CN109440069A - Multi-arc ion coating prepares small modulation cycle T i/TiN super hard nano multilayer film - Google Patents
Multi-arc ion coating prepares small modulation cycle T i/TiN super hard nano multilayer film Download PDFInfo
- Publication number
- CN109440069A CN109440069A CN201910043083.5A CN201910043083A CN109440069A CN 109440069 A CN109440069 A CN 109440069A CN 201910043083 A CN201910043083 A CN 201910043083A CN 109440069 A CN109440069 A CN 109440069A
- Authority
- CN
- China
- Prior art keywords
- multilayer film
- tin
- titanium
- super hard
- arc ion
- 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.)
- Granted
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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
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)
- Cutting Tools, Boring Holders, And Turrets (AREA)
Abstract
The invention discloses multi-arc ion coatings to prepare small modulation cycle T i/TiN super hard nano multilayer film.The preparation method of the film includes: that titanium deposition targets are unidirectionally placed in the inside of cavity；The sample substrate that hard alloy and single-sided polishing monocrystalline silicon piece are grown as film；The air of inside cavity is extracted, so that inside cavity is vacuum state；Under vacuum conditions, cavity is internally heated, and is passed through the argon gas higher than purity of argon threshold value, Glow Discharge Cleaning first time period；By the flow-reduction of argon gas to first flow flow velocity；Titanium deposition targets are opened, and Bombardment and cleaning second time period is carried out to sample substrate under back bias voltage；The titanium layer of the first deposition thickness is previously deposited as transition zone；Argon gas and nitrogen are periodically passed through in cavity, alternating deposit titanium sublayer and titanium nitride sublayer respectively, form multi-arc ion coating and prepare small modulation cycle T i/TiN super hard nano multilayer film, improve the service life based on product made by TiAlN thin film.
Description
Technical field
The present invention relates to titanium nitride thin field of membrane preparation, prepare small modulation cycle T i/TiN more particularly to multi-arc ion coating
Super hard nano multilayer film.
Background technique
Titanium nitride (Titanium Nitride, TiN) ganoine thin film is high with hardness, coefficient of friction is small, wearability is good, face
The advantages that color is weak golden, is commonly used to as protectiveness film and decorative film etc.；Such as it is coated on high-speed steel drill surface
TiAlN thin film, be remarkably improved bit life；Daily stainless steel material article surface is coated with the golden decorative plated film of TiN.It utilizes
It is a kind of common and mature technology that multi sphere ion plating technology, which prepares TiN single thin film, has been used widely at present, so
And with the development of modern industry, the hardness of TiN single thin film, adhesive force, wearability etc. performance gradually can not meet and makes
With requiring, the service life of TiN single thin film is short, so as to cause short based on product service life made by TiAlN thin film.
Summary of the invention
The object of the present invention is to provide multi-arc ion coatings to prepare small modulation cycle T i/TiN super hard nano multilayer film, to solve
Based on the short problem of product service life made by TiAlN thin film.
To achieve the above object, the present invention provides following schemes:
A kind of multi-arc ion coating prepares the preparation facilities of small modulation cycle T i/TiN super hard nano multilayer film, comprising: chamber,
Cylindrical unit and titanium deposition targets；
The cylindrical unit and the titanium deposition targets are unidirectionally placed in the inside of the chamber, and the tubular fills
It sets corresponding with the titanium deposition targets；Sample substrate is equipped with inside the cylindrical unit, the cylindrical unit is rotatable, institute
Cylindrical unit is stated in coating process, makes delay the concentrating on the sample substrate of Period Process of residual gas and remote
In the space in off-target face；The titanium deposition targets are for sample substrate described in Bombardment and cleaning.
A kind of multi-arc ion coating prepares the preparation method of small modulation cycle T i/TiN super hard nano multilayer film, the multi sphere from
The preparation method that sub- plating prepares ditty cycle T i/TiN super hard nano multilayer film is applied to a kind of multi-arc ion coating and prepares ditty
The preparation facilities of cycle T i/TiN super hard nano multilayer film processed, the multi-arc ion coating prepare that small modulation cycle T i/TiN is superhard to be received
The preparation facilities of rice multilayer film includes chamber, cylindrical unit, titanium deposition targets, and the chamber interior is equipped with the cylindrical unit
And titanium deposition targets；
The cylindrical unit and the titanium deposition targets are unidirectionally placed in the inside of the chamber, and the tubular fills
It sets corresponding with the titanium deposition targets；Sample substrate is equipped with inside the cylindrical unit, the cylindrical unit is rotatable, institute
Cylindrical unit is stated in coating process, makes delay the concentrating on the sample substrate of Period Process of residual gas and remote
In the space in off-target face；The titanium deposition targets are for sample substrate described in Bombardment and cleaning；
The multi-arc ion coating prepares the small preparation method for modulating cycle T i/TiN super hard nano multilayer film
Titanium deposition targets are unidirectionally placed in the inside of the cavity；
The sample substrate that hard alloy and single-sided polishing monocrystalline silicon piece are grown as film；
The air of the inside cavity is extracted, so that the inside cavity is vacuum state；
Under vacuum conditions, the cavity is internally heated, and is passed through the argon gas higher than purity of argon threshold value, brightness
Light Discharge Cleaning first time period；
By the flow-reduction of the argon gas to first flow flow velocity；
The titanium deposition targets are opened, and Bombardment and cleaning second time period is carried out to sample substrate under back bias voltage；
The titanium layer of the first deposition thickness is previously deposited as transition zone；
Argon gas and nitrogen are periodically passed through in the cavity respectively, alternating deposit titanium sublayer and titanium nitride sublayer, shape
Small modulation cycle T i/TiN super hard nano multilayer film is prepared at multi-arc ion coating.
Optionally, the pinwheel up and down of the titanium deposition targets is 70-75A away from the range for 250mm, arc current.
Optionally, the vacuum degree of the vacuum state is 2.0-3.0 × 10-2Pa；It is passed through the argon higher than purity of argon threshold value
The flow velocity of gas is 150cm3/min；The first time period is 10-15min.
Optionally, the first flow flow velocity is 100cm3/min。
Optionally, the back bias voltage range is 400-600V, and the second time period is 10-15min.
Optionally, first deposition thickness is 50-70nm.
Optionally, argon gas and nitrogen are periodically passed through in the cavity respectively, the flow velocity of the argon gas is
100cm3/ min, the flow velocity of the nitrogen are 90cm3/min。
Optionally, described to be periodically passed through argon gas and nitrogen in the cavity respectively, alternating deposit titanium sublayer and nitrogen
During changing titanium sublayer, deposition substrate back bias voltage is 200-300V；Duty ratio is 40%；Vacuum degree when plating titanium layer is 2.3-
2.7×10-1Pa；Vacuum degree when titanium-nitride layer is 1.2-1.5 × 10-1Pa.
The specific embodiment provided according to the present invention, the invention discloses following technical effects: the present invention provides one kind
Multi-arc ion coating prepares the preparation facilities and method of small modulation cycle T i/TiN super hard nano multilayer film, by unidirectionally placing titanium
Belong to deposition targets and cylindrical unit, can operative constraint coating film area make the stagnant of residual gas in rationally control coating process
That stays Period Process concentrates on sample far from the space of target surface, and rationally control turn according to the residence time of measurement gas
Speed, to obtain the small modulation cycle T i/TiN nano-multilayer film of even compact.
Meanwhile multi-arc ion coating provided by the present invention prepare small modulation cycle T i/TiN super hard nano multilayer film compared to
TiN single thin film all increases substantially from hardness, adhesive force and wearability etc. performance, improves multi-arc ion coating system
The service life of standby small modulation cycle T i/TiN super hard nano multilayer film, and then improve based on product made by TiAlN thin film
Service life.
Detailed description of the invention
It in order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, below will be to institute in embodiment
Attached drawing to be used is needed to be briefly described, it should be apparent that, the accompanying drawings in the following description is only some implementations of the invention
Example, for those of ordinary skill in the art, without any creative labor, can also be according to these attached drawings
Obtain other attached drawings.
Fig. 1 is the preparation that multi-arc ion coating provided by the present invention prepares small modulation cycle T i/TiN super hard nano multilayer film
Structure drawing of device；
Fig. 2 is the preparation that multi-arc ion coating provided by the present invention prepares small modulation cycle T i/TiN super hard nano multilayer film
Method flow diagram；
Fig. 3 is TiN monofilm provided by the present invention and Ti/TiN nano-multilayer film electron microscope comparison diagram；Wherein, Fig. 3
It (a) is the electron microscope of TiN monofilm provided by the present invention, Fig. 3 (b) is Ti/TiN nano-multilayer film provided by the present invention
Electron microscope；
Fig. 4 is the Ti/TiN nano-multilayer film electron microscope in different modulating period provided by the present invention；Wherein, Fig. 4 (a) is
Modulation period provided by the present invention is the electron microscope of the Ti/TiN nano-multilayer film of 39.2nm, and Fig. 4 (b) is provided by the present invention
Modulation period be 20.3nm Ti/TiN nano-multilayer film electron microscope, Fig. 4 (c) be modulation period provided by the present invention be
The electron microscope of the Ti/TiN nano-multilayer film of 13.2nm, Fig. 4 (d) are the Ti/ for being 7.5nm modulation period provided by the present invention
The electron microscope of TiN nano-multilayer film, Fig. 4 (e) receive for the Ti/TiN that modulation period provided by the present invention is 5.2nm (theoretical value)
The electron microscope of rice multilayer film；
Fig. 5 is the film-substrate cohesion schematic diagram of Ti/TiN nano-multilayer film provided by the present invention；
Fig. 6 is Ti/TiN nano-multilayer film structure chart provided by the present invention.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts all other
Embodiment shall fall within the protection scope of the present invention.
The object of the present invention is to provide multi-arc ion coatings to prepare small modulation cycle T i/TiN super hard nano multilayer film, to solve
Based on the short problem of product service life made by TiAlN thin film.
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to the accompanying drawing and specific real
Applying mode, the present invention is described in further detail.
In recent years, modulation period is concentrated mainly on using the research that multi sphere ion plating technology prepares Ti/TiN nano-multilayer film
For size in the influence of film performance, the lowest modulation period of preparation is 34nm.The study found that the reduction of modulation period is so that thin
Other mechanical properties of film in addition to hardness significantly improve, and therefore, prepare small modulation cycle T i/TiN using multi sphere ion plating technology
Nano-multilayer film can obtain the superhard thin film of excellent combination property；However since multi sphere ion plating technology plating rate is very fast and
Residual gas cannot detach cavity in time, and the nano-multilayer film difficulty for preparing small modulation period using the technology is larger；Currently, still
Have no the research that small modulation period (≤20nm) nano-multilayer film is prepared using multi sphere ion plating technology.
The present invention is improved by the specimen holder to cavity, avoids residual gas to a certain extent and plating rate is too fast
The larger problem of caused intermixing layer.The construction of the side view and specimen holder (cylindrical unit) of coating apparatus is as shown in Figure 1.
Due to the constraint by magnetic field, coating process is concentrated mainly in the fan-shaped region immediately ahead of target.By unidirectionally putting
Target position is set, homemade cylindrical unit is installed, coating process can be rationally controlled with operative constraint coating film area, make residual gas
That is detained Period Process concentrates on sample far from the space of target surface, and rationally control turn according to the residence time of measurement gas
Speed, to obtain the small modulation cycle T i/TiN nano-multilayer film of even compact.
Fig. 2 is the preparation that multi-arc ion coating provided by the present invention prepares small modulation cycle T i/TiN super hard nano multilayer film
Method flow diagram, as shown in Fig. 2, a kind of multi-arc ion coating prepares the preparation side of small modulation cycle T i/TiN super hard nano multilayer film
Method, comprising:
Step 201: titanium deposition targets are unidirectionally placed in the inside of the cavity.
The present invention uses multi sphere ion plating technology, prepares the Ti/TiN nano-multilayer film in different modulating period.Using two
The rounded face Ti metal deposit target that purity is 99.99%, unidirectional to place, upper and lower pinwheel is away from for 250mm, arc current 70-
75A。
Step 202: the sample substrate that hard alloy and single-sided polishing monocrystalline silicon piece are grown as film.
The sample substrate for selecting hard alloy and single-sided polishing monocrystalline silicon (100) piece to grow as film, carbide matrix
Bottom is the block of 15 × 15 × 4mm, and grinding and polishing to surface roughness is R on LCZMP-2 automatic metallic phase sample polished machinea≈
0.8μm；The sample substrate is successively respectively cleaned by ultrasonic 10-15min in deionized water, acetone and dehydrated alcohol, puts after drying
Enter chamber.
In preparation process, the revolution of workbench is 10r/min.
Step 203: the air of the inside cavity is extracted, so that the inside cavity is vacuum state.
Chamber vacuum degree is first evacuated to 2.0-3.0 × 10-2Pa is pre-heated to 200-300 DEG C, is first passed through high-purity argon gas
150cm3/min, Glow Discharge Cleaning 10-15min.
Step 204: under vacuum conditions, the cavity being internally heated, and is passed through higher than purity of argon threshold value
Argon gas, Glow Discharge Cleaning first time period.
Step 205: by the flow-reduction of the argon gas to first flow flow velocity.
The flow-reduction of argon gas is to 100cm3, Ti target is opened, to sample Bombardment and cleaning 10-15 under 400-600V back bias voltage
Minute.
Step 206: when opening the titanium deposition targets, and carrying out Bombardment and cleaning the second to sample substrate under back bias voltage
Between section.
Step 207: being previously deposited the titanium layer of the first deposition thickness as transition zone.
The Ti layer of 50-70nm is previously deposited as transition zone, to improve film-substrate cohesion.
Step 208: argon gas and nitrogen being periodically passed through in the cavity respectively, alternating deposit titanium sublayer and titanium nitride
Sublayer forms multi-arc ion coating and prepares small modulation cycle T i/TiN super hard nano multilayer film.
By switching argon gas and stream of nitrogen gas periodically come alternating deposit Ti sublayer and TiN sublayer, argon stream amount is
100cm3/ min, nitrogen flow 90cm3/min.In experiment, deposition substrate back bias voltage is 200-300V, duty ratio 40%, plating
Ti vacuum degree is 2.3-2.7 × 10-1Pa, plating TiN vacuum are 1.2-1.5 × 10-1Pa。
By adjusting plated film time, 5 kinds of different Ti/TiN nano-multilayer films of periodicity are prepared for, table 1 is institute of the present invention
5 kinds of different Ti/TiN nano-multilayer film contrast tables of the periodicity of offer, as shown in table 1.
Table 1
The preparation of small modulation cycle T i/TiN super hard nano multilayer film is prepared based on multi-arc ion coating provided by the present invention
Device and method is described further with specific embodiment.
Embodiment one
Use two purity for 99.99% rounded face deposition targets, unidirectional to place, for upper and lower pinwheel away from being 250mm, arc is electric
Stream is 70A.The substrate for selecting hard alloy and single-sided polishing monocrystalline silicon (100) piece to grow as film, cement carbide substrate are
The block of 15 × 15 × 4mm, grinding and polishing to surface roughness is R on LCZMP-2 automatic metallic phase sample polished machinea≈0.8μ
m.Sample is successively cleaned by ultrasonic 10min in deionized water, acetone and dehydrated alcohol, is put into chamber after drying.In preparation process,
The revolution of workbench is 10r/min.Before experiment, chamber vacuum degree is first evacuated to 2 × 10-2Pa is pre-heated to 300 DEG C, is first passed through
High-purity argon gas 150cm3/min, Glow Discharge Cleaning matrix 10-15min, argon flow are reduced to 100cm3, Ti target is opened,
Sample is bombarded ten minutes under 600V back bias voltage.The Ti layer of 50nm is previously deposited as transition zone, to improve film-substrate cohesion, is led to
It crosses periodically switch argon gas and stream of nitrogen gas and comes alternating deposit Ti sublayer and TiN sublayer, Ti is coated with the time as 48S, and TiN is coated with
Time is 144S.In experiment, deposition substrate back bias voltage is 200V, and duty ratio 40%, plating Ti vacuum degree is 2.3-2.7 × 10- 1Pa, plating TiN vacuum are 1.2-1.5 × 10-1Pa.Finally being prepared into periodicity is 30, and the monocycle is more with a thickness of the nanometer of 39.2nm
Tunic.
Embodiment two
Use two purity for 99.99% rounded face deposition targets, unidirectional to place, for upper and lower pinwheel away from being 250mm, arc is electric
Stream is 70A.The substrate for selecting hard alloy and single-sided polishing monocrystalline silicon (100) piece to grow as film, cement carbide substrate are
The block of 15 × 15 × 4mm, grinding and polishing to surface roughness is R on LCZMP-2 automatic metallic phase sample polished machinea≈0.8μ
m.Sample is successively cleaned by ultrasonic 10min in deionized water, acetone and dehydrated alcohol, is put into chamber after drying.In preparation process,
The revolution of workbench is 10r/min.Before experiment, chamber vacuum degree is first evacuated to 2 × 10-2Pa is pre-heated to 300 DEG C, is first passed through
High-purity argon gas 150cm3/ min, Glow Discharge Cleaning matrix 10-15min, argon flow are reduced to 100cm3, Ti target is opened,
Sample is bombarded ten minutes under 600V back bias voltage.The Ti layer of 50nm is previously deposited as transition zone, to improve film-substrate cohesion, is led to
It crosses periodically switch argon gas and stream of nitrogen gas and comes alternating deposit Ti sublayer and TiN sublayer, Ti is coated with the time as 24S, and TiN is coated with
Time is 72S.In experiment, deposition substrate back bias voltage is 200V, and duty ratio 40%, plating Ti vacuum degree is 2.3-2.7 × 10- 1Pa, plating TiN vacuum are 1.2-1.5 × 10-1Pa.Finally being prepared into periodicity is 60, and the monocycle is more with a thickness of the nanometer of 20.3nm
Tunic.
Embodiment three
Use two purity for 99.99% rounded face deposition targets, unidirectional to place, for upper and lower pinwheel away from being 250mm, arc is electric
Stream is 70A.The substrate for selecting hard alloy and single-sided polishing monocrystalline silicon (100) piece to grow as film, cement carbide substrate are
The block of 15 × 15 × 4mm, grinding and polishing to surface roughness is R on LCZMP-2 automatic metallic phase sample polished machinea≈0.8μ
m.Sample is successively cleaned by ultrasonic 10min in deionized water, acetone and dehydrated alcohol, is put into chamber after drying.In preparation process,
The revolution of workbench is 10r/min.Before experiment, chamber vacuum degree is first evacuated to 2 × 10-2Pa is pre-heated to 300 DEG C, is first passed through
High-purity argon gas 150cm3/min, Glow Discharge Cleaning matrix 10-15min, argon flow are reduced to 100cm3, Ti target is opened,
Sample is bombarded ten minutes under 600V back bias voltage.The Ti layer of 50nm is previously deposited as transition zone, to improve film-substrate cohesion, is led to
It crosses periodically switch argon gas and stream of nitrogen gas and comes alternating deposit Ti sublayer and TiN sublayer, Ti is coated with the time as 12S, and TiN is coated with
Time is 36S.In experiment, deposition substrate back bias voltage is 200V, and duty ratio 40%, plating Ti vacuum degree is 2.3-2.7 × 10- 1Pa, plating TiN vacuum are 1.2-1.5 × 10-1Pa.Finally be prepared into periodicity be 120, the monocycle with a thickness of 13.2nm nanometer
Multilayer film.
Example IV
Use two purity for 99.99% rounded face deposition targets, unidirectional to place, for upper and lower pinwheel away from being 250mm, arc is electric
Stream is 70A.The substrate for selecting hard alloy and single-sided polishing monocrystalline silicon (100) piece to grow as film, cement carbide substrate are
The block of 15 × 15 × 4mm, grinding and polishing to surface roughness is R on LCZMP-2 automatic metallic phase sample polished machinea≈0.8μ
m.Sample is successively cleaned by ultrasonic 10min in deionized water, acetone and dehydrated alcohol, is put into chamber after drying.In preparation process,
The revolution of workbench is 10r/min.Before experiment, chamber vacuum degree is first evacuated to 2 × 10-2Pa is pre-heated to 300 DEG C, is first passed through
High-purity argon gas 150cm3/min, Glow Discharge Cleaning matrix 10-15min, argon flow are reduced to 100cm3, Ti target is opened,
Sample is bombarded ten minutes under 600V back bias voltage.The Ti layer of 50nm is previously deposited as transition zone, to improve film-substrate cohesion, is led to
It crosses periodically switch argon gas and stream of nitrogen gas and comes alternating deposit Ti sublayer and TiN sublayer, Ti is coated with the time as 9S, and TiN is coated with
Time is 21S.In experiment, deposition substrate back bias voltage is 200V, and duty ratio 40%, plating Ti vacuum degree is 2.3-2.7 × 10- 1Pa, plating TiN vacuum are 1.2-1.5 × 10-1Pa.Finally being prepared into periodicity is 180, and the monocycle is more with a thickness of the nanometer of 7.5nm
Tunic.
Embodiment five
Use two purity for 99.99% rounded face deposition targets, unidirectional to place, for upper and lower pinwheel away from being 250mm, arc is electric
Stream is 70A；The substrate for selecting hard alloy and single-sided polishing monocrystalline silicon (100) piece to grow as film, cement carbide substrate are
The block of 15 × 15 × 4mm, grinding and polishing to surface roughness is R on LCZMP-2 automatic metallic phase sample polished machinea≈0.8μ
m；Sample is successively cleaned by ultrasonic 10min in deionized water, acetone and dehydrated alcohol, is put into chamber after drying；In preparation process,
The revolution of workbench is 10r/min；Before experiment, chamber vacuum degree is first evacuated to 2 × 10-2Pa is pre-heated to 300 DEG C, is first passed through
High-purity argon gas 150cm3/min, Glow Discharge Cleaning matrix 10-15min, argon flow are reduced to 100cm3, Ti target is opened,
Sample is bombarded ten minutes under 600V back bias voltage；The Ti layer of 50nm is previously deposited as transition zone, to improve film-substrate cohesion, is led to
It crosses periodically switch argon gas and stream of nitrogen gas and comes alternating deposit Ti sublayer and TiN sublayer, Ti is coated with the time as 6S, and TiN is coated with
Time is 18S.In experiment, deposition substrate back bias voltage is 200V, and duty ratio 40%, plating Ti vacuum degree is 2.3-2.7 × 10- 1Pa, plating TiN vacuum are 1.2-1.5 × 10-1Pa.Finally being prepared into periodicity is 240, and the monocycle is more with a thickness of the nanometer of 5.2nm
Tunic.
It is specific as follows in order to as a comparison, prepare traditional TiN single thin film using multi sphere ion plating technology:
Use two purity for 99.99% rounded face Ti metal deposit target, arc current 70A；Select hard alloy and
The substrate that single-sided polishing monocrystalline silicon (100) piece is grown as film, cement carbide substrate are the block of 15 × 15 × 4mm,
Grinding and polishing to surface roughness is R on LCZMP-2 automatic metallic phase sample polished machinea≈0.8μm；Sample is successively in deionization
Respectively it is cleaned by ultrasonic 10min in water, acetone and dehydrated alcohol, is put into chamber after drying；In preparation process, the revolution of workbench is
10r/min.Before experiment, chamber vacuum degree is first evacuated to 2.0 × 10-2Pa is pre-heated to 300 DEG C, and being passed through high-purity Ar is 100cm3/
Min, to sample Bombardment and cleaning 10 minutes under 600V back bias voltage；The Ti layer of 50nm is previously deposited as transition zone, to improve film
Base junction resultant force；After transition zone deposits, stop being passed through for Ar gas, this is passed through 90cm3The N of/min2Depositing TiN；In experimentation
Deposition substrate back bias voltage is 200V, duty ratio 40%.
Fig. 3 is TiN monofilm provided by the present invention and Ti/TiN nano-multilayer film electron microscope comparison diagram, as shown in figure 3,
The performance test and comparison of Ti/TiN nano-multilayer film and TiAlN thin film:
Using the automatic scratching instrument testing coating adhesive force of WS-2005 coating adhesion, loaded load 70N, loading speed
70N/min, scratch length 7mm.
(1) comparison of hardness, modulus and H/E
It is using the TTX-NHT2 type nano-hardness tester testing coating hardness and modulus, pressure head of Anton Paar company, Switzerland production
Berkovich triangular pyramid, loaded load 5mN, loading speed 2000nm/min will be pressed into deep-controlled in coating layer thickness
10%, it measures 5 points and is averaged, table 2 is the nano-multilayer film firmness change table in different modulating period provided by the present invention,
As shown in table 2.
Table 2
Fig. 4 is the Ti/TiN nano-multilayer film electron microscope in different modulating period provided by the present invention, as shown in figure 4,5 kinds
Then nanometer multilayer film hardness becomes larger with the reduction of modulation period to be reduced, hardness has been up to 42.9GPa, minimum
26.9GPa is above the 25.5GPa of single layer TiAlN thin film, and then modulus becomes larger with the reduction of modulation period to be reduced, highest
For 357.88GPa, minimum 294.52GPa.H/E value first increases and then decreases is up to 0.1198, minimum 0.0921, high
Have obviously in the hardness and wearability of the 0.084.Ti/TiN nano-multilayer film of single layer TiAlN thin film compared to single layer TiAlN thin film
It is promoted.
Ti/TiN nano-multilayer film provided by the present invention is obviously improved compared to TiAlN thin film, hardness, wearability etc.,
Highest hardness has reached 42.9GPa, much larger than the 25.5GPa of TiN single thin film；Adhesive force, wearability etc. are also obviously improved.
Ti/TiN nano-multilayer film provided by the present invention also has in various degree according to the difference of modulation period, film hardness
Promotion, highest hardness reached 42.9GPa, and much higher than the 25.5GPa of TiN single thin film, hardness improves 68.23%.
H/E value is the ratio of hardness and modulus, which reflects the wearability of film to a certain extent, and the ratio the big resistance to
Mill property is better；The H/E value of TiN monofilm be 0.084, Ti/TiN nano-multilayer film H/E value be up to 0.1198, compared to
TiN monofilm improves 42.62%.
The presence at multiple interface and the addition of soft formation Ti can be released effectively membrane stress, in addition in multi sphere ion plating technology
The pinning effect of energy ion pair matrix is carried, positive effect is played to the film-substrate cohesion for improving Ti/TiN nano-multilayer film, this
So that film is still able to maintain biggish film-substrate cohesion (58 ± 0.9) N while obtaining ultrahigh hardness.
(2) test and comparison of adhesive force
Using the automatic scratching instrument testing coating adhesive force of WS-2005 coating adhesion, loaded load 70N, loading speed
70N/min, scratch length 7mm.
Fig. 5 is the film-substrate cohesion schematic diagram of Ti/TiN nano-multilayer film provided by the present invention, as shown in figure 5, having
The adhesive force of the Ti/TiN nano-multilayer film of multilayered structure is significantly greater than the adhesive force 29N of single layer TiN；It is when modulation period
When 39.2nm, film has maximum film-substrate cohesion value (62 ± 1) N；However when being decreased to 20.3nm modulation period, due to
Shortening for Ti sublayer sedimentation time increases with mixed layer accounting, and the actual (real) thickness of Ti sublayer reduces, and the stress that can be carried reduces,
Film-substrate cohesion reduces；It is decreased to 7.5nm from 20.3nm however as modulation period, the film-substrate cohesion of film is increased to (58
±0.9)N。
Fig. 6 is Ti/TiN nano-multilayer film structure chart provided by the present invention, as shown in fig. 6, small prepared by the present invention
Modulation period Ti/TiN nano superhard film, modulation period, minimum reached 7.5nm, and monocycle Ti/TiN thickness is respectively
1.7nm/5.8nm。
The present invention relates to a kind of Ti/TiN super hard nano multilayer films.The hardness of Ti/TiN nano-multilayer film, toughness, adhesive force
Etc. performances be significantly better than that TiN single thin film, alternative TiN single thin film, for fields such as high speed cutting tools, compared to tradition
TiAlN thin film, hardness, wearability etc. perform better than, and can further promote the service life of high speed cutting tool.
Each embodiment in this specification is described in a progressive manner, the highlights of each of the examples are with other
The difference of embodiment, the same or similar parts in each embodiment may refer to each other.For system disclosed in embodiment
For, since it is corresponded to the methods disclosed in the examples, so being described relatively simple, related place is said referring to method part
It is bright.
Used herein a specific example illustrates the principle and implementation of the invention, and above embodiments are said
It is bright to be merely used to help understand method and its core concept of the invention；Meanwhile for those skilled in the art, according to this hair
Bright thought, any modification, equivalent replacement, improvement and so on, such as use multi sphere in specific embodiments and applications
The coating techniques such as ion plating, magnetron sputtering, vapor deposition, chemical vapor deposition, atomic layer deposition, plating prepare Titanium, iron, nickel,
Chromium, manganese, zinc, copper, aluminium, magnesium, calcium, cobalt, silver, zirconium, niobium, hafnium, tantalum, lead, antimony, tungsten, rubidium, molybdenum, gallium, indium, silicon, ytterbium, germanium, rhenium, europium etc.
Metal and its alternate multi-layered films such as oxide, nitride, carbide and nitrogen oxides, carbonitride, for improve film hardness,
The case study on implementation of adhesive force, toughness, wearability and product service life, should all be included in the protection scope of the present invention.It is comprehensive
Upper described, the contents of this specification are not to be construed as limiting the invention.
Claims (9)
1. the preparation facilities that a kind of multi-arc ion coating prepares small modulation cycle T i/TiN super hard nano multilayer film, which is characterized in that
It include: chamber, cylindrical unit and titanium deposition targets；
The cylindrical unit and the titanium deposition targets are unidirectionally placed in the inside of the chamber, and the cylindrical unit with
The titanium deposition targets are corresponding；Sample substrate is equipped with inside the cylindrical unit, the cylindrical unit is rotatable, the cylinder
Shape dress sets the concentrating on the sample substrate of the delay Period Process in coating process, making residual gas and separate target
In the space in face；The titanium deposition targets are for sample substrate described in Bombardment and cleaning.
2. the preparation method that a kind of multi-arc ion coating prepares small modulation cycle T i/TiN super hard nano multilayer film, which is characterized in that
The preparation method that the multi-arc ion coating prepares small modulation cycle T i/TiN super hard nano multilayer film is applied to a kind of multi sphere ion
Plating prepares the preparation facilities of ditty cycle T i/TiN super hard nano multilayer film, and the multi-arc ion coating prepares small modulation period
The preparation facilities of Ti/TiN super hard nano multilayer film includes chamber, cylindrical unit, titanium deposition targets, and the chamber interior is equipped with
The cylindrical unit and titanium deposition targets；
The cylindrical unit and the titanium deposition targets are unidirectionally placed in the inside of the chamber, and the cylindrical unit with
The titanium deposition targets are corresponding；Sample substrate is equipped with inside the cylindrical unit, the cylindrical unit is rotatable, the cylinder
Shape dress sets the concentrating on the sample substrate of the delay Period Process in coating process, making residual gas and separate target
In the space in face；The titanium deposition targets are for sample substrate described in Bombardment and cleaning；
The multi-arc ion coating prepares the small preparation method for modulating cycle T i/TiN super hard nano multilayer film
Titanium deposition targets are unidirectionally placed in the inside of the cavity；
The sample substrate that hard alloy and single-sided polishing monocrystalline silicon piece are grown as film；
The air of the inside cavity is extracted, so that the inside cavity is vacuum state；
Under vacuum conditions, the cavity is internally heated, and is passed through the argon gas higher than purity of argon threshold value, aura is put
Electricity cleaning first time period；
By the flow-reduction of the argon gas to first flow flow velocity；
The titanium deposition targets are opened, and Bombardment and cleaning second time period is carried out to sample substrate under back bias voltage；
The titanium layer of the first deposition thickness is previously deposited as transition zone；
Argon gas and nitrogen are periodically passed through in the cavity, alternating deposit titanium sublayer and titanium nitride sublayer respectively, are formed more
Arc ion plating prepares small modulation cycle T i/TiN super hard nano multilayer film.
3. the preparation side that multi-arc ion coating according to claim 1 prepares small modulation cycle T i/TiN super hard nano multilayer film
Method, which is characterized in that the pinwheel up and down of the titanium deposition targets is 70-75A away from the range for 250mm, arc current.
4. the preparation side that multi-arc ion coating according to claim 1 prepares small modulation cycle T i/TiN super hard nano multilayer film
Method, which is characterized in that the vacuum degree of the vacuum state is 2.0-3.0 × 10-2Pa；It is passed through the argon gas higher than purity of argon threshold value
Flow velocity be 150cm3/min；The first time period is 10-15min.
5. the preparation side that multi-arc ion coating according to claim 1 prepares small modulation cycle T i/TiN super hard nano multilayer film
Method, which is characterized in that the first flow flow velocity is 100cm3/min。
6. the preparation side that multi-arc ion coating according to claim 1 prepares small modulation cycle T i/TiN super hard nano multilayer film
Method, which is characterized in that the range of the back bias voltage is 400-600V, and the second time period is 10-15min.
7. the preparation side that multi-arc ion coating according to claim 1 prepares small modulation cycle T i/TiN super hard nano multilayer film
Method, which is characterized in that first deposition thickness is 50-70nm.
8. the preparation side that multi-arc ion coating according to claim 1 prepares small modulation cycle T i/TiN super hard nano multilayer film
Method, which is characterized in that be periodically passed through argon gas and nitrogen in the cavity respectively, the flow velocity of the argon gas is
100cm3/ min, the flow velocity of the nitrogen are 90cm3/min。
9. the preparation side that multi-arc ion coating according to claim 1 prepares small modulation cycle T i/TiN super hard nano multilayer film
Method, which is characterized in that described to be periodically passed through argon gas and nitrogen in the cavity respectively, alternating deposit titanium sublayer and nitridation
During titanium sublayer, deposition substrate back bias voltage is 200-300V；Duty ratio is 40%；Vacuum degree when plating titanium layer is 2.3-
2.7×10-1Pa；Vacuum degree when titanium-nitride layer is 1.2-1.5 × 10-1Pa。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910043083.5A CN109440069B (en) | 2019-01-17 | 2019-01-17 | Multi-arc ion plating for preparing Ti/TiN superhard nano multilayer film with small modulation period |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910043083.5A CN109440069B (en) | 2019-01-17 | 2019-01-17 | Multi-arc ion plating for preparing Ti/TiN superhard nano multilayer film with small modulation period |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109440069A true CN109440069A (en) | 2019-03-08 |
| CN109440069B CN109440069B (en) | 2021-01-26 |
Family
ID=65544255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910043083.5A Active CN109440069B (en) | 2019-01-17 | 2019-01-17 | Multi-arc ion plating for preparing Ti/TiN superhard nano multilayer film with small modulation period |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109440069B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110205584A (en) * | 2019-05-30 | 2019-09-06 | Oppo广东移动通信有限公司 | Casting of electronic device and preparation method thereof and electronic equipment |
| CN110468259A (en) * | 2019-09-26 | 2019-11-19 | 济宁学院 | A kind of preparation method of wear-resistant hydraulic pump component |
| CN111593297A (en) * | 2020-05-07 | 2020-08-28 | 西北工业大学 | Composite surface strengthening method giving consideration to erosion resistance and fatigue resistance of metal material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW581827B (en) * | 2002-08-07 | 2004-04-01 | Kmc Chain Ind Co Ltd | Method of ion deposition with plural arc sources at the center |
| CN107058943A (en) * | 2017-05-10 | 2017-08-18 | 山东大学 | TiCN/CrCN nano-multilayer films and preparation method thereof |
-
2019
- 2019-01-17 CN CN201910043083.5A patent/CN109440069B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW581827B (en) * | 2002-08-07 | 2004-04-01 | Kmc Chain Ind Co Ltd | Method of ion deposition with plural arc sources at the center |
| CN107058943A (en) * | 2017-05-10 | 2017-08-18 | 山东大学 | TiCN/CrCN nano-multilayer films and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| YANHUI ZHAO,ET AL.: "Ti/TiN multilayer thin films deposited by pulse biased arc ion plating", 《APPLIED SURFACE SCIENCE》 * |
| 李方正: "多弧离子镀沉积TiCN基硬质涂层及其性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 马钟鸣: "NbN/AlN纳米多层膜及AlCN、TiAlCN复合膜的制备、微结构与力学性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110205584A (en) * | 2019-05-30 | 2019-09-06 | Oppo广东移动通信有限公司 | Casting of electronic device and preparation method thereof and electronic equipment |
| CN110205584B (en) * | 2019-05-30 | 2021-05-28 | Oppo广东移动通信有限公司 | Electronic equipment shell, preparation method thereof and electronic equipment |
| CN110468259A (en) * | 2019-09-26 | 2019-11-19 | 济宁学院 | A kind of preparation method of wear-resistant hydraulic pump component |
| CN111593297A (en) * | 2020-05-07 | 2020-08-28 | 西北工业大学 | Composite surface strengthening method giving consideration to erosion resistance and fatigue resistance of metal material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109440069B (en) | 2021-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6236601B2 (en) | Nanolayer coating for high performance tools | |
| CN109440069A (en) | Multi-arc ion coating prepares small modulation cycle T i/TiN super hard nano multilayer film | |
| CN104508171B (en) | Coat system, the matrix of coating and the method with coat system coating matrix surface | |
| Wei et al. | Effects of pulsed bias duty ratio on microstructure and mechanical properties of TiN/TiAlN multilayer coatings | |
| CN106086806B (en) | A kind of AlTiCrN high-temperature wear resistant coating and preparation method thereof | |
| CN100577860C (en) | Method for preparing low stress chromium nitride multilayer hard film | |
| JP2018501408A (en) | Cutting tool with multilayer PVD coating | |
| Zeng | TiN/NbN superlattice hard coatings deposited by unbalanced magnetron sputtering | |
| Anders et al. | Smoothing of ultrathin silver films by transition metal seeding | |
| WO2017156996A1 (en) | Composite functional cutter coating for cutting titanium alloy and preparation method therefor | |
| CN102653855A (en) | Preparation method of abrasion-resistant and oxidation-resisting TiAlSiN nanometer composite superhard coating | |
| CN108517487B (en) | TiAlN/W with high hardness and high wear resistance2N-multilayer coating and method for producing same | |
| CN103212729B (en) | A kind of have NC cutting tool of CrAlTiN superlattice coating and preparation method thereof | |
| Hovsepian et al. | Novel TiAlCN/VCN nanoscale multilayer PVD coatings deposited by the combined high-power impulse magnetron sputtering/unbalanced magnetron sputtering (HIPIMS/UBM) technology | |
| KR101625774B1 (en) | Multilayer hard coating film and method for producing same | |
| CN109097743A (en) | A kind of superhard W-Cr-Al-Ti-N nanometer gradient multilayer film and preparation method thereof | |
| CN103029366A (en) | Product containing NiCrN ternary coating and preparation method thereof | |
| CN103717331A (en) | Surface-modified wc-based cemented carbide member, hard film-coated wc-based cemented carbide member, method for producing surface-modified wc-based cemented carbide member, and method for producing hard film-coated wc-based cemented carbide member | |
| Lu et al. | Influences of target poisoning on the mechanical properties of TiCrBN thin films grown by a superimposed high power impulse and medium-frequency magnetron sputtering | |
| CN113106408B (en) | Self-lubricating refractory high-entropy alloy film and preparation method thereof | |
| CN108728802A (en) | Multilayer high temperature resistant Ti/Zr co-doped diamond coatings and preparation method thereof | |
| CN110643955A (en) | High-entropy alloy coating and preparation method thereof | |
| CN103938157B (en) | A kind of ZrNbAlN superlattice coating and preparation method | |
| Chang et al. | Mechanical properties of amorphous and crystalline CrN/CrAlSiN multilayer coating fabricated using HPPMS | |
| JP5293330B2 (en) | Cutting tool made of surface coated cubic boron nitride based ultra high pressure sintered material |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |