CN115572400B - Preparation method of high-density composite atomic oxygen protective film - Google Patents
Preparation method of high-density composite atomic oxygen protective film Download PDFInfo
- Publication number
- CN115572400B CN115572400B CN202211236543.4A CN202211236543A CN115572400B CN 115572400 B CN115572400 B CN 115572400B CN 202211236543 A CN202211236543 A CN 202211236543A CN 115572400 B CN115572400 B CN 115572400B
- Authority
- CN
- China
- Prior art keywords
- layer
- film
- sio
- oxygen
- siloxane
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000001681 protective effect Effects 0.000 title claims abstract description 16
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000576 coating method Methods 0.000 claims abstract description 32
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 22
- 239000011368 organic material Substances 0.000 claims abstract description 21
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 56
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 239000000178 monomer Substances 0.000 claims description 30
- 239000001301 oxygen Substances 0.000 claims description 29
- 229910052760 oxygen Inorganic materials 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 27
- 229910052710 silicon Inorganic materials 0.000 claims description 27
- 239000010703 silicon Substances 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000010926 purge Methods 0.000 claims description 11
- 238000000151 deposition Methods 0.000 claims description 10
- 229920006268 silicone film Polymers 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 8
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 7
- 239000012159 carrier gas Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 5
- 239000007888 film coating Substances 0.000 claims description 5
- 238000009501 film coating Methods 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- OWKFQWAGPHVFRF-UHFFFAOYSA-N n-(diethylaminosilyl)-n-ethylethanamine Chemical compound CCN(CC)[SiH2]N(CC)CC OWKFQWAGPHVFRF-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002861 polymer material Substances 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 56
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 42
- 210000002381 plasma Anatomy 0.000 abstract description 20
- 230000007547 defect Effects 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 10
- 239000011253 protective coating Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000010408 film Substances 0.000 abstract 4
- 239000010409 thin film Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 69
- 239000000463 material Substances 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 238000011010 flushing procedure Methods 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 239000004447 silicone coating Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
- C08J7/0423—Coating with two or more layers, where at least one layer of a composition contains a polymer binder with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
-
- 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
- C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45536—Use of plasma, radiation or electromagnetic fields
-
- 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
- C23C16/455—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 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45555—Atomic layer deposition [ALD] applied in non-semiconductor technology
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Electromagnetism (AREA)
- Formation Of Insulating Films (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The invention discloses a preparation method of a high-density composite atomic oxygen protective film, which prepares SiO on an organic material substrate by a plasma enhanced atomic layer deposition technology x A thin film seed layer. And preparing a siloxane film intermediate layer on the SiOx film seed layer by adopting a chemical vapor deposition technology. And preparing the SiOx cap layer on the siloxane film intermediate layer by adopting a plasma enhanced atomic layer deposition technology. Wherein the SiOx seed layer can effectively reduce microscopic defects in the siloxane coating and prevent the formation of atomic oxygen denudation channels. The SiOx cap layer can effectively cover defects such as holes, cracks and the like on the surface of the siloxane, and simultaneously enhances the atomic oxygen protection performance. The flexibility of the siloxane coating prepared by the plasmas is exerted, the compactness of the coating deposited by the atomic layer is exerted, and the comprehensive performance of the protective coating is obviously improved.
Description
Technical Field
The invention relates to the technical field of atomic oxygen degradation prevention, in particular to a preparation method of a high-density composite atomic oxygen protective film.
Background
In low earth orbit environment, atomic oxygen is generated by short wavelength in solar irradiation<243 nm) of oxygen. Is one of the major spatial environmental factors in a low-track environment. The on-orbit spacecraft flies around the earth at a speed of about 7.8km/s, with an average energy of impact with atomic oxygen reaching 4.5eV. The material has strong erosion effect on the surface material of the spacecraft, changes the optical, electrical and thermal properties of the surface material of the spacecraft, and influences the service life of the spacecraft. And the atomic oxygen impact energy increases as the orbit height decreases. As the number of low orbit satellites increases, the on-orbit time becomes longer.Atomic oxygen cumulative flux of windward year of a track of, for example, 268km, 4.02X10 22 atoms/cm 2 The total flux of 8 years will reach 3.5X10 23 atoms/cm 2 . Organic structural materials, thermal control film materials, carbon fiber plates, etc., widely used in low-orbit satellites are extremely susceptible to atomic oxygen degradation. Thus, there is an urgent need for high performance atomic oxygen barrier coatings.
At present, only a layer of sufficiently dense protective coating is deposited on the surface of the material, so that the degradation effect of atomic oxygen on the substrate material can be prevented, for example, organic-inorganic hybrid siloxane coating and the like have good low-rail atomic oxygen protective capability, and the substrate can be effectively protected from being corroded by the atomic oxygen. However, the existence of microscopic defects such as holes in the silicone coating, which cause severe erosion of the substrate material by atomic oxygen, is the root cause of the overall quality loss. In addition, organic components exist in the siloxane coating, and under the irradiation of atomic oxygen for a long time, the organic components can be oxidized by the atomic oxygen to form volatile substances, so that the adhesion with a substrate is reduced, holes are gradually formed in the siloxane coating, and the atomic oxygen prevention performance is invalid.
Therefore, in order to improve the performance of the atomic oxygen protective coating, the microscopic defects of the atomic oxygen protective film must be reduced, the adhesive force is improved, and the high-density composite atomic oxygen protective film is developed.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a highly dense composite atomic oxygen protective film, in which the SiOx seed layer can effectively reduce microscopic defects in the siloxane coating and prevent the formation of atomic oxygen degradation channels. The SiOx cap layer can effectively cover defects such as holes, cracks and the like on the surface of the siloxane, and simultaneously enhances the atomic oxygen protection performance. The flexibility of the siloxane coating prepared by the plasmas is exerted, the compactness of the coating deposited by the atomic layer is exerted, and the comprehensive performance of the protective coating is obviously improved.
In order to achieve the above purpose, the technical scheme of the invention is as follows: the preparation method of the high-density composite atomic oxygen protective film comprises the steps of forming a four-layer structure of the high-density composite atomic oxygen protective film, wherein an organic material substrate, a SiOx seed layer, a siloxane film intermediate layer and a SiOx film cap layer are arranged from bottom to top. The preparation method comprises the following steps:
step 1: siOx seed layers are prepared on organic material substrates by plasma enhanced atomic layer deposition techniques.
Step 2: a silicone film interlayer was prepared on the SiOx seed layer using a chemical vapor deposition technique.
Step 3: and preparing the SiOx cap layer on the siloxane film intermediate layer by adopting a plasma enhanced atomic layer deposition technology.
Further, step 1: preparing a SiOx seed layer on an organic material substrate by a plasma enhanced atomic layer deposition technology; the method specifically comprises the following steps:
step 101: placing an organic material substrate in a reaction chamber of a plasma enhanced atomic layer deposition device, and vacuumizing the reaction chamber to 1×10 -3 ～10×10 -3 Pa。
Step 102: setting the growth temperature of the film to be 60-150 ℃; the silicon source monomer is carried by nitrogen into a reaction chamber, the flow rate of carrier gas is 5-30 standard milliliters per minute sccm, and the chemical adsorption reaction is completed on the surface of the sample prepared in the step 102 for 0.03-10 s; then, the excess monomer is purged by pure nitrogen with the flow of 20-80 sccm and the purging time of 5-30 s; introducing oxygen source monomer into the reaction chamber for 0.03-10 s, and performing chemical reaction with the monomer silicon source adsorbed before to generate SiOx film; and (3) flushing the redundant reaction byproducts and oxygen with nitrogen again, wherein the flow is 20-80 sccm, the flushing time is 5-30 s, the process is 1 cycle, and the above-mentioned cycles are repeated until the thickness meets the requirement, and stopping the equipment, thereby preparing the SiOx seed layer.
Further, the SiOx seed layer thickness ranges from 1 to 100nm.
Further, step 2: the preparation method of the siloxane film intermediate layer on the SiOx seed layer by adopting the chemical vapor deposition technology specifically comprises the following steps:
step 201: placing the organic material substrate and SiOx seed layer prepared in step 102 into a reaction chamber of a plasma enhanced chemical vapor deposition device, and vacuumizing the reaction chamber to 1X 10-3 to 10X 10-3Pa.
Step 202: introducing a mixed gas of a silicon source and oxygen into a film coating vacuum chamber, wherein the silicon source is 5-50 sccm, the oxygen flow is 0-500 sccm, the deposition air pressure is 5-40 Pa, the deposition power is 200-500W, and when the thickness of the siloxane coating reaches the required range of 200-600 nm, closing the equipment to obtain the siloxane film intermediate layer.
Further, the thickness of the silicone film intermediate layer is required to be between 200 and 600 nm.
Further, step 3: the SiOx cap layer is prepared on the siloxane film intermediate layer by adopting a plasma enhanced atomic layer deposition technology, and specifically comprises the following steps:
step 301: combining the organic material substrate obtained in the step 2, the SiOx seed layer and the siloxane film intermediate layer, placing the combined organic material substrate, siOx seed layer and siloxane film intermediate layer in a reaction chamber of plasma enhanced atomic layer deposition equipment, and vacuumizing the reaction chamber to 1X 10 -3 ～10×10 -3 Pa。
Step 302: setting the growth temperature of the film to be 60-150 ℃; the silicon source monomer is carried by nitrogen into a reaction chamber, the flow rate of carrier gas is 5-30 standard milliliters per minute sccm, and the chemical adsorption reaction is completed on the surface of the intermediate layer of the siloxane film for 0.03-10 s; then, the excess monomer is purged by pure nitrogen with the flow of 20-80 sccm and the purging time of 5-30 s; introducing oxygen source monomer into the reaction chamber for 0.03-10 s, and performing chemical reaction with the monomer silicon source adsorbed before to generate SiOx film; and (3) flushing the redundant reaction byproducts and oxygen with nitrogen again, wherein the flow is 20-80 sccm, the flushing time is 5-30 s, the process is 1 cycle, and the above-mentioned cycles are repeated until the thickness meets the requirement, and stopping the equipment, thereby preparing the SiOx cap layer.
Further, the SiOx cap layer thickness ranges between 5nm and 200 nm.
Further, the organic material substrate is a polyimide, polytetrafluoroethylene or polyurethane polymer material.
Further, in step 102, the silicon source is bis-diethylaminosilane and the oxygen source is oxygen or water.
Further, in step 202, the silicon source is hexamethyldisiloxane or tetramethyldisiloxane.
The beneficial effects are that:
firstly, depositing a layer of compact SiOx film without microscopic defects on the surface of an organic substrate by adopting a Plasma Enhanced Atomic Layer Deposition (PEALD) method, and taking the SiOx film as a seed layer for growing a siloxane coating; subsequently, plasma Enhanced Chemical Vapor Deposition (PECVD) is used to deposit SiO x A silicone coating is prepared on the seed layer. Finally, a layer of SiO is deposited on the surface of the siloxane by PEALD method x A film as a cap layer. Realization of SiO x siloxane/SiO x And (3) preparation of a composite coating. The advantages of the PEALD and PECVD film-making methods are complemented to reduce micropore defects and cracks in the coating, avoid the generation of permeability defects in the coating, prevent the development of various defects, greatly improve the atomic oxygen prevention performance of the coating, provide atomic oxygen protection for long-term in-orbit operation of low-orbit and ultra-low-orbit satellites, and ensure long service life, in-orbit performance of the low-orbit satellites and service life.
Drawings
Fig. 1 is a schematic diagram of the technical solution of the present invention.
1-substrate material, siOx seed layer prepared by 2-atomic layer deposition method, siloxane intermediate layer prepared by 3-plasma enhanced chemical vapor deposition method, siOx cap layer prepared by 4-atomic layer deposition method.
Detailed Description
The invention will now be described in detail by way of example with reference to the accompanying drawings.
The invention provides a preparation method of a high-density composite atomic oxygen protective film, which is of a four-layer structure, wherein an organic material substrate 1, a SiOx seed layer 2, a siloxane film intermediate layer 3 and a SiOx film cap layer 4 are respectively arranged from bottom to top, and the structure is shown in figure 1.
