CN108823544A - Based on nitridation titanium compound film and preparation method thereof - Google Patents
Based on nitridation titanium compound film and preparation method thereof Download PDFInfo
- Publication number
- CN108823544A CN108823544A CN201811059410.8A CN201811059410A CN108823544A CN 108823544 A CN108823544 A CN 108823544A CN 201811059410 A CN201811059410 A CN 201811059410A CN 108823544 A CN108823544 A CN 108823544A
- Authority
- CN
- China
- Prior art keywords
- layer
- titanium compound
- technique
- compound film
- magnetron sputtering
- 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
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 150000003609 titanium compounds Chemical class 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 56
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 31
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- 238000005516 engineering process Methods 0.000 claims abstract description 12
- 239000010936 titanium Substances 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910010038 TiAl Inorganic materials 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000004544 sputter deposition Methods 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 238000010894 electron beam technology Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- 238000001020 plasma etching Methods 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 3
- 238000000992 sputter etching Methods 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims 24
- 230000005611 electricity Effects 0.000 claims 1
- 239000002346 layers by function Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 22
- 239000011248 coating agent Substances 0.000 abstract description 21
- 230000007547 defect Effects 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 44
- 239000013078 crystal Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910010037 TiAlN Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
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
- 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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
- C23C14/025—Metallic sublayers
-
- 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
- C23C14/0641—Nitrides
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Present invention discloses a kind of nitridation titanium compound films and preparation method thereof, including the metal back layer, supporting layer and titanium nitride layer sequentially formed outward by substrate surface, bottom is prepared using cathodic arc technique, supporting layer is prepared using magnetron sputtering technique, titanium nitride layer is to work at the same time the mixture layer that the two kinds of different structure film layers to be formed are staggeredly stacked using two kinds of technologies of magnetron sputtering and cathode arc, and the thickness of the titanium nitride layer is between 1 ~ 5 μm.Deft design of the present invention, structure is simple, the structure that titanium nitride layer uses two kinds of different structure film layers to be alternately stacked.Give full play to the few advantage of the high compactness of magnetron sputtering film layer, defect, cathode arc prepares the advantages of high rigidity of film layer, good binding force, realize that film layer internal structure is fine and close, can guarantee that the hardness of coating is high again, ultimately form with good binding force, high rigidity, compact structure hard coat.
Description
Technical field
The present invention relates to a kind of composite membranes and preparation method thereof, especially a kind of based on nitridation titanium compound film and its preparation side
Method.
Background technique
Titanium nitride membrane is a kind of metal nitride, have high rigidity and high elastic modulus, low friction coefficient, it is wear-resistant with
And good acid-alkali-corrosive-resisting characteristic, it is well suited as wear-resistant coating, thus the nitridation obtained by physical gas-phase deposition
Titanium film it is numerous have wear-resisting, hardness, acid-alkali-corrosive-resisting requirement part on be used widely.
Conventional titanium nitride thin film preparation often uses single arc technology or magnetron sputtering technique, and single technology exists
There are certain defects when preparing titanium nitride coating.Had such as using the titanium nitride of cathodic arc technique preparation, in preparation process compared with
Much particles, which are deposited on inside film, forms defect, causes the biggish internal stress of coat inside generation and coating structure loose, this
A little defects can reduce the acid-alkali-corrosive-resisting of coating；The titanium nitride prepared using magnetron sputtering is poor, hard with the binding force of substrate
It is poor to spend relatively low and abrasion resistance properties.The grain structure of the coating of single technique preparation is column crystal, is run through from substrate bottom
Entire coat inside, there are gap between crystal grain and crystal grain, these gaps can equally become some defects of coating.
Product under different applying working conditions is different to the performance requirement emphasis of coating, as the coating on tool and mould surface needs
Has the features such as high rigidity, good wearability；Auto parts and components need coating to have good toughness, good adhesive force
And the characteristics of good compactness；The coating of medical instrument needs to have high rigidity, good bio-compatibility, acid-alkali-corrosive-resisting
The features such as property, high temperature steam corrosivity.Cathodic arc technique can satisfy the coating performance requirement of the products such as tool and mould, magnetic control
Sputtering can satisfy the performance of the products such as auto parts and components, but both requirements for medical instrument are unable to satisfy, especially
It is to be unable to satisfy high temperature steam corrosion, because medical device product is using preceding needing to sterilize in high-temp steam sterilizing pot
Processing, temperature reach 150 DEG C or more, and vapor can enter coat inside by the gap between the defect and crystal grain of coating, apply
Potential difference is formed between layer and substrate, so that the structure of titanium nitride changes, and then corrodes, leads to coating failure.Cause
This, titanium nitride coating high-temperature corrosion resistance problem become can security application in the critical issue on medical instrument.
Summary of the invention
The object of the invention is to provide a kind of multiple based on titanium nitride to solve the above-mentioned problems in the prior art
Close film and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions：Based on nitridation titanium compound film, including from substrate surface to
Metal back layer, supporting layer and the titanium nitride layer sequentially formed outside, the bottom are prepared using cathodic arc technique, and supporting layer uses
Magnetron sputtering technique preparation, titanium nitride layer are to work at the same time to be formed two kinds not using two kinds of technologies of magnetron sputtering and cathode arc
With the mixture layer that layer is staggeredly stacked, the thickness of the titanium nitride layer is between 1 ~ 5 μm.
Preferably, described based on nitridation titanium compound film, wherein：One in described metal back layer Cr layers, Ti layers or Ni layers
Kind, and prepared by cathodic arc technique, thickness is between 0.2 ~ 0.8 μm.
Preferably, described based on nitridation titanium compound film, wherein：The thickness of the supporting layer is between 0.8 ~ 2 μm.
Preferably, described based on nitridation titanium compound film, wherein：The supporting layer is CrN layers of either AlTiN
Layer.
Preferably, described based on nitridation titanium compound film, wherein：The titanium nitride layer, and by magnetron sputtering and
Cathodic arc technique works together to complete to prepare.
Based on the preparation method of nitridation titanium compound film, include the following steps.
S1 is put into vacuum chamber after cleaning substrate, carries out plasma etching.
S2, using Cr, Ti or Ni as target, is adopted under the technique vacuum degree of 0.3 ~ 1.2Pa in the substrate surface through over cleaning
One layer of metal back layer is prepared with cathodic arc technique.
S3 opens the magnetron sputtering shielding power supply of Cr or TiAl target, in gold under the technique vacuum degree of 1.0 ~ 2.0Pa
Belong to bottom surface and forms supporting layer.
S4 using the Ti target of two kinds of different structures as target, while opening yin under the technique vacuum degree of 2.0-4.0Pa
Pole electrical arc power supply and magnetron sputtering power supply prepare titanium nitride layer, and the power proportion for passing through two targets of control is 1:2,
Golden support layer surface forms the TiN layer of structure composite.
Preferably, the preparation method based on nitridation titanium compound film, it is characterised in that：The S1 step comprises the following processes.
Substrate is put into ultrasonic cleaning in alkaline solution by S11.
S12, by the substrate Jing Guo S11 step, ultrasonic oscillation is cleaned in filtering pure water.
Substrate Jing Guo S12 step is completed drying by S13 in drying box.
S14 starts after the substrate of S13 step is put into vacuum chamber to vacuumize vacuum chamber, reaches 3 × 10-3Pa's
After vacuum degree, heater heating is kept for 400 DEG C, then passes to argon gas, and continue to vacuumize, and holding technique vacuum degree is
0.3 ~ 1.0Pa, open electron beam, voltage be 1000V ~ 1500V, open grid bias power supply, grid bias power supply be set in 1000V ~
1500V carries out the ion etching of 60 ~ 120min to substrate.
Preferably, the preparation method based on nitridation titanium compound film, wherein：The cathode of Cr, Ti or Ni target
The power control of arc power is between 1 ~ 3kW, and application -80V ~ -1000V back bias voltage on workpiece, sedimentation time be 10 ~
40min, the thickness of the metal back layer of formation is between 0.2 μm ~ 0.8 μm.
Preferably, the preparation method based on nitridation titanium compound film, wherein：The magnetic control of the Cr or TiAl target splashes
Radio 2 ~ 3.5kW of source power, and application -80V ~ -1000V back bias voltage on workpiece, the time of deposition are 60 ~ 100min, are formed
Supporting layer thickness between 0.8 ~ 2 μm.
Preferably, described based on the preparation method based on nitridation titanium compound film, wherein：The arc power of the Ti target
Power be 500 ~ 1500W, the power of magnetron sputtering target power supply is 1000 ~ 3000W, and the two power ratio is 1:2, sedimentation time is
60 ~ 200min, the titanium nitride layer thickness of formation is between 1 ~ 5 μm.
The advantages of technical solution of the present invention, is mainly reflected in：Deft design of the present invention, thin film preparation process step is simple, fills
The characteristics of every kind of coating technology is waved in distribution, bottom are prepared using cathodic arc technique, and coating is made to have good adhesive force；Support
Layer uses magnetron sputtering technique, gives full play to the feature that magnetron sputtering film layer structure is fine and close, internal stress is small；Titanium nitride layer uses magnetic
Control sputtering and cathodic arc technique work at the same time to prepare titanium nitride, the titanium nitride of two kinds of technique preparation, by magnetron sputtering film layer
Compactness and the hardness of cathode arc film layer effectively combine, it is possible to reduce the defect inside film layer both guarantees the film layer of preparation
With good compactness, and it can guarantee film layer hardness with higher, and the internal stress of coating can also reduce, Jin Erti
The internal stress of high film layer.The preparation method of this film layer, using cathode arc, magnetron sputtering and cathode arc in conjunction with magnetron sputtering
Method, the structure of the film layer crystal grain of this method preparation is column crystal, but the continuity of column crystal is interrupted, and formation does not connect
Continuous grain structure can be further reduced the defect of film layer.
The preparation method of film layer of the present invention, process is simple, control convenience, using the independent plated film of two kinds of different film plating process or
Person works at the same time plated film, and the high temperature corrosion for the nitridation titanium compound film that this method obtains is better than traditional titanium nitride film.Together
When, titanium nitride layer is prepared using the method for cathode arc and the method for magnetron sputtering, two kinds of film plating process work at the same time, so that heavy
Product rate is fast, can effectively improve film layer preparation efficiency.By the fusion of a variety of PVD techniques and the setting of technological parameter, provide
A kind of preparation method for the nitridation titanium compound film that technology stability is high, effect is good.
The present invention combines multiple coating films method, whole process pollution-free, environmentally protective.
Detailed description of the invention
Fig. 1 is membrane structure schematic diagram of the invention.
Specific embodiment
The purpose of the present invention, advantage and feature, by by the non-limitative illustration of preferred embodiment below carry out diagram and
It explains.These embodiments are only the prominent examples using technical solution of the present invention, it is all take equivalent replacement or equivalent transformation and
The technical solution of formation, all falls within the scope of protection of present invention.
Present invention discloses based on nitridation titanium compound film, including sequentially formed outward by 4 surface of substrate metal back layer 1,
Supporting layer 2 and titanium nitride layer 3, wherein the metal back layer 1 is one of Cr layers, Ti layers or Ni layers, and passes through cathode arc
Technology generates, and for thickness between 0.2 ~ 0.8 μm, metal Cr, Ti or Ni are conducive to enhance the knot of entire composite thick film and substrate
With joint efforts.
The supporting layer 2 is prepared using magnetron sputtering technique, the film layer in the supporting layer be CrN layers either
AlTiN layers, and prepared by cathodic arc technique, the thickness of supporting layer is between 0.8 ~ 2 μm.
Also, due to when titanium nitride film carries out disinfection under high-temperature vapor environment to sterilize, it may occur that electrochemical reaction,
And then the performance of film layer is influenced, therefore TiN layer is worked together by magnetron sputtering and cathodic arc technique to complete to prepare, it is described
The thickness of TiN layer 3 is between 1 ~ 5 μm.
Invention further discloses a kind of above-mentioned preparation methods based on nitridation titanium compound film, include the following steps.
S1 is put into vacuum chamber after cleaning substrate, carries out plasma etching.
It is specific and includes the following steps.
Substrate is put into ultrasonic cleaning in alkaline solution by S11.
S12, by the substrate Jing Guo S11 step, ultrasonic oscillation is cleaned in filtering pure water.
Substrate Jing Guo S12 step is completed drying by S13 in drying box.
S14 starts after the substrate of S13 step is put into vacuum chamber to vacuumize vacuum chamber, reaches 3 × 10-3Pa's
After vacuum degree, heater heating is kept for 400 DEG C, then passes to the high-purity argon gas that purity is 99.999%, controls the logical of argon gas
Inbound traffics are 10 ~ 50sccm, and continue to vacuumize, and holding technique vacuum degree is 0.3 ~ 1.0Pa, then, open electron beam, voltage
For 1000V ~ 1500V, open grid bias power supply, grid bias power supply is set in 1000V ~ 1500V, to substrate carry out 60 ~ 120min from
Son etching.
S2, under the technique vacuum degree of 0.5 ~ 3.0Pa, using Cr, Ti or Ni as target, in the substrate table Jing Guo ion etching
Face prepares one layer of metal back layer 1, in coating process, the cathode arc of Cr, Ti or Ni target using cathodic arc method
The power control of power supply is between 1 ~ 3kW, and application -80V ~ -1000V back bias voltage on workpiece, and sedimentation time is 10 ~ 40min,
To form metal back layer 1 of the thickness between 0.2 μm ~ 0.8 μm in substrate 4.
S3 is extracted into 3.0 × 10 in vacuum degree-3When Pa, the high pure nitrogen that purity is 99.999% is passed through into vacuum chamber, and
The flow that is passed through of control nitrogen is 30 ~ 80sccm, and under the technique vacuum degree of 1.0 ~ 2.0Pa, opens Cr or TiAl target
Magnetron sputtering shielding power supply, the Cr or TiAl are target, magnetron sputtering 2 ~ 3.5kW of power of target, and applying on workpiece
Add -80V ~ -1000V back bias voltage, the time of deposition is 60 ~ 100min, metal back layer surface formed thickness 0.8 ~ 2 μm it
Between CrN either TiAlN supporting layer.
S4 using Ti target as target, while opening cathode arc power supply and magnetic under the technique vacuum degree of 2.0-4.0Pa
The power ratio controlled shielding power supply, and control the power supply of two targets is 1:2, specifically, control the function of cathode arc power supply
Rate is 500 ~ 1500W,；The magnetron sputtering power is 1000 ~ 3000W, and control is described to be splashed using cathode arc and magnetic control
The time for penetrating technology while deposition is 60 ~ 200min, to form TiN layer of the thickness at 1-5 μm in support layer surface.
Through inventor the study found that the bottom is prepared using cathodic arc technique, since arc technology prepares film layer mistake
Cheng Zhong, particle ionization level is high, and bottom can be made to have good adhesive force.The supporting layer uses magnetron sputtering technique system
It is standby, bottom can be interrupted and supporting layer forms continuous columnar crystal structure, reduce the defect between crystal grain or vacancy, and then reduce
The internal stress that column crystal self-defect generates.
Adhesive force for improving coating and substrate has obvious action, supporting layer to prepare using magnetron sputtering technique,
The coated grains structure of two kinds of different technologies preparations is different, not will form the column crystal through coating whole thickness, so that brilliant
Defect between grain is reduced.The ion of ion and cathode arc that magnetron sputtering comes out forms staggered combination, makes inside film layer
Internal stress be greatly reduced, while the ion of magnetron sputtering has filled up the gap of cathode arc, keeps film layer structure finer and close.
Still there are many embodiment, all technical sides formed using equivalents or equivalent transformation by the present invention
Case is within the scope of the present invention.
Claims (11)
1. based on nitridation titanium compound film, it is characterised in that：Including by substrate（4）The metal back layer that surface sequentially forms outward（1）,
Supporting layer（2）And titanium nitride layer（3）, the bottom（1）It is to be prepared using cathodic arc technique, the supporting layer（2）Using magnetic
Control sputtering technology preparation, the functional layer that the titanium nitride layer is prepared using magnetron sputtering and cathodic arc technique, the titanium nitride
Layer（3）Thickness between 1 ~ 5 μm.
2. nitridation titanium compound film according to claim 1, it is characterised in that：The metal back layer（1）Be Cr layers, Ti layers or
One of Ni layers, and prepared by cathodic arc technique, thickness is between 0.2 ~ 0.8 μm.
3. nitridation titanium compound film according to claim 2, it is characterised in that：The supporting layer（2）Thickness at 0.8 ~ 2 μm
Between.
4. nitridation titanium compound film according to claim 3, it is characterised in that：The supporting layer（2）In film layer be CrN layers
Either AlTiN layers, and prepared by magnetron sputtering technique.
5. nitridation titanium compound film according to claim 1 to 4, it is characterised in that：The titanium nitride layer（3）, pass through magnetic
Control sputtering and cathodic arc technique work together to complete to prepare.
6. the preparation method based on nitridation titanium compound film, it is characterised in that：Include the following steps：
S1 is put into vacuum chamber after cleaning substrate, carries out plasma etching；
S2, under the technique vacuum degree of 0.3 ~ 1.2Pa, using Cr, Ti or Ni as target, in the substrate surface through over cleaning using yin
Pole electrical arc technology prepares one layer of metal back layer（1）；
S3 opens the magnetron sputtering shielding power supply of Cr or TiAl target, in metal bottom under the technique vacuum degree of 1.0 ~ 2.0Pa
Layer（1）Surface forms supporting layer（2）；
S4 using the Ti target of two kinds of different structures as target, while opening cathode electricity under the technique vacuum degree of 2.0-4.0Pa
Arc power and magnetron sputtering power supply, in supporting layer（2）The upper TiN layer for forming 1 ~ 5 μm（3）.
7. the film plating process according to claim 6 based on nitridation titanium compound film, it is characterised in that：The S1 step includes
Following process：
Substrate is put into ultrasonic cleaning in alkaline solution by S11；
S12, by the substrate Jing Guo S11 step, ultrasonic oscillation is cleaned in filtering pure water；
Substrate Jing Guo S12 step is completed drying by S13 in drying box；
S14 starts after the substrate of S13 step is put into vacuum chamber to vacuumize vacuum chamber, reaches 3 × 10-3The vacuum of Pa
After degree, heater heating keep 400 DEG C, then pass to argon gas, and continue to vacuumize, keep technique vacuum degree be 0.3 ~
1.0Pa opens electron beam, and voltage is 1000V ~ 1500V, opens grid bias power supply, grid bias power supply is set in 1000V ~ 1500V, right
Substrate carries out the ion etching of 60 ~ 120min.
8. the preparation method according to claim 7 based on nitridation titanium compound film, it is characterised in that：In S2 step, institute
The power control of cathode arc power supply of Cr, Ti or Ni target is stated between 1 ~ 3kW, and application -80V ~ -1000V on workpiece
Back bias voltage, sedimentation time are 10 ~ 40min, and the thickness of the metal back layer of formation is between 0.2 μm ~ 0.8 μm.
9. the preparation method according to claim 8 based on nitridation titanium compound film, it is characterised in that：In the S3 step, institute
It states between 2 ~ 3.5kW of magnetron sputtering power of Cr or TiAl target, and application -50V ~ -500V back bias voltage on workpiece.
10. the preparation method according to claim 9 based on nitridation titanium compound film, it is characterised in that：In the S3 step, institute
The time for using magnetron sputtering technique to deposit is stated as 60 ~ 100min, the thickness of the supporting layer of formation is between 0.8 ~ 2 μm.
11. according to any preparation method based on nitridation titanium compound film of claim 6-10, it is characterised in that：It is walked in S4
In rapid, the power of the arc power of the Ti target is 500 ~ 1500W, and the power of magnetron sputtering target power supply is 1000 ~ 3000W,
Sedimentation time is 60 ~ 200min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811059410.8A CN108823544A (en) | 2018-09-12 | 2018-09-12 | Based on nitridation titanium compound film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811059410.8A CN108823544A (en) | 2018-09-12 | 2018-09-12 | Based on nitridation titanium compound film and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108823544A true CN108823544A (en) | 2018-11-16 |
Family
ID=64149258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811059410.8A Pending CN108823544A (en) | 2018-09-12 | 2018-09-12 | Based on nitridation titanium compound film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108823544A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111690898A (en) * | 2019-03-15 | 2020-09-22 | 纳峰真空镀膜（上海）有限公司 | Improved coating process |
| CN112144013A (en) * | 2019-06-28 | 2020-12-29 | 陕西航天时代导航设备有限公司 | Preparation method of TiN thick film on inner surface of GT35 ball bowl part |
| CN113881917A (en) * | 2021-12-07 | 2022-01-04 | 河南科技学院 | Port crane anticorrosive coating and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0202855D0 (en) * | 2002-02-07 | 2002-03-27 | Teer Coatings Ltd | A method for depositing very hard and smooth metal alloy nitride or multi layernitride coatings with excellent adhesion |
| CN1680618A (en) * | 2004-11-30 | 2005-10-12 | 大连理工大学 | Method for impulsive bias arc ion plating multi-player super-hard nano films of titanium/titanium nitrate |
| CN102080207A (en) * | 2010-12-25 | 2011-06-01 | 深圳市广大纳米工程技术有限公司 | DLC (diamond-like carbon)/TiAlN (titanium aluminium nitride)/CrN (chromium nitride)/Cr (chromium) multilayer superhard film coating and preparation method thereof |
| RU2010100449A (en) * | 2010-01-11 | 2011-07-20 | Государственное образовательное учреждение высшего профессионального образования "Пермский государственный технический университет | METHOD FOR PRODUCING COVERING BASED ON COMPLEX NITRIDES |
| CN103628032A (en) * | 2013-11-15 | 2014-03-12 | 桂林电子科技大学 | Method of preparing nano titanium nitride layer on conductive base body material |
| CN103789723A (en) * | 2014-01-24 | 2014-05-14 | 四川大学 | Cr/CrN/(Ti, Al, Si, Cr)N composite hard coating and preparation method thereof |
| CN106191794A (en) * | 2016-06-30 | 2016-12-07 | 上海材料研究所 | The coating method of titanium alloy surface superhard anti-friction wear-resistant composite film and titanium alloy material |
| CN107022761A (en) * | 2017-04-28 | 2017-08-08 | 星弧涂层新材料科技（苏州）股份有限公司 | Composite thick film and its film plating process based on DLC film |
| CN209024637U (en) * | 2018-09-12 | 2019-06-25 | 杨杰平 | A kind of nitridation titanium compound film |
-
2018
- 2018-09-12 CN CN201811059410.8A patent/CN108823544A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0202855D0 (en) * | 2002-02-07 | 2002-03-27 | Teer Coatings Ltd | A method for depositing very hard and smooth metal alloy nitride or multi layernitride coatings with excellent adhesion |
| CN1680618A (en) * | 2004-11-30 | 2005-10-12 | 大连理工大学 | Method for impulsive bias arc ion plating multi-player super-hard nano films of titanium/titanium nitrate |
| RU2010100449A (en) * | 2010-01-11 | 2011-07-20 | Государственное образовательное учреждение высшего профессионального образования "Пермский государственный технический университет | METHOD FOR PRODUCING COVERING BASED ON COMPLEX NITRIDES |
| CN102080207A (en) * | 2010-12-25 | 2011-06-01 | 深圳市广大纳米工程技术有限公司 | DLC (diamond-like carbon)/TiAlN (titanium aluminium nitride)/CrN (chromium nitride)/Cr (chromium) multilayer superhard film coating and preparation method thereof |
| CN103628032A (en) * | 2013-11-15 | 2014-03-12 | 桂林电子科技大学 | Method of preparing nano titanium nitride layer on conductive base body material |
| CN103789723A (en) * | 2014-01-24 | 2014-05-14 | 四川大学 | Cr/CrN/(Ti, Al, Si, Cr)N composite hard coating and preparation method thereof |
| CN106191794A (en) * | 2016-06-30 | 2016-12-07 | 上海材料研究所 | The coating method of titanium alloy surface superhard anti-friction wear-resistant composite film and titanium alloy material |
| CN107022761A (en) * | 2017-04-28 | 2017-08-08 | 星弧涂层新材料科技（苏州）股份有限公司 | Composite thick film and its film plating process based on DLC film |
| CN209024637U (en) * | 2018-09-12 | 2019-06-25 | 杨杰平 | A kind of nitridation titanium compound film |
Non-Patent Citations (2)
| Title |
|---|
| 卢春灿等: "阳极线性离子源辅助磁控溅射沉积氮化钛薄膜的研究", 材料导报, no. 10, pages 311 - 318 * |
| 张晓化等: "TiN/Ti复合膜与多层膜对Ti811合金高温摩擦性能及微动疲劳抗力的影响", 摩擦学学报, no. 04, pages 29 - 32 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111690898A (en) * | 2019-03-15 | 2020-09-22 | 纳峰真空镀膜（上海）有限公司 | Improved coating process |
| WO2020187744A1 (en) | 2019-03-15 | 2020-09-24 | Nanofilm Technologies International Pte Ltd | Improved coating processes |
| CN111690898B (en) * | 2019-03-15 | 2024-04-26 | 纳峰真空镀膜（上海）有限公司 | Improved coating process |
| CN112144013A (en) * | 2019-06-28 | 2020-12-29 | 陕西航天时代导航设备有限公司 | Preparation method of TiN thick film on inner surface of GT35 ball bowl part |
| CN113881917A (en) * | 2021-12-07 | 2022-01-04 | 河南科技学院 | Port crane anticorrosive coating and preparation method thereof |
| CN113881917B (en) * | 2021-12-07 | 2022-03-04 | 河南科技学院 | Port crane anticorrosive coating and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107022761A (en) | Composite thick film and its film plating process based on DLC film | |
| Alami et al. | High power pulsed magnetron sputtering: Fundamentals and applications | |
| Wei et al. | Effects of pulsed bias duty ratio on microstructure and mechanical properties of TiN/TiAlN multilayer coatings | |
| CN105925946B (en) | A method of using magnetron sputtering method TiN or CrN films are prepared in aluminum alloy surface | |
| Constantin et al. | Magnetron sputtering technique used for coatings deposition; technologies and applications | |
| CN105908135A (en) | Multistage magnetic field ion plating and twin-target high-power pulse magnetron sputtering composite method | |
| CN107022745A (en) | Incrassation type laminated film and its film plating process based on DLC film | |
| CN106756820B (en) | Containing diamond-like composite coating and preparation method thereof | |
| CN207313693U (en) | Composite thick film based on DLC film | |
| CN111349901B (en) | Preparation method of high-temperature-resistant alumina thick film coating for cutting tool | |
| CN108796453B (en) | High-temperature wear-resistant AlCrSiN nano composite coating and preparation method thereof | |
| CN108823544A (en) | Based on nitridation titanium compound film and preparation method thereof | |
| CN104141109B (en) | Method for in-situ synthesis of composite TiC-DLC coating on surface of titanium | |
| CN109735799A (en) | A kind of cutting tool surface multi-layer step high temperature wear-resistant coating and preparation method thereof | |
| CN113981392B (en) | Ti-Al-C MAX phase coating and low Wen Chengxiang preparation method thereof | |
| CN108118304A (en) | Nano-composite coating and its preparation process | |
| US6451180B1 (en) | Method of making a PVD Al2O3 coated cutting tool | |
| CN105803411A (en) | Combined method of arc ion plating and twin target bipolar high-power pulsed magnetron sputtering | |
| CN209024637U (en) | A kind of nitridation titanium compound film | |
| CN114481071B (en) | Coating device and DLC coating process | |
| CN112941463B (en) | Nano multilayer oxynitride corrosion-resistant protective coating and preparation method and application thereof | |
| CN112853281B (en) | Carbon-based multilayer film and preparation method and application thereof | |
| CN107675136B (en) | A kind of method of workpiece surface PVD plated film | |
| CN101570849B (en) | Method for preparing hard coating of tool and mould by binary evaporation source | |
| CN104593737A (en) | Preparation process for high-silicon super-hard PVD coating |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20181116 |
|
| WD01 | Invention patent application deemed withdrawn after publication |