CN108611638B - Micron diamond thick film with high abrasion ratio and high breaking strength and preparation method thereof - Google Patents

Micron diamond thick film with high abrasion ratio and high breaking strength and preparation method thereof Download PDF

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CN108611638B
CN108611638B CN201810580017.7A CN201810580017A CN108611638B CN 108611638 B CN108611638 B CN 108611638B CN 201810580017 A CN201810580017 A CN 201810580017A CN 108611638 B CN108611638 B CN 108611638B
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film layer
diamond
micron diamond
layer
film
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CN108611638A (en
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于盛旺
郑可
李亮亮
高洁
黑鸿君
公彦鹏
曹岩
申艳艳
贺志勇
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Taiyuan University of Technology
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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
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/48—Ion implantation
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/36—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including layers graded in composition or physical properties

Abstract

The invention relates to a micron diamond thick film with high abrasion ratio and high breaking strength and a preparation method thereof, belonging to the technical field of preparation of superhard materials. The thick film is formed by compounding a plurality of micron diamond film layers and a plurality of metal film layers which are closely connected, the micron diamond film layers and the metal film layers are sequentially arranged at intervals, and the topmost layer and the bottommost layer are the micron diamond film layers; the (110) crystal grain orientation in the micro-diamond film is dominant, the crystal grain size is 10-200 μm, and the film thickness is 50-200 μm; the thickness of the metal film layer is 1-10 μm. During preparation, the diamond film layer is deposited by a chemical vapor deposition method, and the metal film layer is prepared by a film synthesis method. The growth of micron diamond grains is blocked by adding the metal film layer, so that the subsequent diamond is re-nucleated and grows on the surface of the metal layer. The diamond thick film finally obtained is mainly composed of micron diamond with the orientation of fine grains (110) being dominant, and has high abrasion ratio and high breaking strength.

Description

Micron diamond thick film with high abrasion ratio and high breaking strength and preparation method thereof
Technical Field
The invention belongs to the technical field of superhard material preparation, and particularly relates to a micron diamond thick film with high abrasion ratio and high breaking strength and a preparation method thereof.
Background
The Chemical Vapor Deposition (CVD) diamond film has excellent comprehensive physical and chemical properties and has good application prospect in the fields of machinery, aerospace, optics and the like. When CVD diamond film is used as a cutting or dressing tool, wear resistance and fracture strength are two major performance criteria.
Compared with CVD diamond with other orientations, the CVD diamond with the dominant (110) orientation has the characteristics of high wear resistance and moderate growth temperature. However, since the CVD diamond film is generally prepared by plasma assistance, the position of the substrate in the plasma changes with the increase of the film thickness, and the deposition environment of the film, i.e., the temperature field, flow field, electromagnetic field, concentration of hydrogen and carbon groups, etc., changes to different degrees. Thus, the preferred orientation may change. Meanwhile, along with the prolonging of the deposition time, the crystal grains grow, the size of the crystal boundary in the film can be increased, the number of the crystal grains is reduced, and the probability of the occurrence of other large-scale defects such as holes among the crystal boundaries and the like can be increased at the same time. This change in texture causes a decrease in the breaking strength of the CVD diamond film.
Disclosure of Invention
The invention aims to solve the problems of rough surface and poor fracture strength of the diamond thick film prepared by the conventional method, and provides a micron diamond thick film with high abrasion ratio and high fracture strength, which is formed by alternately arranging a plurality of micron diamond film layers/metal film layers. Meanwhile, the invention also aims to provide a preparation method of the thick film.
The invention is realized by the following technical scheme:
a micron diamond thick film with high abrasion ratio and high breaking strength is formed by compounding a plurality of micron diamond film layers and a plurality of metal film layers which are closely connected, wherein the micron diamond film layers and the metal film layers are sequentially arranged at intervals, and the topmost layer and the bottommost layer are the micron diamond film layers; the orientation of (110) crystal grains in the micron diamond film layer is dominant, the size of the crystal grains is 10-200 mu m, the thickness of the micron diamond film layer is 50-200 mu m, and the thickness of the metal film layer is 1-10 mu m.
As a preferable technical scheme, the metal film layer adopts a strong carbide forming element which can form good bonding strength with diamond.
Preferably, the strong carbide forming elements are Mo, W, Cr, Ti, Zr, Ta, V.
The preparation method of the micron diamond thick film with high abrasion ratio and high breaking strength comprises the following steps:
firstly, depositing (110) a micron diamond film layer with dominant orientation on the surface of a silicon substrate by using a chemical vapor deposition method; the method specifically comprises the following steps: using a single-side polished monocrystalline silicon wafer as a substrate, manually grinding the surface of the silicon wafer by using diamond fine powder with the granularity of 0.2-0.5 mu m, then ultrasonically cleaning by using alcohol, drying by using cold air, depositing a first micron diamond film layer on the surface of the silicon wafer by using a chemical vapor deposition method, controlling the diamond grains to be (110) dominant orientation, controlling the size of the diamond grains to be 10-200 mu m, and controlling the thickness of the micron diamond film layer to be 50-200 mu m;
then, preparing a metal film layer on the micron diamond film layer by using a film synthesis method; the method specifically comprises the following steps: ultrasonically cleaning the surface of the substrate deposited with the micron diamond film layer by using alcohol, drying the substrate by using cold air, preparing a first metal film layer on the surface of the micron diamond film layer by using a film synthesis method, and controlling the thickness of the metal film layer to be 1-10 mu m;
then, grinding the surface of the metal film layer and the edge surface of the substrate by using diamond fine powder with the granularity of 0.2-0.5 mu m, then ultrasonically cleaning by using alcohol, blow-drying by using cold air, continuously depositing (110) a micron diamond film layer with the dominant orientation on the metal film layer by using a chemical vapor deposition method, and by the same way, sequentially depositing the micron diamond film layer and preparing the metal film layer according to the interval sequence until the total thickness required by the thick film is reached; wherein, the last layer is a micron diamond film layer;
and finally, removing the silicon substrate to obtain the micron diamond thick film with high abrasion ratio and high breaking strength.
As a preferable technical scheme, the preparation method of the micron diamond film layer adopts a microwave plasma chemical vapor deposition method, a hot wire plasma chemical vapor deposition method or a direct current arc plasma jet chemical vapor deposition method; the preparation method of the metal film layer adopts double-layer glow plasma metal infiltration, magnetron sputtering, electroplating or chemical plating.
As a preferred technical scheme, the method for removing the silicon substrate comprises the following steps: and removing by using acid solution corrosion or laser ablation.
The micron diamond thick film has high wear resistance and high breaking strength, and the metal film layer is used to block the columnar growth of diamond grains, so that the columnar crystal structure of the thick film is changed into a fine crystal grain structure. When the diamond film layer is deposited by chemical vapor deposition, the diamond grows in a competitive growth mode of columnar crystals, crystal grains are gradually increased along with the increase of the film thickness, gaps among the crystal grains are increased, and non-diamond phases are increased, so that the mechanical properties of the diamond film, such as the breaking strength and the like, are seriously reduced, and the breaking failure of the diamond film is caused under the loading condition. And the surface roughness of the diamond film also increases as the thick film increases. The micron diamond thick film prepared by the method of the invention blocks the growth of columnar grains of the grains due to the addition of the plurality of metal film layers, so that the diamond film of each layer re-nucleates and re-grows on the metal film layers, and the thick columnar grains are changed into fine grains, thus the force can be dispersed into more grains for carrying out when the diamond film loads acting force, the stress concentration is small, and the more the grains are, the larger the area of the grain boundary is, the more the grain boundary is tortuous, the more the crack is difficult to expand, thereby the addition of the plurality of intermediate metal film layers improves the fracture strength of the thick film. Meanwhile, the toughness of the composite thick film is improved by adding a plurality of metal film layers and utilizing the metal toughness higher than that of diamond. The metal film layer blocks the growth of crystal grains and the (110) oriented diamond is favorable for reducing the roughness of the micron diamond film and improving the abrasion ratio of the micron diamond film.
Compared with the prior art, the invention has the following beneficial effects:
1) the breaking strength and the abrasion ratio performance of the thick film are obviously improved;
2) the internal stress of the thick film is obviously reduced;
3) the method combining different surface treatment technologies is adopted, and the technical field of preparation of superhard materials is further widened.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate exemplary embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 is a schematic structural diagram of a high wear ratio and high breaking strength micro-diamond thick film according to the present invention.
FIG. 2 is a schematic of a molybdenum die used in the thick film fabrication process.
In the figure: 1-micron diamond film layer, 2-metal film layer, 3-silicon substrate and 4-molybdenum film.
FIG. 3 is a cross-sectional SEM image of a high wear ratio, high fracture strength micro-diamond thick film of the present invention.
FIG. 4 is a surface SEM image of a high wear ratio, high fracture strength micron diamond thick film of the present invention.
FIG. 5 is a surface XRD pattern of the micron diamond thick film with high abrasion ratio and high breaking strength.
Detailed Description
In order that those skilled in the art will better understand the present invention, a more complete and complete description of the present invention is provided below in conjunction with the accompanying drawings and embodiments. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
A micron diamond thick film with high abrasion ratio and high breaking strength is formed by compounding a plurality of micron diamond film layers 1 and a plurality of metal film layers 2 which are closely connected, wherein the micron diamond film layers 1 and the metal film layers 2 are sequentially arranged at intervals, and the topmost layer and the bottommost layer are both the micron diamond film layers 1; the (110) oriented grains in the micron diamond film layer 1 are dominant, the grain size is 10-200 mu m, the thickness of the micron diamond film layer 1 is 50-200 mu m, and the thickness of the metal film layer 2 is 1-10 mu m.
The metal film layer adopts strong carbide forming elements such as Mo, W, Cr, Ti, Zr, Ta and V which can form good bonding strength with diamond.
The preparation method of the micron diamond thick film with high abrasion ratio and high breaking strength comprises the following steps: firstly, depositing (110) a micron diamond film layer with dominant orientation on the surface of a silicon substrate by using a chemical vapor deposition method; then, preparing a metal film layer on the micron diamond film layer by using a film synthesis method; then, continuously depositing (110) a micron diamond film layer with the dominant orientation on the metal film layer by using a chemical vapor deposition method, and so on, and sequentially depositing the micron diamond film layer and preparing the metal film layer according to the interval sequence until the total thickness required by the thick film is reached; wherein, the thickness of each layer of the micron diamond film layer is controlled to be 50-200 μm, the diamond grain size of the micron diamond film layer is controlled to be 10-200 μm, and the thickness of each layer of the metal film layer is controlled to be 1-10 μm; and finally, removing the silicon substrate to obtain the micron diamond thick film with high abrasion ratio and high breaking strength.
The preparation method of the micron diamond film layer adopts a microwave plasma chemical vapor deposition method, a hot wire plasma chemical vapor deposition method or a direct current arc plasma jet chemical vapor deposition method; the preparation method of the metal film layer adopts double-layer glow plasma metal infiltration, magnetron sputtering, electroplating or chemical plating; the silicon substrate is removed by acid solution corrosion or laser ablation.
The preparation method of the present invention is further illustrated by a specific preparation example, in which the equipment used in the preparation example includes TYUT type microwave plasma chemical vapor deposition equipment and dual-glow plasma metal infiltration equipment, and the method specifically includes the following steps:
microwave plasma chemical vapor deposition micron diamond film layer
① cleaning the surface of the silicon substrate, namely, using a single-side polished monocrystalline silicon wafer with the diameter of 60mm and the thickness of 5mm as the silicon substrate 3, manually grinding the polished surface of the monocrystalline silicon for 30min by using diamond fine powder with the granularity of 0.5 mu m, then putting the monocrystalline silicon wafer into alcohol for ultrasonic cleaning for 20min, and drying the monocrystalline silicon by using cold air;
Figure DEST_PATH_IMAGE001
opening a reaction cavity of the TUT type MPCVD equipment, and wiping the base station clean; placing the molybdenum die 4 with the silicon substrate 3 in the central position of a base station in a reaction cavity, closing the cavity, starting a mechanical pump for vacuumizing, starting a molecular pump when the pressure of the cavity is pumped to be below 5Pa, and pumping the vacuum degree of the cavity to be 1 x 10-4After Pa, closing the molecular pump, introducing hydrogen with the purity of 99.9999%, controlling the flow at 400sccm, setting the microwave power at 0.6KW when the air pressure of the cavity is increased to 0.8KPa, turning on the microwave power supply, then simultaneously increasing the air pressure and the power, introducing methane with the purity of 99.999% when the microwave power is increased to 5KW and the pressure of the cavity is 10KPa, and controlling the flow of the methane to be 1% -3% of the flow of the hydrogen; when the temperature of the silicon substrate 3 rises to 900 +/-5 ℃, stabilizing parameters, and depositing the diamond film for 20 hours to ensure that the thickness of the micron diamond film layer is 100 +/-5 mu m;
Figure 348919DEST_PATH_IMAGE002
after the deposition time reaches 20 hours, stopping introducing methane, reducing the air pressure of the reaction cavity to 0.8KPa, reducing the power to 0.6KW, turning off the microwave power supply, stopping introducing hydrogen, and turning off the mechanical pump;
Figure DEST_PATH_IMAGE003
and opening the air release valve to ensure that the pressure of the reaction cavity is consistent with the external pressure, then opening the equipment reaction cavity, and taking out the silicon substrate 3 deposited with the micron diamond film layer, wherein the thickness of the micron diamond film layer is 100 +/-5 microns.
Molybdenum cementation treatment by double-layer glow ion cementation technology
① cleaning the surface of the silicon substrate, namely putting the silicon substrate 3 on which the micron diamond film layer is deposited into alcohol for ultrasonic treatment for 30min, and then drying by cold air;
Figure 569816DEST_PATH_IMAGE001
charging: placing the silicon substrate 3 deposited with the first micron diamond film layer into a molybdenum die 2 shown in figure 2, wherein the molybdenum die 2 has the outer diameter of 65mm, the height of 10mm, the groove diameter of 60.1mm and the depth of 5.5 mm; then placing the target material on a base station in a double-layer glow metal infiltration device, wherein the target material is molybdenum with the diameter of 80mm, the thickness of 5mm and the purity of 99.999 percent, the target material is placed in a suspension mode, the distance between the target material and a silicon substrate 3 is 20mm, and the sputtering gas is high-purity argon with the purity of 99.999 percent;
Figure 595541DEST_PATH_IMAGE002
vacuumizing and sputtering and cleaning: starting a mechanical pump, vacuumizing to below 5Pa, starting a cathode power supply, and carrying out surface sputtering on the substrate, wherein the specific parameters are set in the process: working air pressure is 35Pa, cathode tool voltage is 450V, and cleaning time is 20 min;
Figure 206782DEST_PATH_IMAGE003
molybdenum infiltration treatment: starting a target source power supply, adjusting the target source voltage to 750V and the cathode voltage to 250V under the working air pressure of 35Pa, and entering a heat preservation stage when the temperature of the sample reaches 800 ℃;
⑤ heat preservation treatment, namely after heat preservation is carried out for 15min, the power supply of the sputtering target and the power supply of the base material are closed, argon gas is closed after 1.5h, the sputtering target and the base material are cooled to room temperature along with the furnace and then taken out, and the thickness of the metal Mo film layer is 1 mu m.
Thirdly, grinding the surface of the metal film layer and the edge surface of the substrate by using diamond fine powder with the granularity of 0.2-0.5 mu m, then ultrasonically cleaning the metal film layer and drying the metal film layer by using cold air, continuously depositing (110) a micron diamond film layer with the dominant orientation on the metal film layer by using a chemical vapor deposition method, repeating the steps, sequentially depositing the micron diamond film layer and preparing the metal film layer according to the interval sequence, stopping preparation when the overall thickness of the thick film reaches 400 +/-10 mu m, putting the finished product into a hydrofluoric acid and nitric acid mixed solution with the volume ratio of 1: 2 for 40h, and corroding the silicon substrate 3 to obtain the micron diamond thick film with high abrasion ratio and high breaking strength.
The prepared micron diamond thick film has no local cracks, and has average Raman half-peak width: 3.0cm-1The breaking strength: 950 +/-5 MPa, abrasion ratio: 60-80 ten thousand.
FIG. 3 is a cross-sectional SEM image of a high wear ratio, high fracture strength micro-diamond thick film of the present invention. The conclusions that can be drawn from the figure are: the thickness of each layer of diamond is not much different, about 100 μm. The middle Mo interlayer is flat and has a very thin thickness of 1 μm. It can be seen that the columnar grains of diamond are blocked and each layer re-nucleates and grows, which contributes to the improvement of the fracture strength of the diamond thick film.
Fig. 4 is a surface SEM image of the multilayer diamond film/metal film composite thick film with high wear ratio and high breaking strength according to the present invention. The conclusions that can be drawn from the figure are: the diamond crystal grains on the surface are fine (20-100 mu m), and the surface mostly presents rectangular (110) diamond crystal faces, so that the abrasion ratio of the thick film is greatly improved.
FIG. 5 is a surface XRD pattern of the multilayer diamond film/metal film composite thick film with high wear ratio and high breaking strength according to the present invention. As can be seen from the figure, the diffraction peak intensity of the (110) crystal face is highest, which indicates that the crystal face on the surface of the composite micron diamond thick film is mainly the diamond (110) crystal face.
The technical solutions in the embodiments of the present invention are clearly and completely described above, and the described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Claims (6)

1. A micron diamond thick film with high abrasion ratio and high breaking strength is characterized in that: the thick film is formed by compounding a plurality of micron diamond film layers and a plurality of metal film layers which are closely connected, wherein the micron diamond film layers and the metal film layers are sequentially arranged at intervals, and the topmost layer and the bottommost layer are the micron diamond film layers; the orientation of (110) crystal grains in the micron diamond film layer is dominant, the size of the crystal grains is 10-200 mu m, the thickness of the micron diamond film layer is 50-200 mu m, and the thickness of the metal film layer is 1-10 mu m.
2. The high wear ratio, high fracture strength micro-diamond thick film of claim 1, wherein: the metal film layer adopts a strong carbide forming element which can form good bonding strength with diamond.
3. The high wear ratio, high fracture strength micro-diamond thick film of claim 2, wherein: the strong carbide forming elements are Mo, W, Cr, Ti, Zr, Ta and V.
4. The method for preparing a high wear ratio and high breaking strength micro-diamond thick film according to any one of claims 1 to 3, comprising the steps of: firstly, depositing (110) a micron diamond film layer with dominant orientation on the surface of a silicon substrate by using a chemical vapor deposition method; then, preparing a metal film layer on the micron diamond film layer by using a film synthesis method; then, continuously depositing (110) a micron diamond film layer with the dominant orientation on the metal film layer by using a chemical vapor deposition method, and so on, and sequentially depositing the micron diamond film layer and preparing the metal film layer according to the interval sequence until the total thickness required by the thick film is reached; wherein, the thickness of each micron diamond film layer is controlled to be 50-200 μm, and the thickness of each metal film layer is controlled to be 1-10 μm; and finally, removing the silicon substrate.
5. The method for preparing a micron diamond thick film with high abrasion ratio and high breaking strength according to claim 4, wherein the method comprises the following steps: the preparation method of the micron diamond film layer adopts a microwave plasma chemical vapor deposition method, a hot wire plasma chemical vapor deposition method or a direct current arc plasma jet chemical vapor deposition method; the preparation method of the metal film layer adopts double-layer glow plasma metal infiltration, magnetron sputtering, electroplating or chemical plating.
6. The method for preparing a high wear ratio and high breaking strength micro-diamond thick film according to claim 4 or 5, wherein: the silicon substrate is removed by etching with an acid solution or by laser ablation.
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CN114318287B (en) * 2021-12-23 2023-11-03 深圳技术大学 Preparation method of diamond self-supporting film and diamond self-supporting film
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