The preparation method comprises the following steps:
step 1: the SiOx seed layer 2 is prepared on the organic material substrate 1 by a plasma enhanced atomic layer deposition technique. In the step 1, the substrate is made of polymer materials such as polyimide, polytetrafluoroethylene or polyurethane.
The step 1 consists of the following two steps:
step 101: placing an organic material substrate 1 in a reaction chamber of a plasma enhanced atomic layer deposition apparatus, and evacuating the reaction chamber to 1×10 -3 ～10×10 -3 Pa；
Step 102: setting the growth temperature of the film to be 60-150 ℃; the silicon source monomer is carried by nitrogen into a reaction chamber, the flow rate of carrier gas is 5-30 standard milliliters per minute sccm, and the chemical adsorption reaction is completed on the surface of the sample prepared in the step 102 for 0.03-10 s; then, the excess monomer is purged by pure nitrogen with the flow of 20-80 sccm and the purging time of 5-30 s; introducing oxygen source monomer into the reaction chamber for 0.03-10 s, and performing chemical reaction with the monomer silicon source adsorbed before to generate SiOx film; the excess reaction by-products and oxygen were purged again with nitrogen gas at a flow rate of 20 to 80sccm for 5 to 30 seconds, the above-mentioned process was 1 cycle, and the above-mentioned multiple cycles were repeated until the thickness satisfied the requirement to stop the equipment, thereby producing the SiOx seed layer 2. In the embodiment of the invention, the silicon source is bis (diethylamino) silane or silicon tetrachloride, and the oxygen source is oxygen or water.
The thickness of the SiOx seed layer 2 in the embodiment of the invention is 1-100 nm.
Step 2: a silicone film intermediate layer 3 is prepared on the SiOx seed layer 2 using a chemical vapor deposition technique.
The step 2 consists of the following two steps:
step 201: the organic material substrate 1 and the SiOx seed layer 2 prepared in step 102 are placed in a reaction chamber of a plasma enhanced chemical vapor deposition apparatus, and the reaction chamber is evacuated to 1X 10-3 to 10X 10-3Pa.
Step 202: introducing a mixed gas of a silicon source and oxygen into a film coating vacuum chamber, wherein the silicon source is 5-50 sccm, the oxygen flow is 0-500 sccm, the deposition air pressure is 5-40 Pa, the deposition power is 200-500W, and when the thickness of the siloxane coating reaches the required range of 200-600 nm, closing the equipment to obtain the siloxane film intermediate layer 3. In the embodiment of the invention, the silicon source is hexamethyldisiloxane or tetramethyldisiloxane.
In the embodiment of the present invention, the thickness of the silicone film intermediate layer 3 is required to be between 200 and 600 nm.
Step 3: a SiOx cap layer 4 was prepared on the silicone film intermediate layer 3 using a plasma enhanced atomic layer deposition technique.
This step 3 is similar to the step of preparing the SiOx seed layer 2 in step 1, and consists of the following 2 steps.
Step 301: combining the organic material substrate 1 obtained in the step 2, the SiOx seed layer 2 and the siloxane film intermediate layer 3, placing the combined materials in a reaction chamber of a plasma enhanced atomic layer deposition device, and vacuumizing the reaction chamber to 1 multiplied by 10 -3 ～10×10 - 3 Pa；
Step 302: setting the growth temperature of the film to be 60-150 ℃; the silicon source monomer is carried by nitrogen into a reaction chamber, the flow rate of carrier gas is 5-30 standard milliliters per minute sccm, and the chemical adsorption reaction is completed on the surface of the siloxane film intermediate layer 3 for 0.03-10 s; then, the excess monomer is purged by pure nitrogen with the flow of 20-80 sccm and the purging time of 5-30 s; introducing oxygen source monomer into the reaction chamber for 0.03-10 s, and performing chemical reaction with the monomer silicon source adsorbed before to generate SiOx film; the excess reaction by-products and oxygen were purged again with nitrogen gas at a flow rate of 20 to 80sccm for 5 to 30 seconds, the above-mentioned process was 1 cycle, and the above-mentioned multiple cycles were repeated until the thickness satisfied the requirement to stop the equipment, thereby producing the SiOx cap layer 4.
The thickness of the SiOx cap layer 4 in the embodiment of the invention is in the range of 5nm to 200 nm.
Compared with the prior art, the invention has the following advantages: the SiOx cap layer is prepared by preparing a SiOx seed layer by a plasma enhanced atomic layer deposition technology, preparing an organosiloxane atomic oxygen prevention coating intermediate layer by a chemical vapor deposition technology, and finally preparing a SiOx cap layer by a plasma enhanced atomic layer deposition technology. The SiOx seed layer can effectively reduce microscopic defects in the siloxane coating and prevent the formation of atomic oxygen degradation channels. The SiOx cap layer can effectively cover defects such as holes, cracks and the like on the surface of the siloxane, and simultaneously enhances the atomic oxygen protection performance. The flexibility of the siloxane coating prepared by the plasmas is exerted, the compactness of the coating deposited by the atomic layer is exerted, and the comprehensive performance of the protective coating is obviously improved.
Example 1:
the preparation method comprises the following steps of: the high-density composite atomic oxygen protective film is respectively an organic material substrate 1 and SiO from bottom to top x A seed layer (2), a silicone film intermediate layer (3) and SiO x A cap layer (4); and x is 2, namely the silicon dioxide.
And (1) placing the polyimide substrate into a reaction chamber of plasma atomic layer deposition equipment, and vacuumizing the reaction chamber to 5 multiplied by 10 < -3 > Pa.
And (2) controlling the film growth temperature to be 90 ℃. The bis (diethylamino) silane is carried by argon into a reaction chamber, the flow rate of carrier gas is 20sccm, and the chemical adsorption reaction is completed on the surface of the sample prepared in the step (2) for 0.1s; then, the excess monomer is purged by pure argon, the flow is 50sccm, and the purging time is 10s; introducing monomer oxygen into the reaction chamber for 0.1s, and carrying out chemical reaction with a monomer silicon source adsorbed before to generate a silicon dioxide film; the excess reaction by-products and oxygen were again purged with argon at a flow rate of 5sccm for 10 seconds. The above procedure was 1 cycle. And repeating the above multiple periods until the thickness meets the requirement, and stopping the equipment, wherein the thickness range of the silicon dioxide is 5nm. Samples with a silica coating were prepared.
Step (3), placing the sample prepared in the step (1) in a coating vacuum chamber, and pumping the vacuum degree of the coating vacuum chamber to 5 multiplied by 10 < -3 > Pa;
and (4) heating the silicon source monomer hexamethyldisiloxane in a water bath to 35 ℃ to change the silicon source monomer from a liquid state into a gas. Mixing hexamethyldisiloxane monomer gas and oxygen together, and introducing into a vacuum chamber for coating. The hexamethyldisiloxane gas flow rate was 20sccm and the oxygen flow rate was 20sccm. The pressure of the coating vacuum chamber is controlled to be 0.8Pa; and starting a plasma source, ionizing the mixed gas in the vacuum chamber of the film plating by utilizing a PECVD method, and then depositing a siloxane coating on the polyimide substrate, wherein the deposition power is set to be 400W. By controlling the deposition time, controlling the thickness of the deposited coating to be about 400nm, and closing the apparatus, a sample of the silicone coating was obtained.
Step (5) this step is similar to step (2) and gives a sample with a silica coating of 20nm thickness. The preparation of the SiO 2/siloxane/SiO 2 composite coating is completed, and the total thickness of the composite coating is controlled to be about 450 nm.
Experiments show that the adhesive force of the siloxane protective film with the silicon dioxide seed layer is improved from 0.5N/mm to 0.8N/mm; compared with a siloxane film, the erosion rate of the composite film with the silicon dioxide cap layer is reduced from 2.3X10-26 cm-3/atom to 9X 10-28cm-3/atom, and the protective coating is subjected to 1000 times of alternation at the temperature of minus 100 ℃ to plus 100 ℃ and has no delamination, falling off or cracking.
In summary, the above embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. A preparation method of a high-density composite atomic oxygen protective film is characterized in that the prepared high-density composite atomic oxygen protective film has a four-layer structure, and an organic material substrate (1) and SiO are respectively arranged from bottom to top x A seed layer (2), a silicone film intermediate layer (3) and SiO x A cap layer (4); the value of x is [1,2 ]]Real numbers within the range;
the preparation method comprises the following steps:
step 1: preparation of SiO on an organic material substrate (1) by means of a plasma-enhanced atomic layer deposition technique x A seed layer (2); the method specifically comprises the following steps:
step 101: placing an organic material substrate (1) in a reaction chamber of a plasma enhanced atomic layer deposition device, and vacuumizing the reaction chamber to 1×10 -3 ～10×10 -3 Pa；
Step 102: setting the growth temperature of the film to be 60-150 ℃; the silicon source monomer is carried by nitrogen into the reaction chamber, and the flow rate of the carrier gas is 5-30 standard milliliters per minutesccm, completing chemical adsorption reaction on the surface of the sample prepared in the step 102, wherein the time is 0.03-10 s; then, the excess monomer is purged by pure nitrogen with the flow rate of 50-80 sccm and the purging time of 5-30 s; introducing oxygen source monomer into the reaction chamber for 0.03-10 s, and performing chemical reaction with the monomer silicon source adsorbed before to generate SiO x A film; purging the excess reaction by-product and oxygen with nitrogen gas again at a flow rate of 20-80 sccm for 5-30 s, wherein the purging time is 1 cycle, and repeating the above-mentioned cycles until the thickness meets the requirement, stopping the equipment, thereby preparing SiO x A seed layer (2);
step 2: siO is deposited on the substrate by chemical vapor deposition technique x Preparing a siloxane film intermediate layer (3) on the seed layer (2); the method specifically comprises the following steps:
step 201: the organic material substrate (1) and SiO obtained in step 102 are subjected to a reaction x The seed layer (2) is placed in a reaction chamber of the plasma enhanced chemical vapor deposition equipment, and the reaction chamber is vacuumized to 1 multiplied by 10 < -3 > to 10 multiplied by 10 < -3 > Pa;
step 202: introducing a mixed gas of a silicon source and oxygen into a film coating vacuum chamber, wherein the silicon source flows into the film coating vacuum chamber at a rate of 5-50 sccm, the oxygen flows into the film coating vacuum chamber at a rate of 0-500 sccm, the deposition air pressure is 5-40 Pa, the deposition power is 200-500W, and when the thickness of a siloxane coating reaches the required thickness of 200-600 nm, closing the equipment to obtain a siloxane film intermediate layer (3);
step 3: preparation of SiO on a silicone film intermediate layer (3) by means of a plasma-enhanced atomic layer deposition technique x A cap layer (4), the thickness of the silicone film intermediate layer (3) being required to be between 200 and 600 nm;
the method specifically comprises the following steps:
step 301: the organic material substrate (1) and SiO obtained in the step 2 are subjected to x The seed layer (2) and the siloxane film intermediate layer (3) are combined, placed in a reaction chamber of a plasma enhanced atomic layer deposition device, and the reaction chamber is vacuumized to 1 multiplied by 10 -3 ～10×10 - 3 Pa；
Step 302: setting the growth temperature of the film to be 60-150 ℃; the silicon source monomer is carried by nitrogen into the reaction chamber, the flow rate of the carrier gas is 5-30 standard milliliters per minute sccm,the chemical adsorption reaction is completed on the surface of the siloxane film intermediate layer (3) for 0.03-10 s; then, the excess monomer is purged by pure nitrogen with the flow rate of 50-80 sccm and the purging time of 5-30 s; introducing oxygen source monomer into the reaction chamber for 0.03-10 s, and performing chemical reaction with the monomer silicon source adsorbed before to generate SiO x A film; purging the excess reaction by-product and oxygen with nitrogen gas again at a flow rate of 20-80 sccm for 5-30 s, wherein the purging time is 1 cycle, and repeating the above-mentioned cycles until the thickness meets the requirement, stopping the equipment, thereby preparing SiO x A cap layer (4);
the SiO is x The thickness range of the seed layer (2) is 5-100 nm;
the SiO is x The thickness of the cap layer (4) ranges from 20nm to 200 nm.
2. The method for preparing a highly dense composite atomic oxygen protective film according to claim 1, wherein the organic material substrate (1) is polyimide, polytetrafluoroethylene or polyurethane polymer material.
3. The method of claim 1, wherein the silicon source in the step 102 is bis-diethylaminosilane and the oxygen source is oxygen or water.
4. The method of claim 1, wherein the silicon source in the step 202 is hexamethyldisiloxane or tetramethyldisiloxane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211236543.4A CN115572400B (en) | 2022-10-10 | 2022-10-10 | Preparation method of high-density composite atomic oxygen protective film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211236543.4A CN115572400B (en) | 2022-10-10 | 2022-10-10 | Preparation method of high-density composite atomic oxygen protective film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115572400A CN115572400A (en) | 2023-01-06 |
| CN115572400B true CN115572400B (en) | 2023-11-07 |
Family
ID=84585807
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211236543.4A Active CN115572400B (en) | 2022-10-10 | 2022-10-10 | Preparation method of high-density composite atomic oxygen protective film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115572400B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116271213B (en) * | 2023-03-13 | 2023-10-20 | 浙江广慈医疗器械有限公司 | Polyether-ether-ketone-based high-activity biological fusion device, preparation method and application thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000127286A (en) * | 1998-10-27 | 2000-05-09 | Dainippon Printing Co Ltd | Barrier film and laminate employing the same |
| CN1446124A (en) * | 2000-08-01 | 2003-10-01 | 西德尔公司 | Plasma Deposited barrier coating comprising and interface layer, method for obtaining same and container coated therewith |
| CN103187455A (en) * | 2006-11-01 | 2013-07-03 | 普林斯顿大学理事会 | Hybrid layers for use in coatings on electronic devices or other articles |
| CN106366337A (en) * | 2016-08-30 | 2017-02-01 | 兰州空间技术物理研究所 | Preparation method of composite atomic oxygen protecting coating |
| WO2018060953A1 (en) * | 2016-09-30 | 2018-04-05 | Sabic Global Technologies B.V. | Method for plasma coating on thermoplastic |
| CN108411279A (en) * | 2018-03-30 | 2018-08-17 | 华中科技大学 | A kind of preparation method of high-speed steel tool protective coating |
| WO2019064154A1 (en) * | 2017-09-29 | 2019-04-04 | Sabic Global Technologies B.V. | Container including a plasma-enhanced chemical vapor deposition film |
| CN109608678A (en) * | 2018-11-07 | 2019-04-12 | 无锡泓瑞航天科技有限公司 | A kind of sandwich structure siloxane film and preparation method thereof |
| WO2019151495A1 (en) * | 2018-02-02 | 2019-08-08 | 凸版印刷株式会社 | Gas-barrier film and manufacturing method therefor |
| CN111116962A (en) * | 2019-12-26 | 2020-05-08 | 兰州空间技术物理研究所 | Preparation method of atomic oxygen prevention film for space polymer material |
| CN112725765A (en) * | 2020-12-29 | 2021-04-30 | 兰州空间技术物理研究所 | Composite preparation method of high-density coating |
| CN115116839A (en) * | 2022-07-28 | 2022-09-27 | 西安电子科技大学 | Silicon carbide substrate based gate dielectric material with high dielectric constant and preparation method thereof |
-
2022
- 2022-10-10 CN CN202211236543.4A patent/CN115572400B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000127286A (en) * | 1998-10-27 | 2000-05-09 | Dainippon Printing Co Ltd | Barrier film and laminate employing the same |
| CN1446124A (en) * | 2000-08-01 | 2003-10-01 | 西德尔公司 | Plasma Deposited barrier coating comprising and interface layer, method for obtaining same and container coated therewith |
| CN103187455A (en) * | 2006-11-01 | 2013-07-03 | 普林斯顿大学理事会 | Hybrid layers for use in coatings on electronic devices or other articles |
| CN106366337A (en) * | 2016-08-30 | 2017-02-01 | 兰州空间技术物理研究所 | Preparation method of composite atomic oxygen protecting coating |
| WO2018060953A1 (en) * | 2016-09-30 | 2018-04-05 | Sabic Global Technologies B.V. | Method for plasma coating on thermoplastic |
| CN109923239A (en) * | 2016-09-30 | 2019-06-21 | 沙特基础工业全球技术公司 | Method for the coating of thermoplastic material plasma |
| WO2019064154A1 (en) * | 2017-09-29 | 2019-04-04 | Sabic Global Technologies B.V. | Container including a plasma-enhanced chemical vapor deposition film |
| WO2019151495A1 (en) * | 2018-02-02 | 2019-08-08 | 凸版印刷株式会社 | Gas-barrier film and manufacturing method therefor |
| CN108411279A (en) * | 2018-03-30 | 2018-08-17 | 华中科技大学 | A kind of preparation method of high-speed steel tool protective coating |
| CN109608678A (en) * | 2018-11-07 | 2019-04-12 | 无锡泓瑞航天科技有限公司 | A kind of sandwich structure siloxane film and preparation method thereof |
| CN111116962A (en) * | 2019-12-26 | 2020-05-08 | 兰州空间技术物理研究所 | Preparation method of atomic oxygen prevention film for space polymer material |
| CN112725765A (en) * | 2020-12-29 | 2021-04-30 | 兰州空间技术物理研究所 | Composite preparation method of high-density coating |
| CN115116839A (en) * | 2022-07-28 | 2022-09-27 | 西安电子科技大学 | Silicon carbide substrate based gate dielectric material with high dielectric constant and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| A combinatorial approach to enhance barrier properties of thin films on polymers: Seeding and capping of PECVD thin films by PEALD;Maximilian Gebhard et al;《PLASMA PROCESSES AND POLYMERS》;第15卷(第5期);1-11 * |
| 硅氧烷原子氧防护膜工艺及防护性能研究;郑阔海;《航天器环境工程》;第27卷(第6期);第751-755页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115572400A (en) | 2023-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6370816B2 (en) | High performance coating deposition equipment | |
| US8436533B2 (en) | Hybrid layers for use in coatings on electronic devices or other articles | |
| US5824198A (en) | Process for barrier coating of plastic objects | |
| US8592253B2 (en) | Hybrid layers for use in coatings on electronic devices or other articles | |
| EP2466665A1 (en) | Hybrid layers for use in coatings on electronic devices or other articles | |
| Kim et al. | Transparent hybrid inorganic/organic barrier coatings for plastic organic light-emitting diode substrates | |
| KR101210859B1 (en) | Coated substrates and methods for their preparation | |
| US9281420B2 (en) | Chemical vapor deposited film formed by plasma CVD method | |
| CN115572400B (en) | Preparation method of high-density composite atomic oxygen protective film | |
| WO2007145075A1 (en) | Silicon thin-film and method of forming silicon thin-film | |
| JP2019050196A (en) | Electronic device and manufacturing method thereof | |
| JP4881153B2 (en) | Method for producing a hydrogenated silicon oxycarbide film. | |
| WO2013132890A1 (en) | Silicon-containing film and method for forming silicon-containing film | |
| JP2013185206A5 (en) | ||
| KR20140087470A (en) | Deposition method of passivation film for light emitting diode | |
| JP2012206448A (en) | Gas barrier laminate, method for producing the same, member for electronic device, and electronic device | |
| Bozso et al. | Electron‐induced chemical vapor deposition by reactions induced in adsorbed molecular layers | |
| KR100965847B1 (en) | A board having layer for preventing humidity | |
| CN115537813A (en) | Preparation method of antistatic composite atomic oxygen protective coating for space | |
| CN112831769B (en) | Composite antireflection film for infrared optical product and preparation method thereof | |
| Rao | Development of Flexible Electronics Packaging Technology | |
| CN117501455A (en) | Preparation method of CIGS light absorption layer for solar cell by chemical vapor deposition method | |
| JP2020041183A (en) | Superhydrophilic coating and forming method thereof | |
| JP2020205293A (en) | Solar cell module | |
| Kaabeche et al. | Development of Plasma Enhanced Chemical Vapor Deposition for Moisture Barrier On Polyethylene Terephthalate Substrates |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |