CN111188032B - Hydrophobic film plating method by plasma chemical vapor deposition method in inter-film combination mode - Google Patents
Hydrophobic film plating method by plasma chemical vapor deposition method in inter-film combination mode Download PDFInfo
- Publication number
- CN111188032B CN111188032B CN202010097649.5A CN202010097649A CN111188032B CN 111188032 B CN111188032 B CN 111188032B CN 202010097649 A CN202010097649 A CN 202010097649A CN 111188032 B CN111188032 B CN 111188032B
- Authority
- CN
- China
- Prior art keywords
- hydrophobic
- film
- reaction cavity
- hydrophilic
- workpiece
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C23C16/513—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 plasma jets
-
- 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
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
Abstract
The invention discloses a method for plating a hydrophobic film by a plasma chemical vapor deposition method in an inter-film combination mode, which comprises the following steps: (1) and pretreatment: putting a workpiece to be processed into a reaction cavity, introducing C3F6 and/or C4F8 into the reaction cavity, and processing the surface of the workpiece by ionized C3F6 and/or C4F8 under a vacuum condition; (2) activating; (3) and (3) vaporization: uniformly mixing a hydrophilic material and a hydrophobic material to obtain a mixed coating material, and allowing the vaporized mixed coating material to enter a reaction cavity; (4) and deposition: setting a first power of a radio frequency power level in the reaction cavity, depositing a hydrophilic film under the vacuum degree, then adjusting a second power of the radio frequency power level in the reaction cavity, and depositing a hydrophobic film under the vacuum degree; (5) and (5) post-treatment. The method has the advantages of high deposition speed of the hydrophobic film, firm adhesion, compact film layer and short production period.
Description
Technical Field
The invention relates to the technical field of plasma chemical vapor deposition method coating, in particular to a hydrophobic film coating method in an inter-film combination mode by using a plasma chemical vapor deposition method.
Background
In a plasma chemical enhanced vapor deposition coating process, particularly a hydrophobic coating process, a collision reaction of plasma gas carrier gas and vaporized hydrophobic materials is maintained for a period of time, a layer of hydrophobic film is formed on the surface of a workpiece, and the length of the reaction time is controlled according to the thickness requirement of the hydrophobic film. The coating process can form a single-layer hydrophobic film with a certain thickness, but the single-layer hydrophobic film has the problems of low comprehensive performance, easy falling and poor durability. To solve this problem, multilayer coating has been described, but it is difficult to fundamentally solve the problem of the degree of bonding strength between the film layer and the substrate.
Disclosure of Invention
The invention aims to provide a method for plating a hydrophobic film by a plasma chemical vapor deposition method in an inter-film bonding mode, which has the characteristic of high bonding firmness of a film layer and a base material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a hydrophobic film plating method by an inter-film combination plasma chemical vapor deposition method, which comprises the following steps:
(1) and pretreatment: putting a workpiece to be treated into a reaction cavity, and introducing C into the reaction cavity3F6And/or C4F8In ionized C under vacuum3F6And/or C4F8Processing the surface of the workpiece;
(2) and activating: activating the surface of the workpiece by using plasma gas in the reaction cavity;
(3) and (3) vaporization: uniformly mixing a hydrophilic material and a hydrophobic material to obtain a mixed coating material, and allowing the vaporized mixed coating material to enter a reaction cavity;
(4) and deposition: setting a first power of a radio frequency power level in the reaction cavity, depositing a hydrophilic film under the vacuum degree, then adjusting a second power of the radio frequency power level in the reaction cavity, and depositing a hydrophobic film under the vacuum degree;
(5) and (5) post-treatment.
Further, in the step (1), C is introduced into the reaction cavity3F6And/or C4F8While introducing inert gas.
Further, in the step (1), the RF power in the reaction chamber is 300-.
Further, in the step (2), O is used2Plasma gas surface activation is performed.
