CN1133756C - Multi-layer compounded superhard C3N4/MN film and its synthesizing equipment and process - Google Patents
Multi-layer compounded superhard C3N4/MN film and its synthesizing equipment and process Download PDFInfo
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- CN1133756C CN1133756C CNB981216803A CN98121680A CN1133756C CN 1133756 C CN1133756 C CN 1133756C CN B981216803 A CNB981216803 A CN B981216803A CN 98121680 A CN98121680 A CN 98121680A CN 1133756 C CN1133756 C CN 1133756C
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Abstract
The present invention discloses a C3N4/MN multilayer composite superhard thin film, and a device and a method thereof for synthesizing the C3N4/MN multilayer composite superhard thin film. The C3N4/MN multilayer composite superhard thin film comprises an MN transition layer, a C3N4/MN main antiwear layer and an MN surface antiwear layer, and has high microhardness. When the device and the method of the present invention are used for preparing the C3N4/MN multilayer composite superhard thin film, the time is short, the efficiency is high, the synthetic cost is low and the microhardness is as high as 40 to 55mpa; therefore, the carbon nitride superhard thin film can be plated on rapid steel tools and other antiwear coating workpieces, and has great use value.
Description
Technical field
The present invention relates to a kind of C
3N
4/ MN (M=Ti, Zr) multi-layer compounded superhard film, the synthesizer of film and synthetic method, it belongs to the thin-film material technical field.
Background technology
The early 1990s is since American scientist A.Y.Liu and M.L.Cohen prophesy novel solid covalent bond compound β-C
3N
4May have approaching or surpass in the world the hardest material diamond [A.Y.Liu and M.L.Cohen, Science, 245 (1989) 841; A.M.Liu and M.L.Cohen, Phys.Rev.B, 42 (1990) 10727], countries in the world have started research and have used the upsurge of this novel super-hard thin-film material, become the very popular research topic of material science.Originally the someone adopts the synthetic β-C of plasma CVD method of methane and nitrogen
3N
4, owing to opening c h bond and the N-N key fails.Until Harvard University [C.Niu et al., Science, 261 (1993) 334] method that adopts laser evaporation and atomic beam spray to combine in 1993 successfully obtains C
3N
4Film.After this synthetic C of additive method also appears
3N
4The report of film, for example: houston, u.s.a university adopts electron cyclotron resonace method [A.Bousetta.et al., J.Vac.Sci.Technol.A, 13 (3) (1995) 1639], Japan T.Okada company adopts radio frequency reaction magnetron sputtering method [J.Ortega et al., Phys.Rev.B, 51 (1995) 2624], Japan Okayama Univ. adopts electron beam evaporation to add ion beam assisted depositing method [F.Fujimoto et al., Jpn.J.Appl.Phys., 32 (1993) L420] etc. in succession synthesized carbon nitride films.[the Song H.W. of China Tsing-Hua University, Cui F.Z.et al., J.Phys.Matter., 6 (1994) 6125], [the Ren Z.M.etal. of Fudan University, Phys.Rev.B, 51 (1995) 5274], Beijing physics institute of the Chinese Academy of Sciences, the metallurgical institute in Shanghai etc. also take similar approach research carbonitride.The method of these many synthetic carbonitrides is except their advantages separately, and their common shortcomings are film growth rate low (growth velocity 0.2～0.5 μ m/ hours), are not suitable for suitability for industrialized production.Film can't avoid graphite to separate out mutually in addition, thereby the hardness of film is not high, and (Hv≤20GPa) differs greatly with the desired value of carbonitride, and the key that improves film hardness is to avoid separating out of graphite phase in the film growth.
Summary of the invention
The object of the present invention is to provide a kind of C of suitable suitability for industrialized production
3N
4/ MN multi-layer compounded superhard film, this film should have higher hardness.Adopt this device and method to prepare C
3N
4/ MN multi-layer compounded superhard film the time is short, the efficient height, and production cost is low, is applicable on high-speed steel workpiece and other wear-resisting workpiece to be coated with superhard thin film.
Be the technical measures that realize that purpose of the present invention is taked:
1.C
3N
4The design of/MN multi-layer compounded superhard membrane structure:
The hard coat of surface of the work requires this coating material hardness height, and abrasion resistance properties is good, stable chemical performance, and with workpiece material generation chemical reaction, heat-resistant oxidized, coefficient of friction is not low, with matrix adhesion-tight etc.Obviously, the single coating material is difficult to all satisfy above-mentioned specification requirement.
C of the present invention
3N
4The design of/MN multi-layer compounded superhard membrane structure comprises three layers, bottom (transition zone) is the MN of 0.1～0.2 μ m thickness or forms (M=Ti or Zr) by the Titanium of 30～50nm thickness or the MN of zirconium and 0.1～0.2 μ m thickness, it plays a part to increase hard coat adhesive force, gives simultaneously C
3N
4Growth a good growth basis is provided.The thick C of 3～4 μ m then
3N
4/ MN multilayer alternate films (main wearing layer) because it has very high microhardness, plays main wear-resisting effect in the workpiece hard coat.Be the thick MN surface anti-attrition layer of 0.3～0.5 μ m at last, performance MN film has the characteristic of low-friction coefficient.The microhardness of this composite membrane can be up to 40～55GPa.
2. synthesize C
3N
4The device of/MN multi-layer compounded superhard film:
Synthetic C as shown in Figure 1
3N
4The device of/MN multi-layer compounded superhard film.On vacuum film coating chamber 16 outer walls, a multi sphere source M target 1 and two magnetron sputtering high purity graphite targets 2 are set.Two graphite target are staggered relatively, form closed magnetic field, and the M target becomes 90 ° of placements with graphite target, and 4 is the multi sphere power supply, and 6 is shielding power supply.The work rest 3 that is positioned at vacuum chamber central authorities connects grid bias power supply 5, and work rest is driven by direct-current machine and is rotated, and rotating speed can be regulated.Heating lamp 7 has been installed around the vacuum chamber inwall.Workpiece temperature is set measures controller 18, gas source and flow control system (11～15).Diffusion pump 9 and mechanical pump 10 are formed the running of vacuum unit and are obtained the vacuum chamber high vacuum, and final vacuum reaches 5 * 10
-4Pa.For MN and C
3N
4Formation speed can mate, M target needs two graphite target of adapted.
This device is combined multi-arc ion coating and magnetron sputtering, and carries out processing parameter control respectively.Owing to the rotation of work rest, can on workpiece, alternately deposit the C of nano-scale
3N
4/ MN superlattice film, different rotary speeies can be regulated C
3N
4With the thickness cycle of MN.
3. synthesize C
3N
4The method of/MN multi-layer compounded superhard film:
The workpiece that cleans up is placed in the vacuum chamber on the work rest, be evacuated to 1 * 10
-3More than the Pa, feed Ar. and open grid bias power supply, workpiece is carried out sputter clean, bias voltage transfers to 800～1000V gradually, and keeps 10～12 minutes, after the workpiece Heating temperature arrives 300～450 ℃, open the multi sphere power supply of M target, control multi sphere source electric current 50 ± 5A slowly feeds nitrogen, argon-mixed (N
2: Ar=2: 1), control air pressure is 0.5～0.8Pa, and bias voltage is reduced to 150～200V.8～10 minutes MN that grow, 10～15 rev/mins of control rotating speeds are opened graphite target magnetron sputtering power supply again, control sputtering voltage 600V ± 10V, sputtering current 2～3A.Growth C
3N
4/ MN multilayer film (thickness reaches 3～4 μ m) is closed the graphite target shielding power supply then, again 15～18 minutes MN of continued growth.Be cooled to below 100 ℃, open vacuum chamber, take out workpiece.
According to conventional multi-arc ion coating method, depositing TiN and ZrN, microhardness can only reach 18-20GPa.Deposit single C
3N
4Although the film microhardness can reach greater than 40GPa, the thickness that deposits 3～5 μ m needs 15～20 hours approximately, and growth rate is very slow, is difficult to be generalized to industrial the application, and can not guarantee its crystalline state and quality.
For this novel super-hard film of Accelerate nitriding carbon in industrial practical application, the present invention adopts the synthetic C of the method be different from domestic and international report
3N
4Superhard thin film is with multi-arc ion coating MN and direct current reaction magnetron sputtering C
3N
4Organically combine, the bi-material of growing simultaneously, along with work rest constantly rotates, workpiece to be plated passes through graphite target and M target surface successively, respectively each self-generating C
3N
4Layer and MN layer deposit C alternately at workpiece
3N
4/ MN multilayer film.The rotary speed of control workpiece makes each C
3N
4The thickness of layer and each MN layer is 1～3nm, forms the overlapping superlattice film material of cycle of nano-scale.Because the characteristic of nano material and super crystal lattice material, the film that deposits has very high hardness.Simultaneously, because MN is a kind of hard coating material of very easy crystallization, it is the cubic system crystallization, at the MN layer C that grows
3N
4, be conducive to the β-C of hexaplanar
3N
4C-C with cubic system
3N
4Hard crystalline phase growth, and be unfavorable for that rhombohedral graphite-phase separates out, thereby the present invention can obtain the not purer carbonitride hard films of graphitiferous phase.C
3N
4At alternately growth of MN, C
3N
4Be subjected to the crystallization that forces of MN, mainly generate the hard crystalline phase, and other many synthetic C
3N
4Method can only obtain amorphous phase.
By method deposition C of the present invention
3N
4Multilayer film, the superhard thin film of sedimentary facies coating layer thickness together only needs more than one hour, has practical growth rate, and the microhardness of film is very high, and the present invention plates for rapid steel tool, and very big practical value is arranged.
The present invention synthesizes C
3N
4Characteristics be that film has higher growth rate and very high microhardness, thereby be C
3N
4The application of this super-hard film material in coated cutting tool provides quality assurance, promotes the development of quality coating cutter.
In a word, C provided by the invention
3N
4/ MN multi-layer compound film has the hardness height, and it is short that its synthesizer and method have the time, the efficient height, and therefore the characteristics such as cost is low have very big using value.
Description of drawings:
Fig. 1 is C
3N
4The synthesizer schematic diagram of/MN multi-layer compound film, Fig. 2 and Fig. 3 are respectively carbon C (1s) electron binding energy curve and nitrogen N (1s) the electron binding energy curves of carbonitride analysis of components, and Fig. 4 is C
3N
4The X-ray diffraction spectrum of/TiN/Si film, Fig. 5 are C
3N
4Transmission electron microscope electronic diffraction Laue point picture, Fig. 6 is C
3N
4Transmission electron microscope electronic diffraction Laue point and polycrystal ring be the picture of superposition mutually.
Among Fig. 1,1-multi sphere ion source, 2-magnetron sputtering target, 3-work rest, the 4-arc power, 5-grid bias power supply, 6-magnetron sputtering power supply, 7-workpiece heating lamp, 8-vision slit, 9-diffusion pump, 10-mechanical pump, 11-be from the dynamic pressure instrument, the 12-piezo electric valve, the 13-mass flowmeter, 14-stopping valve, 15-pressure reducer, the 16-vacuum film coating chamber, 17-work rest rotary actuator, the 18-workpiece temperature shows and controller.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment technical scheme of the present invention is further described.
Embodiment 1 C
3N
4The film layer structure of/TiN multi-layer compounded superhard film:
C
3N
4/ TiN multi-layer compounded superhard membrane structure comprises three layers, and bottom (transition zone) is made up of the Titanium of 50nm thickness and the TiN of 0.1 μ m thickness, is the thick C of 4 μ m then
3N
4/ TiN multilayer alternate films (main wearing layer), the microhardness of this composite membrane can be up to 40～55GPa.
Embodiment 2 synthetic C
3N
4The device of/TiN multi-layer compounded superhard film:
Synthetic C as shown in Figure 1
3N
4The device of/MN multi-layer compounded superhard film on vacuum chamber 16 outer walls, arranges a multi sphere M target 1 and two magnetron sputtering high purity graphite targets 2.Two graphite target are staggered relatively, form closed magnetic field, and the M target becomes 90 ° of placements with graphite target, and 4 is the multi sphere power supply, and 6 is shielding power supply.The work rest 3 that is positioned at vacuum chamber central authorities connects grid bias power supply 5, and work rest is driven by direct-current machine and is rotated, and rotating speed can be regulated.Around the vacuum chamber inwall heating lamp 7 has been installed, also has been provided with workpiece temperature and measures controller 18, gas source and flow control system (11～15).Diffusion pump 9 and mechanical pump 10 are formed the running of vacuum unit and are obtained the vacuum chamber high vacuum, and final vacuum reaches 5 * 10
-4Pa.For MN and C
3N
4Formation speed can mate, M target needs two graphite target of adapted.
The titanium target is loaded onto in the multi sphere source, and magnetron sputtering target is a high purity graphite.The workpiece and the specimen that clean up are contained on the work rest, open the vacuum unit.Vacuum degree in vacuum chamber reaches 5 * 10
-3After the Pa, feed Ar, start grid bias power supply and gradually voltage is risen to 1000V, to workpiece sputter clean 10 minutes.Then, feed N again
2: Ar=2: 1 gas mixture, workpiece is heated to 400 ℃, open the work rest rotation, 15 rev/mins of rotating speeds, bias voltage 150V.Open titanium target multi sphere power supply earlier, control arc current 50A is about arc voltage 25 ± 5V.Behind the working stability, connect the graphite target shielding power supply, control sputtering voltage 620V, sputtering current 3A deposits C at workpiece
3N
4/ TiN multilayer film, about 90 minutes of sedimentation time, thickness 4 μ m.After thickness is enough, disconnect earlier the graphite target power supply, disconnect again titanium target power supply and grid bias power supply, when workpiece cools to the furnace below 80 ℃, can take out.The microhardness of measure sample, Hv=50～55GPa.
Embodiment 4 synthetic C
3N
4/ ZrN multi-layer compounded superhard film:
The zirconium target is loaded onto in the multi sphere source, and magnetron sputtering target is a high purity graphite.According to embodiment 3 described processing steps, deposition C
3N
4/ ZrN multilayer film.The microhardness of measure sample, Hv=40～45GPa.
The composition of embodiment 5 carbonitrides is measured:
Specimen preparation: after monocrystalline silicon sheet surface deposits the thick TiN of 0.2 μ m, deposit again the above carbonitride of 0.5 μ m, measure as x-ray photoelectron spectroscopy (XPS), according to embodiment 3 described technologies difference depositing TiN and C
3N
4Sample be used for X-ray diffraction (XRD) and transmission electron microscope electronic diffraction (TED) measurement.
The nitrogen content of carbon nitride films is the important quality index of synthetic carbonitride, and the present invention adopts the composition of x-ray photoelectron spectroscopy (XPS) MEASUREMENTS OF THIN, and its result is as follows:
RUN：P7A041
Title：5-29-1
Scan：1Element Position Width Area Quant Factor Atomic Mass Atomic Conc％ Ratio Mass Conc％N1s 401.20 3.29 4770 0.37 14.00 36.28 0.000∶1 39.89Cls 287.00 3.51 9624 0.43 12.00 63.72 0.000∶1 60.11
The C of carbonitride (1s) electron binding energy 287.0eV compares with diamond C (1s) 285.5eV, graphite C (1s) 283.5eV, and big chemical shift is arranged.N (1s) electron binding energy 401.2eV and N
2In N (1s) 399.0eV compare certain chemical shift also arranged.Explanation C, N atom in film are to exist with combined form.The nitrogen-atoms percentage ratio of film is 36.28%.At N
2In the Ar mixed atmosphere, reaction magnetocontrol sputtering high purity graphite target has generated carbonitride.
The structure measurement of embodiment 6 carbon nitride films:
Adopt the structure of the carbonitride in X-ray diffraction (XRD) method and transmission electron microscope electron diffraction (TED) the method MEASUREMENTS OF THIN.Fig. 3 is the XRD spectrum of pressing the specimen of embodiment 3 described technologies preparations, according to the carbonitride data of delivering and the contrast of relevant calculation data, occurs the diffraction maximum of three TiN among Fig. 3, four β-C abroad
3N
4Diffraction maximum, three c-C
3N
4Diffraction maximum.β-C
3N
4And c-C
3N
4Two kinds of superhard phases of carbonitride.
To be coated with C
3N
4/ TiN/Si replaces the silicon chip of composite membrane, puts into dense HF acid and soaks, and rete strips down from silicon chip, and TiN wherein is very fast and chemical reaction takes place HF and dissolve remaining C
3N
4Film carries out the transmission electron microscope electron diffraction analysis after rinsed with deionized water.Fig. 5 demonstrates Laue point TED picture, and Fig. 6 then is a Laue point and the polycrystalline diffraction ring TED picture of superposition mutually.
According to diffraction data, the configuration data of comparing with overseas carbonitride, the crystallization direction that calculates carbonitride is listed in table 1 and table 2, and lattice parameter and literature value are relatively listed in table 3.Measured data of the present invention is compared with document, meets finely.
The TED of table 1 Fig. 5 compares as d experiment and d calculating
| D tests (nm) | 0.3840 | 0.2224 | 0.2087 | 0.1469 | 0.1309 | 0.1146 | 0.0857 | 0.0764 |
| hkl | <110> | <211> | <210> | <301> | <221> | <332> | <610.> | <543> |
| D calculates (nm) | 0.3816 | 0.2203 | 0.2095 | 0.1465 | 0.1332 | 0.1151 | 0.0846 | 0.0763 |
| Relative intensity | A little less than | By force | In | A little less than | By force | In | A little less than | A little less than |
| C 3N 4Crystallization phases | c | c | β | β | β | c | β | c |
The TED of table 2 Fig. 6 compares as d experiment and d calculating
| D tests (nm) | 0.2188 | 0.1801 | 0.1310 | 0.1057 | 0.0925 | 0.0831 |
| hkl | <211> | <201> | <221> | <431> | <530> | <541> |
| D calculates (nm) | 0.2203 | 0.1816 | 0.1332 | 0.1059 | 0.0926 | 0.0833 |
| Relative intensity | By force | In | By force | In | A little less than | In |
| C 3N 4Crystallization phases | c | β | β | c | c | c |
The deviation of table 3 actual measurement lattice paprmeter and literature value
| TED | C-C 3N 4 | β-C 3N 4 | ||||
| a 0(nm) | Deviation | a 0(nm) | Deviation | c 0(nm) | Deviation | |
| Fig. 5 | 0.54477 | + 0.93% | 0.64095 | + 0.12% | 0.24431 | + 1.60% |
| Fig. 6 | 0.53797 | -0.33% | 0.64435 | + 0.65% | 0.24210 | + 0.70% |
Lattice paprmeter c-C
3N
4a
0=0.53973nm; β-C
3N
4a
0=0.64017nm, c
0=0.24041nm is taken from document: D.M.Tetet and R.J.Hemleg, Science, 271 (1996) 53.
Spacing d calculated value is taken from document: J.B.Wang, L.Lei and R.H.Wang.Phys.Rev.B, 58 (18) (1998) 1189.
Claims (3)
1. C
3N
4/ MN multi-layer compounded superhard film, it is characterized in that: this rete has comprised the transition zone of cementation, main wearing layer and surperficial anti-attrition layer, transition zone is the thick MN of 0.1～0.2 μ m or is made up of the thick Ti of 30～50nm or Zr and the thick MN of 0.1～0.2 μ m that main wearing layer is the thick C of 3～4 μ m
3N
4The MULTILAYER COMPOSITE layer that/MN replaces, surperficial anti-attrition layer are the thick MN layer of 0.4～0.5 μ m, and wherein M is Ti or Zr.
2. one kind for the synthesis of C
3N
4The device of/MN multi-layer compounded superhard film, on vacuum film coating chamber (16) outer wall, a multi-arc source M target (1) and two magnetron sputtering high purity graphite targets (2) and supporting power supply thereof are set, wherein M is Ti or Zr, the work rest (3) that is positioned at vacuum chamber central authorities connects grid bias power supply (5), work rest is driven by direct current generator and is rotated, rotating speed can be regulated, workpiece heating lamp (7) is set around the vacuum chamber inwall, also be provided with temperature measurement controller (18), gas source (13～15) and flow control system (11,12), diffusion pump (9) and mechanical pump (10) form the running of vacuum unit and obtain the vacuum chamber high vacuum, and end vacuum can reach 5 * 10
-4Pa is for MN and C
3N
4Formation speed can mate, M target needs two graphite target of adapted, two graphite target are staggered relatively, form closed magnetic field, the M target becomes 90 ° of placements with graphite target.
3. one kind with the synthetic C of the described device of claim 2
3N
4The method of/MN multi-layer compounded superhard film is characterized in that: workpiece cleaning is clean, and work rest is loaded onto workpiece, and vacuum chamber is extracted into 1 * 10
-3After the above vacuum tightness of Pa, feed Ar, open grid bias power supply then, control voltage 800～1000V, workpiece was carried out sputter clean 10～12 minutes, workpiece temperature remains in 300～450 ℃ of scopes, bias voltage is reduced to 150～200V, and feed nitrogen: argon is 2: 1 a gas mixture, and control air pressure is 0.5～0.8Pa, adjust 10～15 rev/mins of work rest rotating speeds, opening metal M multi sphere source, control multi sphere source electric current 50 ± 5A, deposition M and unlatching graphite target shielding power supply after MN 8-10 minute, control shielding power supply 600 ± 10V, sputtering current 2～3A, alternately cvd nitride carbon and titanium nitride or zirconium nitride on workpiece, reach desired thickness after, deposit one deck MN top layer again, grew 15～18 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB981216803A CN1133756C (en) | 1998-11-26 | 1998-11-26 | Multi-layer compounded superhard C3N4/MN film and its synthesizing equipment and process |
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|---|---|---|---|
| CNB981216803A CN1133756C (en) | 1998-11-26 | 1998-11-26 | Multi-layer compounded superhard C3N4/MN film and its synthesizing equipment and process |
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|---|---|
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| CN1133756C true CN1133756C (en) | 2004-01-07 |
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| CN101654771B (en) * | 2009-09-04 | 2011-02-09 | 上海交通大学 | Method for preparing anti-attrition MoS2/C/Ti composite film by magnetron sputtering |
| CN103071819B (en) * | 2012-12-31 | 2015-06-17 | 四川大学 | Ti/TiN/MaN composite coating on surface of cutter and preparation method of Ti/TiN/MaN composite coating |
| CN103469158B (en) * | 2013-09-24 | 2015-06-10 | 辽宁北宇真空科技有限公司 | Horizontal multi-arc coating chamber |
| CN105543780B (en) * | 2015-12-28 | 2018-02-09 | 富耐克超硬材料股份有限公司 | Superhard cutter surface recombination hard coat and preparation method thereof |
| CN110016650B (en) * | 2019-03-27 | 2021-07-16 | 吉林大学 | Method for regulating and controlling surface roughening rate of film in situ in large range |
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