CN112707367A - Diamond-like protective film and preparation method thereof - Google Patents
Diamond-like protective film and preparation method thereof Download PDFInfo
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- 230000001681 protective effect Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 36
- 239000010703 silicon Substances 0.000 claims abstract description 36
- 239000000758 substrate Substances 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000007747 plating Methods 0.000 claims description 60
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 52
- 229910052721 tungsten Inorganic materials 0.000 claims description 52
- 239000010937 tungsten Substances 0.000 claims description 52
- 239000000463 material Substances 0.000 claims description 23
- 238000000151 deposition Methods 0.000 claims description 8
- 238000004549 pulsed laser deposition Methods 0.000 claims description 8
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000004544 sputter deposition Methods 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000000313 electron-beam-induced deposition Methods 0.000 claims description 2
- 238000001451 molecular beam epitaxy Methods 0.000 claims description 2
- 238000007738 vacuum evaporation Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims 1
- 238000011161 development Methods 0.000 abstract description 6
- 238000009413 insulation Methods 0.000 abstract description 6
- 239000010410 layer Substances 0.000 abstract 21
- 239000011247 coating layer Substances 0.000 abstract 1
- 238000005240 physical vapour deposition Methods 0.000 abstract 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 10
- 229910010271 silicon carbide Inorganic materials 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 7
- 230000017525 heat dissipation Effects 0.000 description 6
- 238000009825 accumulation Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B7/00—Microstructural systems; Auxiliary parts of microstructural devices or systems
- B81B7/02—Microstructural systems; Auxiliary parts of microstructural devices or systems containing distinct electrical or optical devices of particular relevance for their function, e.g. microelectro-mechanical systems [MEMS]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81B—MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES
- B81B7/00—Microstructural systems; Auxiliary parts of microstructural devices or systems
- B81B7/0009—Structural features, others than packages, for protecting a device against environmental influences
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00349—Creating layers of material on a substrate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00642—Manufacture or treatment of devices or systems in or on a substrate for improving the physical properties of a device
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Abstract
本发明公开了一种类金刚石保护薄膜及其制备方法，所述类金刚石保护薄膜由下而上依次包括微纳电子器件基材、绝缘层带、内应力缓冲层和耐磨层带；所述绝缘层带最下层为含硅薄层，然后依次交替分布有无掺杂DLC层及含硅薄层，所述内应力缓冲层由下而上依次包括H‑W:DLC层、M‑W:DLC层、L‑W:DLC层，所述内应力缓冲层最上层依次交替分布有金属层Ⅱ及S‑W:DLC层，所述类金刚石保护薄膜的最上层为S‑W:DLC层。上述镀层可以采用包括PLD在内的物理气相沉积方法依次镀制得到，在制备过程中通过采用不同浓度的钨掺杂的DLC层及微浓度的钨掺杂的DLC层，制备得到的类金刚石薄膜具有绝缘、导热、耐磨类的特性，能够满足电子器件的使用需求及微型化发展方向，具有广阔的应用前景。
The invention discloses a diamond-like protective film and a preparation method thereof. The diamond-like protective film comprises a micro-nano electronic device substrate, an insulating layer tape, an internal stress buffer layer and a wear-resistant layer tape in order from bottom to top; The bottom layer of the layer belt is a silicon-containing thin layer, and then there are alternately distributed undoped DLC layers and silicon-containing thin layers, and the internal stress buffer layer sequentially includes H-W:DLC layer, M-W:DLC layer from bottom to top layer, L-W:DLC layer, the uppermost layer of the internal stress buffer layer is alternately distributed with metal layer II and S-W:DLC layer, and the uppermost layer of the diamond-like protective film is the S-W:DLC layer. The above-mentioned coating layers can be sequentially prepared by using physical vapor deposition methods including PLD. During the preparation process, the prepared diamond-like carbon films are prepared by using different concentrations of tungsten-doped DLC layers and micro-concentrations of tungsten-doped DLC layers. It has the characteristics of insulation, heat conduction and wear resistance, which can meet the use requirements of electronic devices and the development direction of miniaturization, and has broad application prospects.
Description
Technical Field
The invention belongs to the technical field of film materials, and particularly relates to a diamond-like protective film and a preparation method thereof.
Background
Miniaturization is always the key direction of the development of micro-nano electronic devices. On one hand, the normal operation of the electronic device has corresponding requirements on heat dissipation and insulation; on the other hand, the device material has low thermal conductivity (the thermal conductivity of semiconductor and ceramic materials is generally only 0.1-10 W.m)-1·K-1) Factors such as closed or semi-closed devices, dense device arrangement and the like restrict the heat dissipation of the devices; therefore, the technical development of heat dissipation of the device has important practical significance for the miniaturization development of the electronic device and the improvement of the working efficiency of the device. Many researchers have studied micro-nano electronic devices with good thermal conductivity, and for example, patent documents CN108752724A, CN111635548A and CN205258365U have related reports. However, the functional materials mentioned in the above publications have large thickness in use, generally reaching 100 μm or more, even millimeter level, and are comparable to or even exceeding the size of micro-nano electronic devices, which significantly increases the size and weight of the system.
Meanwhile, in the use process of the micro-nano electronic device, the abrasion problem is increasingly prominent, and the long-term accumulation of abrasion can cause serious problems such as system failure and the like. The abrasion of the micro-nano electronic device mainly comes from two aspects: firstly, part of the structure/device has a relative motion surface (or point-surface), and the friction and the abrasion are caused as the macroscopic mechanical system; secondly, adhesive wear caused by the contact adhesion effect between micro-surfaces.
Aiming at the problems of low-efficiency heat dissipation and abrasion accumulation of micro-nano electronic devices, a high-heat-conduction and low-friction high-stability diamond-like carbon (DLC) film is plated on the surface of the micro-nano electronic device, the functions of heat dissipation, insulation and abrasion resistance are realized by the thickness from submicron to several microns, the diamond-like carbon film is a better choice for improving the safety, reliability and service life of the device, and the micro-scale development of a microelectronic device is promoted.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the diamond-like carbon protective film and the preparation method thereof, the diamond-like carbon protective film prepared by the diamond-like carbon protective film has the characteristics of insulation, heat conduction and wear resistance, the problem of difficult heat dissipation of a micro-nano electronic device and the problem of wear in application are solved, and the requirement of surface insulation of the electronic device is considered at the same time.
In order to achieve the purpose, the invention adopts the following technical scheme:
a diamond-like protective film sequentially comprises a micro-nano electronic device substrate, an insulating layer band, an internal stress buffer layer and a wear-resistant layer band from bottom to top; the insulating layer belt comprises a silicon-containing thin layer and an undoped DLC layer, the lowermost layer of the insulating layer belt is the silicon-containing thin layer, then the undoped DLC layer and the silicon-containing thin layer are sequentially and alternately distributed, the internal stress buffer layer sequentially comprises an H-W DLC layer, an M-W DLC layer and an L-W DLC layer from bottom to top, the wear-resistant layer belt comprises a metal layer II and an S-W DLC layer, the metal layer II and the S-W DLC layer are sequentially and alternately distributed on the uppermost layer of the internal stress buffer layer, and the uppermost layer of the wear-resistant layer belt is the S-W DLC layer.
Further, a metal layer I is arranged between the micro-nano electronic device substrate and the insulating layer belt.
The invention also claims a preparation method of the diamond-like carbon protective film, which comprises the following steps:
s1: selecting a micro-nano electronic device substrate, and carrying out corresponding treatment according to the material type of the device substrate;
s2: plating a silicon-containing thin layer on the material obtained in the step S1, and then circularly plating an undoped DLC layer and the silicon-containing thin layer in sequence to obtain an insulating layer belt; the thickness of the undoped DLC layer in the cyclic plating process is 300-500 nm, the thickness of the thin silicon-containing layer is 40-80 nm, the plating cycle times are 5-20 times, and the total thickness of the undoped DLC layer is not less than 2000 nm;
s3: plating a DLC layer with high-concentration tungsten doping on the insulating layer belt in the step S2 to obtain an H-W DLC layer, wherein the thickness of the H-W DLC layer is 100-200 nm, and the concentration of the tungsten doping in the H-W DLC layer is 25-30 at%;
s4: plating a DLC layer with medium-concentration tungsten doping on the H-W: DLC layer in the step S3 to obtain an M-W: DLCW layer, wherein the thickness of the M-W: DLC layer is 100-200 nm, and the concentration of the tungsten doping in the M-W: DLC layer is 20-25 at.%;
s5: plating a DLC layer doped with low-concentration tungsten on the M-W DLC layer in the step S4 to obtain an L-W DLC layer, wherein the thickness of the L-W DLC layer is 100-200 nm, and the concentration of the tungsten doping in the L-W DLC layer is 15-20 at.%;
s6: circularly plating a metal tungsten layer and a DLC layer doped with micro-concentration tungsten on the DLC layer in sequence in the step S5 to obtain a wear-resistant layer belt with a metal layer II and S-W DLC layers alternately distributed; the thickness of the metal layer II is 50-100 nm; the thickness of the S-W DLC layer is 300-500 nm, and the concentration of tungsten doping in the S-W DLC layer is 5-15 at.%; the plating cycle times are 3-6 times, and the total thickness of the S-W DLC layer is 1500-2000 nm.
Further, the thin layer containing silicon is plated by one or two of intrinsic Si or undoped SiC.
Further, when the micro-nano electronic device substrate is one of metal or ceramic in step S1, the micro-nano electronic device substrate is processed as follows: plating one of tungsten or titanium on the micro-nano electronic device substrate to obtain a metal layer I, wherein the thickness of the metal layer I is 50-100 nm, and the thickness of the thin layer containing silicon before circular plating in the step S2 is 50-100 nm.
Further, when the micro-nano electronic device base material is one of silicon or germanium material in the step S1, the micro-nano electronic device base material is not processed, and the thickness of the silicon-containing thin layer before cyclic plating in the step S2 is 20-30 nm.
Further, the plating method is one or more of vacuum evaporation, sputtering coating, arc deposition, ion coating, electron beam deposition or molecular beam epitaxy.
Preferably, the plating in the steps S2, S3, S4, S5 and S6 is performed by a pulsed laser deposition method, wherein a deposition source in the pulsed laser deposition method is ultraviolet excimer KrF laser, and the pulsed laser deposition method has the emission wavelength of 248nm, the pulse width of 20-30 ns and the repetition frequency of less than 300 Hz;
preferably, the degree of vacuum of plating in step S2 is better than 1X 10-3Pa, pulse energy density on the target surface of 8-10 J.m-1；
Preferably, the degree of vacuum of plating in step S3, step S4, and step S5 is better than 1 × 10-4Pa, pulse energy density on the target surface of 6-8 J.m-1；
Preferably, the degree of vacuum of plating in step S6 is better than 1X 10-4Pa, pulse energy density on the target surface of 8-10 J.m-1。
Preferably, the nano hardness of the undoped DLC layer is 45-60 GPa, and the resistivity is more than or equal to 1 multiplied by 109Omega.m, thermal conductivity not less than 600 W.m-1·K-1；
Preferably, the nano-hardness of the H-W DLC layer, the M-W DLC layer and the L-W DLC layer is 30-45 GPa, and the heat conductivity coefficient is more than or equal to 400 W.m-1·K-1；
Preferably, the nano-hardness of the S-W DLC layer is 45-55 GPa, and the heat conductivity coefficient is more than or equal to 500 W.m-1·K-1The dry friction coefficient of the silicon nitride friction pair is less than or equal to 0.08.
