle plate afterwards, matrix is deposited, the MAX phases of crystalline state are obtained Ceramic coating, i.e. V2AlxC2-xCoating.
5. the preparation method of MAX phase ceramics coating according to claim 4, it is characterised in that step (3) coating was deposited Cheng Zhong, is applied with back bias voltage to matrix, biases as 0～-50V.
6. the preparation method of MAX phase ceramics coating according to claim 4, it is characterised in that step (3) coating was deposited Cheng Zhong, is heated to matrix, and heating-up temperature is 550～650 DEG C.
7. the preparation method of MAX phase ceramics coating according to claim 4, it is characterised in that step (3) coating was deposited Cheng Zhong, sedimentation rate are 10～20nm/min.
8. the preparation method of MAX phase ceramics coating according to claim 4, it is characterised in that described matrix is amorphous glass Glass substrate, Si matrixes or stainless steel base.
9. a kind of preparation facilitiess of the MAX phase ceramics coatings according to any one of claims 1 to 3, including equipped with matrix Sample stage (1), is connected with the intermediate frequency power supply of RF-assisted and installs VnAl1-nFirst magnetic control target head (2) of target, with medium frequency electric Source is connected and installs VmC1-mSecond magnetic control target head (3) of target, and baffle plate is installed on sample stage and two target heads, which is special Levy and be, the line at two magnetic control target head centers and sample stage center constitutes a triangle, and two magnetic control target head centers are to sample The distance at sample platform center is equal, and magnetic control target head is inclination alpha with the line of sample stage and the angle of two target head line of centres formation, Sample stage center to two magnetic control target head lines of centres distance be height h, the inclination alpha be 45～60 °, height h be 8～ 15cm。
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CN109487209A (en) * 2018-12-13 2019-03-19 中国科学院宁波材料技术与工程研究所 A kind of high rigidity MAX phase ceramics coating and preparation method thereof
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CN117867644A (en) * 2024-03-13 2024-04-12 中国科学院宁波材料技术与工程研究所 Preparation method of monocrystal vanadium-aluminum-carbon material

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