CN110484883A - A kind of synthetic method and application of hard Zr-B-O nano compound film - Google Patents

A kind of synthetic method and application of hard Zr-B-O nano compound film Download PDF

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CN110484883A
CN110484883A CN201910831042.2A CN201910831042A CN110484883A CN 110484883 A CN110484883 A CN 110484883A CN 201910831042 A CN201910831042 A CN 201910831042A CN 110484883 A CN110484883 A CN 110484883A
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film
zrb
nano compound
compound film
target
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李德军
徐阳
董磊
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Tianjin University
Tianjin Normal University
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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
    • C23C14/02—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
    • 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
    • C23C14/22—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

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  • 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 present invention relates to a kind of synthetic methods of hard Zr-B-O nano compound film.It is using more target magnetic control co-sputtering technologies, under Ar compression ring border, by changing ZrB2The sputtering power of target, combined influence of the research technological parameter to film.In optimum proportioning: ZrB2When sputtering power is 120 W, the Zr-B-O nano compound film of generation is non crystalline structure, this structure can effectively hinder the entrance of extraneous O atom, oxidation weight gain is only 0.1 % or so in 1000 DEG C of aerobic environments below, finally obtain nano hardness and elasticity modulus up to 26.76 GPa and 268.05 GPa Zr-B-O nano compound film.Hard Zr-B-O nano-composite coating has higher hardness, high film-substrate cohesion, the excellent combination characteristic of good oxidation resistance.ZrO2With ZrB2Laminated film will have important application prospect in fields such as cutting element, component of machine.

Description

A kind of synthetic method and application of hard Zr-B-O nano compound film
The present invention obtains project of national nature science fund project (51772209), Tianjin Nsfc Projects (18JCQNJC72000), Tianjin science and technology item (18PTZWHZ00020), University Of Tianjin's innovation Project (approval number TD13- 5077) subsidy.
Technical field
The invention belongs to ganoine thin film fields.More particularly to a kind of more target magnetic control co-sputtering depositing systems of JGP-450 type Prepare Zr-B-O nano compound film, using magnetron sputtering technique synthesis by zirconium diboride and zirconium dioxide form have it is higher Hardness, high film-substrate cohesion, good oxidation resistance surface peening nano compound film new process.
Background technique
From 1970s, as industrialization, membrane science and skill are realized in the application of various vacuum coating technologies comprehensively Art experienced the high-speed developing period, and not only the preparation method of film is increasingly diversified, and thin film technique is in electronic component, optics The fields such as instrument, aerospace are all widely used.The type of thin-film material has very much, wherein function film and structure Film is two big main Types of film.Function film is to pass through compound mode using the unique energy of nanoparticle institute Make new material that there is specific function not available for collective, it includes optical thin film, photovoltaic film, lithium ion cell film etc.. Another kind of film is structural membrane, by the compound of nanoparticle, the mechanical performance of reinforcing material.Nowadays, belong to nano junction The super-hard film material research achievement of structure film one kind is more, and main nano-hard film research is concentrated mainly on nanometer at present Laminated film and nano-multilayer film both direction.Nano composite membrane is the material different by two or more ingredient or structure Expect the film formed, it can effectively adjust the ingredient and structure of each component in film, inhibit the movement of dislocation and defect, thus Higher mechanical performance is obtained, in recent years, people have carried out a large amount of research in this regard, has prepared many performance knots The excellent nano material of structure.Nanocomposite boride is as one of Modern High-Tech's material, due to hard with high-melting-point, height The performances such as degree, high antioxidant and wearability and as hard tool materials, abrasive material, wear resistant corrosion resistant component, while this material Material has excellent electrical property again, as inert electrode material and high temperature electrical material by the great attention of people.Transition Metal boride is due to its unique chemical constituent stability, excellent mechanical performance, high-termal conductivity and corrosion-resistant anti-oxidant etc. Characteristic obtains extensive concern, wherein both at home and abroad to HfB2And ZrB2Study relatively deeply and thorough.ZrB2As hexagonal crystal system C32 type metalloid structural compounds, the strong bond of the Zr-B ionic bond between B-B covalent bond and boron atom face and zirconium atom face Property determines high intensity, high rigidity, brittleness and the stability of this material, therefore ZrB2With high rigidity, high-melting-point, Gao Wen The features such as qualitative, good thermally conductive, electric conductivity and good corrosion resistance, it can be used as heat-resisting material, resistant material, wear-resisting material Material and superhard material, such as corrosion-resistant and abrasion electroplated coating, sewer pipe mouth and nozzle material；In steel and iron industry, it can use In stainless steel coating；It also is used as the protection pipe of molten metal crucible, armor and steel and iron industry continuous temperature measurement simultaneously；This Outside, it can prepare the conductance to work under severe conditions as electronic device and electrical contact material, continuous casting body tundish add twice Thermode and protecting tube etc..
As most of fragile materials, transition metal boride fracture toughness is lower, and Mechanical Reliability is lower and right Slow or subcritical Crack Growth sensibility, hinders its application industrially significantly.It can be by introducing and O element parent The second phase substance bigger with power, makes it effectively buffer the defect in its structural behaviour.ZrO2Most develop as 21 century One of functional material and structural material of future have high rigidity, high intensity, high tenacity and high wearability and good Chemical stability and thermal stability are widely used in many fields.Due to ZrO2Fusing point is high, thermal coefficient is low, changes It learns performance to stablize, have and thermal expansion coefficient similar in metal；In conjunction with the advantage of nano material, by nanoscale ZrO2It is coated in As protective layer, coating is stronger in conjunction with matrix for metal surface, and not easy to crack, and coating material can improve matrix Performance, the service life of member for prolonging.At present for ZrB2And ZrO2The research of single material is more, and for the two combination phase The research of pass has focused largely on powder, ceramics aspect, in terms of study coating on mostly use vapor deposition and sol-gel technique Deng.And ZrB2And ZrO2It is combined nano compound film but few people's research of magnetically controlled sputter method preparation.Using magnetic control The mode of sputtering is synthesized based on ZrB2Nano compound film, be conducive to give full play of ZrB2It is high rigidity itself that have, high-strength The features such as degree, high stability, while its, poor toughness low with the binding force of engineering material matrix, high temperature oxidation resistance can be overcome again The shortcomings that poor, corrosion-resistant etc..
The relative amount of the two is controlled by way of changing sputtering power, due to influencing each other for the two, Zr-B-O is received Rice laminated film forms a kind of closely knit armorphous, but the microcrystalline growth of some small sizes is still suffered from inside film, because of nanometer Brilliant dimensional effect makes composite membrane keep higher hardness, at the same time, soft phase ZrO2Addition, restrained effectively mould The raising of amount weakens the brittleness of film, enhances the toughness of composite membrane.This illustrates ZrO2Addition same to film toughening When that its hardness can't be made to reduce is very much, improve the mechanical performance of film well.Then to Zr-B-O under aerobic environment Nano compound film carries out 1000 DEG C of multiple groups high-temperature oxydation tests below, and the matter of rear film before oxidation is found by comparison Amount variation is maintained at 0.1 % or so, illustrates that the Zr-B-O nano compound film prepared has preferable inoxidizability, it is one It is a that there is the nano composite system for being suitable for future in engineering applications.
ZrB2Film itself fusing point with higher, excellent thermal conductivity, good electric conductivity, stronger corrosion resistance And the features such as stable crystal structure, it is widely used in aerospace, refractory material, high-temperature electrode material and cutting tool In equal neighborhoods.ZrO2Have many advantages, such as that good toughness, inoxidizability are strong, corrosion resistance is good, so that it be made to be widely used in thermal boundary Coating, high-temperature device and the wear-resistant and anti-corrosion protection coating as alloy substrates；Nanometer ZrO2It is received due to owned The binding performance of rice characteristic, coating and matrix is good, so that it be made to be more widely applied.With the development of related industry, people Higher, tightened up requirement is proposed to the performance of material, the shortcomings that monophase materials are be exposed and limitation limit material Expect the application range of itself.Oxygen element is mixed in nanometer boride coating can be enhanced the toughness of nano composite membrane, improve it The performances such as inoxidizability and corrosion resistance, however the correlation for preparing Zr-B-O nano compound film using magnetron sputtering technique It studies also fewer.
Summary of the invention
The invention discloses a kind of synthetic methods of hard Zr-B-O nano compound film, which is characterized in that it is in argon Under gas (Ar) environment, by ZrB2Target (99.99 %) and ZrO2Target (99.99 %) is utilized respectively pulse direct current and radio frequency magnetron The mode of sputtering deposits ZrB simultaneously on the base silicon (Si)2And ZrO2Prepare Zr-B-O nano compound film；Sedimentation time is 3 small When, wherein ZrB2And ZrO2The ratio between deposition about 2:1, total film thickness is 600-800 nanometers.
The synthetic method of hard Zr-B-O nano compound film of the present invention, it is characterized in that: utilizing the more targets of JGP-450 type Magnetic control co-sputtering system designs one group of difference ZrB2Sputtering power is that the Zr-B-O nano compound film of the W of 80 W ~ 120 is made comparisons Experiment, utilizes Ar+ZrB is bombarded respectively2And ZrO2Two targets deposit ZrB simultaneously in silicon (Si) substrate2And ZrO2Prepare Zr-B-O Nano compound film；Using mechanical pump and molecular pump, chamber pressure value is measured by ionization gauge, base vacuum is made to be evacuated to 4.0 ×10-4~5.0×10-4Pa, sputter gas selects high-purity Ar in deposition process2(99.999 %), with mass flow controller control It makes its flow and is maintained at 40 ~ 41 sccm, base reservoir temperature is room temperature, and total operating air pressure is maintained at 0.4 Pa in sputtering process.
It is of the present invention to deposit ZrB simultaneously in silicon (Si) substrate2And ZrO2Zr-B-O nano compound film is prepared, is referred to It is: is first successively immersed in acetone, ethyl alcohol, ultrasonic cleaning 15 minutes in deionized water, vacuum deposition chamber is immediately fed into after drying In, before deposition film, the operating air pressure condition of 5.0 Pa is first kept, Ar is utilized under -400 V biass+Sample is carried out 15 minutes biass cleaning, when deposition film, by high-purity ZrB2Target (99.99 %) and ZrO2Target (99.99 %) alternately revolves It goes to sputtering position and accurately controls the sputtering time of each target；Use Ar+Sputter two target sources, radio frequency target ZrO2Sputtering Power is 80 W, pulse direct current target ZrB2Sputtering power be 120 W, target-substrate distance be 7 cm, substrate bias be -80 V.Substrate Temperature is room temperature；Obtaining nano hardness is 26.76 GPa, and elasticity modulus is 268.05 GPa, while there is good film base junction to close The nano compound film of power and antioxygenic property.The synthetic method of hard Zr-B-O nano compound film of the present invention, is not have In the case where having the requirement of the harsh conditions of any Assisted by Ion Beam and high temperature and pressure, in Ar2Growth deposition Zr-B-O receives under environment Rice laminated film.
More detailed description of the present invention is as follows:
A kind of preparation method of the Zr-B-O nano compound film of hard is deposited using the more target magnetic control co-sputterings of JGP-450 type System prepares ZrB respectively2With hard Zr-B-O nano compound film.Purity is the ZrB of 99.99 %2Compound target and 99.99 % ZrO2For compound target respectively by pulse direct current and radio frequency cathodic control, target-base spacing is maintained at 7 cm.ZrO2Sputtering power For 80 W, ZrB2Sputtering power be 120 W.Substrate uses silicon (Si) piece, uses acetone, ethyl alcohol, deionized water respectively before film Ultrasonic cleaning 15 minutes, drying was placed on rotatable sample stage.Base vacuum is lower than 5.0 × 10 when plated film-4Pa splashes Body of emanating uses Ar2(99.999 %), in entire deposition process, total operating air pressure is maintained at 0.4 Pa.Substrate bias is kept In -80 V, base reservoir temperature is room temperature.Before depositing composite membrane, stable ar gas environment is kept, passes through computer system control base Piece is exposed to ZrB2And ZrO2Time before target, so that the overall thickness for controlling nano compound film is about 600-800 nanometers.
Base reservoir temperature is room temperature；Design one group of difference ZrB2Sputtering power is that the Zr-B-O of the W of 80 W ~ 120 is nano combined thin The purpose is to find the optimal conditions of Zr-B-O nano compound film for film.Use Ar+ZrB is bombarded respectively2And ZrO2Two targets, in list ZrB is deposited simultaneously in the silicon base of face polishing2And ZrO2Composite membrane is constituted, using mechanical pump and molecular pump, base vacuum 4.0 × 10-4~5.0×10-4Pa, atmospheric pressure value are measured by ionization gauge, and sputter gas selects pure Ar in deposition process2, use mass flow Controller controls its flow and is maintained at 40 ~ 41 sccm；Total operating air pressure is maintained at 0.4 Pa in deposition process.The present invention exists In the case where there is no Assisted by Ion Beam and high temperature and pressure, using more target magnetic control co-sputtering systems in Ar2Hard is generated under environment Zr-B-O nano compound film, in order to solve component of machine and cutting element, existing hardness is low in use, film and base The bear building-up resultant force technical problems such as poor, anti-oxidant and provide one kind with ZrB2And ZrO2For pure metals, using magnetron sputtering technique One kind is synthesized by ZrB2And ZrO2The Zr-B-O nano compound film of the New Rigid of composition, find prepare with higher hardness, The process of application in terms of high film-substrate cohesion, good inoxidizability nano thin-film.
Experiment, first by the base silicon of use (Si) piece, is first successively surpassed with acetone, ethyl alcohol, deionized water before built up membrane Sound wave cleans 15 minutes, is immediately fed into vacuum deposition chamber after drying.Before deposition film, first with -400 V substrate bias, The Ar+ of 40 sccm carries out bias to sample under the operating air pressure of 5 Pa and cleans 15 minutes.It, can be by high-purity when deposition film ZrB2(99.99 %) and ZrO2(99.99 %) target is fixed on sputtering position and is precisely controlled the sputtering time of target to obtain film thickness For 600 ~ 800 nanometers of nano compound film.Use Ar+ZrB is sputtered simultaneously2And ZrO2Target, sputtering source technological parameter: substrate bias For -80 V, argon flow is 40 ~ 41 sccm, ZrO2Sputtering power is 80 W.By changing ZrB280 W ~ 120 of sputtering power W prepares a series of Zr-B-O nano compound film of hard.
The present invention further discloses the Zr-B-O nano compound films of hard to receive in preparation high rigidity, high film-substrate cohesion Application in terms of rice laminated film.The experimental results showed that do not have to any subsidiary conditions under, to ZrB2Sputtering power be The Zr-B-O nano compound film of the hard prepared under 120 W, hardness are apparently higher than the single thin film synthesized under the conditions of, and Elasticity modulus increases there is no excessive, makes the thin film system more suitable for actual needs.The film synthesized under this condition has Higher hardness (26.76 GPa), high film-substrate cohesion (2984.4 mN) and good antioxygenic property.
Present invention employs the composite theories of compound structure film growth, have carried out modulation ratio to each variable for participating in experiment Example analysis, as a result matches with expected, while also having confirmed the independence of selected variable.The present invention takes full advantage of more target magnetic The good function that control cosputtering system many reference amounts independently can be controlled accurately, has obtained reliable experimental data, and obtain The Parameter Conditions such as preferable mechanical performance.
The present invention joined important technology step: Ar during synthesizing composite membrane240 sccm of flow, work gas 0.5 Pa is pressed, the deposition power of substrate bias -80 V, Zr are 80 W.First deposition Zr is as transition zone, advantage and good effect It is that the stress of interface is enable to alleviate, to clearly enhance the binding force of film and substrate.
The present invention has carried out the X-ray of high angle to the single thin film and nano compound film that synthesize under various process conditions Diffraction (XRD) structural analysis.Nano hardness is carried out to film using Austrian Anton Paar company STEP6 type nano impress instrument It is tested with scratch.Using LFM1200C molding box formula Muffle furnace, a series of high-temperature oxydation for carrying out different temperatures to film is tested, from Room temperature continuous warming 30 minutes, after being separately heated to 650 DEG C ~ 950 DEG C, heat preservation 1 hour, Temperature fall was cooled to room temperature.
Present invention discover that: hard Zr-B-O nano compound film of the invention has higher hardness, high film-substrate cohesion, good Good inoxidizability etc., in ZrB2The laminated film hardness that sputtering power synthesizes under the conditions of being 120 W is up to 26.76 GPa, bullet Property 268.05 GPa of modulus, film substrate bond strength be 2984.4 mN, mass change exists after 1000 DEG C of high-temperature oxydations below 0.1 % or so.
Fig. 1 is the structural schematic diagram of the Zr-B-O nano compound film of deposition gained hard；
Fig. 2 is the SEM pattern in the Zr-B-O nano compound film cross section of deposition gained hard, shows that laminated film is shown In the structure that expected design is consistent；
Fig. 3 is the XRD diffracting spectrum of the Zr-B-O nano compound film of deposition gained hard, utilizes Bruker D8a type X-ray Diffractometer carries out object phase and crystal structure analysis to sample, the Cu Ka x-ray bombardment sample for being 1.5405 with wavelength, will be by The diffracting spectrum that XRD is obtained, which carries out qualitative object phase and crystal structure analysis to sample, can be observed how that the nanometer is multiple by this figure It closes in film and ZrB occurs2(001) and the hybrid orientation of (101), and it grown the ZrO of some tiny low temperature monoclinic phases2 (111) crystallite of crystal face；
Fig. 4 is that the Zr-B-O nano compound film of deposition gained hard compares the single layer ZrB under the conditions of sputtering power of 120 W2 Hardness and elastic modulus variation, in the ZrB of laminated film2When sputtering power is 120 W, the hardness of composite membrane reaches maximum；
Fig. 5 is that the Zr-B-O nano compound film of deposition gained hard compares the single layer ZrB under the conditions of sputtering power of 120 W2 Critical load figure, in the ZrB of laminated film2When sputtering power is 120 W, the Zr-B-O nano compound film prepared has Preferable film-base junction resultant force；
Fig. 6 is that the Zr-B-O nano compound film of deposition gained hard compares the single layer ZrB under the conditions of sputtering power of 120 W2 In the mass change figure respectively after aoxidizing in 650 DEG C ~ 950 DEG C air, show the ZrB in laminated film2Sputtering power When for 120 W, the Zr-B-O nano compound film prepared has preferable inoxidizability.
Result above proves: the present invention " the Zr-B-O nano compound film of magnetron sputtering technique preparation and application " has excellent Good machinery and mechanical property and good antioxygenic property, in Ar2Zr-B-O nanometers of the hard prepared under environment multiple Important application prospect will be had in fields such as component of machine, cutting elements by closing film.
Detailed description of the invention
Fig. 1: the structural schematic diagram of Zr-B-O nano compound film in this series；
Fig. 2: the SEM pattern in the cross section of Zr-B-O nano compound film in this series；
Fig. 3: the XRD diffraction spectra of Zr-B-O nano compound film in this series；
Fig. 4: the hardness and elastic modulus change of Zr-B-O nano compound film in this series；
Fig. 5: the critical load figure of Zr-B-O nano compound film in this series；
Fig. 6: mass change figure before and after the oxidation of Zr-B-O nano compound film in this series；
Fig. 7: the model JGP-450 magnetron sputtering depositing system that this series uses；
1. controllable sample rotates platform；2. sample baffle rotary manual operation valve；3. substrate heats tungsten wire；4. sample；5. sample is kept off Plate；6. gas feed；7.HTFB turbomolecular pump；8. pulse direct current target；9. radio frequency cathode target.
Specific embodiment
The present invention is described below by specific embodiment.Unless stated otherwise, technological means used in the present invention It is method known in those skilled in the art.In addition, embodiment is interpreted as illustrative, it is not intended to limit the present invention Range, the spirit and scope of the invention are limited only by the claims that follow.To those skilled in the art, without departing substantially from this Under the premise of invention spirit and scope, to the various changes or change of material component and dosage progress in these embodiments It belongs to the scope of protection of the present invention.The raw materials used in the present invention is commercially available.
For that can further appreciate that the contents of the present invention, feature and effect, cooperation Detailed description of the invention are as follows:
Use equipment, step and method:
Use equipment: the more target magnetic control co-sputtering depositing systems of JGP-450 type are used to synthesize by ZrB2And ZrO2The hard Zr- of composition B-O nano compound film is by Tianjin Normal University and Shenyang Scientific Instrument Factory, Chinese Academy of Sciences's joint research and development " JGP-450 type Magnetron sputtering depositing system ", structure is as shown in Figure 7.Purity is the ZrB of 99.99 %2And ZrO2Target material is individually positioned in very On empty indoor magnetic control pulse direct current target platform 8 and on radio frequency cathode target platform 9, sample 4 is placed on controllable sample rotates in vacuum chamber On turntable sample stage 1；Pumping system is completed by mechanical pump and HTFB turbomolecular pump 7, and atmospheric pressure value is measured by ionization gauge, Ar Enter vacuum chamber through air inlet 6, and controls its gas flow by mass flowmenter.Computer program accurately controls each target Sputtering time.They available single thin film deposition and two targets of sedimentation time by changing each target The sputtering sedimentation time obtains the deposition rate of Zr-B-O nano compound film to material simultaneously.
Specific synthesis technologic parameter:
Ar flow: 40 ~ 41 sccm；Background vacuum: 4.0 × 10-4~5.0×10-4Pa；Operating air pressure: 0.4 Pa；Sputtering source Technological parameter: radio frequency target ZrO2Sputtering power is 80 W.Other technological parameters: target-substrate distance is 7 cm, and substrate bias is -80 V.
It should be understood that magnetic control sputtering system (MS) equipment of other models can use.
Embodiment 1
Change pulse direct current target ZrB2Sputtering power condition synthesizes Zr-B-O nano compound film:
(1) 15 min successively are cleaned by ultrasonic to silicon (Si) substrate with acetone, absolute alcohol and deionized water before experiment, are put after drying Into magnetron sputtering plating room.
(2) chamber is vacuumized, makes the indoor background vacuum of chamber 3.9 × 10-4~4.0×10-4 Pa。
(3) gate valve is adjusted, 5 Pa of operating air pressure is made, Ar charge flow rate is controlled with mass flow flowmeter, is allowed to protect It holds in 40 sccm, opens grid bias power supply, adjust substrate bias to -400 V, it is normal that electric current plays table, uses Ar+Sample is at least banged After hitting 15 min of cleaning, grid bias power supply is closed.
(4) radio-frequency power supply is opened, Ar charge flow rate is controlled with mass flowmenter, is allowed to be maintained at 40 ~ 41 sccm, adjust Radio-frequency power supply is to normal build-up of luminance；Pulse dc power is opened, adjusts voltage knob to normal build-up of luminance；Operating air pressure is adjusted to 0.4 Pa, radio frequency target ZrO2Sputtering power is 80 W, opens grid bias power supply and adjusts substrate bias to -80 V.
(5) 0.4 Pa of operating air pressure is kept at this time.They available list of sedimentation time by changing each target Layer film and Zr-B-O nano compound film.Wherein ZrB2And ZrO2The ratio between deposition about 2:1, total film thickness is 800 to receive Rice.
(6) film is down to room temperature until temperature and just opens chamber taking-up in high vacuum chamber.
Change pulse direct current target ZrB2Sputtering power condition synthesizes Zr-B-O nano compound film:
Ar flow: 40 ~ 41 sccm；Background vacuum: 3.9 × 10-4~4.0×10-4Pa；Operating air pressure: 0.4 Pa；Sputtering source Technological parameter: ZrO2Sputtering power is 80 W, ZrB2Sputtering power is 120 W；Target-substrate distance is 7 cm；- 80 V of substrate bias.
For optimum condition, the preparation before experiment is as above (1)-(4) described, according to radio frequency target ZrO2It is straight with pulse Flow target ZrB2Deposition, calculate corresponding sputtering time.Sedimentation time is set as 10800 s, base reservoir temperature is room temperature.In this way In Ar2It can be obtained by the Zr-B-O nano compound film of needs under environment.
The present invention is utilized respectively Austrian NST to the single thin film and nano compound film that synthesize under various process conditions and receives Rice scratching instrument carries out nano hardness to film and scratch is tested.Simultaneously by Muffle furnace, a series of different temperatures are carried out to film High-temperature oxydation test.
The data main result of test is as follows:
1, for single thin film: ZrB2The hardness of single thin film is not high, is 18.41 GPa.
2, for laminated film: in ZrB appropriate2It is synthesized under the conditions of sputtering power combination argon flow nano combined The hardness of film is generally higher than two single thin films.In ZrB2Sputtering power is the Zr-B-O nano compound film prepared under 120 W Hardness is up to 26.76 GPa, while its elasticity modulus is 268.05 GPa.
3, for laminated film: in ZrB appropriate2It is synthesized under the conditions of sputtering power combination argon flow nano combined The critical load of film is higher than single thin film.In ZrB2Sputtering power is the Zr-B-O nano compound film prepared under 120 W, Its critical load is up to 2984.4 mN.
Generally speaking: the synthesis such as hardness, film-substrate cohesion of the Zr-B-O nano compound film synthesized under the conditions of each Single layer ZrB of the mechanical performance than being synthesized under similarity condition2The corresponding performance of film has clear improvement；In contrast, synthesis ZrB2Sputtering power is the Zr-B-O nano compound film under 120 W, and mechanical property improves the most obvious, and nano hardness can To reach 26.76 GPa, while elasticity modulus is 268.05 GPa.Compared to ZrB2Single thin film, the performances such as inoxidizability Have and be obviously improved, provides the foundation for actual application.It can further be prepared by controlling technological parameter with excellent Mechanical performance Zr-B-O nano compound film.
Embodiment 2
The application direction of hard Zr-B-O nano compound film: wear-and corrosion-resistant component, high-temperature protection coating, hard engineering material.
As mechanical engineering material, such as cutting element, turbine components, computer magnetic recording hard disk require film into Row surfacecti proteon.As film is in the extensive use of the neighborhoods such as machinery, electronics, metallurgy, aerospace, hardness number is no longer There is new requirement in terms of mechanics of surface, fretting wear, resistance to high temperature oxidation and corrosion resistance in unique index. And utilize the Zr-B-O nano compound film of the more target magnetic control co-sputtering depositing system preparations of JGP-450 type that there is higher hardness, height Film-substrate cohesion, good crocking resistance and high temperature oxidation resistance.ZrO2And ZrB2Laminated film in extreme circumstances The fields such as cutting element, component of machine are with important application prospects.
Using the more target magnetic control co-sputtering depositing systems of JGP-450 type by ZrO2And ZrB2Zr-B-O nanometers of hard of synthesis are multiple Film is closed, the mechanical performances such as material, hardness, film-film-substrate binding strength not only can be improved, and can further improve material High temperature oxidation resistance.
Modified provide in the surface of the materials such as hard Zr-B-O nano compound film is cutting element, component of machine can Can, compared to single layer ZrB2Film, the Zr-B-O using the more target magnetic control co-sputtering depositing system preparations of JGP-450 type are nano combined Film has wider application in structural membrane technology neighborhood:
The more target magnetic control co-sputtering depositing systems of the JGP-450 type that the present invention is disclosed and proposed prepare Zr-B-O nano compound film, Those skilled in the art can be by using for reference present disclosure, and the links such as appropriate feed change, technological parameter are realized.Method of the invention Pass through preferred embodiment with product to be described, related technical personnel can obviously not depart from the content of present invention, essence Method described herein and product are modified or appropriate changes and combinations in mind and range, Lai Shixian the technology of the present invention.It is special Not it should be pointed out that so similar replacement and apparent to those skilled in the art, the Ta Mendou of change It is deemed to be included in spirit of that invention, range and content.

Claims (6)

1. a kind of synthetic method of hard Zr-B-O nano compound film, which is characterized in that it be under argon gas (Ar) environment, by ZrB2Target (99.99 %) and ZrO2Target (99.99 %) is utilized respectively the mode of pulse direct current and rf magnetron sputtering in silicon (Si) ZrB is deposited on base simultaneously2And ZrO2Prepare Zr-B-O nano compound film；Sedimentation time is 3 hours, wherein ZrB2With ZrO2The ratio between deposition be 2:1, total film thickness is 600-800 nanometers.
2. the synthetic method of hard Zr-B-O nano compound film described in claim 1, it is characterized in that: more using JGP-450 type Target magnetic control co-sputtering system designs one group of difference ZrB2Sputtering power is that the Zr-B-O nano compound film of the W of 80 W ~ 120 makees ratio Compared with experiment, Ar is utilized+ZrB is bombarded respectively2And ZrO2Two targets deposit ZrB simultaneously in silicon (Si) substrate2And ZrO2Prepare Zr- B-O nano compound film；Wherein ZrB2And ZrO2The ratio between deposition be 2:1, using mechanical pump and molecular pump, by ionization gauge It measures chamber pressure value, base vacuum is made to be evacuated to 4.0 × 10-4~5.0×10-4Pa, sputter gas is selected high in deposition process Pure Ar2(99.999 %) controls its flow with mass flow controller and is maintained at 40 ~ 41 sccm, and base reservoir temperature is room temperature, is splashed Total operating air pressure is maintained at 0.4 Pa during penetrating.
3. the synthetic method of hard Zr-B-O nano compound film described in claim 2, wherein sinking simultaneously in silicon (Si) substrate Product ZrB2And ZrO2Zr-B-O nano compound film is prepared, is referred to: being first successively immersed in acetone, ethyl alcohol, ultrasound in deionized water Wave cleans 15 minutes, is immediately fed into vacuum deposition chamber after drying, before deposition film, first keeps the operating air pressure of 5.0 Pa Condition utilizes Ar under -400 V biass+The cleaning of 15 minutes biass carried out to sample, when deposition film, by high-purity ZrB2Target (99.99 %) and ZrO2When target (99.99 %) alternately rotates to sputtering position and accurately controls the sputtering of each target Between；Use Ar+Sputter two target sources, radio frequency target ZrO2Sputtering power be 80 W, pulse direct current target ZrB2Sputtering power be 120 W, target-substrate distance are 7 cm, and substrate bias is -80 V.
4. the synthetic method of hard Zr-B-O nano compound film described in claim 2, wherein base reservoir temperature is room temperature, received Rice hardness is 26.76 GPa, and elasticity modulus is 268.05 GPa, while having receiving for good film-substrate cohesion and antioxygenic property Rice laminated film.
5. the synthetic method of hard Zr-B-O nano compound film described in claim 2, it is characterized in that auxiliary without any ion beam It helps in the case where being required with the harsh conditions of high temperature and pressure, in Ar2Growth deposition Zr-B-O nano compound film under environment.
6. using the hard Zr-B-O nano compound film of claim 1 method preparation in preparation high film-substrate cohesion, good Application in terms of inoxidizability nano thin-film.
CN201910831042.2A 2019-09-04 2019-09-04 A kind of synthetic method and application of hard Zr-B-O nano compound film Pending CN110484883A (en)

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Application publication date: 20191122