CN113299534A - Coating device for plasma graft copolymerization film - Google Patents
Coating device for plasma graft copolymerization film Download PDFInfo
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- CN113299534A CN113299534A CN202110536954.4A CN202110536954A CN113299534A CN 113299534 A CN113299534 A CN 113299534A CN 202110536954 A CN202110536954 A CN 202110536954A CN 113299534 A CN113299534 A CN 113299534A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
- H01J37/32082—Radio frequency generated discharge
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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
- C23C16/44—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 method of coating
- C23C16/50—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 method of coating using electric discharges
- C23C16/505—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 method of coating using electric discharges using radio frequency discharges
- C23C16/509—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 method of coating using electric discharges using radio frequency discharges using internal electrodes
- C23C16/5096—Flat-bed apparatus
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/3244—Gas supply means
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/3244—Gas supply means
- H01J37/32449—Gas control, e.g. control of the gas flow
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
- H01J37/32—Gas-filled discharge tubes
- H01J37/32431—Constructional details of the reactor
- H01J37/32532—Electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
- H01J2237/32—Processing objects by plasma generation
- H01J2237/33—Processing objects by plasma generation characterised by the type of processing
- H01J2237/332—Coating
- H01J2237/3321—CVD [Chemical Vapor Deposition]
Abstract
The invention provides a film coating device of a plasma graft copolymerization film layer, which is provided with a radio frequency power supply, a reaction unit, an air extraction unit and an air distribution unit; the interior of the reaction unit is formed into a cavity for reaction; the radio frequency power supply is arranged outside the reaction unit and is communicated with the cavity of the reaction unit; the air extraction unit is arranged outside the reaction unit and is communicated with the cavity of the reaction unit; the gas distribution unit is arranged outside the reaction unit and is communicated with the cavity of the reaction unit through a supply pipeline; a slot antenna is arranged in the chamber of the reaction unit and close to the radio frequency power supply. According to the invention, high-density uniform surface wave plasma can be generated, and the graft copolymerization film layer is generated on the surface of the base material based on the surface wave plasma chemical vapor deposition mode, so that the uniformity of the film layer thickness of the product is greatly improved, the yield of batch processing products is improved, and the film forming characteristic is good especially for workpieces with complex curved surfaces.
Description
Technical Field
The invention relates to the technical field of plasma chemical engineering, in particular to a coating device for a plasma graft copolymerization film layer.
Background
The plasma is in a fourth state except solid, liquid and gas, and is in an electrically neutral macroscopic state. At present, the plasma chemical vapor deposition technology is a commonly used coating technology, and on substrates such as PCB circuit boards, electronic devices, mobile phones, keyboards, computers and the like, plasma is driven by an electric field to cause a chemical reaction of gaseous substances containing coating constituent atoms, so as to deposit a coating on the surface of the substrate, thereby endowing good physical and chemical durability and enhancing the strength of the surface of the substrate. Other various functional films can be deposited according to the needs, and the performances of hydrophobicity, scratch resistance, water resistance, abrasion resistance, corrosion resistance, heat dissipation and the like of the surface of the base material are improved.
The plasma can be divided into high-temperature plasma and low-temperature plasma according to temperature, and the low-temperature plasma is divided into hot plasma and cold plasma. Among them, the method of using various plasma sources to perform bulk chemical vapor deposition generates a graft copolymer film (thin film) on the surface of a substrate, especially a substrate with a complex structure and deep voids, by deposition to perform surface modification or protection, which is a very popular and important surface treatment method. For example, patent document 1 discloses an apparatus and method for a gate-controlled plasma-initiated gas-phase polymerization of surface coatings, and patent document 2 discloses a method for applying conformal nano-coatings by a low-pressure plasma process, each using pulse-modulated high-frequency glow discharge to generate plasma to prepare polymer coatings, and periodically switching off to excite the activity of monomer molecules when switched on and initiate polymerization when switched off.
However, due to the influence of the distribution characteristics of the plasma in the large-size space, the patent documents 1 and 2 cannot form large-area highly uniform plasma, so that the film is discontinuous, the thickness of each film is not uniform, the yield of the product is not high, and the large-scale application potential is limited.
Prior art documents:
patent documents:
patent document 1: chinese patent publication CN 105949836A;
patent document 2: chinese patent publication CN 102821873A.
Disclosure of Invention
The problems to be solved by the invention are as follows:
in view of the above problems, an object of the present invention is to provide a coating apparatus for a plasma graft copolymer film, which can solve the problem of low yield of processed products caused by uneven spatial distribution of the existing plasma apparatus.
The technical means for solving the problems are as follows:
the invention provides a film coating device of a plasma graft copolymerization film layer, which is provided with a radio frequency power supply, a reaction unit, an air extraction unit and an air distribution unit; wherein the reaction unit is internally formed into a chamber for reaction; the radio frequency power supply is arranged outside the reaction unit and is communicated with the cavity of the reaction unit so as to generate plasma; the air extraction unit is arranged outside the reaction unit, is communicated with the cavity of the reaction unit and is used for extracting gas in the reaction unit; the gas distribution unit is arranged outside the reaction unit, is communicated with the cavity of the reaction unit through a supply pipeline and is used for adding monomer steam serving as a gas source of the graft copolymerization film layer; and a slit antenna is arranged in the chamber of the reaction unit and close to the radio frequency power supply.
According to the invention, high-density uniform surface wave plasma can be generated, and the graft copolymerization film layer is generated on the surface of the base material based on the surface wave plasma chemical vapor deposition mode, so that the uniformity of the film layer thickness of the product is greatly improved, the yield of batch processing products is improved, and the film forming characteristic is good especially for workpieces with complex curved surfaces. Specifically, the interior of the reaction unit is vacuumized through an air extraction system, a workpiece to be processed as a base material is placed in the reaction chamber, a radio frequency power supply is started, after plasma is generated, monomer steam is supplied into the reaction chamber through an air distribution unit, and a fixed cross-linked structure is formed on the surface of the base material through graft copolymerization reaction initiated by plasma in the vacuum reaction chamber and in a surface wave plasma atmosphere.
More specifically, the invention utilizes the principle that external high-frequency electromagnetic waves can induce plasmon polaritons generated on the interface of a medium and plasma, the high-frequency electromagnetic waves are attenuated exponentially in the normal direction quickly to form electromagnetic surface waves propagating along the tangential direction, the physical process of the invention is that the electromagnetic waves are coupled into a vacuum reaction chamber through a slit antenna between the reaction chamber and a radio frequency power supply, gas discharge is firstly broken down under the slit antenna to form high-density plasma, and the high-density plasma is similar to a metal film at the moment, and the relative dielectric constant is negative. The high-frequency electromagnetic wave is reflected back to the critical density layer and propagates around the interface of the medium and the plasma, and the energy of the high-frequency electromagnetic wave is confined in the area near the interface, so that the surface wave is reflected back and forth in the reaction chamber, electrons are accelerated under the left and right electric fields of the surface wave to continuously provide energy for the plasma, and the large-area uniform high-density plasma can be generated.
In the present invention, the reaction unit may include: the radio frequency power supply comprises a reaction unit, an electrode plate, a planar quartz plate, a slit antenna and a reaction chamber, wherein the electrode plate is arranged in the reaction unit and connected with the radio frequency power supply, the planar quartz plate is arranged in the reaction unit in a mode of being close to the electrode plate, the slit antenna is arranged on the surface, facing the radio frequency power supply, of the quartz plate, and the reaction chamber is surrounded by the quartz plate and the inner wall of the reaction unit.
In this way, the electrode plate is connected to a radio frequency power source for introducing electromagnetic waves, the quartz plate serves as a dielectric plate for propagating surface waves, and the energy of the electromagnetic waves is coupled into the reaction chamber located on one side of the quartz plate by a slit antenna attached to the other side of the quartz plate.
In the present invention, the plurality of slit antennas may be arranged in parallel on the quartz plate, and the excitation intensity may be changed by changing the size and the array distribution of the slit antennas. Therefore, the multiple slits arranged in parallel form an antenna array, which is beneficial to obtaining a stable radiation energy field, and the required amplitude distribution can be obtained by changing the size and the distribution, so that the generation density of the plasma can be accurately controlled.
In the present invention, the electrode plate may be a copper plate, the quartz plate may be a quartz glass plate or a quartz ceramic plate, and the slit antenna may be made of aluminum. The conductivity of the aluminum is 3.53 multiplied by 107S/m, which is convenient for coupling electromagnetic wave energy, and the aluminum has low price and low energy loss.
In the present invention, the electrode plate and the quartz plate may be fixed in the reaction cell by PTFE insulating workpieces, respectively. Thus, the fixing and the insulation of the chamber can be realized to avoid short circuit.
In the present invention, the gas distribution unit may include a monomer vapor line for supplying monomer vapor to the reaction chamber; one end of the monomer steam pipeline is connected with the monomer steam source, and the other end of the monomer steam pipeline is connected with the reaction unit.
In the present invention, two monomer vapor supply ports, which are respectively communicated with the monomer vapor pipeline, are provided on the reaction unit, and are symmetrically provided on both sides of the reaction unit. Therefore, the supply ports are arranged on two sides, so that the uniform diffusion of the gasified monomer steam is facilitated, a uniform film layer is formed, and the product yield is improved.
In the present invention, the gas distribution unit may further include a process gas line independent of the monomer vapor line; and one end of the process gas pipeline is connected with a process gas source, and the other end of the process gas pipeline is connected with the reaction unit and used for introducing process gas into the reaction chamber.
In the present invention, two process gas supply ports, which are respectively communicated with the process gas pipeline, are provided on the reaction unit, and are symmetrically provided on both sides of the reaction unit. Therefore, the supply ports are arranged on two sides, so that the process gas and the monomer steam are further favorably and uniformly diffused, a uniform film layer is formed, and the product yield is improved.
The invention has the following effects:
the invention can provide a film coating device of a plasma graft copolymerization film layer, greatly improve the uniformity of the thickness of the film layer of a product, improve the yield of batch processed products, and particularly have good film forming property for workpieces with complex curved surfaces.
Drawings
FIG. 1 is a schematic structural view of a coating apparatus according to an embodiment of the present invention;
FIG. 2 is a schematic structural view of a coating apparatus according to still another embodiment of the present invention;
FIG. 3 shows the test results of the finished plated product according to example 1 of the present invention, the upper graph shows the drip test results of the finished product, and the lower graph shows the static contact angle test results;
FIG. 4 shows the test results of the finished plated product according to example 2 of the present invention, the upper graph shows the drip test results of the finished product, and the lower graph shows the static contact angle test results;
description of the symbols:
D. d1-coating device;
1-a radio frequency power supply; 11-cable wires; 12-vacuum infeed;
2-a reaction unit; 21-a reaction chamber 21; 23-a slot antenna; 24-an electrode plate; 25-quartz plate; 26. 27-an insulating fixture;
3-an air extraction unit; 31-an air extraction pipeline; 32-suction on-off valve; 33-a pressure regulating valve; a vacuum pump 34;
4-a gas distribution unit; 41-monomer vapor line; 42-process gas line; 43-source of monomer vapor; 44-source of process gas.
Detailed Description
The present invention is further described below in conjunction with the following embodiments, which are to be understood as merely illustrative, and not restrictive, of the invention. The following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. The same or corresponding reference numerals denote the same components in the respective drawings, and redundant description is omitted.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", "front", "rear", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
Fig. 1 is a perspective view of a coating apparatus D according to an embodiment of the present invention, which discloses a coating apparatus D for a plasma graft copolymer film (hereinafter, simply referred to as a coating apparatus D) including an rf power supply 1, a reaction unit 2, an air-extracting unit 3, and an air-distributing unit 4. Wherein, a reaction chamber 21 is formed inside the reaction unit 2, the radio frequency power supply 1 is installed outside the reaction unit 2 and communicated with the reaction chamber for generating high frequency electromagnetic wave, the air extraction unit 3 is installed outside the reaction unit 2 and communicated with the reaction unit 2 for extracting gas in the reaction chamber 21, and the air distribution unit 4 is installed outside the reaction unit 2 and communicated with the reaction unit 2 through a supply pipeline for adding gas or steam required by the coating reaction. In some embodiments, the "monomer vapor" is a vapor formed by vaporizing "a chemical monomer for forming a graft copolymerization film layer".
The radio frequency power supply 1 is a high frequency power supply with high frequency alternating current variation electromagnetic wave variation more than 20000 times per second, the reaction unit 2 is formed into a hollow chamber, the top of the reaction unit is provided with a vacuum feed-in piece 12 which is electrically connected with the radio frequency power supply 1 through a cable 11, the other end of the vacuum feed-in piece 12 is connected with an electrode plate 24 arranged inside the reaction unit 2, and the high frequency electromagnetic wave is fed into the reaction unit 2 by virtue of the vacuum feed-in piece 12.
The reaction unit 2 and its internal chamber are preferably formed in a cube in the present embodiment, having six faces, front, rear, left, right, upper and lower, in the orientation shown in the figure, but may be formed in a cylindrical, rectangular, hexagonal or other special-shaped structure. The radio frequency power supply 1 is installed on the top of the reaction unit 2 through a cable 11, the air extraction unit 3 is installed on the other surfaces except the upper surface (top surface) in the reaction unit 2, and the air distribution unit 4 is installed on two opposite surfaces except the upper surface and the lower surface (top surface and bottom surface) in the reaction unit 2. In this embodiment, the rf power supply 1 is mounted on the top surface (upper surface), the air extraction unit 3 is mounted on the lower surface (bottom surface), and the air distribution unit 4 is mounted on the left and right side surfaces, that is, each unit is mounted on a non-repeating surface, and one of the remaining two surfaces is provided with an opening for picking and placing a substrate workpiece. However, for example, in the case of a special structure, the suction unit 3 is not necessarily attached to a surface not facing the radio frequency power source 1.
The reaction unit 2 includes an electrode plate 24, a quartz plate 25, a slit antenna 23, and a reaction chamber 21. The electrode plate 24 is fixed to the top end of the reaction unit 2 through an insulating fixing member 26, and is electrically connected to the rf power supply 1 through the vacuum feeding electrode 12 and the cable 11, and the size of the electrode plate can meet the discharge requirement of the rf power supply 1 without any limitation, for example, 30mm × 30 mm.
The quartz plate 25 is formed in a flat surface, is disposed in the reaction unit 2 below the electrode plate 24, and has a plurality of slit antennas 23 for generating surface wave plasma pressed on a surface facing the radio frequency power supply 1. The quartz plate 25 is closely pressed against the slot antenna 23 without a gap therebetween. In the present embodiment, the quartz plate 25 has a size substantially equal to the cross-sectional size of the internal chamber of the reaction unit 2, and both sides thereof are fixed to the inner side wall surface of the reaction unit 2 by means of another insulating fixing member 27. The reaction chamber 21 is a space surrounded by the other side surface of the quartz plate 25 where the slit antenna 23 is not installed and the inner wall of the reaction unit 2, in which a graft copolymerization reaction occurs.
The slit antennas 23 are arranged in parallel on the quartz plate 25, the radio frequency power supply 1 releases high frequency electromagnetic waves through the electrode plate 24, the high frequency electromagnetic waves generate a plasmon effect through the slit antennas 23 arranged in an array, surface waves are generated at the interface between the quartz plate 25 serving as a dielectric plate and plasma and propagate along the interface, and thus highly uniform plasma gas is maintained, at the time, monomer vapor is subjected to graft copolymerization in a plasma atmosphere and a predefined film layer is deposited and grown on a substrate to be coated which is placed in the reaction chamber 21 in advance. The deposition rate in unit time is calculated by controlling the use amount of monomer steam and the coating time, the film thickness is controlled, and finally a continuous and uniform film is formed. The excitation intensity can also be changed by changing the size and the array distribution of the slot antenna 23, so as to obtain a stable radiation energy field and a desired amplitude distribution, thereby accurately controlling the generation density of the plasma.
In the present embodiment, the electrode plate 24 is a copper plate, the quartz plate 25 is a quartz glass plate, and the insulating fixtures 26 and 27 are PTFE insulating workpieces, but the present invention is not limited thereto. The slot antenna 23 is preferably made of aluminum, which has a conductivity of 3.53 × 107S/m, facilitates coupling of electromagnetic wave energy, and is inexpensive compared to copper and has a low energy loss compared to stainless steel.
More specifically, in the present embodiment, the reaction cell 2 is provided with a ground line. The radio frequency power supply 1 can be an RF source with the frequency of 20 KHz-13.56 MHz and the power of 50W-5 KW, and the frequency of the microwave power supply is 915 MHz-2.45 GHz and the power of 50W-50 KW. The reaction unit 2 may be a cube having a length ranging from 200mm to 1500mm, a width ranging from 200mm to 1500mm, and a height ranging from 200mm to 1500 mm. The electrode plate 23 may be mounted, for example, at about 5-100mm from the top surface of the internal chamber. The width of the slot antenna 23 is, for example, 0.5-2 mm, the thickness is, for example, 3mm-5mm, the length is, for example, 5 mm-15 mm, the number of the slot antennas 23 distributed equidistantly on the quartz plate 25 is, for example, 25-50, and the arrangement thereof can be adjusted accordingly to adapt to a stable radiation energy field, for example, according to actual conditions.
As shown in fig. 1, the pumping unit 3 is connected to the reaction chamber 21 of the reaction unit 2 through a pumping line 31, and the pumping line 31 is provided with a pumping switch valve 32, a pressure regulating valve 33 and a vacuum gauge for controlling the vacuum degree of the reaction chamber 21 to be in a suitable process condition. Specifically, when the sensor detects that the degree of vacuum of the reaction chamber 21 of the reaction unit 2 satisfies a predetermined requirement, the pressure regulating valve 33 performs real-time dynamic control according to a feedback value of the vacuum gauge. In the present embodiment, the air-extracting unit 3 further includes a vacuum pump 34, and other types of pressure control units may be used. More specifically, in the present embodiment, the pumping unit 3 pumps the reaction unit 2 to a predetermined operating pressure of 0.01 to 0.5mbar, and maintains the vacuum pressure of 0.01 to 0.35mbar when supplying gas into the reaction chamber 21 at a later stage.
The gas distribution unit 4 is provided with an independent monomer steam pipeline 41, one end of the monomer steam pipeline 41 is connected with a monomer steam source 43, the other end of the monomer steam pipeline is communicated with the reaction chamber 21 of the reaction unit 2, the monomer steam enters the reaction chamber 21 of the reaction unit 2 from the monomer steam source 43 through the monomer steam pipeline 41 to participate in reaction, and unreacted substances and auxiliary reaction products are pumped out and discharged through the air pumping unit 3 at the lower part of the reaction chamber 21. The port at which the monomer vapor line 41 is connected to the reaction unit 2 is a monomer vapor supply port 45 for supplying monomer vapor, and two monomer vapor supply ports 45 are symmetrically formed at both sides of the reaction unit 2. The pipeline and the port are connected with the reaction unit 2 through a flange and a rubber ring, so that the vacuum sealing performance is ensured.
Further, the monomer steam source 43 is connected to the monomer steam pipeline 41 through a monomer steam branch pipeline 411, and a monomer steam mass flow meter 51 is arranged on the monomer steam branch pipeline 411 to control the output flow of the monomer steam source 43. The monomer steam branch pipe 411 and the monomer steam pipe 41 form a junction, the monomer steam output from the monomer steam source 43 is divided into two streams at the junction, and then the two streams enter the reaction chamber 21 through the monomer steam pipe 41, so that the uniform diffusion of the gasified monomer steam is facilitated, a uniform film layer is formed, and the product yield is improved. Feed valves 52, 52 are provided on the monomer vapor line 41 on both sides of the junction, respectively, for more precisely controlling the feed amount of the monomer vapor as a source gas for the graft copolymerization membrane layer.
In this embodiment, the monomer vapor is a monomer vapor capable of forming a functional coating film. For example, the monomer vapor can be a monomer vapor that enhances one or more of the hydrophobic, hydrophilic, scratch resistant, abrasion resistant, corrosion resistant, heat dissipating, etc., properties of the substrate surface. As described above, in some embodiments, the "monomer vapor" is a vapor generated by vaporizing the "chemical monomer for forming the graft copolymerization film layer". The chemical monomers include, but are not limited to, silane-based monomers, acrylate-based unsaturated monomers, and the like. The silane monomer can be hexamethyldisiloxane and/or triethoxysilane. The monomer vapor source 44 is specifically a chemical monomer evaporation device, and the flow meter 53 is, for example, a thermal mass flow meter, and can control the flow rate more precisely.
According to the coating apparatus D1 of the present invention, the supply amounts of the ports on both sides can be adjusted, and the flow rate of the monomer vapor supplied from the supply ports can be adjusted in real time according to the specific reaction conditions, so that the uniformity of the plasma graft copolymer film layer prepared on the surface of the substrate can be greatly improved in the surface wave plasma atmosphere. Specifically, a substrate workpiece to be coated is placed in a reaction chamber 21 of a reaction unit 2, the substrate workpiece is pumped to a specified vacuum condition through an air pumping unit 3, a radio frequency power supply 1 is started, high frequency electromagnetic waves are released through an electrode plate 24, the high frequency electromagnetic waves generate a plasmon effect through a slit antenna 23, surface waves are generated at the interface of a quartz plate 25 and plasma and spread along the interface, and highly uniform plasma is maintained, then monomer steam is supplied into the reaction chamber 21 according to a preset flow rate, and in the atmosphere of the surface wave plasma, graft copolymerization reaction occurs among molecules of the monomer steam, so that a continuous polymerization film layer is formed on the complex surface of the substrate by continuous deposition.
[ modified examples ]
FIG. 2 is a schematic structural view of a coating device D1 according to another embodiment of the present invention. The following description will be made in detail only for differences between the film deposition apparatus D1 of the present embodiment and the film deposition apparatus D of the previous embodiment, and the same reference numerals are used for the same parts, while omitting their related descriptions.
The gas distribution unit 4 is further provided with a process gas pipeline 42 independent of the monomer vapor pipeline 41, one end of the process gas pipeline 42 is connected with a process gas source 44, the other end of the process gas pipeline is communicated with the reaction chamber 21 of the reaction unit 2, the process gas enters the reaction chamber 21 of the reaction unit 2 from the process gas source 44 through the process gas pipeline 42 to participate in reaction, and then unreacted substances and auxiliary reaction products are pumped out through the pumping unit 3 at the lower part of the reaction chamber 21. The port of the process gas line 42 connected to the reaction unit 2 is a process gas supply port 46 for supplying a process gas, and two process gas supply ports 46 are symmetrically formed at both sides of the reaction unit 2. The pipeline and the port are connected with the reaction unit 2 through a flange and a rubber ring, so that the vacuum sealing performance is ensured.
Further, the process gas source 44 is connected to a process gas mass flow meter 54 and a process gas flow switch valve 53 in sequence, and is connected to the process gas pipeline 42 through the process gas branch pipeline 412, the process gas mass flow meter 54 is used for controlling the flow rate of the process gas source 43 output to the process gas branch pipeline 412, and the process gas flow switch valve 53 is used for controlling whether the process gas source 43 outputs. The process gas branch line 412 and the process gas line 42 form a junction, and the process gas output from the process gas source 43 is divided into two streams at the junction, and then respectively enters the reaction chamber 21 through the process gas line 42, which is beneficial to uniform diffusion of the process gas and improves the product yield.
In this embodiment, the process gas may be a process gas that activates and/or purifies the substrate surface, such as a carrier gas, for example, an inert gas including, but not limited to, argon, helium, and/or oxygen. The process gas source 44 is not limited to one, and may be formed in plural. Taking the two examples shown in fig. 2, each process gas source is provided with a process gas mass flow meter and a process gas flow switching valve, and the process gas mass flow meter and the process gas flow switching valve are connected in sequence and then respectively connected to the process gas branch pipes 412. Since each process gas source 44 can be independently operated, the delivery time and flow rate of the process gas can be adjusted at any time and independently according to the process recipe.
According to the coating device D1 of the present invention, the supply amounts of the ports at both sides can be adjusted, so that the flow rates of the monomer vapor and the process gas supplied from the supply ports can be adjusted in real time according to the specific reaction conditions, and the uniformity of the plasma graft copolymer film layer prepared on the surface of the substrate can be greatly improved in the surface wave plasma atmosphere. Specifically, a substrate workpiece to be coated is placed in a reaction chamber 21 of a reaction unit 2, the substrate workpiece is pumped to a specified vacuum condition through an air pumping unit 3, a radio frequency power supply 1 is started, high frequency electromagnetic waves are released through an electrode plate 24, the high frequency electromagnetic waves generate a plasmon effect through a slit antenna 23, surface waves are generated at the interface of a quartz plate 25 and plasma and spread along the interface and maintain highly uniform plasma, then monomer steam and process gas are supplied into the reaction chamber 21 according to a preset flow rate, in the surface wave plasma atmosphere, a graft copolymerization reaction occurs between molecules of the monomer steam, the process gas is continuously supplied to maintain a copolymerization reaction, and therefore a continuous polymerization film layer is continuously deposited on the complex surface of the substrate.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
[ example 1]
The reaction unit 2 of the coating device D and the reaction chamber 21 inside the reaction unit are cubic, 1100mm long, 800mm wide and 1100mm high, and the material is stainless steel. The frequency of the radio frequency power supply 1 is 13.5MHz, the power is 500W, and the radio frequency power supply is connected with the top of the reaction unit 2 through a cable 11 and a vacuum feed-in piece 12 and can discharge to the inner wall of the reaction unit 2 to generate plasma. Specifically, one end of the vacuum feed-in member 12 is connected to the radio frequency power supply 1 through the cable 11, the other end of the vacuum feed-in member extends into the inside from the top of the outer side of the reaction unit 2 and is connected to the electrode plate 24 through a flange, the joint is sealed in vacuum through a sealing ring, the electrode plate 24 is a copper planar metal plate, the size of the electrode plate is 30mm × 30mm, and the electrode plate is fixed to the top of the inner side of the reaction unit 2 through a PTFE insulation workpiece. The quartz plate 25 is a flat quartz glass plate, is installed at a position about 30mm from the electrode plate 24 in a manner of covering the cross-sectional area of the internal chamber, has a specific size of 550mm × 400mm, a thickness of 50mm, and is spliced together in 2 pieces, and is fixed to the inner side wall surface of the reaction unit 2 by a PTFE insulating workpiece. On the surface of the quartz plate 25 on the side facing the electrode plate 24, the slot antennas 23 are pressed, the slot antennas 23 are made of aluminum alloy and have the size of 0.5mm wide by 20mm long and the thickness of 3mm, for example, and are uniformly distributed at equal intervals on the quartz plate 25, the number of the slot antennas 23 is 25, and the slot antennas 23 are fixed on the inner side surface of the inner chamber through an insulating PTFE workpiece. The process gas pipeline 42 and the coating gas pipeline 41 are respectively connected with two sides of the reaction unit 2 and communicated with the reaction chamber 2, four ports are opposite to each other in pairs, and the vacuum sealing is ensured at the connection part through a flange and a rubber ring. Process gas line 42 and monomer vapor line 41 are connected to process gas source 44 and monomer vapor source 43, respectively. The vacuum pump 34 of the pumping unit 3 is connected to the bottom of the reaction unit 2 through a vacuum line and communicates with the reaction chamber 21.
Firstly, a substrate workpiece to be coated is placed in a reaction chamber 21 of a reaction unit 2, the reaction chamber 21 is pumped to a preset working pressure of 0.01mbar by an air pumping unit 3, a flow switch valve 53 on a process gas source 43 of a first process gas is opened, a process gas switch valve 55 in a process gas pipeline 42 is opened, and the supply of the first process gas, namely, argon, helium and CF, into the reaction chamber 21 is precisely controlled by a flow meter 548The flow rate of the mixed gas, the first process gas, was 150sccm while maintaining an operating pressure of 0.25 mbar. The radio frequency power supply 1 is turned on, high frequency electromagnetic waves are released through the electrode plate 24, the high frequency electromagnetic waves generate a plasmon effect through the slit antenna 23, surface waves are generated at the interface between the quartz plate 25 and the plasma, and the surface waves propagate along the interface and maintain highly uniform plasma. The feed valve 52 on the monomer steam pipeline 41 is opened to supply monomer steam into the reaction chamber 21, the flow rate of the monomer steam supplied into the reaction chamber 21 is accurately controlled through the monomer steam mass flow meter 51, meanwhile, the process gas flow switch valve 53 at the process gas source 43 of the second process gas is opened, the flow rate of the second process gas supplied into the reaction chamber 21 is accurately controlled through the process gas mass flow meter 54, namely, helium gas, so that the flow rate of the second process gas in the reaction chamber 21 is 100sccm, the flow rate of the monomer steam is 50sccm, and the working pressure is maintained at 0.15 mbar. In the vacuum reaction chamber 21, in the surface wave plasma atmosphere, a graft copolymerization reaction occurs between molecules of the monomer vapor, and a second process gas is continuously supplied to maintain the copolymerization reaction, so that a continuous polymerization film layer is continuously deposited on the complex surface of the substrate.
After the above-mentioned experiments are performed for a plurality of times, the experimental detection is performed on the polymeric film layer formed on the surface of the product. The following table shows the film thickness test results:
based on the experimental data, multiple rounds of film thickness tests show that the film thickness does not differ more than +/-1nm at each position, and better uniformity is shown. As shown in fig. 3, the upper diagram shows the result of the water dropping test of the finished product, and the lower diagram shows the result of the static contact angle test, so that the water dropping test is performed at a plurality of positions on the surface of the finished product, and the water dropping test shows that the water dropping test has a good hydrophobic property and a good uniformity of the surface film layer, and the static contact angle test shows that the water contact angle of the surface of the product is 135.6 degrees, and the surface of the product has a strong hydrophobic property.
[ example 2]
The reaction unit 2 of the coating device D and the reaction chamber 21 inside the reaction unit are cubic, 500mm long, 400mm wide and 500mm high, and the material is stainless steel. The frequency of the radio frequency power supply 1 is 2.45GHz, the power is 200W, the radio frequency power supply is connected with the top of the reaction unit 2 through a cable 11 and a vacuum feed-in piece 12, and the radio frequency power supply can discharge to the inner wall of the reaction unit 2 to generate plasma. Specifically, one end of the vacuum feed-in member 12 is connected to the radio frequency power supply 1 through the cable 11, the other end of the vacuum feed-in member extends into the inside from the top of the outer side of the reaction unit 2 and is connected to the electrode plate 24 through a flange, the joint is sealed in vacuum through a sealing ring, the electrode plate 24 is a copper planar metal plate, the size of the electrode plate is 30mm × 30mm, and the electrode plate is fixed to the top of the inner side of the reaction unit 2 through a PTFE insulation workpiece. The quartz plate 25 is a flat quartz glass plate, is installed at a position about 30mm from the top of the electrode plate 24 in a manner of covering the cross-sectional area of the internal chamber, has a specific size of 250mm × 200mm, has a thickness of 50mm, and is spliced together in 2 pieces, and is fixed to the inner wall of the internal chamber by a PTFE insulating work piece. The slit antennas 23 are pressed on the surface of the quartz plate 25 facing the electrode plate 24, the slit antennas 23 are made of aluminum alloy, the size of the antennas is 1mm wide × 15mm long, the thickness is 4mm for example, the antennas are uniformly distributed on the quartz plate 25 at equal intervals, the number of the antennas is 30, and the slit antennas 23 are fixed on the inner side surface of the inner chamber through an insulating PTFE workpiece. The process gas pipeline 42 and the coating gas pipeline 41 are respectively connected with two sides of the reaction unit 2 and communicated with the reaction chamber 2, four ports are opposite to each other in pairs, and the vacuum sealing is ensured at the connection part through a flange and a rubber ring. Process gas line 42 and monomer vapor line 41 are connected to process gas source 44 and monomer vapor source 43, respectively. The vacuum pump 34 of the pumping unit 3 is connected to the bottom of the reaction unit 2 through a vacuum line and communicates with the reaction chamber 21.
Placing a substrate workpiece to be coated in a reaction chamber 21 of a reaction unit 2, pumping to a preset working pressure of 0.02mbar through a pumping unit 3, opening a flow switch valve 53 on a process gas source 43 of a first process gas and opening a process gas switch valve 55 in a process gas pipeline 42, and accurately controlling the supply of the first process gas, namely, argon, helium and C, into the reaction chamber 21 through a flow meter 544F8The flow rate of the mixed gas, the first process gas, was 100sccm while maintaining an operating pressure of 0.25 mbar. The radio frequency power supply 1 is turned on, high frequency electromagnetic waves are released through the electrode plate 24, the high frequency electromagnetic waves generate a plasmon effect through the slit antenna 23, surface waves are generated at the interface between the quartz plate 25 and the plasma, and the surface waves propagate along the interface and maintain highly uniform plasma. The feed valve 52 on the monomer steam pipeline 41 is opened to supply monomer steam into the reaction chamber 21, the flow rate of the monomer steam supplied into the reaction chamber 21 is accurately controlled through the monomer steam mass flow meter 51, meanwhile, the process gas flow switch valve 53 at the process gas source 43 of the second process gas is opened, the flow rate of the second process gas supplied into the reaction chamber 21 is accurately controlled through the process gas mass flow meter 54, namely, argon gas, so that the flow rate of the second process gas in the reaction chamber 21 is 80sccm, the flow rate of the monomer steam is 80sccm, and the working pressure is maintained at 0.12 mbar. In the vacuum reaction chamber 21, in the surface wave plasma atmosphere, a graft copolymerization reaction occurs between molecules of the monomer vapor, and a second process gas is continuously supplied to maintain the copolymerization reaction, so that a continuous polymerization film layer is continuously deposited on the complex surface of the substrate.
After the above-mentioned experiments are performed for a plurality of times, the experimental detection is performed on the polymeric film layer formed on the surface of the product. The following table shows the film thickness test results:
based on the experimental data, multiple rounds of film thickness tests show that the film thickness does not differ more than +/-1nm at each position, and better uniformity is shown. As shown in fig. 4, the upper diagram shows the result of the water dropping test of the finished product, and the lower diagram shows the result of the static contact angle test, so that the water dropping test is performed at a plurality of positions on the surface of the finished product, and the water dropping test shows that the water dropping test has a good hydrophobic property and a good uniformity of the surface film layer, and the static contact angle test shows that the water contact angle of the surface of the product is 135.7 degrees, and the surface of the product has a strong hydrophobic property.
Based on the above, the film coating device D for the plasma graft copolymerization film layer provided by the invention can generate highly uniform plasma, and simultaneously improves the conventional supply manner of monomer vapor and/or process gas, greatly improves the uniformity of the thickness of the film layer of the product, improves the yield of batch processing products, and particularly has good film forming property for workpieces with complex curved surfaces.
The above embodiments are intended to illustrate and not to limit the scope of the invention, which is defined by the claims, but rather by the claims, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
Claims (9)
1. A coating device of a plasma graft copolymerization film layer is provided with a radio frequency power supply, a reaction unit, an air exhaust unit and an air distribution unit; wherein the content of the first and second substances,
the reaction unit is internally formed into a chamber for reaction;
the radio frequency power supply is arranged outside the reaction unit and is communicated with the cavity of the reaction unit so as to generate plasma;
the air extraction unit is arranged outside the reaction unit, is communicated with the cavity of the reaction unit and is used for extracting gas in the reaction unit;
the gas distribution unit is arranged outside the reaction unit, is communicated with the cavity of the reaction unit through a supply pipeline and is used for adding monomer steam serving as a gas source of the graft copolymerization film layer;
and a slit antenna is arranged in the chamber of the reaction unit and close to the radio frequency power supply.
2. The coating device of a plasma graft copolymer film according to claim 1,
the reaction unit is provided with: the radio frequency power supply comprises a reaction unit, an electrode plate, a planar quartz plate, a slit antenna and a reaction chamber, wherein the electrode plate is arranged in the reaction unit and connected with the radio frequency power supply, the planar quartz plate is arranged in the reaction unit in a mode of being close to the electrode plate, the slit antenna is arranged on the surface, facing the radio frequency power supply, of the quartz plate, and the reaction chamber is surrounded by the quartz plate and the inner wall of the reaction unit.
3. The coating device of a plasma graft copolymer film according to claim 2,
the slit antennas are arranged in parallel on the quartz plate, and the excitation intensity is changed by changing the size and the array distribution of the slit antennas.
4. The coating device of a plasma graft copolymer film according to claim 2,
the electrode plate is a copper plate, the quartz plate is a quartz glass plate or a quartz ceramic plate, and the slit antenna is made of aluminum.
5. The coating device of a plasma graft copolymer film according to claim 2,
the electrode plate and the quartz plate are respectively fixed in the reaction unit through PTFE insulation workpieces.
6. The coating device of a plasma graft copolymer film according to claim 5,
the gas distribution unit is provided with a monomer steam pipeline for supplying monomer steam to the reaction chamber; one end of the monomer steam pipeline is connected with the monomer steam source, and the other end of the monomer steam pipeline is connected with the reaction unit.
7. The coating device of a plasma graft copolymer film according to claim 1,
the reaction unit is provided with two monomer steam supply ports which are respectively communicated with the monomer steam pipelines and symmetrically arranged at two sides of the reaction unit.
8. The coating device of a plasma graft copolymer film according to claim 1,
the gas distribution unit is also provided with a process gas pipeline independent of the monomer steam pipeline;
and one end of the process gas pipeline is connected with a process gas source, and the other end of the process gas pipeline is connected with the reaction unit and used for introducing process gas into the reaction chamber.
9. The coating apparatus of a plasma graft copolymer film as set forth in claim 8,
the reaction unit is provided with two process gas supply ports which are respectively communicated with the process gas pipelines and symmetrically arranged at two sides of the reaction unit.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2000096239A (en) * | 1998-09-21 | 2000-04-04 | Tokuyama Corp | Induction coupling type plasma cvd method and induction coupling type plasma cvd device therefor |
| US20030026920A1 (en) * | 2000-10-03 | 2003-02-06 | Tomohiro Okumura | Plasma processing method and apparatus |
| JP2006179691A (en) * | 2004-12-22 | 2006-07-06 | Mitsui Eng & Shipbuild Co Ltd | Apparatus and method of forming thin film |
| CN206359612U (en) * | 2017-01-04 | 2017-07-28 | 无锡荣坚五金工具有限公司 | One kind improves nano-coating equipment plasma uniformity device |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000096239A (en) * | 1998-09-21 | 2000-04-04 | Tokuyama Corp | Induction coupling type plasma cvd method and induction coupling type plasma cvd device therefor |
| US20030026920A1 (en) * | 2000-10-03 | 2003-02-06 | Tomohiro Okumura | Plasma processing method and apparatus |
| JP2006179691A (en) * | 2004-12-22 | 2006-07-06 | Mitsui Eng & Shipbuild Co Ltd | Apparatus and method of forming thin film |
| CN206359612U (en) * | 2017-01-04 | 2017-07-28 | 无锡荣坚五金工具有限公司 | One kind improves nano-coating equipment plasma uniformity device |
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