CN111304591A - Diamond-like carbon film with multilayer structure and preparation method thereof - Google Patents

Diamond-like carbon film with multilayer structure and preparation method thereof Download PDF

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Publication number
CN111304591A
CN111304591A CN201811516132.4A CN201811516132A CN111304591A CN 111304591 A CN111304591 A CN 111304591A CN 201811516132 A CN201811516132 A CN 201811516132A CN 111304591 A CN111304591 A CN 111304591A
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Prior art keywords
diamond
sub
layers
workpiece
hard
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CN201811516132.4A
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刘畅
刘晓阳
张钦辉
张海峰
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Beijing Scitlion Technology Corp ltd
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Beijing Scitlion Technology Corp ltd
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Priority to CN201811516132.4A priority Critical patent/CN111304591A/en
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/021—Cleaning or etching treatments
    • C23C14/022—Cleaning or etching treatments by means of bombardment with energetic particles or radiation
    • 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
    • C23C14/0605—Carbon

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention discloses a diamond-like carbon film with a multilayer structure, which comprises a base layer, N soft diamond-like carbon sub-layers and M hard diamond-like carbon sub-layers, wherein M is equal to N and is a natural number, the N soft diamond-like carbon sub-layers correspond to each other one by one, the base layer is arranged at the lowermost end, the hard diamond-like carbon sub-layers are arranged on the upper surface of the base layer, the soft diamond-like carbon sub-layers are arranged on the upper surface of the hard diamond-like carbon sub-layers, and the soft diamond-like carbon sub-layers and the hard diamond-like carbon sub-layers. Compared with the prior art, when the duty ratio of the substrate pulse direct current bias voltage is higher (such as 40%), the diamond-like film and the internal stress are improved.

Description

Diamond-like carbon film with multilayer structure and preparation method thereof
Technical Field
The invention relates to a diamond-like carbon film with a multilayer structure and a preparation method thereof.
Background
Diamond-like Carbon (DLC) film having high hardness ((DLC))>20GPa), low coefficient of friction (<0.1), excellent wear resistance, high rednessThe characteristics of external transmittance and good corrosion resistance, etc. have recently received general attention from academic and industrial fields. The microstructure and mechanical properties of diamond-like films depend on a number of factors, such as: doping element species and content thereof, bonding state of carbon atoms inside film layer, sp3/sp2Bond ratios and distribution of various "carbon groups", etc. At present, most of the hydrogen-free diamond-like films can be obtained by the technical methods of magnetron sputtering, cathodic arc deposition or pulsed laser deposition and the like. Wherein, the magnetron sputtering method is one of the main methods for preparing the hydrogen-free diamond-like film. However, other problems exist in the process of preparing the hydrogen-free diamond-like film by magnetron sputtering, such as excessive internal (compressive) stress, reduced film adhesion and increased crack generation probability.
Therefore, how to provide a method which can improve the diamond-like film and the internal stress when the substrate pulse direct current bias duty ratio is high (such as 40%), and the method is simple to operate, and the bias duty ratio can be controlled and adjusted by a computer, thereby facilitating the automatic production. The technical problem to be solved by the invention is solved.
Disclosure of Invention
In view of the above-mentioned drawbacks and problems of the prior art, the present invention is directed to provide a diamond-like carbon film with a multi-layer structure and a method for preparing the same, wherein the diamond-like carbon film and internal stress are improved when the duty ratio of the pulsed dc bias of the substrate is high (e.g., 40%), and the method is simple to operate, and the duty ratio of the bias voltage can be controlled and adjusted by a computer, thereby facilitating automated production.
In order to achieve the above object, the present invention provides the following technical solutions
The diamond-like film with the multilayer structure comprises a base layer, N soft diamond-like sub-layers and M hard diamond-like sub-layers, wherein M is equal to N and is a natural number, the base layer is arranged at the lowermost end, the hard diamond-like sub-layers are arranged on the upper surface of the base layer, the soft diamond-like sub-layers are arranged on the upper surface of the hard diamond-like sub-layers, and the soft diamond-like sub-layers and the hard diamond-like sub-layers are alternately stacked.
Further, the hard diamond-like carbon sub-layer is fixed on the base layer in a plating mode, and the soft diamond-like carbon sub-layer is fixed on the upper surface of the hard diamond-like carbon sub-layer in a plating mode.
A preparation method of a diamond-like film with a multilayer structure comprises the following steps:
thirdly, preparation of workpieces to be plated
Placing a workpiece to be plated in acetone and isopropanol solutions in sequence, performing ultrasonic cleaning for 10 minutes respectively, and then drying the workpiece by using dry air to remove oil stains, impurities and the like attached to the surface of the workpiece to be plated;
fourthly, ion cleaning and activation of the workpiece to be plated
(3) Placing the processed workpiece to be plated on a rotary base body table in a vacuum chamber for fixing, and vacuumizing the cavity of the vacuum chamber to 2 x 10-3Introducing argon after Pa, and maintaining the pressure of the vacuum chamber at 3 Pa;
(4) opening the substrate bias device, applying medium-frequency pulse direct-current negative bias 500V pulse to the workpiece to be plated for 30 minutes, and ionizing argon to generate Ar+Cleaning the surface of the workpiece to be deposited by ion bombardment;
thirdly, cleaning the target material
(1) Closing the bias voltage applied to the workpiece to be plated, reducing the flow of argon introduced into the cavity, and maintaining the vacuum degree of the cavity of the vacuum chamber at 0.5 Pa;
(2) the target bias device is turned on, and the intermediate frequency pulse DC negative bias 800W pulse is applied to the C target for 15 minutes to generate Ar+Ion cleaning the surface of the target material;
fourthly, coating process
(1) And applying medium-frequency pulse direct current negative bias 800W to the C target, and simultaneously applying medium-frequency pulse direct current negative bias to the substrate to plate a softer diamond-like carbon sub-layer.
(2) And maintaining the intermediate frequency pulse direct current bias on the C target, and applying the intermediate frequency pulse direct current negative bias to the substrate at the same time to plate the hard diamond-like carbon sub-layer.
(3) Repeating steps (1) and (2) to deposit diamond-like films of alternating soft/hard sub-layers.
Further, the argon in the second step is argon with the purity of 99.9%.
Compared with the prior art, the invention comprises the base layer, N soft diamond-like sub-layers and M hard diamond-like sub-layers, wherein M is equal to N and is a natural number, the N soft diamond-like sub-layers and the hard diamond-like sub-layers are arranged in a one-to-one correspondence mode, and the soft diamond-like sub-layers and the hard diamond-like sub-layers are alternately superposed, so that the adhesive force between the film layers is increased, the generation of cracks is reduced, the maximum thickness of the film layer is reduced, and the service life of the film layer is prolonged.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a structural view of a diamond-like carbon film of a multilayer structure of the present invention.
Figure 2 is the results of the hardness and internal stress tests of the soft and hard diamond-like sub-layer of the present invention.
Wherein, 1 layer is a soft diamond-like carbon sub-layer, 2 layers are hard diamond-like carbon sub-layers, and 3 layers are basal bodies.
Detailed Description
For the purpose of promoting a clear understanding of the objects, aspects and advantages of the embodiments of the invention, reference will now be made to the drawings and detailed description, wherein there are shown in the drawings and described in detail, various modifications of the embodiments described herein, and other embodiments of the invention will be apparent to those skilled in the art.
The exemplary embodiments of the present invention and the description thereof are provided to explain the present invention and not to limit the present invention. Additionally, the same or similar numbered elements/components used in the drawings and the embodiments are used to represent the same or similar parts.
As used herein, the terms "first," "second," …, etc., do not denote any order or sequence, nor are they used to limit the present invention, but rather are used to distinguish one element from another or from another element or operation described in the same technical language.
With respect to directional terminology used herein, for example: up, down, left, right, front or rear, etc., are simply directions with reference to the drawings. Accordingly, the directional terminology used is intended to be illustrative and is not intended to be limiting of the present teachings.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
As used herein, "and/or" includes any and all combinations of the described items.
As used herein, the terms "substantially", "about" and the like are used to modify any slight variation in quantity or error that does not alter the nature of the variation. Generally, the range of slight variations or errors modified by such terms may be 20% in some embodiments, 10% in some embodiments, 5% in some embodiments, or other values. It should be understood by those skilled in the art that the aforementioned values can be adjusted according to actual needs, and are not limited thereto.
Certain words used to describe the present application are discussed below or elsewhere in this specification to provide additional guidance to those skilled in the art in describing the present application.
As shown in fig. 1, the diamond-like film of the first multilayer structure of the present invention comprises a base layer 3, N soft diamond-like sub-layers 1, and M hard diamond-like sub-layers 2, wherein M is equal to N and is a natural number, the base layer is disposed at the lowermost end, the hard diamond-like sub-layer 2 is disposed on the upper surface of the base layer 3, the soft diamond-like sub-layers 1 are disposed on the upper surface of the hard diamond-like sub-layer 2, and the soft diamond-like sub-layers 1 and the hard diamond-like sub-layers 2 are alternately stacked.
According to the above, it is found that the film comprises a base layer 3, N soft diamond-like sub-layers 1 and M hard diamond-like sub-layers 2, wherein M is equal to N and is a natural number, the N and the N correspond to each other one by one, and the soft diamond-like sub-layers and the hard diamond-like sub-layers are alternately stacked, so that the adhesion between the film layers is increased, the generation of cracks is reduced, the maximum thickness of the film layer is reduced, and the service life of the film layer is prolonged.
In another aspect, as shown in fig. 2, the present invention includes: a preparation method of a diamond-like film with a multilayer structure comprises the following steps:
first, preparation of workpiece to be plated
Placing a workpiece to be plated in acetone and isopropanol solutions in sequence, performing ultrasonic cleaning for 10 minutes respectively, and then drying the workpiece by using dry air to remove oil stains, impurities and the like attached to the surface of the workpiece to be plated;
secondly, ion cleaning and activation of the workpiece to be plated
(5) Placing the processed workpiece to be plated on a rotary base body table in a vacuum chamber for fixing, and vacuumizing the cavity of the vacuum chamber to 2 x 10-3Introducing high-purity argon (with the purity of 99.9%) after Pa, and maintaining the pressure of the vacuum chamber at 3 Pa;
(6) opening the substrate bias device, applying medium-frequency pulse direct-current negative bias (fixed voltage mode) 500V (250kHz frequency, 40% duty ratio) for 30 minutes to the workpiece to be plated, and ionizing argon to generate Ar+Cleaning the surface of the workpiece to be deposited by ion bombardment;
thirdly, cleaning the target material
(1) Closing the bias voltage applied to the workpiece to be plated, reducing the flow of argon introduced into the cavity, and maintaining the vacuum degree of the cavity of the vacuum chamber at 0.5 Pa;
(2) the target bias device was turned on, and an intermediate frequency pulsed DC negative bias (fixed power mode) of 800W (120kHz frequency, 10% duty cycle) was applied to the C target for 15 minutes to generate Ar+Ion cleaning the surface of the target material;
fourthly, coating process
(1) And applying medium-frequency pulse direct-current negative bias (fixed power mode) 800W (120kHz frequency and 10% duty ratio) to the C target, and simultaneously applying medium-frequency pulse direct-current negative bias (110V and 10% duty ratio) to the substrate to plate a softer diamond-like sublayer.
(2) And maintaining the medium-frequency pulse direct current bias voltage on the C target, and simultaneously applying the medium-frequency pulse direct current negative bias voltage (110V,40 percent duty ratio) to the substrate to plate the hard diamond-like carbon sub-layer.
(3) Repeating steps (1) and (2) to deposit diamond-like films of alternating soft/hard sub-layers.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (4)

1. The diamond-like film with the multilayer structure is characterized by comprising a base layer, N soft diamond-like sub-layers and M hard diamond-like sub-layers, wherein M is equal to N and is a natural number, the base layer is arranged at the lowermost end, the hard diamond-like sub-layers are arranged on the upper surface of the base layer, the soft diamond-like sub-layers are arranged on the upper surface of the hard diamond-like sub-layers, and the soft diamond-like sub-layers and the hard diamond-like sub-layers are alternately stacked.
2. The diamond-like film of multilayer structure of claim 1, wherein: the hard diamond-like carbon sub-layer is fixed on the base layer in a plating mode, and the soft diamond-like carbon sub-layer is fixed on the upper surface of the hard diamond-like carbon sub-layer in a plating mode.
3. A preparation method of a diamond-like film with a multilayer structure comprises the following steps:
first, preparation of workpiece to be plated
Placing a workpiece to be plated in acetone and isopropanol solutions in sequence, performing ultrasonic cleaning for 10 minutes respectively, and then drying the workpiece by using dry air to remove oil stains, impurities and the like attached to the surface of the workpiece to be plated;
secondly, ion cleaning and activation of the workpiece to be plated
(1) Placing the processed workpiece to be plated on a rotary base body table in a vacuum chamber for fixing, and vacuumizing the cavity of the vacuum chamber to 2 x 10-3Introducing argon after Pa, and maintaining the pressure of the vacuum chamber at 3 Pa;
(2) opening the substrate bias device, applying medium-frequency pulse direct-current negative bias 500V pulse to the workpiece to be plated for 30 minutes, and ionizing argon to generate Ar+Cleaning the surface of the workpiece to be deposited by ion bombardment;
thirdly, cleaning the target material
(1) Closing the bias voltage applied to the workpiece to be plated, reducing the flow of argon introduced into the cavity, and maintaining the vacuum degree of the cavity of the vacuum chamber at 0.5 Pa;
(2) the target bias device is turned on, and the intermediate frequency pulse DC negative bias 800W pulse is applied to the C target for 15 minutes to generate Ar+Ion cleaning the surface of the target material;
fourthly, coating process
(1) Applying medium frequency pulse DC negative bias 800W to the C target, applying medium frequency pulse DC negative bias to the substrate, plating a softer diamond-like carbon sub-layer,
(2) maintaining the intermediate frequency pulse DC bias on the C target, applying the intermediate frequency pulse DC negative bias to the substrate, plating a hard diamond-like carbon sub-layer,
(3) repeating steps (1) and (2) to deposit diamond-like films of alternating soft/hard sub-layers.
4. The method for producing a diamond-like film of a multilayer structure according to claim 3, characterized in that: and in the second step, the argon gas has the purity of 99.9 percent.
CN201811516132.4A 2018-12-12 2018-12-12 Diamond-like carbon film with multilayer structure and preparation method thereof Pending CN111304591A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106507848B (en) * 2011-10-08 2014-03-19 成都飞机工业（集团）有限责任公司 A kind of diamond-film-like depositing operation
CN103938211A (en) * 2014-05-08 2014-07-23 西南交通大学 Deposition method of low-stress corrosion-resistant multilayer diamond-like carbon (DLC) film
CN108411258A (en) * 2018-05-29 2018-08-17 大连维钛克科技股份有限公司 A kind of super thick non-hydrogen diamond membrane and preparation method thereof
CN108754450A (en) * 2018-07-03 2018-11-06 广东省新材料研究所 A kind of low stress diamond-like multi-layer film and preparation method thereof
CN208218947U (en) * 2018-05-29 2018-12-11 大连维钛克科技股份有限公司 A kind of super thick non-hydrogen diamond membrane

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106507848B (en) * 2011-10-08 2014-03-19 成都飞机工业（集团）有限责任公司 A kind of diamond-film-like depositing operation
CN103938211A (en) * 2014-05-08 2014-07-23 西南交通大学 Deposition method of low-stress corrosion-resistant multilayer diamond-like carbon (DLC) film
CN108411258A (en) * 2018-05-29 2018-08-17 大连维钛克科技股份有限公司 A kind of super thick non-hydrogen diamond membrane and preparation method thereof
CN208218947U (en) * 2018-05-29 2018-12-11 大连维钛克科技股份有限公司 A kind of super thick non-hydrogen diamond membrane
CN108754450A (en) * 2018-07-03 2018-11-06 广东省新材料研究所 A kind of low stress diamond-like multi-layer film and preparation method thereof

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