CN106917066B - A kind of quaternary single layer of super hard thin-film material and preparation method thereof - Google Patents

A kind of quaternary single layer of super hard thin-film material and preparation method thereof Download PDF

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CN106917066B
CN106917066B CN201710160391.7A CN201710160391A CN106917066B CN 106917066 B CN106917066 B CN 106917066B CN 201710160391 A CN201710160391 A CN 201710160391A CN 106917066 B CN106917066 B CN 106917066B
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film
single layer
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super hard
film material
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CN106917066A (en
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韩克昌
林国强
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Dalian University 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
    • C23C14/325—Electric arc evaporation
    • 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
    • C23C14/0021—Reactive sputtering or evaporation
    • 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
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • 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
    • C23C14/0676—Oxynitrides

Abstract

The present invention provides a kind of quaternary single layer of super hard thin-film materials and preparation method thereof, belong to metal surface properties modification and technical field of mechanical processing.A kind of Zr-Al-O-N quaternary single layer of super hard thin-film material and the method for preparing the film on tool die material surface using arc ion plating (aip).The ingredient design considerations chemical bonding and electronic band structure of the material be theoretical, it then follows covalency coupled band theory is completed；The preparation method is carried out using arc ion plating apparatus and by the regulation of separation target arc stream and nitrogen, partial pressure of oxygen regulation, can deposit that synthetic raw material is simple, at low cost, but hardness is higher than wear-resistant, the anticorrosive and antioxygenic property good high performance-price ratio Zr-Al-O-N quaternary single thin film of 40GPa.This method deposition velocity is fast, high production efficiency, it is easy to operate, be conducive to batch production, particularly suitable for technical field of mechanical processing.

Description

A kind of quaternary single layer of super hard thin-film material and preparation method thereof
Technical field
The invention belongs to metal surface properties modifications and technical field of mechanical processing, are related to a kind of Zr-Al-O-N quaternary list Layer super-hard film material and preparation method thereof.
Background technique
TiAlN thin film is successfully applied to from the Vac-Tech company in the last century 80's U.S. and Mul-Arc company Since on tool surface coating, tool hard coating technology has been passed by nearly 40 years courses.During this period, in order to constantly full The demand that sufficient mechanical industry develops and is on active service under more harsh conditions to higher speed and continuous production direction, hard films Layer material is transitioned into TiCN, TiAlN etc. of the second generation from initial first generation TiN, and is developed to multiple groups of all shapes and colors at present First composite membrane and Multilayer system.Multilayer film can regulate and control the property of film material by the modulation of collocation and period to film layer Can, such as hardness, toughness, abrasion resistance.But complicated modulation process is equal to material and technological means etc. needed for film layer preparation There is higher requirement, film material preparation cost is higher, and multilayered structure can also can be with during the military service of film layer Layer structure takes the lead in failing and dropping film performance suddenly, to seriously constrain the application industrially of assembly of thin films.With Assembly of thin films is compared, and single thin film preparation process is simple, at low cost, and cost performance is high, is the widely applied excellent selection of industry.But Current existing conventional monolayers hard laminated film, such as TiN, TiCN, TiAlN, since their hardness is generally all in 20- 24GPa or so, it is difficult to reach superhard standard, not be able to satisfy the requirement of machining industry harshness.And current single layer multicomponent is thin Membrane material, it is intended to by collocation to each constituent element and the content regulation material property that the phase has obtained, but due to film constituent element crowd More, ingredient collocation regulation theoretical foundation is indefinite, and the high performance-price ratio surface that can satisfy machining industry requirements at the higher level in recent years changes Property super-hard film material rarely has appearance.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of Zr-Al-O-N quaternary single layer of super hard film materials of high performance-price ratio Material and preparation method thereof.The thin-film material possesses the ultrahigh hardness, good wear-resistant, anticorrosive and anti-oxidant of 40GPa or more Performance.And preparation method is simple to operation, preparation efficiency is high, film material low manufacture cost, and being very suitable for machining industry makes With.
Scientific basis of the invention is: the intrinsic strength of hard film layer material depends primarily on the chemistry on atomic scale The internal factors such as bonding, electronic band structure.In multiple elements design hard nitride, between metal valence electron and nonmetallic valence electron The coupling of high directivity is capable of forming the covalency combination for being effective against shearing deformation, causes positive influence to hardness.This is covalently Property coupled band valence electron number and be 8.4 when obtain saturation filling, the intensity of respective material herein at branch obtain peak value. And in the presence of having vacant position in lattice structure, due to the superposition of vacancy invigoration effect, material peak point will appear in valence electron Number summation is slightly below at 8.4.
As theoretical foundation, the ingredient design of the superhard Zr-Al-O-N thin-film material of single layer quaternary nitride is carried out.Selection On the basis of possessing the ternary ZrAlN film of preferable high-temperature stability and mechanical performance, introduces and increase the 4th of bond strength Constituent element, i.e. oxygen (O) element of VI A race.ZrAlN film is that III A race Al element is added to binary nitride ZrN to be formed, because of Al The arrangement of atom outermost electron is 2s22p1, valence electron number 3, opposite IV B race Zr atom, Al atom for valence electron concentration and Contribution reduce, it is difficult to meet the needs of valence electron number at intensity peak；And O atom outermost layer configuration of extra-nuclear electron is 2s22p4, Valence electron number is 6, and opposite V A race N atom, introducing portion O atom increases valence electron concentration and contribution, and compensation is due to Al member Valence electron number caused by element is added is insufficient, and O atom bond strength is higher, can further increase film mechanical performance and resist Oxidability.For the optimum content proportion of four kinds of elements, on the basis of computer Simulation calculation obtains PRELIMINARY RESULTS, then lead to Cross experimental verification acquisition.
To realize that above-mentioned material is imagined, arc ion plating can be used to separate target technology, because its ionization degree is high, deposition quality It is good, film forming speed is fast, film base is tightly combined, technology relative maturity, industrial application is at low cost.Specially use arc ions Coating apparatus, metal Zr and Al target needed for placement prepares film respectively on symmetrical cathode target, and it is logical by plenum system Enter reaction gas N2And O2To prepare Zr-Al-O-N thin-film material.The great advantage of the method is, by regulating and controlling two target arc streams IAl/IZrDifferent matching and nitrogen oxide flow opposite regulation, can very easily obtain the Zr- of multicomponent optimization composition proportion Al-O-N thin-film material.
Technical solution of the present invention:
A kind of quaternary single layer of super hard thin-film material is made of, i.e. Zr tetra- kinds of elements of Zr, Al, O and N1-x-y-zAlxOyNz, Relative atom content score is respectively x=0.06-0.10, y=0.10-0.14, z=0.29-0.33；Quaternary single layer of super hard film For the phase structure of material based on face-centered cubic Zr and N atom, O and Al atom is the partial dot replaced atom and occupy Zr or N atom Battle array position；The crystal particle scale of quaternary single layer of super hard thin-film material is 10nm-50nm；With a thickness of 0.5 μm -15 μm.
A kind of preparation method of quaternary single layer of super hard thin-film material, steps are as follows:
It is put by workpiece substrate after ultrasonic cleaning and drying and processing using with arc ion plating (aip) deposition preparation It is placed on the sample stage of arc ion plating vacuum chamber, vacuum chamber is evacuated to 5.0 × 10 by vacuum system-3Pa~5.0 ×10-4Pa；Workpiece substrate temperature is heated to 100 DEG C~450 DEG C, and keeps stable；It is filled with argon gas later to 0.8Pa~4Pa, and The back bias voltage for applying 600V~1500V to sample stage causes glow plasma, carries out argon ion sputtering cleaning to workpiece substrate, Time is 5min~30min；Reaction gas nitrogen and oxygen are then passed to, nitrogen partial pressure is 0.3Pa~0.6Pa, oxygen partial pressure For 0.1Pa~0.2Pa, and it is complementary with argon gas maintain chamber pressure to stabilize to 0.6Pa~1.2Pa by whole pressure control, The pure zirconium target of starter cathode and pure aluminum target electric arc later, adjusting pure zirconium target arc stream is 60A~120A, and adjustment pure aluminum target arc stream is 30A ~120A, adjustment pulsed bias be amplitude be 300V~1000V, frequency is 5kHz~40kHz and duty ratio is 5%~50%, Start film deposition process, the time is 30min~300min；The work that vacuum takes out plated film is bled off after cold using abundant furnace Part matrix.
The workpiece substrate is high-speed steel, hard alloy, cold work die steel and hot die steel.
Beneficial effects of the present invention: a kind of quaternary single layer of super hard Zr-Al- of high performance-price ratio is prepared with arc ion plating (aip) O-N thin-film material, each element relative atom content score is respectively Al:0.06-0.10, O:0.10-0.14, N:0.29- 0.33, remaining is Zr；The phase structure of film is based on face-centered cubic ZrN；The crystal particle scale of film is 10nm-50nm；Film With a thickness of 0.5 μm -15 μm.Film gathers around the hardness of 40Gpa or more, good wear-resistant, anticorrosive and antioxygenic property.
Specific embodiment
A specific embodiment of the invention is described in detail below in conjunction with technical solution.
Embodiment 1:
By hard alloy cutter workpiece substrate after ultrasonic cleaning and drying and processing, it is placed in arc ion plating vacuum chamber Sample stage on, the pure zirconium target of symmetrical placement and fine aluminium target, are evacuated to 5.0 × 10 on cathode arc source position-3P；Workpiece Substrate temperature is heated to 400 DEG C, and keeps stable；Argon gas is filled with later to 1.8Pa, to sample stage application -850V × 30kHz × 50% pulsed bias causes glow plasma, carries out argon ion sputtering cleaning, time 30min to workpiece substrate；Then Adjustment pulsed bias is 350V × 30kHz × 30%, is passed through nitrogen and oxygen, nitrogen flow 120sccm, oxygen flow is 20sccm makes nitrogen partial pressure 0.4Pa, oxygen partial pressure 0.1Pa, and adjusts partial pressure of ar gas and maintain chamber pressure steady with complementation It is set to 0.6Pa, starts zirconium target and aluminium target electric arc, zirconium target arc stream is 80A, and aluminium target arc stream is 60A, start to carry out deposition process, when Between be 120min；It then carries out unloading bias afterwards, stops arc, stop the supple of gas or steam, vacuum is maintained to carry out furnace cold 1 hour, finally bleed off vacuum taking-up The hard alloy cutter workpiece substrate of plated film.So on workpiece substrate surface, deposition synthesizes the quaternary single layer with a thickness of 3.0 μm Superhard Zr-Al-O-N film, specific ingredient are Zr0.49Al0.08N0.31O0.12, make hard alloy cutter workpiece substrate surface hardness For 40.2GPa, and there is good wear-resistant, anticorrosive and antioxygenic property.
Embodiment 2:
By mould steel die workpiece matrix after ultrasonic cleaning and drying and processing, it is placed in arc ion plating vacuum chamber On sample stage, the pure zirconium target of symmetrical placement and fine aluminium target, are evacuated to 5.0 × 10 on cathode arc source position-3Pa；Workpiece base Temperature is heated to 300 DEG C, and keeps stable；Argon gas is filled with later to 1.8Pa, to sample stage application -850V × 30kHz × 50% pulsed bias causes glow plasma, carries out argon ion sputtering cleaning, time 30min to workpiece substrate；Then Adjustment pulsed bias is 350V × 30kHz × 30%, is passed through nitrogen and oxygen, nitrogen flow 150sccm, oxygen flow is 30sccm makes nitrogen partial pressure 0.5Pa, oxygen partial pressure 0.2Pa, and adjusts partial pressure of ar gas and maintain chamber pressure steady with complementation It is set to 0.8Pa, starts zirconium target and aluminium target electric arc, zirconium target arc stream is 90A, and aluminium target arc stream is 80A, start to carry out deposition process, when Between be 180min；It then carries out unloading bias afterwards, stops arc, stop the supple of gas or steam, vacuum is maintained to carry out furnace cold 1 hour, finally bleed off vacuum taking-up The mould steel die workpiece matrix of plated film；Such die workpiece matrix surface deposition synthesizes the quaternary single layer with a thickness of 4.5 μm Superhard Zr-Al-O-N film, specific ingredient are Zr0.50Al0.10N0.30O0.10, make hard alloy cutter workpiece substrate surface hardness For 41.0GPa, and there is good wear-resistant, anticorrosive and antioxygenic property.

Claims (2)

1. a kind of preparation method of quaternary single layer of super hard thin-film material, which is characterized in that the quaternary single layer of super hard film material Material is made of tetra- kinds of elements of Zr, Al, O and N, i.e. Zr1-x-y-zAlxOyNz, relative atom content score is respectively x=0.06- 0.10, y=0.10-0.14, z=0.29-0.33；The phase structure of quaternary single layer of super hard thin-film material is former with face-centered cubic Zr and N Based on son, O and Al atom is the part lattice position replaced atom and occupy Zr or N atom；Quaternary single layer of super hard thin-film material Crystal particle scale is 10nm-50nm；With a thickness of 0.5 μm -15 μm；
The preparation step of quaternary single layer of super hard thin-film material is as follows:
Electricity is placed in by workpiece substrate after ultrasonic cleaning and drying and processing using arc ion plating (aip) deposition preparation On the sample stage of arc ion plating vacuum chamber, vacuum chamber is evacuated to 5.0 × 10 by vacuum system-3Pa~5.0 × 10- 4Pa；Workpiece substrate temperature is heated to 100 DEG C~450 DEG C, and keeps stable；It is filled with argon gas later to 0.8Pa~4Pa, and gives sample The back bias voltage that sample platform applies 600V~1500V causes glow plasma, carries out argon ion sputtering cleaning, time to workpiece substrate For 5min~30min；Reaction gas nitrogen and oxygen are then passed to, nitrogen partial pressure is 0.3Pa~0.6Pa, and oxygen partial pressure is 0.1Pa~0.2Pa, and it is complementary with argon gas maintain chamber pressure to stabilize to 0.6Pa~1.2Pa by whole pressure control, it The pure zirconium target of starter cathode and pure aluminum target electric arc afterwards, adjust pure zirconium target arc stream be 60A~120A, adjustment pure aluminum target arc stream for 30A~ 120A, adjustment pulsed bias be amplitude be 300V~1000V, frequency is 5kHz~40kHz and duty ratio is 5%~50%, i.e., Start film deposition process, the time is 30min~300min；The workpiece that vacuum takes out plated film is bled off after cold using abundant furnace Matrix.
2. preparation method according to claim 1, which is characterized in that the workpiece substrate be high-speed steel, hard alloy, Cold work die steel and hot die steel.
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CN109252140A (en) * 2018-10-19 2019-01-22 扬州大学 A kind of method that cold work die steel surface prepares AlCrCN coating

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