Further, in the step (4), the first power is 300-;
the vacuum degree in the reaction cavity is 0.01-0.05mbar when the hydrophilic film is deposited, and the vacuum degree in the reaction cavity is 0.08-0.15mbar when the hydrophobic film is deposited.
Further, gas enters from a gas inlet end of the reaction cavity and is pumped out in a vacuumizing mode from the other end opposite to the gas inlet end; in the step (4), in the process of depositing the hydrophilic film and the hydrophobic film, the vaporized mixed coating material is continuously introduced into the reaction cavity, and simultaneously the gas in the reaction cavity is continuously discharged.
Further, in the step (3), the mixed coating material is vaporized in the heating cup, the adding amount of the mixed coating material in the heating cup is 4-10ul/s, and the heating temperature of the heating cup is 75-100 ℃.
Further, the hydrophilic material and the hydrophobic material are both silane-based materials, the hydrophobic material contains fluorine, and the hydrophilic material contains hydrophilic groups.
Further, in the step (4), when the hydrophilic material is deposited, the auxiliary gas oxygen is synchronously introduced into the reaction cavity; and when the hydrophobic material is deposited, synchronously introducing auxiliary gas nitrogen into the reaction cavity.
Further, in the step (4), in the process of depositing the hydrophobic material, pulse waves are adopted, and the thickness growth speed of the hydrophobic film is 10-20 nm/min.
The invention has the beneficial effects that:
in the present invention, C is used3F6And/or C4F8Pretreating the workpiece to activate C3F6And/or C4F8Gas molecules collide with the surface to be treated, C3F6And/or C4F8The F element in the molecular structure is embedded on the surface of the workpiece through plasma free radical reaction and is riveted with the molecules on the surface of the workpiece, so that the effect of condensation nuclei is achieved. The pretreatment process realizes the pre-deposition of-CF 3 groups on the surface of the workpiece, and the surface of the workpiece can be locally grafted with-CF 3 groups. When the subsequent coating deposition is carried out, the condensation nucleus low surface energy elements have the function of absorbing and gathering F elements, and have the directional attraction function with the low surface energy elements in the vaporized coating material, so that the deposition of the hydrophobic material in the subsequent coating operation is facilitated, the deposition speed of the hydrophobic film is increased, and the firmness of the attachment of the hydrophobic film is improved.
Meanwhile, the workpiece with the hydrophobic surface is obtained by plating the hydrophilic film on the surface of the workpiece and then plating the hydrophobic film on the hydrophilic film, more hydrophilic groups are gathered on the surface of the hydrophilic film, and the groups have polarity, so that the surface of the base material has extremely strong reaction activity, when the hydrophobic material is used for deposition, the deposition and adhesion are easier on the surface of the workpiece with extremely high activity, and the film thickness is increased rapidly and compactly.
In the invention, the hydrophilic material and the hydrophobic material are uniformly mixed, are simultaneously introduced into the reaction cavity after being vaporized, and are selectively deposited by adjusting the radio frequency power. Compared with the method that the hydrophilic material is firstly introduced into the reaction cavity and then the hydrophobic material is introduced, the shutdown and startup time, the discharging and feeding time and the time for cleaning the material liquid tank in the production process can be saved, and the whole production period is shortened. Moreover, the hydrophilic material and the hydrophobic material are the same type of material, and the materials of the same type are mixed with each other, so that the mixed material is easier to vaporize than a single material, the heating temperature is reduced, and the normal-temperature production and the equipment control and maintenance are facilitated.
Drawings
FIG. 1 is a hydrophobic angle measurement of examples 3 and 6 of the present invention;
fig. 2 is a thickness profile of inventive examples 3 and 6.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings and the detailed description.
The invention provides a hydrophobic film plating method by an inter-film combination plasma chemical vapor deposition method, which comprises the following steps:
(1) and pretreatment: putting a workpiece to be treated into a reaction cavity, and introducing C into the reaction cavity3F6And/or C4F8In ionized C under vacuum3F6And/or C4F8Processing the surface of the workpiece;
(2) and activating: activating the surface of the workpiece by using plasma gas in the reaction cavity;
(3) and (3) vaporization: uniformly mixing a hydrophilic material and a hydrophobic material to obtain a mixed coating material, and allowing the vaporized mixed coating material to enter a reaction cavity;
(4) and deposition: setting a first power of a radio frequency power level in the reaction cavity, depositing a hydrophilic film under the vacuum degree, then adjusting a second power of the radio frequency power level in the reaction cavity, and depositing a hydrophobic film under the vacuum degree;
(5) and (5) post-treatment.
In the present invention, C is used3F6And/or C4F8Pretreating the workpiece to activate C3F6And/or C4F8Gas molecules collide with the surface to be treated, C3F6And/or C4F8The F element in the molecular structure is embedded on the surface of the workpiece through plasma free radical reaction and is riveted with the molecules on the surface of the workpiece, so that the effect of condensation nuclei is achieved. The pretreatment process realizes-CF3The group is pre-deposited on the surface of the workpiece, and the surface of the workpiece can be locally grafted with a-CF 3 group. When the subsequent coating deposition is carried out, the condensation nucleus low surface energy elements have the function of absorbing and gathering fluorine elements, and have the directional attraction function with the low surface energy elements in the vaporized coating material, so that the deposition of the hydrophobic material in the subsequent coating operation is facilitated, and the deposition speed of the hydrophobic film is improved.
Meanwhile, the workpiece with the hydrophobic surface is obtained by plating the hydrophilic film on the surface of the workpiece and then plating the hydrophobic film on the hydrophilic film, more hydrophilic groups are gathered on the surface of the hydrophilic film, and the groups have polarity, so that the surface of the base material has extremely strong reaction activity, when the hydrophobic material is used for deposition, the deposition and adhesion are easier on the surface of the workpiece with extremely high activity, and the film thickness is increased rapidly and compactly.
In the invention, the hydrophilic material and the hydrophobic material are uniformly mixed, are simultaneously introduced into the reaction cavity after being vaporized, and are selectively deposited by adjusting the radio frequency power. Compared with the method that the hydrophilic material is firstly introduced into the reaction cavity and then the hydrophobic material is introduced, the shutdown and startup time, the discharging and feeding time and the time for cleaning the material liquid tank in the production process can be saved, and the whole production period is shortened. Moreover, the hydrophilic material and the hydrophobic material are the same type of material, and the materials of the same type are mixed with each other, so that the mixed material is easier to vaporize than a single material, the heating temperature is reduced, and the normal-temperature production and the equipment control and maintenance are facilitated.
In the invention, the hydrophobic material adopts one or more of trifluoropropyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, tridecafluorooctyltrichlorosilane, hexafluoropropylene and octafluorobutene. The hydrophilic material adopts one or more of 3- (2, 3-epoxypropoxy) propyl trimethoxy silane, gamma-aminopropyl triethoxy silane, gamma-glycidoxypropyl trimethoxy silane and gamma-methacryloxypropyl trimethoxy silane.
In the invention, the temperature of the reaction chambers in the steps (1) - (4) is maintained at 40-60 ℃.
Further, in the step (1), C is introduced into the reaction cavity3F6And/or C4F8While introducing inert gas. The inert gas functions to enhance ionization and promote the degree of plasmatization of C3F6 and C4H 8. Meanwhile, the inert gas is ionized into plasma gas to etch the surface of the workpiece, so that-CF3Grafting of the groups is easier. The inert gas is helium, neon or argon.
Further, in the step (1), the RF power in the reaction chamber is 300-. Under the conditions of the radio frequency power and the vacuum degree, C3F6And/or C4F8The molecule has better ionization effect, so that-CF3The radicals are better pre-deposited on the surface of the workpiece.
Further, in the step (2), O is used2Plasma gas surface activation is performed. The plasma surface activation is carried out on the surface of the workpiece through oxygen, so that the activity of the surface of the workpiece is enhanced, the reaction potential energy is reduced, the introduction quantity of active functional groups is increased, and the reaction is easier to be carried out in the positive direction. Oxygen activation is adopted, so that hydrophilic materials are conveniently deposited, and the binding force of the film layer is improved. The flow rate of oxygen gas introduced into the reaction cavity is 1000-.
By the use of O2When activated, in step (1), the surface of the workpiece is grafted with-CF3The groups can remain present due to-CF3The fluorine-containing group has the advantages of low surface energy, chemical inertness, good stability and difficult reaction.
Further, in the step (4), the first power is 300-; the vacuum degree in the reaction cavity is 0.01-0.05mbar when the hydrophilic film is deposited, and the vacuum degree in the reaction cavity is 0.08-0.15mbar when the hydrophobic film is deposited. The deposition of new hydrophilic materials and hydrophobic materials is respectively realized under the conditions of different powers and vacuum degrees, the film deposition can be more compact due to the switching of the vacuum degrees, and the compactness of the film is improved.
The hydrophilic material can be deposited at a first power and the hydrophobic material can be deposited at a second power because the hydrophobic material contains fluorine and the C-F bond is larger and requires more energy to break the bond, so that a relatively higher power is required. Whereas hydrophilic materials do not contain fluorine, so that less power is required and the corresponding energy is not as high. Setting two powers can ensure that different materials are deposited respectively.
Further, gas enters from a gas inlet end of the reaction cavity and is pumped out in a vacuumizing mode from the other end opposite to the gas inlet end; in the step (4), in the process of depositing the hydrophilic film and the hydrophobic film, the vaporized mixed coating material is continuously introduced into the reaction cavity, and simultaneously the gas in the reaction cavity is continuously discharged. The inlet and the outlet are arranged at the two opposite ends of the reaction cavity, so that the gas flow in the reaction cavity is directional and ordered, and a film layer with uniform thickness and compact structure is favorably formed on the surface of a workpiece. Keeping gas to be continuously discharged in the coating process, discharging waste gas, and being beneficial to quick formation of a film layer, for example, when hydrophilic materials are deposited, hydrophobic materials introduced into the reaction cavity need to be discharged in time, and when hydrophobic materials are deposited, hydrophilic materials introduced into the reaction cavity need to be discharged in time.
Further, in the step (3), the mixed coating material is vaporized in the heating cup, the adding amount of the mixed coating material in the heating cup is 4-10ul/s, and the heating temperature of the heating cup is 75-100 ℃. Under the vaporization condition, the hydrophilic material and the hydrophobic material in the mixed coating material can be vaporized simultaneously, and the lower heating temperature can reduce the production energy consumption.
Further, the hydrophilic material and the hydrophobic material are both silane-based materials, the hydrophobic material contains fluorine, and the hydrophilic material contains hydrophilic groups. The hydrophilic material and the hydrophobic material are adopted, so that the mixed coating material can be better vaporized, and the two coating materials can be better deposited on the surface of a workpiece.
Further, in the step (4), when the hydrophilic material is deposited, the auxiliary gas oxygen is synchronously introduced into the reaction cavity; and when the hydrophobic material is deposited, synchronously introducing auxiliary gas nitrogen into the reaction cavity. When the hydrophilic material is deposited, oxygen can participate in the reaction, and the deposition of the hydrophilic material under a lower vacuum degree is realized. When the hydrophobic material is deposited, the assistance of inert gas is adopted to prevent the interference of oxygen, and the deposition of the hydrophobic film layer is realized under the condition of higher vacuum degree.
Further, in the step (4), pulse waves are adopted, and the thickness growth speed of the hydrophobic film is 10-20 nm/min in the hydrophobic material deposition process. And (3) adopting pulse wave and energy conditions to deposit the film layer at a certain rate.
The post-treatment steps of the invention are as follows: and (5) hermetically packaging the workpiece subjected to the step (4), and placing the workpiece in a constant-temperature constant-humidity environment for 20-45min, wherein the temperature and the humidity of the environment are 45 ℃ and 5%. The post-treatment step can ensure that the sample is isolated from oxygen and moisture in the air, and the pollution of the film layer is well avoided. The post-treatment step also enables the hydrophobic membrane to be further stabilized.
The invention is further illustrated by the following examples and comparative examples.
The method for plating the hydrophobic film by the plasma chemical vapor deposition method in the inter-film bonding manner in the embodiments 1 to 6 includes the following steps:
(1) and pretreatment: putting a workpiece to be treated into a reaction cavity, and introducing C into the reaction cavity3F6And/or C4F8Introducing inert gas simultaneously, and ionizing under vacuum condition to obtain C3F6And/or C4F8Processing the surface of the workpiece; the radio frequency power in the reaction cavity is 300-400W, and the vacuum degree is 0.04-0.08 mbar;
(2) and activating: using O in the reaction chamber2Carrying out plasma gas activation treatment on the surface of the workpiece;
(3) and (3) vaporization: uniformly mixing a hydrophilic material and a hydrophobic material to obtain a mixed coating material, wherein the hydrophilic material and the hydrophobic material are both silane materials; the hydrophobic material comprises fluorine element, and the hydrophilic material comprises hydrophilic group;
the mixed coating material is vaporized in a heating cup, the adding amount of the mixed coating material in the heating cup is 4-10ul/s, the heating temperature of the heating cup is 75-100 ℃, and the vaporized mixed coating material enters a reaction cavity;
(4) and deposition: setting the first power of the radio frequency power level in the reaction cavity to be 300-;
then adjusting the radio frequency power in the reaction cavity to be pulse wave 600-800W, depositing a hydrophobic film under the vacuum degree of 0.08-0.15mbar, synchronously introducing auxiliary gas nitrogen into the reaction cavity, wherein the thickness growth speed of the hydrophobic film is 10-20 nm/min;
one end of the reaction cavity is provided with a gas inlet, and the other end of the reaction cavity is provided with a vacuumizing outlet; in the processes of depositing the hydrophilic film and depositing the hydrophobic film, the vaporized mixed coating material is continuously introduced into the reaction cavity and the gas in the reaction cavity is continuously discharged;
(5) and (5) post-treatment.
The parameters of each step in examples 1 to 6 are shown in the following table.
It should be noted that the time for depositing the hydrophilic material and the time for depositing the hydrophobic material can be set according to actual requirements, and under the same coating condition, the longer the deposition time, the larger the film thickness. In embodiments 1 to 6, when the hydrophilic material is deposited in step (4), the same coating effect is achieved by using both continuous waves and pulsed waves for the radio frequency, i.e., the radio frequency type has little influence on the deposition of the hydrophilic material.
The hydrophobic membranes obtained from examples 1-6 were subjected to the hydrophobic angle test, and the static contact hydrophobic angle of the hydrophobic membranes was between 144 ° and 146 °, wherein the tests of examples 3 and 6 are shown in fig. 1. The film layers obtained in examples 1 to 6 were subjected to thickness measurement, and the measurement results are shown in the following table, and the thickness curves of examples 3 and 6 are shown in fig. 2.
The obtained hydrophobic films of examples 1 to 6 were subjected to an abrasion resistance test with a sand test eraser to examine the bonding strength of the film layer to the workpiece. The abrasion resistance test method is as follows:
1. reciprocating motion abrasion test method
Under the specified test conditions, a special sand test eraser with a load of 500g is used for applying force on the surface of the coating, a back-and-forth rubbing cycle is carried out at a certain speed and stroke, and after the test is finished, the bottom penetrating condition of the coating is observed for judging and evaluating the wear resistance of the coating.
2. Testing the tool: the special sand quality test eraser.
The test method comprises the following steps: a500 g load was applied to the eraser, and the eraser with the load was rubbed on the surface of the specimen with a stroke of about 20mm at a speed of 40 to 60 times/min for 300 cycles.
3. And (4) evaluating the result: and (4) finishing the test, wherein the surface of the sample coating is not scratched or does not penetrate through the bottom, and the test is qualified, otherwise, the test is unqualified.
Comparative example 1
The method of applying the hydrophobic film by the plasma chemical vapor deposition method of this comparative example is substantially the same as that of example 3 except that step (1) is omitted.
Comparative example 2
The method of applying the hydrophobic film by the plasma chemical vapor deposition method of this comparative example is substantially the same as that of example 3, except that in step (3), only the hydrophobic material is introduced into the reaction chamber.
Comparative example 3
The method of applying the hydrophobic film by the plasma chemical vapor deposition method of this comparative example is substantially the same as that of example 3, except that in step (4), the first power and the second power are the same and are both 600W.
Comparative example 4
The method of depositing the hydrophobic film by the plasma chemical vapor deposition method of this comparative example is substantially the same as that of example 3, except that the degrees of vacuum at the time of depositing the hydrophilic film and the hydrophobic film are the same in step (4).
Comparative example 5
The method of applying the hydrophobic film by the plasma chemical vapor deposition method of this comparative example is substantially the same as that of example 3, except that in step (4), a continuous wave is used for depositing the hydrophobic material.
The membrane layers obtained in comparative examples 1 to 5 were subjected to a hydrophobic angle test, a thickness test, a membrane layer density test and an abrasion resistance test, and the results are shown in the following table.
In comparative examples 3 and 4, the rf power and the coating vacuum degree of the hydrophilic material and the hydrophobic material were not simultaneously adjusted during the coating process, resulting in poor film quality.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Claims (8)
1. A hydrophobic film plating method by plasma chemical vapor deposition in an inter-film combination mode is characterized by comprising the following steps:
(1) and pretreatment: putting a workpiece to be treated into a reaction cavity, and introducing into the reaction cavityC3F6And/or C4F8In ionized C under vacuum3F6And/or C4F8Processing the surface of the workpiece;
(2) and activating: activating the surface of the workpiece by using plasma gas in the reaction cavity;
(3) and (3) vaporization: uniformly mixing a hydrophilic material and a hydrophobic material to obtain a mixed coating material, and allowing the vaporized mixed coating material to enter a reaction cavity; the hydrophilic material and the hydrophobic material are both silane materials, the hydrophobic material comprises fluorine elements, and the hydrophilic material comprises hydrophilic groups;
(4) and deposition: setting the radio frequency power in the reaction cavity as 300-400W of first power, and depositing the hydrophilic membrane under the vacuum degree of 0.01-0.05 mbar; then adjusting the radio frequency power in the reaction cavity to be the second power of 600-800W, and depositing the hydrophobic membrane under the vacuum degree of 0.08-0.15 mbar;
(5) and post-treatment: and (4) hermetically packaging the workpiece after the step (4), and placing the workpiece in a constant temperature and humidity environment for 20-45min to ensure that the sample is isolated from oxygen and moisture in the air.
2. The plasma CVD method according to claim 1, wherein in the step (1), the reaction chamber is filled with C3F6And/or C4F8While introducing inert gas.
3. The method as claimed in claim 1, wherein in the step (1), the RF power in the reaction chamber is 300-400W, and the vacuum degree is 0.04-0.08 mbar.
4. The plasma CVD method according to claim 1, wherein the step (2) is performed by using O2Plasma gas surface activation is performed.
5. The plasma CVD method according to claim 1, wherein the gas is introduced from a gas inlet end of the reaction chamber and is evacuated from the other end opposite to the gas inlet end; in the step (4), in the process of depositing the hydrophilic film and the hydrophobic film, the vaporized mixed coating material is continuously introduced into the reaction cavity, and simultaneously the gas in the reaction cavity is continuously discharged.
6. The method for hydrophobic film coating by plasma CVD in combination between films as claimed in claim 1, wherein in the step (3), the mixed coating material is vaporized in a heating cup, the amount of the mixed coating material added in the heating cup is 4-10ul/s, and the heating temperature of the heating cup is 75-100 ℃.
7. The method for plating a hydrophobic membrane by plasma CVD in an inter-membrane bonding manner according to claim 1, wherein in the step (4), an auxiliary gas oxygen is synchronously introduced into the reaction chamber during the deposition of the hydrophilic material; and synchronously introducing auxiliary gas nitrogen into the reaction cavity when the hydrophobic material is deposited.
8. The method for plating the hydrophobic film by the plasma chemical vapor deposition method in the inter-film bonding manner according to claim 7, wherein in the step (4), a pulse wave is adopted in the process of depositing the hydrophobic material, and the thickness growth speed of the hydrophobic film is 10-20 nm/min.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010097649.5A CN111188032B (en) | 2020-02-17 | 2020-02-17 | Hydrophobic film plating method by plasma chemical vapor deposition method in inter-film combination mode |
| PCT/CN2021/076043 WO2021164616A1 (en) | 2020-02-17 | 2021-02-08 | Method for coating of dense hydrophobic film by plasma chemical vapor deposition method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010097649.5A CN111188032B (en) | 2020-02-17 | 2020-02-17 | Hydrophobic film plating method by plasma chemical vapor deposition method in inter-film combination mode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111188032A CN111188032A (en) | 2020-05-22 |
| CN111188032B true CN111188032B (en) | 2021-07-09 |
Family
ID=70703906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010097649.5A Active CN111188032B (en) | 2020-02-17 | 2020-02-17 | Hydrophobic film plating method by plasma chemical vapor deposition method in inter-film combination mode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111188032B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021164616A1 (en) * | 2020-02-17 | 2021-08-26 | 佛山市思博睿科技有限公司 | Method for coating of dense hydrophobic film by plasma chemical vapor deposition method |
| CN111992476A (en) * | 2020-08-26 | 2020-11-27 | 佛山市思博睿科技有限公司 | Plasma chemical vapor deposition nano super-hydrophilic anti-fog coating and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103469205A (en) * | 2013-08-01 | 2013-12-25 | 合肥永信等离子技术有限公司 | Coating process for lotus leaf-like diamond film |
| CN107587121A (en) * | 2017-08-03 | 2018-01-16 | 深圳市科益实业有限公司 | The preparation method of DLC film and eyeglass |
| CN107921474A (en) * | 2015-08-27 | 2018-04-17 | 萨里纳米系统有限公司 | Ultra-low reflectance hydrophobic coating and its method |
| CN109535785A (en) * | 2018-11-27 | 2019-03-29 | 东莞市和域战士纳米科技有限公司 | A kind of super-hydrophobic transparent waterproof membrane and preparation method thereof |
| CN110029327A (en) * | 2019-04-24 | 2019-07-19 | 佛山市思博睿科技有限公司 | A kind of hydrophobic film method of plasma chemical vapor deposition circulation plating |
| CN110665768A (en) * | 2019-07-26 | 2020-01-10 | 江苏菲沃泰纳米科技有限公司 | Waterproof nano film and preparation method, application and product thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150100414A (en) * | 2014-02-25 | 2015-09-02 | 성균관대학교산학협력단 | Preparing method of abrasion resistible, hydrophobic and oleophobic coating film, and coating film thereby |
-
2020
- 2020-02-17 CN CN202010097649.5A patent/CN111188032B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103469205A (en) * | 2013-08-01 | 2013-12-25 | 合肥永信等离子技术有限公司 | Coating process for lotus leaf-like diamond film |
| CN107921474A (en) * | 2015-08-27 | 2018-04-17 | 萨里纳米系统有限公司 | Ultra-low reflectance hydrophobic coating and its method |
| CN107587121A (en) * | 2017-08-03 | 2018-01-16 | 深圳市科益实业有限公司 | The preparation method of DLC film and eyeglass |
| CN109535785A (en) * | 2018-11-27 | 2019-03-29 | 东莞市和域战士纳米科技有限公司 | A kind of super-hydrophobic transparent waterproof membrane and preparation method thereof |
| CN110029327A (en) * | 2019-04-24 | 2019-07-19 | 佛山市思博睿科技有限公司 | A kind of hydrophobic film method of plasma chemical vapor deposition circulation plating |
| CN110665768A (en) * | 2019-07-26 | 2020-01-10 | 江苏菲沃泰纳米科技有限公司 | Waterproof nano film and preparation method, application and product thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111188032A (en) | 2020-05-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111519171B (en) | Hydrophobic film plating method by plasma chemical vapor deposition method with compact film layer | |
| CN111188032B (en) | Hydrophobic film plating method by plasma chemical vapor deposition method in inter-film combination mode | |
| EP1632280B1 (en) | Plasma treated porous materials | |
| CN110139719B (en) | Hydrophilic multifunctional ultrathin coating with excellent stability and durability | |
| Sun et al. | Surface modification of poly (tetrafluoroethylene) films via plasma treatment and graft copolymerization of acrylic acid | |
| JP5360963B2 (en) | Catalyst-free metallization method on dielectric substrate surface and dielectric substrate with metal film | |
| Babaei et al. | Tuning the surface properties of oxygen-rich and nitrogen-rich plasma polymers: functional groups and surface charge | |
| CN109913855B (en) | Hydrophobic material and hydrophobic film coating method | |
| Myung et al. | Chemical structure and surface morphology of plasma polymerized-allylamine film | |
| JP2001525493A (en) | Improvement of metal surfaces by plasma polymerization for use in cooling and air conditioning | |
| Ogumi et al. | Modification of Ion Exchange Membrane Surface by Plasma Process: I. H+ Ion Perm‐Selective Membrane from Nafion for Redox‐Flow Battery | |
| CN109750276A (en) | Based on inert gas/oxygen plasma membrane deposition method and device | |
| CN111020535B (en) | Preparation method of plasma chemical vapor deposition nano-film of cell counting plate | |
| Hartwig et al. | Surface amination of poly (acrylonitrile) | |
| EP1040210B1 (en) | Plasma polymerization on surface of material | |
| CZ2001431A3 (en) | Process for producing electric insulator | |
| WO2021164616A1 (en) | Method for coating of dense hydrophobic film by plasma chemical vapor deposition method | |
| CN113275217B (en) | Preparation method of plasma graft copolymerization film layer | |
| Weichart et al. | Preparation and characterization of glassy plasma polymer membranes | |
| Lai et al. | Plasma graft polymerization membrane of acrylamide for pervaporation separation of aqueous alcohol mixtures | |
| Biederman et al. | Plasma treatment of solid surfaces for biomedical applications | |
| JP2023174602A (en) | Resin surface hydrophilizing method, resin surface hydrophilizing device, and electronic substrate treatment device | |
| CN117487229A (en) | Material surface treatment method and cell culture vessel | |
| PL241483B1 (en) | Method of producing durable hydrophobic coating on the surface of ceramic tiles by plasma technique | |
| CN117483162A (en) | Surface treatment equipment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 528000 No.102, 1st floor, No.3 building, industrial zone, zone B, Hantian science and Technology City, north of Dongping Road, Pingxi Shanghai Village, Guicheng Street, Nanhai District, Foshan City, Guangdong Province Applicant after: FOSHAN SIBORUI TECHNOLOGY Co.,Ltd. Address before: 528051 Workshop on the fifth floor (1-6 axis) of 7 buildings in the core Park of Guangdong new light source industrial base, Luocun, Shishan town, Nanhai District, Foshan City, Guangdong Province Applicant before: FOSHAN SIBORUI TECHNOLOGY Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |