CN111378956A - Preparation method of orderly-arranged diamond micro-nano cone array tool - Google Patents

Preparation method of orderly-arranged diamond micro-nano cone array tool Download PDF

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CN111378956A
CN111378956A CN202010210732.9A CN202010210732A CN111378956A CN 111378956 A CN111378956 A CN 111378956A CN 202010210732 A CN202010210732 A CN 202010210732A CN 111378956 A CN111378956 A CN 111378956A
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nano
diamond
micro
array
substrate
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CN111378956B (en
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徐锋
孙烁
施莉莉
赵延超
刘宇
左敦稳
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Nanjing University of Aeronautics and Astronautics
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Nanjing University of Aeronautics and Astronautics
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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
    • 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
    • C23C16/271—Diamond only using hot filaments
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/25—Diamond
    • C01B32/26—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/25—Diamond
    • C01B32/28—After-treatment, e.g. purification, irradiation, separation or recovery
    • 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
    • C23C14/04—Coating on selected surface areas, e.g. using masks
    • C23C14/042—Coating on selected surface areas, e.g. using masks using masks
    • 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
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • 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
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • 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
    • C23C16/56—After-treatment

Abstract

A preparation method of a tool for orderly arranging diamond micro-nano cone arrays is characterized in that a nano diamond film is deposited on a substrate, a micropore array sputtering mask plate with controllable pore diameter and position is prepared by methods of ultrashort pulse laser and the like, and a metal mask point array which is orderly arranged is deposited on the nano diamond film through the micropore array mask plate by using magnetron sputtering equipment. And heating the substrate by using equipment such as microwave chemical vapor deposition (MPCVD) and the like to liquefy and shrink the metal mask points into mask point balls, and etching the micro-cone array with a certain forward inclination angle, thereby preparing the diamond tool with the micro-cone array which is controllable in appearance, size and inclination angle and is arranged orderly. The invention has the characteristics of simple processing technology, easy operation, low cost, high precision and high efficiency.

Description

Preparation method of orderly-arranged diamond micro-nano cone array tool
Technical Field
The invention relates to a preparation method of a diamond tool for processing a pyramid-shaped surface micro-nano structure, in particular to a preparation method of a diamond micro-nano cone array tool which is orderly arranged, and specifically relates to a preparation method of a diamond micro-nano cone array tool which is orderly arranged and has a certain forward inclination angle, wherein the diamond micro-nano cone array tool is prepared by preparing a metal mask point array which is orderly arranged on the surface of a nano diamond, liquefying and shrinking the metal mask point array into a mask point ball, repairing shape defects and using reactive ion etching.
Background
In the prior art, most pyramid micro-nano structures are prepared by methods such as chemical corrosion, a femtosecond laser technology, a photoetching technology and the like, but the problems of random distribution of micro-nano structures in different degrees, low efficiency, high cost and the like exist in the current pyramid micro-nano structure processing. By preparing the orderly-arranged diamond micro-nano cone array tool with controllable appearance, size and inclination angle, the pyramid-shaped micro-nano structure can be processed efficiently at low cost.
Disclosure of Invention
The invention aims to solve the problems of high manufacturing cost, low efficiency, different sizes of microstructures, random distribution and the like of the existing pyramid-shaped micro-nano structure, and provides a preparation method of an orderly-distributed diamond micro-nano cone array tool capable of processing the orderly-distributed pyramid-shaped micro-nano structure at low cost, high efficiency and high precision.
The technical scheme of the invention is as follows:
a preparation method of a diamond micro-nano cone array tool which is arranged in order is characterized by comprising the following steps:
the method comprises the following steps of firstly, placing a silicon wafer in hydrofluoric acid for ultrasonic cleaning for 10-15 minutes to remove a surface oxide layer, cleaning with absolute ethyl alcohol, drying, placing diamond micro powder acetone suspension for ultrasonic oscillation for 15-30 minutes, cleaning with deionized water, and drying in a nitrogen environment for standby application to obtain a treated substrate;
placing the silicon substrate subjected to the series of treatments in hot wire chemical vapor deposition (HFCVD) equipment to deposit a nano-diamond film; the first step and the second step are the preparation method of the nano diamond film, and the nano diamond film can be directly purchased during specific implementation.
Preparing a micropore array sputtering mask plate with controllable aperture and position by using ultrashort pulse laser;
fixing a mask plate on the nano-diamond film, and depositing the metal mask point array which is arranged in order by using magnetron sputtering equipment;
step five, heating the substrate (silicon wafer) by using MPCVD equipment to liquefy and shrink the metal mask points into mask point balls, and repairing the shape defects of the metal mask points prepared by magnetron sputtering;
and sixthly, etching the nano-diamond film by using an MPCVD device to prepare the cone array diamond tool which is orderly arranged, as shown in figure 3 (a). If the silicon wafer substrate is inclined at a certain angle, the reactive ions of the MPCVD equipment are used for etching the nano-diamond film, and a diamond micro-cone with a certain front inclination angle is etched, as shown in figure 3(b), so that the orderly-arranged diamond micro-nano cone array tool is prepared.
The concentration of the HF solution is 4-6%, the concentration of the diamond micro powder suspension is 3g/50ml, and the size of diamond particles is 50 nm.
The parameters used when the HFCVD equipment is adopted to deposit the nano-diamond film on the surface of the substrate are as follows: before experiment, the background in the vacuum chamber is vacuumized to 1Pa, and H is used2And CH4As a working gas, H2Gas flow of 600SCCM, CH4Has a gas flow of 18 SCCM. The hot wire is tungsten wire, the temperature of the hot wire is 2250-2300 ℃, the distance from the hot wire to the sample table is 10mm, the substrate temperature is 750-780 ℃, the working air pressure is 500Pa, and the deposition time is 3 hours. Other chemical vapor deposition equipment can also be used for the deposition of the nano-diamond film.
The thickness of the mask plate is 20 microns, and the material is stainless steel. The ultrashort pulse laser adopts picosecond laser, the used parameters are repetition frequency 40K and power 1.6W, each point is repeated for 200 times, and the laser processing time is 20 microseconds each time. The aperture array period and diameter are consistent with the desired cone array period and size. The micropore array mask plate can also be prepared according to the diameter and the position of the required hole by using methods such as femtosecond laser and the like.
The parameters of the metal mask point array which is orderly arranged on the nano-diamond film and is prepared by using magnetron sputtering equipment are that the target material is selected from metals such as gold, aluminum, nickel and the like, the background in a vacuum cavity before the experiment is vacuumized to 5 × 10-4Pa, working pressure of 1Pa, sputtering gas of Ar, gas flow of Ar of 20SCCM, constant current mode of the equipment and current of 0.15A.
The parameters used for heating the substrate by using the MPCVD equipment to liquefy the metal mask points are as follows: before the experiment, the background in the vacuum cavity is vacuumized to 1Pa, the working pressure is 2-4 KPa, and the working gas is H2，H2Has a gas flow of 200 SCCM. The liquefaction temperature is 400 ℃ and 950 ℃, and the liquefaction time is 10 minutes.
The parameters used when the MPCVD equipment is adopted to carry out reactive ion etching on the diamond film are as follows: the background vacuum in the vacuum chamber before the experiment was pumped to 1 Pa. Tilting the substrate by 15-45 degrees, controlling the microwave source power to 800-1200W, and using H2And Ar as a reaction gas, H2The gas flow of the substrate is 30SCCM, the gas flow of Ar is 20SCCM, the reaction pressure is 1-1.5 KPa, the bias voltage of the substrate is-100 to-200V, and the etching time is 2-4 hours; other chemical vapor deposition equipment can be used for etching the diamond film.
The use method of the orderly-arranged diamond micro-nano cone array tool is shown in figure 1:
processing a pyramid-shaped micro-nano structure in a micro-cutting mode, firstly processing a V-shaped groove along the X-axis direction of the surface of a workpiece, and then processing the pyramid-shaped micro-nano structure along the Y-axis direction of the surface of the workpiece.
The invention has the beneficial effects that:
the method adopts the metal mask point array which is prepared and orderly arranged to control the arrangement of the diamond micro-cone array, controls the appearance of the diamond micro-cone through reactive ion etching, and controls the cone forward inclination angle through the substrate inclination angle, thereby preparing the micro-cone array diamond tool which is orderly arranged. The tool prepared by the invention can be used for processing pyramid-shaped micro-nano structures, and has the characteristics of simple processing technology, easy operation, low cost, high precision and high efficiency.
The tool for orderly arranging the diamond micro-nano cone array can be used for processing pyramid-shaped micro-nano structures on the surfaces of hard and brittle materials such as monocrystalline silicon and optical glass, and the optical performance of workpieces such as the monocrystalline silicon and the optical glass is improved.
Drawings
FIG. 1 is a schematic diagram of processing a pyramid-shaped micro-nano structure.
FIG. 2 is a schematic view of the liquefaction of the mask dots.
Fig. 3(a) is a schematic diagram of a tool for preparing a diamond micro-nano cone array, and (b) is a schematic diagram of a tool for preparing a diamond micro-nano cone array with a front rake angle.
Detailed Description
The invention is further illustrated by the following examples and figures.
As shown in fig. 2-3.
A preparation method of a diamond micro-nano cone array tool with orderly arranged comprises the following steps:
step one, placing a silicon wafer in hydrofluoric acid (with the concentration of 4% -6%) for ultrasonic cleaning for 10-15 minutes to remove a surface oxide layer, cleaning with absolute ethyl alcohol, drying, placing a diamond micro powder acetone suspension for ultrasonic oscillation for 15-30 minutes, cleaning with deionized water, and drying in a nitrogen environment for later use to obtain a treated substrate;
secondly, placing the silicon substrate after a series of treatments in a container with the concentration of diamond micro powder suspension of 3g/50ml and the diamond particle size of 50nm, and then placing the container in hot wire chemical vapor deposition (HFCVD) equipment to deposit the nano-diamond filmThe parameters used were: before experiment, the background in the vacuum chamber is vacuumized to 1Pa, and H is used2And CH4As a working gas, H2Gas flow of 600SCCM, CH4Has a gas flow of 18 SCCM. The hot wire is made of tungsten wires, the temperature of the hot wire is 2250-2300 ℃, the distance from the hot wire to the sample table is 10mm, the temperature of the substrate is 750-780 ℃, the working air pressure is 500Pa, and the deposition time is 3 hours. Other chemical vapor deposition equipment can also be used for the deposition of the nano-diamond film.
Preparing a micropore array sputtering mask plate with controllable aperture and position by using ultrashort pulse laser; the thickness of the mask plate is 20 microns, and the material is stainless steel. The ultrashort pulse laser adopts picosecond laser, the used parameters are repetition frequency 40K and power 1.6W, each point is repeated for 200 times, and the laser processing time is 20 microseconds each time. The aperture array period and diameter are consistent with the desired cone array period and size. The micropore array mask plate can also be prepared according to the diameter and the position of the required hole by using methods such as femtosecond laser and the like.
Fixing a mask plate on the nano-diamond film, and depositing a metal mask point array which is orderly arranged by using a magnetron sputtering device, wherein the parameters are that the target material is selected from metals such as gold, aluminum, nickel and the like, and the background in a vacuum cavity before the experiment is vacuumized to 5 × 10-4Pa, working pressure of 1Pa, sputtering gas of Ar, gas flow of Ar of 20SCCM, constant current mode of the equipment and current of 0.15A.
Step five, heating the substrate (silicon wafer) by using an MPCVD device to liquefy and shrink the metal mask points into mask point balls, as shown in FIG. 2. And repairing the shape defect of the metal mask point prepared by magnetron sputtering; the parameters used for heating the substrate by using the MPCVD equipment to liquefy the metal mask points are as follows: before the experiment, the background in the vacuum cavity is vacuumized to 1Pa, the working pressure is 2-4 KPa, and the working gas is H2，H2Has a gas flow of 200 SCCM. The liquefaction temperature is 300 ℃ and 950 ℃, and the liquefaction time is 10 minutes.
And sixthly, etching the nano-diamond film by using an MPCVD device to prepare the cone array diamond tool which is orderly arranged, as shown in figure 3 (a). If the silicon chip substrate is inclined at a certain angle, the silicon chip substrate is inclined at a certain angleAnd (3) etching the nano-diamond film by using reactive ions of an MPCVD (multi-phase plasma chemical vapor deposition) device to etch a diamond micro-cone with a certain front inclination angle, as shown in a figure 3(b), thereby preparing the diamond micro-cone array tool which is orderly arranged. The parameters used when the MPCVD equipment is adopted to carry out reactive ion etching on the diamond film are as follows: the background vacuum in the vacuum chamber before the experiment was pumped to 1 Pa. Tilting the substrate by 15-45 degrees, controlling the microwave source power to 800-1200W, and using H2And Ar as a reaction gas, H2The gas flow of the substrate is 30SCCM, the gas flow of Ar is 20SCCM, the reaction pressure is 1-1.5 KPa, the bias voltage of the substrate is-100 to-200V, and the etching time is 2-4 hours; other chemical vapor deposition equipment can be used for etching the diamond film.
Example 1.
1. A silicon wafer with a thickness of 0.5mm was used as a substrate, and the silicon wafer was placed in 5% HF for ultrasonic cleaning for 10 minutes to remove a surface oxide layer, and was cleaned with deionized water. And (3) placing the silicon wafer with the surface oxide layer removed in a diamond micro powder suspension of 3g/50ml for ultrasonic oscillation for 20 minutes, wherein the diameter of the diamond micro powder is 50 nanometers. And cleaning with deionized water, and blow-drying in a nitrogen environment for later use to obtain the substrate.
2. And (3) placing the silicon substrate subjected to the series of treatments in HFCVD equipment to prepare the nano-diamond film. The parameters used were: before experiment, the background in the vacuum chamber is vacuumized to 1Pa, and H is used2And CH4As a working gas, H2Gas flow of 600SCCM, CH4The gas flow of the reactor is 18SCCM, the hot wire is a tungsten wire, the temperature of the hot wire is 2300 ℃, the distance between the hot wire and the sample table is 10mm, the temperature of the substrate is 750 ℃, the reaction pressure is 500Pa, and the deposition time is 3 hours.
3. And (3) preparing a micropore array sputtering mask plate with controllable aperture and position by using picosecond laser, wherein the aperture array period and the aperture are consistent with the required cone array period and size. The parameters are that the repetition frequency is 40K, the power is 1.6W, each point is repeated for 200 times, the laser processing time is 20 microseconds each time, the thickness of the mask plate is 20 micrometers, and the material is stainless steel.
4. Preparing ordered arrangement on nano diamond film by using magnetron sputtering equipmentThe metal mask dot array is prepared by selecting nickel as target material, vacuumizing to 5 × 10-4Pa, working pressure of 1Pa, sputtering gas of Ar, gas flow of Ar of 20SCCM, constant current mode of the equipment and current of 0.15A.
5. The substrate was heated using an MPCVD apparatus to liquefy the nickel mask dots. The parameters used were: before the experiment, the background in the vacuum cavity is vacuumized to 1Pa, the working pressure is 4KPa, and the working gas is H2，H2Has a gas flow of 200 SCCM. The substrate temperature was 950 ℃ and the heating time was 10 minutes.
6. And performing reactive ion etching on the diamond film by using an MPCVD device. The parameters used were: the background vacuum in the vacuum chamber before the experiment was pumped to 1 Pa. Tilting the substrate by 30 degrees, the power of the microwave source is 1000W, and the reaction gas is H2And Ar, H2The gas flow of (2) was 30SCCM, the gas flow of Ar was 20SCCM, the reaction gas pressure was 1.5KPa, the substrate bias was-150V, and the etching time was 3 hours.
Example 2.
1. A silicon wafer with a thickness of 0.5mm was used as a substrate, and the silicon wafer was placed in 5% HF for ultrasonic cleaning for 10 minutes to remove a surface oxide layer, and was cleaned with deionized water. And (3) placing the silicon wafer with the surface oxide layer removed in a diamond micro powder suspension of 3g/50ml for ultrasonic oscillation for 20 minutes, wherein the diameter of the diamond micro powder is 50 nanometers. And cleaning with deionized water, and blow-drying in a nitrogen environment for later use to obtain the substrate.
2. And (3) placing the silicon substrate subjected to the series of treatments in HFCVD equipment to prepare the nano-diamond film. The parameters used were: before experiment, the background in the vacuum chamber is vacuumized to 1Pa, and H is used2And CH4As a working gas, H2Gas flow of 600SCCM, CH4The gas flow of the reactor is 18SCCM, the hot wire is a tungsten wire, the temperature of the hot wire is 2300 ℃, the distance between the hot wire and the sample table is 10mm, the temperature of the substrate is 750 ℃, the reaction pressure is 500Pa, and the deposition time is 3 hours.
3. And (3) preparing a micropore array sputtering mask plate with controllable aperture and position by using femtosecond laser, wherein the aperture array period and the aperture are consistent with the required cone array period and size. The parameters are 130fs of pulse width, 1K of repetition frequency, 110mW of power and 0.1 second of processing time, the thickness of the mask plate is 20 microns, and the material is stainless steel.
4. Preparing metal mask dot array arranged in order on the nano-diamond film by using magnetron sputtering equipment, wherein the used parameters comprise that a target material is selected from gold, background vacuum in a vacuum cavity before an experiment is pumped to 5 × 10-4Pa, working pressure of 1Pa, sputtering gas of Ar, gas flow of Ar of 20SCCM, constant current mode of the equipment and current of 0.15A.
5. The substrate was heated using an MPCVD apparatus to liquefy the gold mask dots. The parameters used were: before the experiment, the background in the vacuum cavity is vacuumized to 1Pa, the working pressure is 4KPa, and the working gas is H2，H2Has a gas flow of 200 SCCM. The substrate temperature was 850 ℃ and the heating time was 10 minutes.
6. And performing reactive ion etching on the diamond film by using an MPCVD device. The parameters used were: the background vacuum in the vacuum chamber before the experiment was pumped to 1 Pa. Tilting the substrate by 30 degrees, the power of the microwave source is 1000W, and the reaction gas is H2And Ar, H2The gas flow of (2) was 30SCCM, the gas flow of Ar was 20SCCM, the reaction gas pressure was 1.5KPa, the substrate bias was-150V, and the etching time was 3 hours.
Example 3.
1. A silicon wafer with a thickness of 0.5mm was used as a substrate, and the silicon wafer was placed in 5% HF for ultrasonic cleaning for 10 minutes to remove a surface oxide layer, and was cleaned with deionized water. And (3) placing the silicon wafer with the surface oxide layer removed in a diamond micro powder suspension of 3g/50ml for ultrasonic oscillation for 20 minutes, wherein the diameter of the diamond micro powder is 50 nanometers. And cleaning with deionized water, and blow-drying in a nitrogen environment for later use to obtain the substrate.
2. And (3) placing the silicon substrate subjected to the series of treatments in HFCVD equipment to prepare the nano-diamond film. The parameters used were: before experiment, the background in the vacuum chamber is vacuumized to 1Pa, and H is used2And CH4As a working gas, H2Gas flow of 600SCCM, CH4The gas flow of the gas is 18SCCM, the hot wire is tungsten wire, the temperature of the hot wire is 2300 ℃, the distance between the hot wire and the sample table is 10mm, the substrate temperature is 750 ℃, and the reaction pressure is 500PaThe deposition time was 3 hours.
3. And (3) preparing a micropore array sputtering mask plate with controllable aperture and position by using picosecond laser, wherein the aperture array period and the aperture are consistent with the required cone array period and size. The parameters are that the repetition frequency is 40K, the power is 1.6W, each point is repeated for 200 times, the laser processing time is 20 microseconds each time, the thickness of the mask plate is 20 micrometers, and the material is stainless steel.
4. Preparing metal mask dot array arranged in order on the nano-diamond film by using magnetron sputtering equipment, wherein the used parameters comprise that a target material is selected from gold, background vacuum in a vacuum cavity before an experiment is pumped to 5 × 10-4Pa, working pressure of 1Pa, sputtering gas of Ar, gas flow of Ar of 20SCCM, constant current mode of the equipment and current of 0.15A.
5. The substrate was heated using an MPCVD apparatus to liquefy the gold mask dots. The parameters used were: before the experiment, the background in the vacuum cavity is vacuumized to 1Pa, the working pressure is 4KPa, and the working gas is H2，H2Has a gas flow of 200 SCCM. The substrate temperature was 850 ℃ and the heating time was 10 minutes.
6. The diamond film was subjected to reactive ion etching using an HFCVD apparatus. The parameters used were: the background vacuum in the vacuum chamber before the experiment was pumped to 1 Pa. Tilt of substrate 15 < o > with reaction gas H2The gas flow was 300 SCCM. The hot filament is tungsten filament, and the distance from the hot filament to the sample table is 10 mm. The temperature of the hot wire is 2300 ℃, the reaction pressure is 3KPa, the bias voltage of the substrate is-200V, and the etching time is 3 hours.
The present invention is not concerned with parts which are the same as or can be implemented using prior art techniques.

Claims (10)

1. A preparation method of a diamond micro-nano cone array tool which is arranged in order is characterized by comprising the following steps:
preparing a micropore array sputtering mask plate with controllable aperture and position by using ultrashort pulses;
fixing a mask plate on the nano-diamond film, depositing the nano-diamond film on a silicon wafer substrate, and selectively depositing by using a magnetron sputtering device through the micropore array mask plate to obtain a metal mask point array which is orderly arranged;
thirdly, heating the substrate by using MPCVD equipment, liquefying and shrinking the metal mask points into mask point balls and repairing the shape defects of the metal mask points prepared by magnetron sputtering;
and step four, etching the nano-diamond film by using reactive ions of the MPCVD equipment to prepare the cone array diamond tool which is orderly arranged.
2. The method as claimed in claim 1, wherein the silicon wafer substrate is tilted at a certain angle, the nano-diamond film is etched by using reactive ions of the MPCVD equipment, and the diamond micro-cones with a certain front tilt angle are etched, thereby preparing the diamond micro-cone array tool with orderly arrangement.
3. The method as set forth in claim 1, wherein the preparing of the nano-diamond film comprises the steps of:
the method comprises the following steps of firstly, placing a silicon wafer in hydrofluoric acid for ultrasonic cleaning for 10-15 minutes to remove a surface oxide layer, cleaning with absolute ethyl alcohol, drying, placing diamond micro powder acetone suspension for ultrasonic oscillation for 15-30 minutes, cleaning with deionized water, and drying in a nitrogen environment for standby application to obtain a treated substrate;
and step two, placing the silicon wafer substrate subjected to the series of processing in Hot Filament Chemical Vapor Deposition (HFCVD) equipment to deposit the nano-diamond film.
4. The method as claimed in claim 3, wherein the hydrofluoric acid solution has a concentration of 4% to 6%, the suspension of diamond micropowder has a concentration of 3g/50ml, and the diamond particle size is 50 nm.
5. The method as claimed in claim 3, wherein the parameters used for depositing the nano-diamond film on the surface of the silicon wafer substrate by using the hot wire chemical vapor deposition equipment are as follows: before experiment, the background in the vacuum chamber is vacuumized to 1Pa, and H is used2And CH4As a working gas, H2Gas flow of 600SCCM, CH4The gas flow of (2) is 18 SCCM; the hot wire is made of tungsten wires, the temperature of the hot wire is 2250-2300 ℃, the distance from the hot wire to the sample table is 10mm, the temperature of the substrate is 750-780 ℃, the working air pressure is 500Pa, and the deposition time is 3 hours.
6. The method as claimed in claim 1, wherein the parameters for processing the mask plate of the micro-hole array by using the ultrashort pulse laser are as follows: the thickness of the mask plate is 20 microns, and the material is stainless steel; picosecond laser is used, the repetition frequency of the picosecond laser is 40K, the power is 1.6W, each point is repeated for 200 times, and the laser processing time is 20 microseconds each time; the micropore array period is consistent with the diamond cone array arrangement period, and the hole diameter is consistent with the cone size; the micro-pore array mask plate can also be prepared by using a femtosecond laser method according to the diameter of the required hole.
7. The method as set forth in claim 1, wherein the parameters of the magnetron sputtering apparatus for preparing the metal mask dots arranged in an orderly manner on the nano-diamond film include that the target material is selected from gold, aluminum and nickel, and the background vacuum in the vacuum chamber before the experiment is pumped to 5 × 10-4Pa, the working air pressure is 1 Pa; the sputtering gas is Ar, and the gas flow of the Ar is 20 SCCM; the device used a constant current mode with a current of 0.15A.
8. The method of claim 1, wherein the parameters for liquefying and shrinking the metal mask dots into mask dot balls and repairing shape defects by heating the substrate using the MPCVD apparatus are: before the experiment, the background in the vacuum cavity is vacuumized to 1Pa, and the working air pressure is 2-4 kPa; the working gas is H2，H2The gas flow of (2) is 200 SCCM; the liquefaction temperature is 400 ℃ and 950 ℃, and the liquefaction time is 10 minutes.
9. The method as set forth in claim 1, wherein the parameters for reactive ion etching of the diamond film using the MPCVD apparatus are: before the experiment, the background in the vacuum cavity is vacuumized to 1 Pa; tilting the substrate by 15-45 ℃, wherein the microwave source power is 800-1200W; using H2And Ar is used asAs a reaction gas, H2The gas flow of the gas is 30SCCM, the gas flow of Ar is 20SCCM, the reaction pressure is 1-1.5 KPa, the substrate bias is-100 to-200V, and the etching time is 2-4 hours.
10. The tool for orderly arranging the diamond micro-nano cone array according to claim 1, wherein when the tool is formed facing a pyramid surface micro-nano structure, the pyramid surface micro-nano structure is processed in a micro-cutting mode, a V-shaped groove is processed along the X-axis direction of the surface of a workpiece, and then the pyramid surface micro-nano structure is processed along the Y-axis direction of the surface of the workpiece.
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