Through the technical scheme, compared with the prior art, the invention can realize the following beneficial effects:
(1) in step S1, the micro-nano electronic device is processed according to different base materials. When the substrate of the micro-nano electronic device is a non-semiconductor material such as metal, ceramic and the like, the diamond-like material is directly plated and easily falls off, so that transition metal tungsten or titanium with good bonding force with the diamond-like material is plated firstly to serve as an adhesion layer, and then the bonding force with the diamond-like layer is enhanced through an intrinsic Si or undoped SiC thin layer; when the micro-nano electronic device substrate is a semiconductor material (such as silicon, germanium, and the like), the operation in step S1 can be omitted, the intrinsic silicon (Si) or undoped silicon carbide (SiC) layer in step S2 can be directly plated, and the thickness of the intrinsic silicon (Si) or undoped silicon carbide (SiC) layer can be properly reduced to 30-50 nm.
(2) In the step S2, the insulating layer belt has high resistance and can play a role in insulating low voltage; meanwhile, considering the problems of large stress in the undoped DLC layer and easy crack of the undoped DLC layer, the intrinsic Si layer or the undoped SiC layer is added in the thicker undoped DLC layer to relieve the internal stress accumulation and play a role in stabilizing the DLC layer.
(3) The nano hardness of the undoped DLC layer prepared in the step S2 reaches 45-60 GPa, and the resistivity is higher than 1 multiplied by 109Omega m, thermal conductivity higher than 600W m-1·K-1The method has the advantage of high diamond phase content; meanwhile, the properties of high nano-hardness, high resistivity and high heat conductivity coefficient are closer to those of natural diamond, and the extrusion and scraping resistance of the upper film layer can be effectively supported.
(4) Considering that the higher the tungsten doping concentration, the lower the internal stress of the tungsten doped DLC layer, the higher the adhesion properties. Therefore, in order to improve the adhesion performance of the micro-concentration tungsten-doped DLC layer and simultaneously take account of the internal stress of the DLC layer, in the steps S3-S5, the internal stress buffer layer is prepared by adopting a method of gradually reducing the tungsten-doped concentration.
(5) Step S6 is a key step of the invention, the micro-concentration tungsten-doped DLC layer (with the tungsten doping concentration of 5-15 at.%) is the optimized result with the lowest friction coefficient, and the DLC layer under the concentration has the best wear resistance, so the DLC layer is used as the outermost layer of the protective film; meanwhile, the DLC layer is alternately inserted with a thin metal tungsten layer, which has two main functions: 1) considering that the micro-concentration tungsten-doped DLC layer still has higher internal stress, the insertion of the thinner metal tungsten layer can relieve the accumulation of the internal stress and improve the adhesion performance of the film layer; 2) the tungsten-doped DLC layer with the micro concentration has high resistivity (slightly lower than that of a non-doped DLC layer), a large number of electrons can be generated and accumulated by friction and cannot be released, the breakdown voltage of the insulating layer belt can be higher after a certain amount of electrons are generated, the damage to the protective film layer and even the micro-nano electronic device is caused, the inserted metal tungsten layer can lead out the electrons and eliminate the accumulation of the electrons through grounding or other modes, and the safety of the device is further improved.
(6) The preparation method provided by the invention is simple, controllable and easy to realize, and the prepared diamond-like carbon protective film has the characteristics of insulation, heat conduction and wear resistance, can meet the use requirements and the miniaturization development direction of micro-nano electronic devices, and has wide application prospect.
Drawings
FIG. 1 is a schematic view of the structure of the diamond-like carbon film in example 1.
Wherein the reference numerals are as follows:
1. a micro-nano electronic device substrate; 2. a metal layer I; 3. an insulating layer tape; 31. a silicon-containing thin layer; 32. an undoped DLC layer; 4. an internal stress buffer layer; 41. H-W is a DLC layer; 42. M-W is a DLC layer; 43. L-W is a DLC layer; 5. a wear resistant layer band; 51. a metal layer II; 52. S-W is DLC layer.
Detailed Description
The technical scheme of the invention is further illustrated by the following specific examples. The following examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
Particularly, the test indexes of the diamond-like carbon protective film prepared by the invention mainly comprise hardness, resistivity, thermal conductivity and dry friction coefficient, wherein the hardness test and dry friction coefficient determination method comprises the following steps:
and (3) hardness testing: the nano-hardness and Young's modulus of the film were measured using the Dynamic Contact Module (DCM) of Nanoinder model G200 nano-indenter from Agilent, Inc. of America; according to the principle of measuring the film thickness of 10%, a Continuous Stiffness Method (CSM) is adopted, 5-10 different areas are respectively selected for testing, and then an average value is obtained. The test method is referred to GB/T25898-.
Dry friction coefficient test: miningThe dry coefficient of friction of the film was measured by a UMT-2 type micro-friction abrasion tester (straight reciprocating test method) of CETR (center for tribology) Co. The friction pair is Si3N4The ceramic ball (radius is 2mm), the load is 1N, 2N, 5N, the stroke is 5mm, the reciprocating frequency is 0.5Hz, the rubbing time is set according to different test requirements, the environmental humidity is 45 +/-3%, and the environmental temperature is 27 +/-2 ℃.
Example 1
A diamond-like protective film sequentially comprises a micro-nano electronic device substrate, a metal layer I, an insulating layer band, an internal stress buffer layer and a wear-resistant layer band from bottom to top; the insulating layer belt comprises a silicon-containing thin layer and an undoped DLC layer, the lowermost layer of the insulating layer belt is the silicon-containing thin layer, then the undoped DLC layer and the silicon-containing thin layer are sequentially and alternately distributed, the internal stress buffer layer sequentially comprises an H-W DLC layer, an M-W DLC layer and an L-W DLC layer from bottom to top, the wear-resistant layer belt comprises a metal layer II and an S-W DLC layer, the metal layer II and the S-W DLC layer are sequentially and alternately distributed on the uppermost layer of the internal stress buffer layer, and the uppermost layer of the wear-resistant layer belt is the S-W DLC layer.
The preparation method of the diamond-like carbon protective film comprises the following steps:
s1: selecting ceramic as a micro-nano electronic device substrate, and plating transition metal tungsten on the ceramic substrate, wherein the thickness of the transition metal tungsten is 80 nm;
s2: firstly plating an intrinsic Si layer on the material obtained in the step S1, wherein the thickness of the intrinsic Si layer is 80nm, and then circularly plating an undoped DLC layer and the intrinsic Si layer in sequence to obtain an insulating layer belt; the thickness of the intrinsic Si layer is 50nm, the thickness of the undoped DLC layer is 400nm, the plating cycle number is 6 times, and the total thickness of the undoped DLC layer is 2400 nm;
s3: plating a DLC layer with high-concentration tungsten doping on the insulating layer belt in the step S2 to obtain an H-W DLC layer, wherein the thickness of the H-W DLC layer is 150nm, and the concentration of the tungsten doping in the H-W DLC layer is 26 at%;
s4: plating a DLC layer with medium-concentration tungsten doping on the H-W: DLC layer in the step S3 to obtain an M-W: DLCW layer, wherein the thickness of the M-W: DLC layer is 150nm, and the concentration of the tungsten doping in the M-W: DLC layer is 21 at.%;
s5: plating a DLC layer doped with low-concentration tungsten on the M-W DLC layer in the step S4 to obtain an L-W DLC layer, wherein the thickness of the L-W DLC layer is 150nm, and the concentration of the tungsten in the L-W DLC layer is 16 at%;
s6: circularly plating a metal tungsten layer and a DLC layer doped with micro-concentration tungsten on the DLC layer in sequence in the step S5 to obtain a wear-resistant layer belt with a metal layer II and S-W DLC layers alternately distributed; the thickness of the metal layer II is 80 nm; the thickness of the S-W DLC layer is 360nm, and the concentration of tungsten doping in the S-W DLC layer is 8 at%; the plating cycle times are 5 times, and the total thickness of the S-W DLC layer is 1800 nm.
In this example, all the plating layers were prepared by pulsed laser deposition with a vacuum pressure of 1 × 10- 4Pa, ultraviolet excimer KrF as deposition source, laser wavelength of 248nm, pulse width of 25ns, repetition frequency of 30Hz, and pulse energy density of 8 J.m-1。
In the embodiment, the nano hardness of the undoped DLC layer is 54GPa, and the resistivity is more than or equal to 1 multiplied by 109Omega.m, thermal conductivity not less than 600 W.m-1·K-1；
The nano-hardness of the H-W DLC layer, the M-W DLC layer and the L-W DLC layer is respectively 48GPa, 43GPa and 38GPa, and the heat conductivity coefficient is more than or equal to 400 W.m-1·K-1；
The nano hardness of the S-W DLC layer is 52GPa, and the heat conductivity coefficient is more than or equal to 500 W.m-1·K-1The dry friction coefficient of the silicon nitride friction pair is 0.07.
The resistivity of the diamond-like protective film in this example was tested to be about 7.9X 1010Omega m, thermal conductivity higher than 151W m-1·K-1The dry friction coefficient of the friction pair made of silicon nitride is 0.083.
Example 2
A diamond-like protective film sequentially comprises a micro-nano electronic device substrate, an insulating layer band, an internal stress buffer layer and a wear-resistant layer band from bottom to top; the insulating layer belt comprises a silicon-containing thin layer and an undoped DLC layer, the lowermost layer of the insulating layer belt is the silicon-containing thin layer, then the undoped DLC layer and the silicon-containing thin layer are sequentially and alternately distributed, the internal stress buffer layer sequentially comprises an H-W DLC layer, an M-W DLC layer and an L-W DLC layer from bottom to top, the wear-resistant layer belt comprises a metal layer II and an S-W DLC layer, the metal layer II and the S-W DLC layer are sequentially and alternately distributed on the uppermost layer of the internal stress buffer layer, and the uppermost layer of the wear-resistant layer belt is the S-W DLC layer.
The preparation method of the diamond-like carbon film comprises the following steps:
s1: selecting a silicon material as a micro-nano electronic device substrate;
s2: firstly plating an intrinsic Si layer with the thickness of 25nm on the material obtained in the step S1, and then circularly plating an undoped DLC layer and an undoped SiC layer in sequence to obtain an insulating layer belt; the thickness of the undoped SiC layer is 60nm, the thickness of the undoped DLC layer is 450nm, the number of plating cycles is 5, and the total thickness of the undoped DLC layer is 2250 nm;
s3: plating a DLC layer with high-concentration tungsten doping on the insulating layer belt in the step S2 to obtain an H-W DLC layer, wherein the thickness of the H-W DLC layer is 180nm, and the concentration of the tungsten doping in the H-W DLC layer is 28 at%;
s4: plating a DLC layer with medium-concentration tungsten doping on the H-W: DLC layer in the step S3 to obtain an M-W: DLCW layer, wherein the thickness of the M-W: DLC layer is 130nm, and the concentration of the tungsten doping in the M-W: DLC layer is 23 at.%;
s5: plating a DLC layer doped with low-concentration tungsten on the M-W DLC layer in the step S4 to obtain an L-W DLC layer, wherein the thickness of the L-W DLC layer is 170nm, and the concentration of the tungsten in the L-W DLC layer is 17 at%;
s6: circularly plating a metal tungsten layer and a DLC layer doped with micro-concentration tungsten on the DLC layer in sequence in the step S5 to obtain a wear-resistant layer belt with a metal layer II and S-W DLC layers alternately distributed; the thickness of the metal layer II is 60 nm; the thickness of the S-W DLC layer is 400nm, and the concentration of tungsten doping in the S-W DLC layer is 7 at%; the plating cycle times are 4 times, and the total thickness of the S-W DLC layer is 1600 nm.
In this example, all the plating layers were prepared by pulsed laser deposition with a vacuum pressure of 1 × 10- 4Pa, ultraviolet excimer KrF as deposition source, laser wavelength of 248nm, pulse widthImpulse width 25ns, repetition frequency 30Hz, target surface pulse energy density 8 J.m-1。
The resistivity of the diamond-like protective film in this example was tested to be about 7.7X 1010Omega m, thermal conductivity higher than 157W m-1·K-1The dry friction coefficient of the friction pair of silicon nitride is 0.078.
Example 3
A diamond-like protective film sequentially comprises a micro-nano electronic device substrate, an insulating layer band, an internal stress buffer layer and a wear-resistant layer band from bottom to top; the insulating layer belt comprises a silicon-containing thin layer and an undoped DLC layer, the lowermost layer of the insulating layer belt is the silicon-containing thin layer, then the undoped DLC layer and the silicon-containing thin layer are sequentially and alternately distributed, the internal stress buffer layer sequentially comprises an H-W DLC layer, an M-W DLC layer and an L-W DLC layer from bottom to top, the wear-resistant layer belt comprises a metal layer II and an S-W DLC layer, the metal layer II and the S-W DLC layer are sequentially and alternately distributed on the uppermost layer of the internal stress buffer layer, and the uppermost layer of the wear-resistant layer belt is the S-W DLC layer.
The preparation method of the diamond-like carbon film comprises the following steps:
s1: selecting a germanium material as a micro-nano electronic device substrate;
s2: plating an undoped SiC layer with the thickness of 28nm on the material obtained in the step S1, and then circularly plating an undoped DLC layer and an intrinsic Si layer in sequence to obtain an insulating layer band; the thickness of the undoped SiC layer is 45nm, the thickness of the undoped DLC layer is 350nm, the number of plating cycles is 7, and the total thickness of the undoped DLC layer is 2450 nm;
s3: plating a DLC layer with high-concentration tungsten doping on the insulating layer belt in the step S2 to obtain an H-W DLC layer, wherein the thickness of the H-W DLC layer is 140nm, and the concentration of the tungsten doping in the H-W DLC layer is 25 at%;
s4: plating a DLC layer with medium-concentration tungsten doping on the H-W: DLC layer in the step S3 to obtain an M-W: DLCW layer, wherein the thickness of the M-W: DLC layer is 170nm, and the concentration of the tungsten doping in the M-W: DLC layer is 24 at.%;
s5: plating a DLC layer doped with low-concentration tungsten on the M-W DLC layer in the step S4 to obtain an L-W DLC layer, wherein the thickness of the L-W DLC layer is 130nm, and the concentration of the tungsten in the L-W DLC layer is 18 at%;
s6: circularly plating a metal tungsten layer and a DLC layer doped with micro-concentration tungsten on the DLC layer in sequence in the step S5 to obtain a wear-resistant layer belt with a metal layer II and S-W DLC layers alternately distributed; the thickness of the metal layer II is 80 nm; the thickness of the S-W DLC layer is 350nm, and the concentration of tungsten doping in the S-W DLC layer is 8 at%; the plating cycle times are 5 times, and the total thickness of the S-W DLC layer is 1750 nm.
In this embodiment, the cyclic plating in step S2, and the plating in steps S3, S4, S5, and S6 are performed by a pulsed laser deposition method, wherein the vacuum pressure is 1 × 10-4Pa, ultraviolet excimer KrF as deposition source, wavelength of laser 248nm, pulse width of 25ns, and repetition frequency of 30 Hz.
In this example, the pulse energy density on the target surface in step S2 was 9 J.m-1；
The pulse energy density on the target surface in step S3, step S4, and step S5 is 7J · m-1；
The pulse energy density on the target surface in step S6 was 9J · m-1。
In this embodiment, the plating of the undoped SiC layer in step S2 is performed by magnetron sputtering, the target material is silicon, and the basic vacuum is better than 8 × 10-4Pa, filling Ar/CH4After mixing the gases, the gas pressure is maintained at 3-5 Pa, the sputtering power is 150W, and after glow starting, the gas pressure is adjusted to 0.6-1 Pa.
The resistivity of the diamond-like protective film in this example was tested to be about 7.8X 1010Omega.m, thermal conductivity higher than 150 W.m-1·K-1The dry friction coefficient of the friction pair of silicon nitride was 0.080.
It should be noted that the above-described embodiments may enable those skilled in the art to more fully understand the present invention, but do not limit the present invention in any way. Thus, it will be appreciated by those skilled in the art that the invention may be modified and equivalents may be substituted; all technical solutions and modifications thereof which do not depart from the spirit and technical essence of the present invention should be covered by the scope of the present patent.
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