CN100424224C - Reaction and magnetically controlled sputtering process of preparing hard nanometer layered TiN/SiO2 coating - Google Patents

Reaction and magnetically controlled sputtering process of preparing hard nanometer layered TiN/SiO2 coating Download PDF

Info

Publication number
CN100424224C
CN100424224C CNB2006100291322A CN200610029132A CN100424224C CN 100424224 C CN100424224 C CN 100424224C CN B2006100291322 A CNB2006100291322 A CN B2006100291322A CN 200610029132 A CN200610029132 A CN 200610029132A CN 100424224 C CN100424224 C CN 100424224C
Authority
CN
China
Prior art keywords
target
sio
tin
coating
laminated coating
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.)
Expired - Fee Related
Application number
CNB2006100291322A
Other languages
Chinese (zh)
Other versions
CN1888131A (en
Inventor
孔明
李戈扬
刘艳
戴嘉维
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.)
Shanghai Jiaotong University
Original Assignee
Shanghai Jiaotong University
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 Shanghai Jiaotong University filed Critical Shanghai Jiaotong University
Priority to CNB2006100291322A priority Critical patent/CN100424224C/en
Publication of CN1888131A publication Critical patent/CN1888131A/en
Application granted granted Critical
Publication of CN100424224C publication Critical patent/CN100424224C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The reaction and magnetically controlled sputtering process of preparing hard nanometer layered TiN/SiO2 coating belongs to the field of tool and mold coating preparing technology. In a multiple target magnetically controlled sputtering and coating apparatus with low pressure mixed Ar and N2 atmosphere and independent RF cathodes controlled Ti target and compound SiO2 target, the substrate is made to stay alternately in the plasmas these two targets generate to form the layered coating including TiN layers formed through the reaction between Ti material and N2 gas and the SiO2 layers formed directly with the sputtered SiO2 compound and containing no nitrogen. The present invention has high efficiency, and the formed coating has high hardness and excellent antioxidant performance and is suitable for high speed cutting and dry cutting.

Description

Reaction magnetocontrol sputtering TiN/SiO 2The preparation method of hard nanometer laminated coating
Technical field
That the present invention relates to is a kind of preparation method of hard coat, specifically is a kind of reaction magnetocontrol sputtering TiN/SiO 2The preparation method of hard nanometer laminated coating.Be used for cutting tool material top coat preparing technical field.
Background technology
The high speed cutting of cutting speed 〉=100m/min and the DRY CUTTING that uses no or little cooling fluid are because its mechanical workout efficient height, and be low in the pollution of the environment, becomes the main flow of cutting technology development just day by day.But this processing technology not only requires cutter coat hardness height to the demands for higher performance of cutter coat, and frictional coefficient is little, but also need have higher resistance of oxidation.Existing cutter coat does not satisfy these requirements as yet comprehensively.As the TiN coating, hardness 23 ± 2GPa, oxidizing temperature is about 500 ℃; The hardness of TiCN coating is up to 40GPa, and oxidation resistance temperature but has only 400 ℃; Best at present TiAlN coating hardness is 35 ± 5GPa, and oxidation resistance temperature can reach 800 ℃, but still can not satisfy the needs of high speed cutting and the harsh service condition of DRY CUTTING.Owing to have the excellent high-temperature chemical stability, oxide ceramics is acknowledged as the hard coat that has potential application foreground most, and regrettably the mechanical property of oxide coating, especially hardness is far away from nitride, and is not good as the cutter coat result of use separately.
Find that through retrieval U.S. Pat 6333099B1 then provides a kind of MeN/Al with excellent antioxidant performance to prior art 2O 3Nano laminated coating, this laminated coating are MeN layer and the Al of 0.1～30nm by bed thickness 2O 3Layer alternating deposit and forming, wherein the Me among the MeN can be element or their mixtures such as Ti, Nb, Hf, V, Ta, Mo, Zr, Cr, W, Al.This total coating thickness is 0.5～20 μ m, and its hardness is not less than constituent MeN and Al 2O 3The hardness of single-layer coating.Though this MeN/A1 that this patent proposes 2O 3Nano laminated coating can be used chemical gaseous phase depositing process (CVD) and physical gas-phase deposite method (PVD) preparation, but concrete making detailed rules and regulations are not provided.
Chinese patent (publication number: CN1587434) provide a kind of high rigidity oxycompound TiN/SiO 2Nano laminated coating.This coating is by control SiO 2The thickness of layer makes SiO 2Layer produces crystallization by means of the crystalline structure of TiN layer less than 1.2nm the time, and with the epitaxy of TiN layer coherence, form the polycrystalline superstructure.This superstructure feature makes above nano laminated coating present the superhard effect that the consistency and elasticity modulus raises, and its hardness can reach more than the 40GPa.And, because stratiform SiO 2Existence, this laminated coating has the excellent high-temperature oxidation-resistance.But, the TiN/SiO that this patent proposes 2The preparation method of nano laminated coating is by radio-frequency (RF) sputtering method sputtered with Ti N and SiO in Ar atmosphere 2Ceramic target obtains.Though this technology of preparing has realized preparing simultaneously nitride (TiN) and oxide compound (SiO in same vacuum chamber 2), and can realize the nano laminated coating that very fast alternately speed deposition cycle changes, still, wherein the sedimentation effect of the ceramic target of Cai Yonging far below the employing metallic target by with reactant gases (as N 2Gas) carry out the efficient of reactive sputter-deposition coating, also fail to reach the level that realizes that industrial scale is produced at present.
In addition, for the nano laminated coating of forming by nitride and oxide compound, though also can adopt dual gas supply (i.e. two kinds of reactant gases N 2And O 2) mode, continuous switching by two kinds of reactant gasess comes reactive sputtering acquisition nitride and oxide compound respectively, but because of the time that gas switch to need longer, and to the having relatively high expectations of the equipment of industrial product, this method is not suitable for the suitability for industrialized production of nano laminated coating yet.
Summary of the invention
At above nitride/oxide nano laminated coating preparation efficiency problem on the low side, the invention provides a kind of reaction magnetocontrol sputtering TiN/SiO 2The preparation method of hard nanometer laminated coating adopts at Ar gas and N it 2Reaction magnetocontrol sputtering prepares TiN/SiO in the mixed atmosphere of gas 2Nano laminated coating can obtain very high coating growth efficiency, satisfies suitability for industrialized production and have high rigidity and superior oxidation resistance energy, is applicable to high speed cutting and the needs Dry Cutting Tool coating.
The present invention is achieved by the following technical solutions, and the present invention adopts multi-target magnetic control sputtering coating preparation equipment, metal Ti target and ceramic SiO 2Target is respectively by independently radio frequency cathodic control, at Ar and N 2Carry out reaction magnetocontrol sputtering in the mixed atmosphere.TiN/SiO 2TiN layer in the nano laminated coating is by splash-proofing sputtering metal Ti target and and N 2Solid/liquid/gas reactions generates, and SiO 2Layer is then by SiO 2The direct sputter of compound target obtains.Laminated coating by matrix at Ti target and SiO 2Alternately accept sputter before the target and form laminate structure.
Described reaction magnetocontrol sputtering, its sputter gas are Ar, and dividing potential drop is P Ar=0.4～0.5Pa.
Described reaction magnetocontrol sputtering, its reactant gases are N 2, dividing potential drop is P N2=0.04～0.08Pa.
Described reaction magnetocontrol sputtering, TiN layer and SiO 2The thickness of layer stays in the time control of accepting sputter material before each target by the sputtering power of two targets and matrix respectively, and the influence of nitrogen partial pressure slightly changes when being subjected to sputter.
Described matrix is metal, Wimet or pottery, temperature＜200 in its when deposition ℃.
Efficient production TiN/SiO provided by the invention 2The key problem in technology of nano laminated coating is: the 1) SiO that is adopted 2Pottery is the highly stable oxide compound of a kind of chemical property, and the present invention adopts the TiN/SiO of described reaction magnetocontrol sputtering technology preparation 2SiO in the nano laminated coating 2Layer can nitriding.2) prepared TiN/SiO 2Nano laminated coating, (4.0～15nm) much larger than SiO for the thickness of TiN layer in its each double-deck cycle 2The thickness (0.3～1.3nm) of layer.Thereby, as long as improve the sedimentation rate of TiN layer, just can make TiN/SiO 2The preparation efficiency of nano laminated coating is significantly improved, and the present invention has adopted the direct and reactant gases N of metal Ti target just 2The solid/liquid/gas reactions sputter comes the depositing TiN layer, is compared to the direct sputter of TiN ceramic target in Ar atmosphere, and sedimentation rate is greatly improved.3) N 2Within the specific limits the change of gas dividing potential drop (0.04Pa～0.09Pa), little to the microstructure and the mechanical property influence of resulting laminated coating, brought facility for the actual production operation of industry.
The laminated coating that the present invention makes can obtain the above hardness of 35GPa, and has the high-temperature oxidation resistance above 800 ℃ simultaneously.Can be applicable to the industrial scale production of cutter protection coating and other abrasion-resistant coating of high speed cutting and DRY CUTTING.
Embodiment
The inventive method concrete steps are as follows:
1. adopt multi-target magnetic control sputtering coating apparatus with the radio frequency negative electrode that can independently control;
2. metal or ceramic matrix surface are done the mirror polish processing, be installed on the interior rotating substrate frame of vacuum chamber;
3. with metal Ti target and compound S iO 2Target places respectively independently on the radio frequency negative electrode.
4. carry on the back end vacuum≤10 in the vacuum chamber -3Behind the Pa, to wherein feeding Ar, N 2Mixed gas, wherein Ar gas dividing potential drop is 0.4～0.5Pa, N 2The gas dividing potential drop is 0.04～0.08Pa;
5. rotation substrate frame makes substrate respectively at Ti target and SiO 2Accept sputter material before the target and form laminated coating.Wherein the TiN layer is by metal Ti target and N 2Reactive sputtering obtains, and SiO 2Layer is then by SiO 2The direct sputter preparation of ceramic target.
6. TiN layer and SiO in each modulation period in the nano laminated coating 2The time control that sputtering power and the substrate of the thickness of layer by each target stops before each target.TiN/SiO 2Nano laminated coating is by SiO 2Layer and TiN layer alternating deposit are formed SiO on the matrix of metal or pottery 2The thickness of layer is 0.3～1.3nm, and the thickness of TiN layer is 4.0～15nm, and so alternating deposit formation total thickness is the thick TiN/SiO of 2～5 μ m 2Nano laminated coating.
Provide embodiment below in conjunction with content of the present invention:
Example one
TiN/SiO of the present invention 2The preparation method's of laminated coating concrete processing parameter is: Ar gas dividing potential drop is 0.4Pa, N 2The gas dividing potential drop is 0.08Pa, and Ti target sputtering power is 220W, and depositing time is 15 seconds, SiO 2The target sputtering power is 40W, and depositing time is 4 seconds, substrate temperature＜200 ℃.The TiN/SiO that obtains thus 2The thickness of TiN layer is 4.6nm in the laminated coating, SiO 2Bed thickness is 0.3nm, and the hardness of coating is 35.3GPa.
Example two
TiN/SiO of the present invention 2The preparation method's of laminated coating concrete processing parameter is: Ar gas dividing potential drop is 0.4Pa, N 2The gas dividing potential drop is 0.08Pa, and Ti target sputtering power is 220W, and depositing time is 15 seconds, SiO 2The target sputtering power is 40W, and depositing time is 6 seconds, substrate temperature＜200 ℃.The TiN/SiO that obtains thus 2The thickness of TiN layer is 4.6nm in the laminated coating, SiO 2Bed thickness is 0.5nm, and the hardness of coating is 40.0GPa.
Example three
TiN/SiO of the present invention 2The preparation method's of laminated coating concrete processing parameter is: Ar gas dividing potential drop is 0.4Pa, N 2The gas dividing potential drop is 0.08Pa, and Ti target sputtering power is 220W, and depositing time is 15 seconds, SiO 2The target sputtering power is 40W, and depositing time is 14 seconds, substrate temperature＜200 ℃.The TiN/SiO that obtains thus 2The thickness of TiN layer is 4.6nm in the laminated coating, SiO 2Bed thickness is 1.3nm, and the hardness of coating is 32.6GPa.
Example four
TiN/SiO of the present invention 2The preparation method's of laminated coating concrete processing parameter is: Ar gas dividing potential drop is 0.4Pa, N 2The gas dividing potential drop is 0.08Pa, and Ti target sputtering power is 220W, and depositing time is 50 seconds, SiO 2The target sputtering power is 40W, and depositing time is 4 seconds, substrate temperature＜200 ℃.The TiN/SiO that obtains thus 2The thickness of TiN layer is 14nm in the laminated coating, SiO 2Bed thickness is 0.6nm, and the hardness of coating is 36.6GPa.
Example five
TiN/SiO of the present invention 2The preparation method's of laminated coating concrete processing parameter is: Ar gas dividing potential drop is 0.4Pa, N 2The gas dividing potential drop is 0.04Pa, and Ti target sputtering power is 220W, and depositing time is 15 seconds, SiO 2The target sputtering power is 40W, and depositing time is 4 seconds, substrate temperature＜200 ℃.The TiN/SiO that obtains thus 2The thickness of TiN layer is 6.5nm in the laminated coating, SiO 2Bed thickness is 0.5nm, and the hardness of coating is 41.0GPa.

Claims (4)

1. reaction magnetocontrol sputtering TiN/SiO 2The preparation method of hard nanometer laminated coating is characterized in that: adopt multi-target magnetic control sputtering coating preparation equipment, metal Ti target and ceramic SiO 2Target is respectively by independently radio frequency cathodic control, at Ar and N 2Carry out reaction magnetocontrol sputtering in the mixed atmosphere, the TiN layer is by splash-proofing sputtering metal Ti target and and N 2Solid/liquid/gas reactions generates, and SiO 2Layer is then by SiO 2The direct sputter of compound target obtains, laminated coating by matrix at Ti target and SiO 2Alternately accept sputter before the target and form nanometer laminated structure, wherein N 2The gas dividing potential drop is 0.04～0.08Pa, and the TiN layer thickness is 4.0～15nm, and the SiO2 layer thickness is 0.3～1.3nm.
2. reaction magnetocontrol sputtering TiN/SiO according to claim 1 2The preparation method of hard nanometer laminated coating is characterized in that, may further comprise the steps:
1) adopts multi-target magnetic control sputtering coating apparatus with independent radio frequency negative electrode of controlling;
2) will be installed in the vacuum chamber on the rotating substrate frame through pottery behind polishing and the cleaning-drying or metal base;
3) with metal Ti target and compound S iO 2Target places respectively independently on the radio frequency negative electrode;
4) back of the body end vacuum≤10 in the vacuum chamber -3Behind the Pa, to wherein feeding Ar, N 2Mixed gas;
5) open control Ti target and SiO 2The radio frequency cathode power of target makes the preceding plasma body that produces of target, and target is carried out sputter;
6) rotate substrate frame, make substrate respectively at Ti target and SiO 2Accept sputter material before the target and form nano laminated coating, TiN layer and SiO in each modulation period in the nano laminated coating 2The time control that sputtering power and the substrate of the thickness of layer by each target stops before each target, alternating deposit forms TiN/SiO 2Nano laminated coating.
3. according to claim 1 or 2 described reaction magnetocontrol sputtering TiN/SiO 2The preparation method of hard nanometer laminated coating is characterized in that, Ar gas dividing potential drop is 0.4～0.5Pa.
4. reaction magnetocontrol sputtering TiN/SiO according to claim 2 2The preparation method of hard nanometer laminated coating is characterized in that, 2) described in pottery or metal base in temperature＜200 in when deposition ℃.
CNB2006100291322A 2006-07-20 2006-07-20 Reaction and magnetically controlled sputtering process of preparing hard nanometer layered TiN/SiO2 coating Expired - Fee Related CN100424224C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2006100291322A CN100424224C (en) 2006-07-20 2006-07-20 Reaction and magnetically controlled sputtering process of preparing hard nanometer layered TiN/SiO2 coating

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2006100291322A CN100424224C (en) 2006-07-20 2006-07-20 Reaction and magnetically controlled sputtering process of preparing hard nanometer layered TiN/SiO2 coating

Publications (2)

Publication Number Publication Date
CN1888131A CN1888131A (en) 2007-01-03
CN100424224C true CN100424224C (en) 2008-10-08

Family

ID=37577417

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2006100291322A Expired - Fee Related CN100424224C (en) 2006-07-20 2006-07-20 Reaction and magnetically controlled sputtering process of preparing hard nanometer layered TiN/SiO2 coating

Country Status (1)

Country Link
CN (1) CN100424224C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011045974A (en) * 2009-08-28 2011-03-10 Mitsubishi Materials Corp Surface-coated cutting tool

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101869725B (en) * 2010-06-25 2013-06-12 昆明贵金属研究所 Antibacterial bioactivity composite coating comprising nano Ag particles and preparation method
TWI502087B (en) * 2010-11-18 2015-10-01 Hon Hai Prec Ind Co Ltd Erosion resisting treatment for aluminum alloy and aluminum alloy articles
CN107604311A (en) * 2017-08-10 2018-01-19 酒泉职业技术学院 A kind of preparation method of automatically cleaning solar thermal collector antireflective coating

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02237A (en) * 1987-12-21 1990-01-05 Hoechst Celanese Corp Bisacrylate monomer and polymer showing nonlinear optical responce
CN1501444A (en) * 1998-11-26 2004-06-02 索尼株式会社 Manufacturing method of semiconductor device
WO2005010225A1 (en) * 2003-07-25 2005-02-03 Antoine Bittar Solar selective surface coatings, materials for use therein and a method of producing same
CN1587434A (en) * 2004-08-05 2005-03-02 上海交通大学 TiN/SiO2 nano multilayer membrane and its preparing method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02237A (en) * 1987-12-21 1990-01-05 Hoechst Celanese Corp Bisacrylate monomer and polymer showing nonlinear optical responce
CN1501444A (en) * 1998-11-26 2004-06-02 索尼株式会社 Manufacturing method of semiconductor device
WO2005010225A1 (en) * 2003-07-25 2005-02-03 Antoine Bittar Solar selective surface coatings, materials for use therein and a method of producing same
CN1587434A (en) * 2004-08-05 2005-03-02 上海交通大学 TiN/SiO2 nano multilayer membrane and its preparing method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
TiN/SiO2 纳米多层膜的晶体生长与超硬效应. 魏仑等.物理学报，第54卷第4期. 2005
TiN/SiO2 纳米多层膜的晶体生长与超硬效应. 魏仑等.物理学报，第54卷第4期. 2005 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011045974A (en) * 2009-08-28 2011-03-10 Mitsubishi Materials Corp Surface-coated cutting tool

Also Published As

Publication number Publication date
CN1888131A (en) 2007-01-03

Similar Documents

Publication Publication Date Title
Alami et al. High power pulsed magnetron sputtering: Fundamentals and applications
CN102011091B (en) CrAlN protective coating with high hardness and high elastic modulus and preparation method thereof
CN102653855B (en) Preparation method of abrasion-resistant and oxidation-resisting TiAlSiN nanometer composite superhard coating
CN101157289B (en) AIN/Si3N4 nanometer multi-layer horniness coatings as well as its preparing method
CN103757597B (en) A kind of TiN/CrAlSiN nanocomposite laminated coating and preparation method thereof
CN101338411B (en) Zr-Si-N hard composite coating and method for preparing same
CN103510061A (en) Method for preparing high-rigidity and high-elasticity modulus TiSiN protection coating
CN103255373B (en) A kind of TaVN compound coating and preparation method thereof
CN111910159B (en) Nanocrystalline amorphous composite coating, preparation method thereof and cutter
CN100424224C (en) Reaction and magnetically controlled sputtering process of preparing hard nanometer layered TiN/SiO2 coating
CN105296949A (en) Nano-structure coating with ultra-high hardness and manufacturing method thereof
CN101531074B (en) Ultrahard TiB2/Si3N4 nano-multilayer film and preparation method thereof
CN104805408A (en) High-hardness TiSiBN nano-composite structure protective coating and preparation method thereof
CN111471957B (en) Preparation method of multilayer heterostructure high-entropy alloy
CN101618614B (en) TiC/Si3N4 nano laminated coating and preparation method thereof
CN1793415A (en) Process for preparing ZrN/Al2 (O1-xNx)3 hard nano multi-layer coating
CN103243303B (en) Ta-Mo-N composite coating and preparation method thereof
CN1924084A (en) Preparation method of TiN/AlON nano multilayer coating reaction magnetron sputtering for cutting tool
CN106756833B (en) A kind of high rigidity TiCrN/TiSiN nano-multilayered structures coating and preparation method thereof
CN101618615B (en) VC/Si3N4 nano laminated coating and preparation method thereof
CN101451232B (en) Method for preparing nano composite multiple layer hard film
CN101886242A (en) Titanium boride/silicon nitride nano multi-layer coating and preparation method thereof
CN100480043C (en) High hardness ZrN/Al2(O1-xNx)3 nanometer multicoating
CN101157288A (en) AIN/BN superhard nanostructured multilayer film as well as its preparing method
CN1888125A (en) Nanometer layered VN/SiO2 coating and its prepn

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20081008

Termination date: 20110720