CN108998769A - A kind of two-part pulsed magnetron sputtering method - Google Patents

A kind of two-part pulsed magnetron sputtering method Download PDF

Info

Publication number
CN108998769A
CN108998769A CN201810642700.9A CN201810642700A CN108998769A CN 108998769 A CN108998769 A CN 108998769A CN 201810642700 A CN201810642700 A CN 201810642700A CN 108998769 A CN108998769 A CN 108998769A
Authority
CN
China
Prior art keywords
pulse
film
magnetron sputtering
target
sputtering method
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810642700.9A
Other languages
Chinese (zh)
Inventor
杨超
蒋百铃
曹政
董丹
马加豪
王晓楠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian University of Technology
Original Assignee
Xian University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian University of Technology filed Critical Xian University of Technology
Priority to CN201810642700.9A priority Critical patent/CN108998769A/en
Publication of CN108998769A publication Critical patent/CN108998769A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F4/00—Processes for removing metallic material from surfaces, not provided for in group C23F1/00 or C23F3/00
    • C23F4/04—Processes for removing metallic material from surfaces, not provided for in group C23F1/00 or C23F3/00 by physical dissolution
    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3435—Applying energy to the substrate during sputtering
    • C23C14/345—Applying energy to the substrate during sputtering using substrate bias
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3485—Sputtering using pulsed power to the 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
    • C23C14/34—Sputtering
    • C23C14/3492—Variation of parameters during sputtering

Abstract

The invention discloses a kind of two-part pulsed magnetron sputtering methods, two-part impulse electric field environment is constructed mainly between cathode targets and anode vacuum cavity, pass through the allotment to two sections of stage pulse intrinsic parameters, Various Tissues and film of good performance can quickly be prepared, such as: C base, Ti base, Cr base or Si base film etc., anti-attrition film, the TiO of the ganoine thin film of especially TiN/CrN series, Ti-C-N/Cr-C-N series2The photocatalysis film of series or the semiconductive thin film of Si series.Traditional pulse magnetron sputtering can be collected and prepare the advantages that morphology is fine and close, surface is smooth and film base is well combined, and pulsed magnetron sputtering can be improved there are extremely low deposition rate and avoid the defective workmanships such as more difficult maintenance high-power gas discharge.On the other hand, the simple and direct stabilization of preparation method, process is few, and yield is high, is able to satisfy the requirement of industrialized production.

Description

A kind of two-part pulsed magnetron sputtering method
Technical field
The invention belongs to material manufacture technical fields, and in particular to a kind of two-part pulsed magnetron sputtering method.
Background technique
Magnetically controlled DC sputtering technology is one of PVD vacuum coating technology of current main-stream, and because having, depositing temperature is low, prepares The advantages that film surface is smooth, component can be matched accurately, is widely used in semiconductor, optics, dicoration and light metal surface Simple substance or compound film preparation field.But it is because deposited particles ionization level is low, on the one hand causes deposited particles around plating property Difference, it is difficult to obtain film layer in homogeneous thickness in large scale or complex-shaped workpiece surface, on the other hand easily cause stringer The defective workmanships such as poor are closed by tissue looseness, film base junction, therefore influence the production efficiency of magnetically controlled DC sputtering and the service life of film layer.
There is many technical deficiencies caused by lower ionization level, research for deposited particles in magnetically controlled DC sputtering technology Personnel develop high-power magnetron sputtering technique, by significantly promoting yin-yang interpolar DC electric field power, increase yin-yang interpolar The ionization degree of Ar atom, increases Ar with this+The intensity and the frequency of bombarding cathode target surface, realize deposited particles miss the target quantity with from The promotion of rate.But be constrained to the heat-sinking capability of target surface and the general power setting of power supply, for a long time powerful gas etc. from Daughter electric discharge necessarily causes the melting of target part to damage.Therefore pulsed magnetron sputtering technology is developed, on the one hand, utilize pulse The on-off characteristic of electric field reduces the thermal accumlation of target, and the melting of target is avoided to damage；On the other hand, impulse electric field is utilized Isoflux principle obtains high peak value target power density (1~3kW/cm under lesser duty cycle condition2), reached with this and is mentioned Deposited particles are risen to miss the target the purpose of quantity and ionization level.But the technological effect of the technology in actual application reaches far away To expection, mainly due under lower duty cycle condition, the inert gas transient state of yin-yang interpolar is induced to be formed it is strong equal from When daughter, not only need power supply that there is extremely accurate and quick feedback regulation system, but also biggish reaction gas need to be provided Pressure could induce the progress with the strong plasma gas discharge of maintenance in stage pulse.And the raising of reaction pressure can substantially drop The deposition rate of low film.Also, since the gas discharge of magnetron sputtering technique belongs to the abnormal glow discharge stage, it is high-power must So biggish electric field strength need to be generated in interpolar, the deposited particles of ionization is caused to return vulnerable to the attraction of the strong electric field of negative polarity of cathode Target surface.It is above to influence to limit pulsed magnetic so that the deposition rate of film occurs significantly reducing compared with magnetically controlled DC sputtering Control successful popularization of the sputtering technology in industrial circle.
Summary of the invention
For the technical deficiency of existing pulsed magnetron sputtering, the object of the present invention is to provide a kind of two-part impulse magnetrons to splash Shooting method, collection pulsed magnetron sputtering prepares the advantages that morphology is fine and close, surface is smooth and film base is well combined, and can change Kind pulsed magnetron sputtering is there are extremely low deposition rate and avoids one kind of the defective workmanships such as more difficult maintenance high-power gas discharge new Type magnetic control sputtering vacuum coating method,
To achieve the above object the invention adopts the following technical scheme:
The core of two-part pulsed magnetron sputtering technology is the building of novel two-part impulse electric field, two-part impulse electric field Mode is that there are two continuous and relatively independent adjustable plasmas for tool within the pulsed discharge stage in a complete pulse period Discharge regime.And the two different discharge regimes are respectively defined as 1 grade of stage pulse and 2 grades of stage pulses (such as Fig. 1 institute Show), or referred to as prime stage pulse and rear class stage pulse.The two-part pulse power usually 1 grade of stage pulse apply compared with Low power density is gradually ionized with to induce the inert gas between cathode target surface and anode cavity and forms weak plasma, and 2 Grade stage pulse then applies biggish power density, ionizes the weak plasma of interpolar largely rapidly and forms strong plasma. Since the formation of weak plasma in 1 grade of stage pulse has conducive to the acquisition of plasma strong in 2 grades of stage pulses, reduce The critical voltage for inducing the strong plasma of yin-yang interpolar, can reduce the probability that depositing ions again return to cathode target surface, with this Improve the technical deficiency that traditional pulse electric field magnetron sputtering technique has extremely low deposition rate.Meanwhile 1 grade of stage pulse can also Giving the certain ion bombardment of matrix makes its temperature rise, in 2 grades of stage pulses that film deposition mainly occurs, particle deposition to base When body surface face, good surface-active and diffusion energy can get, not only grow conducive to the densification of Thin Film Tissue, but also can subtract Few film stress because of caused by lattice lattice mismatch falls off, and for quick preparation structure densification and film base junction is closed good film and mentioned Advantage is supplied.In addition, according to the service condition of film itself, the power density and duty of Reasonable Regulation And Control two-stage stage pulse Than etc. parameters, to thin film growth process be oriented regulation, it can be achieved that special construction and performance film preparation.
In simple terms, the purpose of the present invention can be realized by following committed step: first with three phase full wave rectification, IGBT The main circuit of inversion and high frequency transformer boosting, which opens up benefit structure, reaches the output characteristics of power supply: 1 grade of stage pulse maximum output Power 4kW, 2 grades of stage pulse peak power output 6kW, output voltage zero load be greater than -1200V (peak value), band carry 0~- 1000V, two-stage pulse output average current are that 0.1~8.0A is continuously adjusted, Maximum Peak Impulse Current is up to 1000A, arteries and veins Rush that 10~100Hz of working frequency is continuously adjustable, 40~60kHz of pulse modulation frequency is continuously adjustable, two-stage pulse duty factor is 2.5~80% continuously adjustable, the total largest duty cycle 90% of two-stage pulse, supply voltages and current precision≤1%.Two-stage pulse rank Section is mutually indepedent, and parameter setting is non-interference, is mutually matched to be formed with the stair-stepping two-part of continous way by control system Pulse signal；The novel two-part impulse electric field cathode terminal of building is loaded on into the circular cathode target that area is Φ 100mm, sun The cylinder vacuum cavity that volume is Φ 450mm × H400mm is extremely loaded on, four cathode targets are installed on vacuum chamber side 304 stainless steel framework of circle on surface having a size of Φ 225mm, framework are mutually in 90 ° uniformly to divide apart from cathode target outer 5mm Cloth, surface roughness is less than 0.8 μm；Heating device is also equipped in vacuum chamber, it can be by temperature control system to the temperature in vacuum chamber Degree is adjusted, to regulate and control depositing temperature when film growth.
A kind of two-part pulsed magnetron sputtering method, comprising the following steps:
Sample to be coated is immersed in alcoholic solution after ultrasonic cleaning 10min by step 1, is taken out with pure N2Air-blowing It is dry, it is placed in vacuum chamber on sample workpiece frame, vacuum chamber is evacuated to 6 × 10 by work rest revolving speed 5r/min-5~9 × 10-4Pa, It is passed through argon gas and vacuum degree is maintained at 0.1~1.2Pa；
Step 2, unlatching two-part pulse target power supply and pulsed negative bias matrix power supply carry out icon bombardment cleaning to sample, Control parameter are as follows: 1 grade of pulse target voltage is -300~-400V, 2 grades of pulses -400~-500V of target voltage, 10~100Hz of frequency, 1 grade of pulse duty factor, 2.5~80%, 2 grades of pulse duty factors 2.5~80%, total duty ratio≤90%, stage pulse modulating frequency 40~60kHz, the back bias voltage of the matrix pulse power are -400~-600V, duty ratio 80~98%, 50~250kHz of frequency, from Sub- 10~30min of scavenging period；
Step 3 is passed through reactant gas (Ar, N2、O2、CH4Deng) and vacuum degree in vacuum chamber maintained 0.4~ 1.0Pa connects adjustable inductance for 1 grade of pulse target voltage and decays to -400~-600V, and 2 grades of pulse target voltages decay to -600 ~-900V, pulse frequency are adjusted to 20~90Hz, 1 grade of pulse duty factor, 10~70%, 2 grades of pulse duty factors 2.5~40%, Total duty ratio≤90%, 40~60kHz of stage pulse modulating frequency, 1 grade of peak value of pulse target current are 10~100A, 2 grades of pulses Peak value target current is 100~400A, and the back bias voltage of the matrix pulse power is -60~-90V, duty ratio 80~98%, frequency 40~ 60kHz, 45~120min of film sedimentation time；
After the completion of step 4, film deposition, the two-part pulse power, pulsed negative bias matrix power supply and reaction gas are closed Valve takes out after sample is cooling.
It further include constructing the novel two-part pulse power, wherein utilize three phase full wave rectification, IGBT inversion and high frequency transformation The main circuit of device boosting, which opens up benefit structure, reaches the output characteristics of power supply: 1 grade of stage pulse peak power output 4kW, 2 grades of pulses Stage peak power output 6kW, output voltage zero load is greater than -1200V (peak value), band carries 0~-1000V, and two-stage pulse output is flat Equal electric current is that 0.1~8.0A is continuously adjusted, Maximum Peak Impulse Current connects up to 1000A, 10~100Hz of pulsed operation frequency It is continuously adjustable to continue adjustable, 40~60kHz of stage pulse modulating frequency, two-stage pulse duty factor be it is 2.5~80% continuously adjustable, The total largest duty cycle 90% of two-stage pulse, supply voltage and current precision≤1%, then by the novel two-part pulse electricity of building Field cathode terminal loads on the circular cathode target that area is Φ 100mm, and it is Φ 450mm × H400mm's that anode tap, which loads on volume, Cylinder vacuum cavity, four cathode targets are installed on 304 stainless steel of circle on vacuum cavity side surface having a size of Φ 225mm Framework, framework is apart from cathode target outer 5mm, and mutually in 90 ° to be uniformly distributed, surface roughness is less than 0.8 μm.
It, can be as desired by temperature control system to vacuum chamber in application two-part pulsed magnetron sputtering method of the invention Interior temperature is adjusted, and controls the film deposition temperature in vacuum chamber with this, convenient for the growth pattern and knot of tissue to film Structure is regulated and controled.
It, can be excellent before deposited compound film as needed in application two-part pulsed magnetron sputtering method of the invention Transition zone similar in pure metal prime coat of a layer thickness less than 300nm or structure is deposited, first to improve between film and matrix Binding force.Such as: on steel/iron sample deposit hard TiAlN thin film when, can after plasma clean one layer of preferential deposition it is pure The film-substrate cohesion between TiAlN thin film and sample can be improved then in depositing TiN thin film in the prime coat of Ti.
The cooling and taking-up of step 4 use any one following mode: the sample for completing plated film is cooled in vacuum chamber It takes out after 30~50 DEG C, is then cooled to room temperature in atmospheric environment；Or the sample of completion plated film is directly cold in vacuum chamber But to taking out after room temperature.
It is Ar, N that step 3, which is passed through reactant gas,2、O2、CH4Deng.
Two-part pulsed magnetron sputtering method is applied to all kinds of membrane samples to be plated of plated film field, including M2 high-speed steel, magnesium Aluminium light-alloy, stainless steel select film coating composition according to the service condition of sample use environment and determine organization structure of film To regulation, including plated film C base, Ti base, Cr base, Si base film, the ganoine thin film of TiN/CrN series, Ti-C-N/Cr-C-N series Anti-attrition film, TiO2The photocatalysis film of series or the semiconductive thin film of Si series.
The invention has the following advantages that two-part pulsed magnetron sputtering method of the invention, can collect traditional pulse magnetic control and splash It penetrates and prepares the advantages that morphology is fine and close, surface is smooth and film base is well combined, and pulsed magnetron sputtering can be improved there are poles Low deposition rate and avoid the defective workmanships such as more difficult maintenance high-power gas discharge.On the other hand, the simple and direct stabilization of preparation method, work Sequence is few, and yield is high, is able to satisfy the requirement of industrialized production.
Detailed description of the invention
Fig. 1 is the waveform diagram of the pulse current different ratio of the two-part pulse power.
Specific embodiment
The present invention is further elaborated in the following with reference to the drawings and specific embodiments.
Embodiment 1
It is thin that in monocrystalline silicon piece and M2 high-speed steel sample surfaces hard TiN is prepared by two-part pulsed magnetron sputtering method Film is implemented according to the following steps:
Step 1: by the M2 high speed steel sample of the monocrystalline silicon piece of size 20mm × 20mm and Φ 50mm through alcoholic solution ultrasound After wave cleans 10min, with pure N2On the dry rotational workpieces frame being put into vacuum chamber of air-blowing, revolving speed 5r/min, target and sample it Between distance be set as 130mm, vacuum degree will be then evacuated in vacuum chamber less than 9 × 10-5Argon gas is passed through when Pa, argon flow is 60mL/min, holding vacuum degree are 0.5Pa.
Icon bombardment cleaning, control are carried out to sample Step 2: opening two-part pulse Ti target power supply and the matrix pulse power Parameter processed are as follows: the Ti target voltage of 1 grade of stage pulse is -394V, average target current is 1.2A, duty ratio 40%, 2 grades of pulse ranks The Ti target voltage of section is 0V, average target current is 0A, duty ratio 0%, pulse frequency 50Hz, pulse modulation frequency 50kHz； The back bias voltage of the matrix pulse power is -500V, frequency 40kHz, duty ratio 95%.Ion Cleaning time 15min.
Step 3: depositing Ti prime coat, control parameter are as follows: the Ti target voltage of 1 grade of stage pulse is -402V, average target is electric Stream is 2.0A, duty ratio 40%, and the Ti target voltage of 2 grades of stage pulses is 0V, average target current is 0A, duty ratio 0%, arteries and veins Rushing frequency is 50Hz, pulse modulation frequency 50kHz；The back bias voltage of the matrix pulse power is adjusted to -120V, frequency 60kHz, duty Than being 90%.Duration of deposition 5min.
Step 4: starting to be passed through N2Gas, flow set 20mL/min, vacuum degree maintain 0.8Pa, start depositing TiN Film.Control parameter are as follows: the Ti target voltage of 1 grade of stage pulse is -329V, average target current is 0.9A, duty ratio 40%, 2 The Ti target voltage of grade stage pulse is -615V, average target current is 3.6A, duty ratio 8%, pulse frequency 50Hz, pulse Modulating frequency 50kHz；The back bias voltage of the matrix pulse power is adjusted to -60V, frequency 60kHz, duty ratio 90%.Deposition continues Time 40min.
Step 5: closing the two-part pulse power, pulsed negative bias matrix power supply and reaction gas after the completion of film deposition Valve takes out after sample is cooled to 40 DEG C, is cooled to room temperature under atmospheric environment.
The tissue topography and physical property of depositing TiN thin film are determined, wherein the surface topography of film and section Pattern is observed by scanning electron microscope (SEM), and film thickness is directly measured by section SEM photograph and obtained；Roughness is using former Sub- force microscope (AFM) is at 5 × 5 μm2Measurement in range；The crystal structure of film is detected by X-ray diffractometer (XRD), Film is calculated along each with halfwidth numerical value using the diffraction peak intensity in the XRD spectrum of pure Ti film using Scherrer formula Crystal face grows the size of crystal grain, and is averaged the average grain size as film.With receiving equipped with Bo Shi diamond penetrator Rice pression sclerometer calculates hardness, and the depth that pressure head is vertically pressed into sample surfaces is the 1/10 of film thickness, uses Oliver- Pharr formula is calculated, and Poisson's ratio takes 0.25；Using ball-disc type micro tribology experiment instrument (temperature 25 ± 1 in atmospheric environment DEG C, 20 ± 1RH% of relative air humidity) measurement coefficient of friction, pressure 2N, using laser co-focusing to the progress of film wear volume It measures and calculates wear rate (WC-Co hard alloy abrading-ball slides 150m in sample surfaces with the linear velocity of 25mm/s).
Test result is as follows:
Fine and close columnar crystal structure is presented in TiAlN thin film, with a thickness of 3.117 μm, deposition rate 70nm/min, average crystal grain ruler Very little is 13nm, surface roughness Ra 10nm, hardness 29.6GPa, coefficient of friction 0.65, wear rate 1.42 × 10-14m3/N· m。
Embodiment 2
M2 high-speed steel sample surfaces by two-part pulsed magnetron sputtering method in mirror finish deposit low-friction coefficient Cr-C film, according to the following steps implement:
Step 1: M2 high-speed steel sample surfaces are ground through 400,600,800,1000,1200 and No. 1500 waterproof abrasive papers respectively It is flat, then mirror-finished, sample is then dipped to progress ultrasonic cleaning 10min in alcoholic solution, is used after the completion of cleaning Pure N2Air-blowing dry doubling is placed in vacuum chamber on rotatable workpiece frame, and revolving speed is set as 4r/min, between target and sample away from From 130mm is set as, vacuum will be evacuated in vacuum chamber less than 9 × 10-5Argon gas is passed through when Pa, argon stream amount is 30mL/min, Vacuum degree maintains 0.2Pa.
Step 2: it is clear to sample surfaces progress plasma etching to open a direct current Cr target power supply and the matrix pulse power It washes, control parameter are as follows: direct current Cr target voltage is -420V, and Cr target current is 0.3A；The back bias voltage of the matrix pulse power is set as- 500V, frequency 40kHz, duty ratio 95%.Ion Cleaning time 15min.
Step 3: depositing pure Cr prime coat, control parameter are as follows: direct current Cr target voltage is set as -550V, Cr target current 1.5A；The back bias voltage of the matrix pulse power is adjusted to -150V, frequency 60kHz, duty ratio 90%.Duration of deposition 5min.
It is left three two-part pulse C target power supplies Step 4: opening, starts to deposit Cr-C film transition layer.Control parameter Are as follows: two-part pulse C target current, 1 grade of pulse C target voltage are gradually decrease to -450V from 0V, and target current is progressively increased to by 0A 0.5A, duty ratio 70%；2 grades of pulse C target voltages are gradually decrease to -650V from 0V, and target current has 0A to be gradually increased to 1.5A, Duty ratio is 10%；Pulse frequency is set as 80Hz, and pulse modulation frequency is set as 50kHz；The back bias voltage of the matrix pulse power It is gradually adjusted by -150V to -120V, frequency 60kHz, duty ratio 90%.Duration of deposition 10min.
Step 5: fixed C target electrical parameter is constant, Cr-C working lining is deposited.Control parameter are as follows: two-part pulse C target current, 1 grade of pulse C target voltage -450V, target current 0.5A, duty ratio 70%；2 grades of pulse C target voltage -650V, target current 1.5A are accounted for Sky is than being 10%；Pulse frequency 80Hz, pulse modulation frequency 50kHz；Direct current Cr target voltage is set as -330V, and target current is 0.05A；The back bias voltage of the matrix pulse power is adjusted to -60V, frequency 60kHz, duty ratio 90%.Duration of deposition 40min。
Step 6: being cooled to room temperature after the completion of plated film and taking out sample.
The institutional framework and physical property of deposition Cr-C film are determined, wherein the surface topography of film and section Pattern is observed by scanning electron microscope (SEM), and film thickness is directly measured by section SEM photograph and obtained；Roughness is using former Sub- force microscope (AFM) is at 5 × 5 μm2Measurement in range；It is hard with the nanometer pression sclerometer measuring and calculating equipped with Bo Shi diamond penetrator Degree, the vertical compression distance of pressure head are the 1/10 of film thickness, are calculated using Oliver-Pharr formula, Poisson's ratio takes 0.25；(25 ± 1 DEG C of temperature, 20 ± 1RH% of the relative air humidity) surveys in atmospheric environment using ball-disc type micro tribology experiment instrument Coefficient of friction is measured, pressure 5N measures film wear volume using laser co-focusing and calculates wear rate (WC-Co is hard Matter Alloy Balls In Milling slides 150m in sample surfaces with the linear velocity of 25mm/s).
Test result is as follows:
Cr-C film shows fine and close institutional framework, and with a thickness of 914nm, surface roughness Ra 3nm, hardness is 18.5GPa, coefficient of friction 0.05, wear rate 4.71 × 10-17m3/N·m。
Embodiment 3
It is thin in monocrystalline silicon piece or the 304 stainless steel sample surfaces deposition pure Ti of nanometer by two-part pulsed magnetron sputtering method Film is implemented according to the following steps:
Step 1: by the M2 high speed steel sample of the monocrystalline silicon piece of size 20mm × 20mm or Φ 50mm through alcoholic solution ultrasound After wave cleans 15min, with pure N2Air-blowing is dry to be put into vacuum chamber on rotational workpieces frame, work rest revolving speed 5r/min, target and sample The distance between product are set as 130mm, and vacuum in vacuum chamber is evacuated to 9 × 10-5Argon gas (argon flow 80mL/ is passed through when Pa Min), vacuum degree maintains 0.6Pa.
Plasma etching is carried out to sample surfaces Step 2: opening two-part pulse Ti target power supply and the matrix pulse power Cleaning, control parameter are as follows: two-part pulse Ti target power supply, 1 grade of pulse Ti target voltage are -400V, target current 0.8A, and duty ratio is 10%；2 grades of pulse Ti target voltages are 0V, target current 0A；Pulse frequency is 50Hz, pulse modulation frequency 60kHz；Matrix pulse Power supply back bias voltage is set as -500V, frequency 40kHz, duty ratio 98.5%.Ion Cleaning time 15min.
Step 3: depositing pure Ti film layer, control parameter are as follows: two-part pulse Ti target power supply, 1 grade of pulse Ti target voltage is- 420V, target current 1.0A, duty ratio 10%；2 grades of pulse Ti target voltages are -635V, target current 5.8A, duty ratio 10%； Pulse frequency is 50Hz, pulse modulation frequency 60kHz；It is gradually adjusted to -70V within matrix pulse power back bias voltage 3min, Frequency 40kHz, duty ratio 90%.Film sedimentation time 60min.
Step 4: sample takes out after being cooled to room temperature in vacuum chamber after the completion of plated film.
The pattern and physical property of pure Ti film obtained are determined, wherein the surface topography of film and section shape Looks are observed by scanning electron microscope (SEM), and film thickness is directly measured by section SEM photograph and obtained；Roughness uses atom Force microscope (AFM) is at 5 × 5 μm2Measurement in range；The crystal structure of film is detected by X-ray diffractometer (XRD), is made Film is calculated along each crystalline substance with halfwidth numerical value using the diffraction peak intensity in the XRD spectrum of pure Ti film with Scherrer formula It looks unfamiliar the size of germination, and is averaged the average grain size as film.With the nanometer that Bo Shi diamond penetrator is housed Pression sclerometer calculates hardness, and pressure head is vertically pressed into sample surfaces 200nm depth, is counted using Oliver-Pharr formula It calculates, Poisson's ratio takes 0.25.
Test result is as follows:
Film thickness is 8.798 μm, deposition rate 147nm/min, surface roughness Ra 15nm, average grain size For 18nm, hardness 3.67GPa.
The above is present pre-ferred embodiments, for the ordinary skill in the art, according to the present invention Introduction, in the case where not departing from the principle of the present invention and spirit, changes, modifications, replacement and change that embodiment is carried out Type is still fallen within protection scope of the present invention.

Claims (7)

1. a kind of two-part pulsed magnetron sputtering method, which comprises the following steps:
Sample to be coated is immersed in alcoholic solution after ultrasonic cleaning 10min by step 1, is taken out with pure N2Air-blowing is dry, puts It is placed in vacuum chamber on sample workpiece frame, vacuum chamber is evacuated to 6 × 10 by work rest revolving speed 5r/min-5~9 × 10-4Pa is passed through Vacuum degree is simultaneously maintained at 0.1~1.2Pa by argon gas；
Step 2 opens two-part pulse target power supply and pulsed negative bias matrix power supply to sample progress icon bombardment cleaning, control Parameter are as follows: 1 grade of pulse target voltage is -300~-400V, 2 grades of pulse -400~-500V of target voltage, frequency 10~100Hz, 1 grade 2.5~80%, 2 grades of pulse duty factors 2.5~80% of pulse duty factor, total duty ratio≤90%, stage pulse modulating frequency 40 ~60kHz, the back bias voltage of the matrix pulse power are -400~-600V, duty ratio 80~98%, 50~250kHz of frequency, ion 10~30min of scavenging period；
Step 3 is passed through reactant gas (Ar, N2、O2、CH4Deng) and vacuum degree in vacuum chamber is maintained into 0.4~1.0Pa, it connects 1 grade of pulse target voltage is decayed to -400~-600V by logical adjustable inductance, 2 grades of pulse target voltages decay to -600~-900V, Pulse frequency is adjusted to 20~90Hz, 1 grade of pulse duty factor, 10~70%, 2 grades of pulse duty factors 2.5~40%, total duty ratio ≤ 90%, 40~60kHz of stage pulse modulating frequency, 1 grade of peak value of pulse target current be 10~100A, 2 grades of peak value of pulse targets electricity Stream is 100~400A, and the back bias voltage of the matrix pulse power is -60~-90V, duty ratio 80~98%, frequency 40~60kHz, thin 45~120min of film sedimentation time；
After the completion of step 4, film deposition, the two-part pulse power, pulsed negative bias matrix power supply and reaction gas valve are closed, It is taken out after sample is cooling.
2. a kind of two-part pulsed magnetron sputtering method as described in claim 1, which is characterized in that further include building novel two The segmentation pulse power, wherein opening up benefit structure using the main circuit that three phase full wave rectification, IGBT inversion and high frequency transformer boost makes The output characteristics of power supply reaches: 1 grade of stage pulse peak power output 4kW, 2 grades of stage pulse peak power output 6kW, output Voltage zero load is greater than -1200V (peak value), band carries 0~-1000V, and it is 0.1~8.0A continuous that two-stage pulse, which exports average current, Adjustable, Maximum Peak Impulse Current is up to 1000A, and 10~100Hz of pulsed operation frequency is continuously adjustable, stage pulse modulating frequency 40~60kHz is continuously adjustable, and two-stage pulse duty factor is 2.5~80% continuously adjustable, the total largest duty cycles of two-stage pulse 90%, supply voltage and current precision≤1%, the novel two-part impulse electric field cathode terminal of building, which is then loaded on area, is The circular cathode target of Φ 100mm, anode tap load on volume be Φ 450mm × H400mm cylinder vacuum cavity, four Cathode targets are installed on the 304 stainless steel framework of circle on vacuum cavity side surface having a size of Φ 225mm, and framework is apart from cathode target Outer 5mm, mutually in 90 ° to be uniformly distributed, surface roughness is less than 0.8 μm.
3. a kind of two-part pulsed magnetron sputtering method as described in claim 1, which is characterized in that applying of the invention two When segmentation pulsed magnetron sputtering method, the temperature in vacuum chamber can be adjusted as desired by temperature control system, be controlled with this Film deposition temperature in vacuum chamber processed, convenient for film growth pattern and institutional framework regulate and control.
4. a kind of two-part pulsed magnetron sputtering method as described in claim 1, which is characterized in that applying of the invention two When segmentation pulsed magnetron sputtering method, can as needed before deposited compound film preferential deposition a layer thickness be less than 300nm Pure metal prime coat or structure similar in transition zone, to improve the binding force between film and matrix.
5. a kind of two-part pulsed magnetron sputtering method as described in claim 1, it is characterised in that the cooling and taking-up of step 4 Using any one following mode: complete plated film sample 30~50 DEG C are cooled in vacuum chamber after take out, then in atmosphere It is cooled to room temperature in environment；The sample that person completes plated film takes out after being directly cooled to room temperature in vacuum chamber.
6. a kind of two-part pulsed magnetron sputtering method as described in claim 1, which is characterized in that step 3 is passed through reactivity Gas is Ar, N2、O2、CH4Deng.
7. a kind of two-part pulsed magnetron sputtering method as described in claim 1, which is characterized in that two-part impulse magnetron splashes Shooting method is applied to all kinds of membrane samples to be plated of plated film field, including M2 high-speed steel, magnalium light-alloy, stainless steel, according to sample The service condition selection film coating composition of use environment and regulation is oriented to organization structure of film, including plated film C base, Ti base, Cr base, Si base film, the ganoine thin film of TiN/CrN series, Ti-C-N/Cr-C-N series anti-attrition film, TiO2The light of series The semiconductive thin film of catalytic film or Si series.
CN201810642700.9A 2018-06-21 2018-06-21 A kind of two-part pulsed magnetron sputtering method Pending CN108998769A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810642700.9A CN108998769A (en) 2018-06-21 2018-06-21 A kind of two-part pulsed magnetron sputtering method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810642700.9A CN108998769A (en) 2018-06-21 2018-06-21 A kind of two-part pulsed magnetron sputtering method

Publications (1)

Publication Number Publication Date
CN108998769A true CN108998769A (en) 2018-12-14

Family

ID=64601758

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810642700.9A Pending CN108998769A (en) 2018-06-21 2018-06-21 A kind of two-part pulsed magnetron sputtering method

Country Status (1)

Country Link
CN (1) CN108998769A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110468381A (en) * 2019-08-30 2019-11-19 西安理工大学 A kind of higher-order of oscillation pulsed magnetron sputtering method
CN115125488A (en) * 2022-07-08 2022-09-30 成都市精鹰光电技术有限责任公司 Thermosensitive film prepared based on frequency mixing pulse reaction magnetron sputtering
CN115717210A (en) * 2022-11-08 2023-02-28 北京科技大学 Method for inhibiting titanium-containing steel fish formation phenomenon by using pulse current

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103397304A (en) * 2013-08-21 2013-11-20 南京浩穰环保科技有限公司 Micro-arc ion plating method

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103397304A (en) * 2013-08-21 2013-11-20 南京浩穰环保科技有限公司 Micro-arc ion plating method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
时惠英等: ""双脉冲磁控溅射峰值靶电流密度对TiN薄膜结构与力学性能的影响"", 《金属学报》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110468381A (en) * 2019-08-30 2019-11-19 西安理工大学 A kind of higher-order of oscillation pulsed magnetron sputtering method
CN110468381B (en) * 2019-08-30 2021-08-10 西安理工大学 High-frequency oscillation pulse magnetron sputtering method
CN115125488A (en) * 2022-07-08 2022-09-30 成都市精鹰光电技术有限责任公司 Thermosensitive film prepared based on frequency mixing pulse reaction magnetron sputtering
CN115125488B (en) * 2022-07-08 2023-11-03 成都市精鹰光电技术有限责任公司 Thermosensitive film prepared based on mixed pulse reaction magnetron sputtering
CN115717210A (en) * 2022-11-08 2023-02-28 北京科技大学 Method for inhibiting titanium-containing steel fish formation phenomenon by using pulse current
CN115717210B (en) * 2022-11-08 2023-11-24 北京科技大学 Method for inhibiting titanium-containing steel-bonded fish phenomenon by using pulse current

Similar Documents

Publication Publication Date Title
Ferreira et al. Effect of peak target power on the properties of Cr thin films sputtered by HiPIMS in deep oscillation magnetron sputtering (DOMS) mode
CN108998769A (en) A kind of two-part pulsed magnetron sputtering method
CN107267916A (en) It is a kind of in method of the carbide surface by Deposited By Dc Magnetron Sputtering W N hard films
CN103397304B (en) Micro-arc ion plating method
CN105925946B (en) A method of using magnetron sputtering method TiN or CrN films are prepared in aluminum alloy surface
CN108796453B (en) High-temperature wear-resistant AlCrSiN nano composite coating and preparation method thereof
Wu et al. Al–Mg–B thin films prepared by magnetron sputtering
CN104141109B (en) Method for in-situ synthesis of composite TiC-DLC coating on surface of titanium
CN104805405B (en) Aluminium nitride piezoelectric film and preparation method thereof
CN108677144A (en) A method of it preparing aluminium nitrogen and is co-doped with diamond-like carbon composite film
CN110468381A (en) A kind of higher-order of oscillation pulsed magnetron sputtering method
Yang et al. Structure and properties of Ti films deposited by dc magnetron sputtering, pulsed dc magnetron sputtering and cathodic arc evaporation
CN107299316A (en) A kind of method for preparing amorphous nanocrystalline coating in Zr alloy surface
CN108977781A (en) A kind of method of carbide surface magnetron sputtering complex technique deposition W-N hard films
CN103276362B (en) The arc ions electroplating method of multi-stage magnetic field straight tube Magnetic filter and pulsed bias compound
CN105463391B (en) A kind of nanocrystalline ZrB2Superhard coating and preparation method
CN105316634A (en) Preparation method for Cr-B-C-N nanocomposite film
Fan et al. Effect of the pulse duty cycle on the microstructure and properties of a jet electrodeposited nanocrystalline copper coating
CN111621756A (en) Method for preparing crystalline transparent alumina film by room temperature sputtering
Liu et al. Microstructure and mechanical properties of alumina coatings prepared by double glow plasma technique
CN109825808A (en) A kind of doped diamond film preparation device and method
CN106884141A (en) A kind of Ti2The preparation method of AlC MAX phase films
CN108505006A (en) A method of using the pure Ti films of magnetron sputtering deposition nanometer
CN102912302B (en) Method for preparing yttrium/silicon nitride compound coating material on surface of magnesium alloy
CN105220122B (en) Has the magnetic control sputtering device of high power pulse ion source

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20181214

RJ01 Rejection of invention patent application after publication