CN111304602B

CN111304602B - Super-hydrophobic diamond-like composite layer structure and preparation method thereof

Info

Publication number: CN111304602B
Application number: CN201811508697.8A
Authority: CN
Inventors: 唐永炳; 闫家肖; 蒋春磊; 石磊
Original assignee: Shenzhen Institute of Advanced Technology of CAS
Current assignee: Shenzhen Institute of Advanced Technology of CAS
Priority date: 2018-12-11
Filing date: 2018-12-11
Publication date: 2023-07-21
Anticipated expiration: 2038-12-11
Also published as: CN111304602A; WO2020119510A1

Abstract

The invention provides a preparation method of a diamond-like composite layer structure, which comprises the following steps: providing a substrate, and sequentially carrying out pretreatment, glow cleaning and ion etching cleaning on the substrate; placing the cleaned substrate in a deposition chamber, introducing argon, adjusting the pressure of the vacuum chamber to be 0.2-1.3 Pa, starting a first target and a second target, controlling the target power of the first target to be 30-70W, controlling the target power of the second target to be 30-70W, and depositing a prefabricated transition layer under the condition that the bias voltage of the substrate is 100-300V; taking out the sample deposited with the prefabricated transition layer, placing the sample in a container containing etching liquid, performing ultrasonic treatment, and performing etching treatment on the prefabricated transition layer to form a transition layer with a micro-nano structure array on the surface, thereby obtaining an etched sample; and placing the etched sample in a deposition chamber after carrying out surface cleaning treatment, and depositing a diamond-like carbon layer on the surface of the transition layer of the etched sample.

Description

Super-hydrophobic diamond-like composite layer structure and preparation method thereof

Technical Field

The invention belongs to the technical field of diamond-like coatings, and particularly relates to a super-hydrophobic diamond-like composite layer structure and a preparation method thereof.

Background

In recent years, the super-hydrophobic materials with special infiltration performance are widely paid attention to, and the super-hydrophobic materials have extremely broad application prospects in medical biology, industrial and agricultural production and daily life, such as self-cleaning materials, oil-water separation materials, anti-fouling fabrics, drag-reducing materials and the like. However, the currently studied super-hydrophobic materials have complex preparation process and high cost, and the prepared super-hydrophobic materials have low hardness and cannot meet the requirement of material diversification. Therefore, the method for developing the high-hardness and super-hydrophobic material has important promotion effect and significance for the wide application of the special wetting property material.

Diamond-like carbon (DLC) is a material containing sp ² And sp (sp) ³ The amorphous carbon material with bonding characteristics is very suitable to be used as a wear-resistant coating due to high hardness, high elastic modulus, low friction factor, wear resistance and good vacuum tribological property, thereby attracting importance of the tribological field and having wide application prospect in the fields of cutters, dies, parts, biomedical devices and the like. But the lack of hydrophobicity greatly limits the industrial application of diamond coatings.

Disclosure of Invention

The invention aims to provide a super-hydrophobic diamond-like composite layer structure and a preparation method thereof, and aims to solve the problem that the existing diamond-like coating does not have hydrophobicity.

In order to achieve the above purpose, the invention adopts the following technical scheme:

in one aspect, the invention provides a diamond-like composite layer structure comprising a substrate, a transition layer disposed on a surface of the substrate, a diamond-like layer disposed on a surface of the transition layer facing away from the substrate, wherein,

the transition layer protrudes at one side away from the substrate to form a micro-nano array structure, and the surface of the diamond-like carbon layer, which is away from the substrate, is a micro-nano array surface.

Preferably, in the transition layer, the height of the micro-nano array structure is 0.5-2 microns, and the distance between adjacent micro-nano units in the micro-nano array structure is 0.1-2 microns.

Preferably, the height of the micro-nano array in the micro-nano array surface of the diamond-like carbon layer is 0.5-2 microns, and the distance between adjacent micro-nano units in the micro-nano array is 0.1-2 microns.

Preferably, the transition layer is selected from a metallic layer or a non-metallic layer, wherein,

the metal layer is one of an iron layer, an aluminum layer, a copper layer, a silver layer, a tin layer, a titanium layer and a germanium layer,

the nonmetallic layer is one of a carbon layer, a silicon layer and an organic polymer layer.

Preferably, the substrate is selected from one of a carbon steel substrate, a stainless steel substrate, a Gao Sugang substrate, a hard alloy substrate and a ceramic substrate.

In another aspect, the present invention provides a method for preparing a diamond-like composite layer structure, comprising the steps of:

providing a substrate, and sequentially carrying out pretreatment, glow cleaning and ion etching cleaning on the substrate;

placing the cleaned substrate in a deposition chamber, introducing argon, adjusting the pressure of the vacuum chamber to be 0.2-1.3 Pa, starting a first target and a second target, controlling the target power of the first target to be 30-70W, controlling the target power of the second target to be 30-70W, and depositing a prefabricated transition layer under the condition that the bias voltage of the substrate is 100-300V;

taking out the sample deposited with the prefabricated transition layer, placing the sample in a container containing etching liquid, performing ultrasonic treatment, and performing etching treatment on the prefabricated transition layer to form a transition layer with a micro-nano structure array on the surface, thereby obtaining an etched sample;

placing the etched sample in a deposition chamber after surface cleaning treatment, and depositing a diamond-like carbon layer on the surface of the transition layer of the etched sample;

wherein the first target and the second target are independently selected from metal or nonmetal materials, the first target is selected from targets which are soluble in the etching liquid, and the second target is selected from targets which are insoluble in the etching liquid; or (b)

The first target is selected from targets of metal or nonmetal materials, the second target is selected from targets of metal or nonmetal materials, and the etching liquid is capable of dissolving the first target but incapable of dissolving the second target.

Preferably, the first target and the second target are selected from metal materials, and the metal materials comprise iron, aluminum, copper, silver, tin, titanium and germanium.

Preferably, the first target and the second target are selected from nonmetallic materials, and the nonmetallic materials comprise carbon, silicon and organic polymers.

Preferably, the first target is selected from a metallic material, the second target is selected from a non-metallic material, or the first target is selected from a non-metallic material, the second target is selected from a metallic material,

wherein the metallic material is selected from iron, aluminum, copper, silver, tin, titanium and germanium, and the nonmetallic material is selected from carbon, silicon and organic polymers.

Preferably, the etching solution is selected from an acidic solution, and the acidic solution is selected from at least one of nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, and an organic acid.

Preferably, the etching solution is selected from alkaline solution, and the alkaline solution is selected from at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide and organic base.

Preferably, in the step of depositing the diamond-like layer on the surface of the transition layer of the etching sample, the etching sample is placed in a deposition chamber after being subjected to surface cleaning treatment, acetylene is used as working gas, the pressure in the vacuum chamber is regulated to be 0.5-1.0 Pa, the ion source voltage is 50-100V, the substrate bias voltage is 50-200V, and the diamond-like layer is deposited on the surface of the transition layer of the etching sample.

According to the diamond-like composite layer structure provided by the invention, the transition layer with the micro-nano array structure is arranged on the surface of the substrate, and further, the diamond-like layer with the micro-nano array surface is formed on the surface of the transition layer. The diamond-like composite layer structure obtained by the method takes diamond-like carbon as a material basis, so that the diamond-like carbon composite layer structure has the advantage of high hardness. Meanwhile, since the diamond-like layer has a micro-nano array surface, excellent hydrophobic property is imparted to the diamond-like composite layer structure, and contact angle experiments show that the contact angle (diamond-like layer surface) of the diamond-like composite layer structure is 153 DEG to 155 deg. In conclusion, the diamond-like composite layer structure not only has high hardness, but also has excellent hydrophobic property, and can be used as an impregnating material with high requirements on hardness and hydrophobic property, so that the industrial application prospect of diamond-like carbon is expanded.

According to the preparation method of the diamond-like carbon composite layer structure, the diamond-like carbon super-hydrophobic composite structure layer is prepared through a deposition etching process in a mode of combining an ion source and arc ion plating. On one hand, the method can realize the firm combination of the diamond-like carbon layer on the substrate by preparing the transition layer, improve the adhesive force of the diamond-like carbon layer on the substrate and prevent the peeling of the diamond-like carbon layer; and on the other hand, etching the transition layer to form a micro-nano array structure, providing a structural foundation for the deposition of diamond-like carbon, and finally obtaining the diamond-like carbon layer with the micro-nano array on the surface, thereby realizing the super-hydrophobic function of the diamond-like carbon layer.

Drawings

FIG. 1 is a schematic structural view of a diamond-like composite layer structure provided by an embodiment of the present invention;

FIG. 2 is a schematic diagram of an ion source coating apparatus according to an embodiment of the present invention;

FIG. 3 is a graph showing the contact angle test results of the diamond-like composite layer structure provided in example 1 of the present invention;

fig. 4 is a graph showing the contact angle test results of the diamond-like composite layer structure provided in example 2 of the present invention.

Detailed Description

In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.

In the description of the present invention, it should be understood that the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.

Diamond-like coatings, due to their excellent properties, in particular high hardness and good scratch resistance, have been increasingly used in various industries, from the field of mechanical manufacturing to the field of optoelectronics, from the medical field to the field of aerospace. However, due to the physical properties of the diamond-like material, the diamond-like material does not have hydrophobic properties, and is difficult to use in technologies requiring good hydrophobic properties. In view of the above, the present invention aims to provide a method for preparing a diamond-like composite layer structure having high hardness and superhydrophobic capability, and a corresponding diamond-like composite layer structure having high hardness and superhydrophobic capability.

Referring to fig. 1, in one aspect, an embodiment of the present invention provides a diamond-like composite layer structure including a substrate 10, a transition layer 20 disposed on a surface of the substrate 10, a diamond-like layer 30 disposed on a surface of the transition layer 20 facing away from the substrate 10, wherein,

the transition layer 20 protrudes on one side facing away from the substrate 10 to form a micro-nano array structure, and the surface of the diamond-like layer 30 facing away from the substrate 10 is a micro-nano array surface.

The diamond-like composite layer structure comprises a three-layer structure, specifically comprising a substrate 10, a diamond-like layer 30, and a transition layer 20 disposed between the substrate 10 and the diamond-like layer 30. The layers are described in detail below.

Substrate 10

In the embodiment of the present invention, the substrate 10 is used as a bearing layer of a diamond-like composite layer structure, and a material having a certain hardness may be selected theoretically. Considering that the micro-nano array structure of the transition layer 20 is preferably formed by etching, the substrate 10 material is preferably a substance with higher stability. The high stability means that the high-stability etching liquid has high stability in conventional acidic etching liquid or alkaline etching liquid and cannot be etched by acid or alkali.

In an embodiment of the present invention, at least one surface of the substrate 10 is a flat surface so as to form a structured transition layer 20 and a diamond-like layer 30 on the surface thereof. In some embodiments, the substrate 10 is selected from one of a carbon steel substrate 10, a stainless steel substrate 10, a Gao Sugang substrate 10, a cemented carbide substrate 10, a ceramic substrate 10, but is not limited thereto. The carbon steel substrate 10, the stainless steel substrates 10 and Gao Sugang substrates 10, the hard alloy substrate 10 and the ceramic substrate 10 not only have better hardness, but also have better stability, and can be suitable for preparing the transition layer 20 and the diamond-like carbon layer 30 under various conditions. Specifically, the type of the substrate 10 may be adjusted according to the actual preparation conditions of the transition layer 20 and the diamond-like layer 30, such as the type of etching solution, and the like.

The thickness of the substrate 10 is 0.5 to 26 micrometers, and in particular, may be adjusted according to the thicknesses of the transition layer 20 and the diamond-like layer 30. When the transition layer 20 and the diamond-like layer 30 to be deposited are thin, the thickness of the substrate 10 is relatively thin; when the transition layer 20 and the diamond-like layer 30 to be deposited are thicker, the thickness of the substrate 10 is relatively thicker. The thickness of the diamond-like composite layer structure is 1.5-30 microns, and the diamond-like composite layer structure has good universal adaptability.

Transition layer 20

In an embodiment of the present invention, the transition layer 20 is bonded to the substrate 10 while being bonded to the diamond-like layer 30. In one aspect, the transition layer 20 is disposed between the substrate 10 and the diamond-like layer 30, and forms a material transition between the substrate 10 and the diamond-like layer 30, improving the bonding ability of the diamond-like layer 30 on the substrate 10, and preventing the diamond-like layer 30 from falling off when directly deposited on the substrate 10. On the other hand, since the diamond-like layer 30 itself is difficult to form a micro-nano structure by etching, a structural basis can be provided for the formation of the micro-nano array surface of the diamond-like layer 30 by structural modification of the transition layer 20.

In the embodiment of the invention, the transition layer 20 protrudes on one side away from the substrate 10 to form a micro-nano array structure, so that the arrangement form is flexible, and the requirement that a structural basis can be provided for forming the micro-nano array surface for the diamond-like layer 30 is only met.

In some embodiments, the transition layer 20 between the substrate 10 and the diamond-like layer 30 may be a structural layer that completely covers the surface of the substrate 10 and that protrudes to form a micro-nano array at a portion of the surface facing away from the substrate. At this time, since the transition layer 20 completely covers the substrate 10, the direct contact of the diamond-like layer 30 and the substrate 10 is isolated, and thus, the bonding of the diamond layer on the substrate 10 is more firm.

In some embodiments, the transition layer 20 between the substrate 10 and the diamond-like layer 30 is formed by the micro-nano array structure itself formed on the surface of the substrate 10, and micro-nano structure units forming the micro-nano array structure are not completely in contact with each other, but may be even regularly arranged without contacting each other. Accordingly, the diamond-like layer 30 fills the gaps between the micro-nano structural units between the transition layers 20, achieving contact with the substrate in a partial region. Of course, as a preferred embodiment, in the micro-nano array structure in the transition layer 20, the micro-nano structural units are regularly arranged and are not contacted with each other, so that the obtained micro-nano array surface can be ensured to have good regularity and uniformity when the diamond-like layer 30 is formed later.

In the micro-nano array structure of the transition layer 20, the shape of the micro-nano unit is not strictly limited, and may be cone, semicircle, column, cylinder, but is not limited thereto.

The thickness of the transition layer 20 is 0.5 to 2 microns. This thickness range is not only sufficient to enhance the adhesion of the diamond-like layer 30 to the substrate 10, but also does not significantly affect the overall hardness of the diamond-like composite layer structure. Furthermore, more importantly, the micro-nano array structure formed in the thickness range can endow the diamond-like layer 30 with excellent super-hydrophobic performance after being replicated by the diamond-like layer 30.

In some embodiments, the height of the micro-nano array structure in the transition layer 20 is 0.5 to 2 microns, and the pitch of adjacent micro-nano cells in the micro-nano array structure is 0.1 to 2 microns. At this time, the micro-nano array structure in the transition layer 20 is replicated by the diamond-like layer 30 as the structural basis of the diamond-like layer 30, and the formed diamond-like layer 30 also has the structural characteristics of "the height of the micro-nano array is 0.5 micrometers to 2 micrometers, and the pitch of the adjacent micro-nano units in the micro-nano array is 0.1 micrometers to 2 micrometers", so that excellent super-hydrophobic performance is imparted to the diamond-like layer 30, thereby providing a material having excellent hardness and super-hydrophobic performance.

In a preferred embodiment, in the micro-nano array structure, the ratio of the height of the micro-nano unit to the pitch of the adjacent micro-nano unit is 1: (0.5-1.5), at this time, the micro-nano array structure in the transition layer 20 is taken as a structural basis of the diamond-like layer 30, and is replicated by the diamond-like layer 30, so that the formed diamond-like layer 30 has more excellent super-hydrophobic performance, the contact angle is between 154.2 degrees and 155 degrees, and the material selection of the transition layer 20 is required to satisfy the whole requirement: the bonding force of the transition layer 20 to the substrate 10 and the bonding force of the transition layer 20 to the diamond-like layer 30 are all greater than the bonding force of the substrate 10 to the diamond-like layer 30. However, the material type of the transition layer 20 is not limited, and may be selected from a metal layer or a non-metal layer.

In some embodiments, the transition layer 20 is a metal layer, and the metal layer is one of an iron layer, an aluminum layer, a copper layer, a silver layer, a tin layer, a titanium layer, a gold layer, a platinum layer, a tantalum layer, a tungsten layer, a vanadium layer, a niobium layer, a cobalt layer, a nickel layer, and a germanium layer, but is not limited thereto. The preferred metal layer has better binding force with the substrate 10 and the diamond-like layer 30, so that the adhesion of the diamond-like layer 30 on the substrate 10 can be improved, and the stability of the composite structure layer can be improved.

In some embodiments, the transition layer 20 is a non-metallic layer, and the non-metallic layer is one of a carbon layer, a silicon layer, a sulfur layer, a selenium layer, a tellurium layer, an organic polymer layer, but is not limited thereto. The preferred metal layer has better binding force with the substrate 10 and the diamond-like layer 30, so that the adhesion of the diamond-like layer 30 on the substrate 10 can be improved, and the stability of the composite structure layer can be improved. Specifically, the organic polymer may be selected from polytetrafluoroethylene, polyethylene, polystyrene, polyvinyl chloride, polyethylene terephthalate, polyacrylonitrile, natural rubber, styrene-butadiene rubber, polyurethane, but is not limited thereto, preferably polytetrafluoroethylene, which has stable chemical properties, is not easily damaged by oxidation, and has simple synthesis process and low cost.

Diamond-like layer 30

In the embodiment of the invention, the diamond-like layer 30 is disposed on the surface of the transition layer 20 facing away from the substrate 10, and the surface of the diamond-like layer 30 facing away from the substrate 10 is a micro-nano array surface, so as to provide the diamond-like layer 30 with excellent super-hydrophobic performance.

The diamond-like layer 30 has a thickness of 0.5 to 2 microns, which has a good general adaptability and substantially meets the industry requirements for diamond-like coatings, and in addition, can be prepared by deposition, thereby ensuring that the resulting diamond-like coating has a good quality.

In some embodiments, the micro-nano array has a height of 0.5 to 2 microns in the micro-nano array surface of the diamond-like layer 30 and a pitch of adjacent micro-nano cells in the micro-nano array of 0.1 to 2 microns. At this time, the diamond-like layer 30 has a good surface structure, thereby having excellent superhydrophobic performance.

In a preferred embodiment, in the micro-nano array structure of the diamond-like layer 30, the ratio of the height of micro-nano cells to the pitch of adjacent micro-nano cells is 1: (0.5-1.5), the diamond-like layer 30 has more excellent super-hydrophobic performance, and the contact angle is between 154.2 DEG and 155 deg.

As a most preferred embodiment, the diamond-like composite layer structure is composed of a substrate 10, a transition layer 20 and a diamond-like layer 30, the transition layer 20 is disposed on the surface of the substrate 10, the diamond-like layer 30 is disposed on the surface of the transition layer 20 facing away from the substrate 10, wherein the transition layer 20 protrudes on the side facing away from the substrate 10 to form a micro-nano array structure, and the surface of the diamond-like layer 30 facing away from the substrate 10 is a micro-nano array surface.

In the diamond-like composite layer structure provided by the embodiment of the invention, the transition layer 20 with the micro-nano array structure is arranged on the surface of the substrate, and further, the diamond-like layer 30 with the micro-nano array surface is formed on the surface of the transition layer 20. The diamond-like composite layer structure obtained by the method takes diamond-like carbon as a material basis, so that the diamond-like carbon composite layer structure has the advantage of high hardness. Meanwhile, since the diamond-like layer 30 has a micro-nano array surface, thereby imparting excellent hydrophobic property to the diamond-like composite layer structure, it is shown through contact angle experiments that the contact angle (diamond-like layer 30 surface) of the diamond-like composite layer structure is 153 ° to 155 °. In conclusion, the diamond-like composite layer structure not only has high hardness, but also has excellent hydrophobic property, and can be used as an impregnating material with high requirements on hardness and hydrophobic property, so that the industrial application prospect of diamond-like carbon is expanded.

The diamond-like composite layer structure provided by the embodiment of the invention can be prepared by the following method.

Another aspect of the embodiment of the present invention provides a method for preparing a diamond-like composite layer structure, including the steps of:

s01, providing a substrate, and sequentially carrying out pretreatment, glow cleaning and ion etching cleaning on the substrate;

s02, placing the cleaned substrate in a deposition chamber, introducing argon, adjusting the pressure of the vacuum chamber to be 0.2-1.3 Pa, starting a first target and a second target, controlling the target power of the first target to be 30-70W, controlling the target power of the second target to be 30-70W, and depositing a prefabricated transition layer under the condition that the bias voltage of the substrate is 100-300V;

s03, taking out the sample deposited with the prefabricated transition layer, placing the sample in a container containing etching liquid, performing ultrasonic treatment, and performing etching treatment on the prefabricated transition layer to form a transition layer with a micro-nano structure array on the surface, thereby obtaining an etched sample;

s04, placing the etched sample in a deposition chamber after surface cleaning treatment, and depositing a diamond-like carbon layer on the surface of the transition layer of the etched sample;

According to the preparation method of the diamond-like composite layer structure, the diamond-like superhydrophobic composite layer is prepared through a deposition etching process by adopting a mode of combining an ion source and arc ion plating. On one hand, the method can realize the firm combination of the diamond-like carbon layer on the substrate by preparing the transition layer, improve the adhesive force of the diamond-like carbon layer on the substrate and prevent the peeling of the diamond-like carbon layer; and on the other hand, etching the transition layer to form a micro-nano array structure, providing a structural foundation for the deposition of diamond-like carbon, and finally obtaining the diamond-like carbon layer with the micro-nano array on the surface, thereby realizing the super-hydrophobic function of the diamond-like carbon layer.

Specifically, in the step S01, the substrate is selected as described above, and in a specific embodiment, the substrate may be selected from one of a carbon steel substrate, a stainless steel substrate, a Gao Sugang substrate, a cemented carbide substrate, and a ceramic substrate.

Sequentially carrying out pretreatment, glow cleaning and ion etching cleaning on the provided substrate, and removing organic matters, particularly oil stains, on the surface of the substrate through pretreatment; the uneven parts of the surface of the substrate such as residual moisture, gas and the like in scratches are removed by glow cleaning and ion etching cleaning, so that the adhesion effect of the coating is improved. The optimal cleaning effect is achieved through gradual cleaning, and the coating has the best binding force on the cleaned substrate.

In some embodiments, the method of pre-treating the substrate is: sequentially using distilled water, acetone and absolute ethyl alcohol to ultrasonically clean the substrate, fully removing organic matters, particularly oil stains, on the surface of the substrate, and then drying and baking.

In a specific embodiment, the substrate is placed in distilled water for ultrasonic cleaning for 5-30 min, then placed in acetone solution for ultrasonic cleaning for 5-30 min, and then placed in absolute ethanol solution for ultrasonic cleaning for 5-30 min; and after the cleaning is finished, drying the surface of the substrate by using dry nitrogen, and finally, putting the sample into a blast drying box for drying at 80-150 ℃.

And after the substrate is pretreated, further carrying out glow cleaning. In some embodiments, the substrate is glow cleaned with pure argon.

Before glow cleaning, adjusting equipment parameters, and specifically, fixing the dried substrate on a rotating frame in ion source coating equipment; closing a vacuum chamber door, opening a water cooling machine to connect the waterways of an ion source, a multi-arc target, a molecular pump and a vacuum chamber, opening an air compressor and a total power supply of the composite coating machine, and then opening a mechanical pump, a side pumping valve and the molecular pump to enable the molecular pump to enter a climbing state; after the molecular pump reaches full speed, closing the side pumping valve, opening the rough pumping valve, and performing rough pumping on the vacuum chamber; when the pressure in the vacuum chamber reaches below 10Pa, opening againA side-pumping valve; and when the pressure of the vacuum chamber reaches below 3Pa, closing the rough pumping valve, and opening the high valve to pump high vacuum to the vacuum chamber. When the vacuum chamber pressure is pumped to 5.0X10 ^-3 After Pa, a heating power supply is turned on to heat and bake the vacuum chamber, the heating temperature is 100-500 ℃, and a rotating frame system is turned on in the heating process to make the sample pass through automatically; when the vacuum degree reaches 3.0X10 ^-3 At Pa, glow cleaning was started.

In a specific embodiment, the glow cleaning method comprises the following steps: after the glow cleaning is finished, opening a main valve, a pressure reducing valve, an ion source valve, an arc valve, a target valve and a mass flowmeter of an argon bottle, introducing argon into a vacuum chamber, controlling the flow of the argon to be 300-500 sccm, controlling the working pressure to be 1.0-1.7 Pa, and carrying out glow cleaning on a substrate under the condition that the substrate is biased to-500 to-800V for 10-30 min. The glow cleaning is carried out under the conditions, so that moisture and gas which are reserved on the uneven surface of the substrate, particularly in scratches, can be rapidly removed, the phenomenon that the film layer has insufficient adhesive force when a prefabricated transition layer is deposited by combining an ion source and arc ion plating in the follow-up process is prevented, and the bonding force of the film layer on the substrate is improved.

In order to further ensure that the moisture and gas in the uneven surface of the substrate, particularly the scratch, are sufficiently removed, after the glow cleaning is finished, the substrate is subjected to ion etching cleaning, and the moisture and gas in the uneven surface of the substrate, particularly the scratch, are completely removed in a relatively soft mode.

In some embodiments, the ion etching cleaning method comprises the following steps: after etching cleaning is finished, an ion source is started to carry out ion bombardment cleaning on the sample, wherein the voltage of the ion source is 50-90V, the flow rate of argon is 70-500 sccm, the working pressure is 0.5-1.7 Pa, and the substrate bias voltage is 100-800V. Under the above conditions, moisture and gas which are not removed during the glow cleaning process can be completely removed. Preferably, the ion bombardment cleaning is carried out for 10-30 min.

According to the embodiment of the invention, the substrate is subjected to pretreatment, glow cleaning and ion etching cleaning in sequence, so that various attachments on the surface of the substrate can be removed step by step with different forces, and the adhesive force of the coating on the surface of the substrate is improved; meanwhile, the method for cleaning the surface of the substrate has good timeliness.

In the step S02, a method of combining an ion source and arc ion plating is adopted to deposit a prefabricated transition layer on the surface of the substrate, and the combination of two plating modes is adopted to improve the bonding force and surface regularity of the plating layer. In the embodiment of the invention, the prefabricated transition layer is used as a material base of the transition layer in the diamond-like composite layer structure, and the transition layer of the diamond-like composite layer structure is finally formed after the following steps of etching treatment.

In the embodiment of the invention, the cleaned substrate is placed in a deposition chamber of ion source coating equipment. The ion source coating equipment is shown in figure 2. Argon is introduced into the deposition chamber, the pressure of the vacuum chamber is regulated to be 0.2-1.3 Pa, the first target material and the second target material are started, the target power of the first target material is controlled to be 30-70W, the target power of the second target material is controlled to be 30-70W, and a prefabricated transition layer is deposited under the condition that the substrate bias voltage is 100-300V.

In the step of preparing the prefabricated transition layer, the vacuum chamber pressure, the target power of the first target material, the target power of the second target material and the substrate bias voltage jointly determine the quality of the prefabricated transition layer. If any one of the vacuum chamber pressure, the target power and the substrate bias voltage is smaller, the deposition rate is too slow, and the deposition time is too long; if any one of the vacuum chamber pressure, the target power and the substrate bias voltage is too high, the deposition speed is too high, crystal grains formed when the two targets are subjected to mixed plating are too large, and the arrangement is irregular, so that the binding force of the prefabricated transition layer on the substrate can be reduced. And the vacuum chamber pressure, the target power of the first target, the target power of the second target and the substrate bias voltage are correlated, and the deposition effect can be changed due to the variation of any parameter. According to the method for prefabricating the transition layer, the vacuum chamber pressure, the target power of the first target material, the target power of the second target material and the substrate bias voltage are in the ranges, so that the grain size of the obtained prefabricated transition layer is proper, and the binding force of the prefabricated transition layer on the surface of the substrate is enhanced.

Further preferably, the argon gas flow is 50-400 sccm to provide a suitable vacuum chamber pressure.

In the step of preparing the prefabricated transition layer, in order to form the transition layer with the micro-nano structure array on the surface, the prefabricated transition layer is prepared by adopting double targets. The double targets are taken as the material basis of the prefabricated transition layer together, the prefabricated transition layer is formed by uniformly depositing through mixed plating, and the first target is taken as the sacrificial material, and is removed through etching of etching liquid in the following steps, and finally, the prefabricated transition layer becomes the transition layer with the micro-nano structure array.

This means that the material selection of the first target and the second target in the embodiment of the present invention is closely related to the type of etchant in the following steps, besides the requirement that the second target needs to meet the material requirement of the transition layer in the diamond-like composite layer structure. Specifically, the first target and the second target are independently selected from metal or nonmetal materials, the first target is selected from targets which are soluble in the etching liquid, and the second target is selected from targets which are insoluble in the etching liquid. It is also understood that the first target is selected from a metal or non-metal material target, the second target is selected from a metal or non-metal material target, and the etching solution is an etching solution capable of dissolving the first target but incapable of dissolving the second target.

In some embodiments, the first target and the second target are selected from metal materials including iron, aluminum, copper, silver, tin, titanium, germanium, gold, platinum, tantalum, tungsten, vanadium, niobium, cobalt, nickel, and combinations thereof.

In some embodiments, the first target, the second target are selected from non-metallic materials, and the non-metallic materials include carbon, silicon, sulfur, selenium, tellurium, organic polymers.

In some embodiments, the first target is selected from a metallic material and the second target is selected from a non-metallic material, wherein the metallic material is selected from iron, aluminum, copper, silver, tin, titanium, germanium, gold, platinum, tantalum, tungsten, vanadium, niobium, cobalt, nickel, and the non-metallic material is selected from carbon, silicon, sulfur, selenium, tellurium, an organic polymer.

In some embodiments, the first target is selected from a non-metallic material and the second target is selected from a metallic material, wherein the metallic material is selected from iron, aluminum, copper, silver, tin, titanium, germanium, gold, platinum, tantalum, tungsten, vanadium, niobium, cobalt, nickel, and the non-metallic material is selected from carbon, silicon, organic polymers.

It will be appreciated that the second target may be selected from any of the above listed materials, i.e., the transition layer is selected from a metal layer or a non-metal layer, where the metal layer is one of an iron layer, an aluminum layer, a copper layer, a silver layer, a tin layer, a titanium layer, a gold layer, a platinum layer, a tantalum layer, a tungsten layer, a vanadium layer, a niobium layer, a cobalt layer, a nickel layer, and a germanium layer, and the non-metal layer is one of a carbon layer, a silicon layer, a sulfur layer, a selenium layer, a tellurium layer, and an organic polymer layer.

The advantages of the preferred targets described above are as described above and are not described in detail herein. Among them, the organic polymer may be selected from polytetrafluoroethylene, polyethylene, polystyrene, polyvinyl chloride, polyethylene terephthalate, polyacrylonitrile, natural rubber, styrene-butadiene rubber, polyurethane, but is not limited thereto, and polytetrafluoroethylene is preferable.

Further, after the deposition is finished, the ion source power supply and the bias power supply are turned off, and then the gas mass flowmeter, the gas bottle main valve and the pressure reducing valve are turned off; setting a cooling program, closing the high valve after the temperature is reduced to below 100 ℃, opening the air release valve, and opening the vacuum chamber door when the pressure in the vacuum chamber is consistent with the external air pressure.

In the step S03, the sample deposited with the prefabricated transition layer is taken out, placed in a container containing etching liquid, subjected to ultrasonic treatment, and subjected to etching treatment. The etching solution is selected to be capable of dissolving the first target but incapable of dissolving the second target, and other requirements are not met.

In some embodiments, the etching solution is selected from an acidic solution, and the acidic solution is selected from at least one of nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, and an organic acid. At this time, the first target corresponds to a target that can be dissolved by the acidic solution, and the second target corresponds to a target that is not affected by the acidic etching solution, i.e., is not affected by the acidic solution.

In some embodiments, the etching solution is selected from an alkaline solution, and the alkaline solution is selected from at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, an organic base. At this time, the first target corresponds to a target that can be dissolved by the alkaline solution, and the second target corresponds to a target that is not affected by the acidic etching solution, i.e., is not affected by the alkaline solution.

After etching treatment, the prefabricated transition layer forms a transition layer with a micro-nano structure array on the surface. According to the embodiment of the invention, the fine structure of the micro-nano array can be further controlled by adjusting etching conditions such as temperature, etching liquid concentration and the like. Preferably, in the transition layer, the height of the micro-nano array structure is 0.5-2 microns, and the distance between adjacent micro-nano units in the micro-nano array structure is 0.1-2 microns.

In the above step S04, the etched sample is subjected to a surface cleaning process, which may be performed by the pretreatment and glow cleaning process described above. Further, it is preferable to use ion etching cleaning after glow cleaning.

And placing the cleaned etching sample in a deposition chamber, and depositing a diamond-like carbon layer on the surface of the transition layer of the etching sample to form the surface with the same structure as the transition layer. Preferably, in the step of depositing the diamond-like layer on the surface of the transition layer of the etching sample, the etching sample is placed in a deposition chamber after being subjected to surface cleaning treatment, acetylene is used as working gas, the pressure in the vacuum chamber is regulated to be 0.5-1.0 Pa, the ion source voltage is 50-100V, the substrate bias voltage is 50-200V, and the diamond-like layer is deposited on the surface of the transition layer of the etching sample.

In the step of preparing the diamond-like layer, the vacuum chamber pressure, ion source voltage and substrate bias voltage together determine the quality of the diamond-like layer. If any one of the vacuum chamber pressure, the ion source voltage and the substrate bias voltage is smaller, the deposition rate is too slow, and the deposition time is too long; if any one of the vacuum chamber pressure, the ion source voltage and the substrate bias voltage is too high, the deposition speed is too high, and the formed crystal grains are not regularly arranged, so that the bonding force of the diamond-like carbon layer on the transition layer is reduced. And the vacuum chamber pressure, the ion source voltage and the substrate bias voltage are related to each other, and the deposition effect can be changed due to the variation of any parameter. The parameter conditions of the transition layer provided by the embodiment of the invention can enhance the bonding force of the obtained diamond-like carbon layer, and the formed coating is compact and uniform.

After the coating deposition is finished, the ion source power supply and the bias power supply are turned off, and then the gas mass flowmeter, the gas bottle main valve and the pressure reducing valve are turned off; setting a cooling program, closing the high valve after the temperature is reduced to below 100 ℃, opening the air release valve, opening the vacuum chamber door when the pressure in the vacuum chamber is consistent with the external air pressure, and taking out the sample.

Preferably, in the micro-nano array surface of the diamond-like carbon layer, the height of the micro-nano array is 0.5-2 microns, and the distance between adjacent micro-nano units in the micro-nano array is 0.1-2 microns, so that the diamond-like carbon layer has better super-hydrophobic performance.

The following description is made with reference to specific embodiments.

Example 1

The preparation method of the diamond-like composite layer structure comprises the following steps:

s11, providing a substrate, and sequentially carrying out pretreatment, glow cleaning and ion etching cleaning on the substrate; specific:

placing the substrate into distilled water for ultrasonic cleaning for 5-30 min, placing the substrate into acetone solution for ultrasonic cleaning for 5-30 min, and placing the substrate into absolute ethanol solution for ultrasonic cleaning for 5-30 min; and after the cleaning is finished, drying the surface of the substrate by using dry nitrogen, and finally, putting the sample into a blast drying box for drying at 80-150 ℃. Before glow cleaning, the parameters of the equipment are adjusted, in particular, the equipment is driedThe substrate is fixed on a rotating frame in ion source coating equipment; closing a vacuum chamber door, opening a water cooling machine to connect the waterways of an ion source, a multi-arc target, a molecular pump and a vacuum chamber, opening an air compressor and a total power supply of the composite coating machine, and then opening a mechanical pump, a side pumping valve and the molecular pump to enable the molecular pump to enter a climbing state; after the molecular pump reaches full speed, closing the side pumping valve, opening the rough pumping valve, and performing rough pumping on the vacuum chamber; when the pressure in the vacuum chamber reaches below 10Pa, the side pumping valve is opened again; and when the pressure of the vacuum chamber reaches below 3Pa, closing the rough pumping valve, and opening the high valve to pump high vacuum to the vacuum chamber. When the vacuum chamber pressure is pumped to 5.0X10 ^-3 After Pa, a heating power supply is turned on to heat and bake the vacuum chamber, the heating temperature is 100-500 ℃, and a rotating frame system is turned on in the heating process to make the sample pass through automatically; when the vacuum degree reaches 3.0X10 ^-3 At Pa, glow cleaning was started.

Opening a main valve, a pressure reducing valve, an ion source valve, an arc valve, a target valve and a mass flowmeter of an argon bottle, introducing argon into a vacuum chamber, controlling the flow of the argon to be 300-500 sccm, the working pressure to be 1.0-1.7 Pa, and biasing a substrate to be-500 to-800V, and cleaning the substrate in a glow way for 10-30 min.

After the glow cleaning is finished, an ion source is started to carry out ion bombardment cleaning on the sample, wherein the voltage of the ion source is 50-90V, the flow rate of argon is 70-500 sccm, the working pressure is 0.5-1.7 Pa, the substrate bias voltage is 100-800V, and the cleaning time of the ion bombardment cleaning is 10-30 min.

S12, placing the cleaned substrate in a deposition chamber, introducing argon, controlling the flow to be 50-400 sccm, adjusting the pressure of the vacuum chamber to be 0.2-1.3 Pa, starting a first target (copper target) and a second target (aluminum target), controlling the target power of the first target to be 30-70W, controlling the target power of the second target to be 30-70W, and depositing a prefabricated transition layer under the condition that the bias voltage of the substrate is 100-300V.

S13, taking out the sample deposited with the prefabricated transition layer, placing the sample in a container containing etching liquid (sodium hydroxide solution), performing ultrasonic treatment, and performing etching treatment on the prefabricated transition layer to form a transition layer with a micro-nano structure array on the surface, thereby obtaining an etched sample.

S14, placing the etched sample in a deposition chamber after surface cleaning treatment, taking acetylene as working gas, adjusting the pressure in the vacuum chamber to be 0.5-1.0 Pa, the ion source voltage to be 50-100V, and the substrate bias voltage to be 50-200V, and depositing a diamond-like carbon layer on the surface of the transition layer of the etched sample.

Example 2

The method for preparing the diamond-like composite layer structure is different from example 1 in that: the first target material is a metal copper target, the second target material is a metal aluminum target, and the etching solution is potassium hydroxide solution.

Example 3

The method for preparing the diamond-like composite layer structure is different from example 1 in that: the first target material is a metal copper target, the second target material is a metal aluminum target, and the etching solution is hydrochloric acid solution.

Example 4

The method for preparing the diamond-like composite layer structure is different from example 1 in that: the first target material is a metal copper target, the second target material is a metal aluminum target, and the etching solution is sulfuric acid solution.

Example 5

The method for preparing the diamond-like composite layer structure is different from example 1 in that: the first target material is a metal aluminum target, the second target material is a non-metal carbon target, and the etching solution is hydrochloric acid solution.

Example 6

The method for preparing the diamond-like composite layer structure is different from example 1 in that: the first target material is a metal aluminum target, the second target material is a non-metal carbon target, and the etching solution is sodium hydroxide solution.

Example 7

The method for preparing the diamond-like composite layer structure is different from example 1 in that: the first target material is a metal aluminum target, the second target material is a non-metal carbon target, and the etching solution is potassium hydroxide solution.

Example 8

The method for preparing the diamond-like composite layer structure is different from example 1 in that: the first target material is a metal aluminum target, the second target material is a nonmetal carbon target, and the etching solution is sulfuric acid solution.

Example 9

The method for preparing the diamond-like composite layer structure is different from example 1 in that: the first target material is a metal aluminum target, the second target material is a non-metal silicon target, and the etching solution is sodium hydroxide solution.

Example 10

The method for preparing the diamond-like composite layer structure is different from example 1 in that: the first target material is a metal aluminum target, the second target material is a non-metal silicon target, and the etching solution is potassium hydroxide solution.

Comparative example 1

The method for preparing the diamond-like composite layer structure is different from example 1 in that: after the step S11 is carried out, step S12 and step S13 are not carried out, the cleaned substrate is directly placed in a deposition chamber, acetylene is used as working gas, the pressure in the vacuum chamber is regulated to be 0.5-1.0 Pa, the ion source voltage is 50-100V, the substrate bias voltage is 50-200V, and a diamond-like carbon layer is deposited on the surface of the transition layer of the etched sample.

The diamond-like composite layer structures prepared in examples 1 to 10 and the diamond-like composite layer structure prepared in comparative example 1 were subjected to a water contact angle test experiment, and the test method was as follows:

the testing method comprises the following steps: appearance image analysis method.

The test results are shown in table 1 below, wherein graphs of the test results of example 1 and example 2 are shown in fig. 2 and 3.

TABLE 1 (contact angle test results for different conditions)

As can be seen from Table 1, the diamond-like composite layer structure with the surface micro-nano array structure prepared by the embodiment of the invention has excellent superhydrophobic performance.

The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.

Claims

1. The preparation method of the diamond-like composite layer structure is characterized by comprising the following steps of:

providing a substrate, and sequentially carrying out pretreatment, glow cleaning and ion etching cleaning on the substrate; the glow cleaning method comprises the following steps: opening a main valve, a pressure reducing valve, an ion source valve, an arc valve, a target valve and a mass flowmeter of an argon bottle, introducing argon into a vacuum chamber, controlling the flow of the argon to be 300-500 sccm, the working pressure to be 1.0-1.7 Pa, and the substrate bias to be-500 to-800V, and cleaning the substrate in a glow manner for 10-30 min;

wherein the first target and the second target are independently selected from metal or nonmetal materials, the first target is selected from targets which are soluble in the etching liquid, and the second target is selected from targets which are insoluble in the etching liquid.

2. The method of preparing a diamond-like composite layer structure according to claim 1, wherein the first target material and the second target material are selected from metal materials, and the metal materials include iron, aluminum, copper, silver, tin, titanium, and germanium; or (b)

The first target and the second target are selected from nonmetallic materials, and the nonmetallic materials comprise carbon, silicon and organic polymers.

3. The method of preparing a diamond-like composite layer structure according to claim 1, wherein the first target is selected from a metallic material, the second target is selected from a non-metallic material, or

The first target is selected from a nonmetallic material, the second target is selected from a metallic material,

4. A method of producing a diamond-like composite layer structure according to any one of claims 1 to 3, wherein the etching liquid is selected from an acidic solution, and the acidic solution is selected from at least one of nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, and an organic acid; or (b)

The etching liquid is selected from alkaline solution, and the alkaline solution is at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide and organic alkali.

5. The method for preparing a diamond-like composite layer structure according to any one of claims 1 to 3, wherein in the step of depositing a diamond-like layer on the surface of the transition layer of the etching sample, the etching sample is placed in a deposition chamber after being subjected to surface cleaning treatment, acetylene is used as a working gas, the pressure in the vacuum chamber is regulated to be 0.5-1.0 Pa, the ion source voltage is 50-100V, the substrate bias voltage is 50-200V, and the diamond-like layer is deposited on the surface of the transition layer of the etching sample.

6. A diamond-like composite layer structure prepared by the method according to any one of claims 1 to 5, wherein the diamond-like composite layer structure comprises a substrate, a transition layer disposed on a surface of the substrate, a diamond-like layer disposed on a surface of the transition layer facing away from the substrate,

The transition layer protrudes at one side away from the substrate to form a micro-nano array structure, and the surface of the diamond-like carbon layer away from the substrate is a micro-nano array surface;

in the micro-nano array structure of the diamond-like carbon layer, the ratio of the height of the micro-nano unit to the distance between adjacent micro-nano units is 1: (0.5 to 1.5).

7. The diamond-like composite layer structure of claim 6, wherein the height of the micro-nano array structure in the transition layer is 0.5-2 microns, and the spacing between adjacent micro-nano cells in the micro-nano array structure is 0.1-2 microns.

8. The diamond-like composite layer structure of claim 6, wherein the micro-nano array has a height of 0.5 to 2 microns in the micro-nano array surface of the diamond-like layer and a pitch between adjacent micro-nano cells in the micro-nano array of 0.1 to 2 microns.

9. The diamond-like composite layer structure according to any one of claims 6 to 8, wherein the transition layer is selected from a metallic layer or a non-metallic layer, wherein,

10. A diamond-like composite layer structure according to any one of claims 6 to 8, wherein the substrate is selected from one of a carbon steel substrate, a stainless steel substrate, a Gao Sugang substrate, a cemented carbide substrate, and a ceramic substrate.