CN113275331A - Method and special device for material surface treatment - Google Patents
Method and special device for material surface treatment Download PDFInfo
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- CN113275331A CN113275331A CN202110594926.8A CN202110594926A CN113275331A CN 113275331 A CN113275331 A CN 113275331A CN 202110594926 A CN202110594926 A CN 202110594926A CN 113275331 A CN113275331 A CN 113275331A
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- 239000000463 material Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000004381 surface treatment Methods 0.000 title claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 claims abstract description 25
- 239000012495 reaction gas Substances 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims description 45
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000005530 etching Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000006552 photochemical reaction Methods 0.000 abstract description 2
- 238000003672 processing method Methods 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 238000000059 patterning Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- 238000003854 Surface Print Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0075—Cleaning of glass
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/02—Elements
- C30B29/06—Silicon
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/005—Oxydation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Metallurgy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- ing And Chemical Polishing (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Drying Of Semiconductors (AREA)
Abstract
The invention discloses a method for treating the surface of a material, which is characterized in that reaction gas is irradiated by ultraviolet rays to generate strong oxidizing active groups, and the strong oxidizing active groups are oriented to the surface of the material for treatment. Meanwhile, the invention also discloses a special device suitable for the processing method. The treatment process of the invention is a soft photochemical reaction, does not damage the material, and has no redundant treatment steps; the active groups are guided to the surface of the material for reaction, the treatment result is controllable, the repeatability is good, the efficiency is high, and the method is suitable for large-area high-precision surface treatment; the adopted equipment has simple structure and low investment cost, and is easy to be upgraded into large-scale large-area treatment equipment.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a method and a special device for material surface treatment.
Background
Chinese patent CN108544084A discloses a processing device for modifying the surface of a material by using laser. The device structure is complicated, and the cost is high, can inevitably lead to the fact the damage and cause deckle edge to the base plate material when handling atomic level thickness material, and the treatment effeciency reduces along with the increase of treatment area.
Chinese patent CN112233955A discloses a method and apparatus for ion etching surface treatment using an ion source. The apparatus is expensive, has poor uniformity of ion energy distribution, and is prone to substrate damage and undesirable excess processing.
Chinese patent CN108212950B discloses an extreme ultraviolet light cleaning device, which stabilizes the oxygen concentration in the chamber by intelligent control, and stabilizes the concentration of the generated active oxygen atoms and ozone to achieve the cleaning effect. However, the active groups generated by the method move above the surface of the substrate in a disordered manner, only part of the active groups randomly reach the surface of the substrate, the surface treatment effect is uncertain, the randomness is strong, and the treatment effect is poor.
Chinese patents CN110862083A and CN107611020A disclose a method for patterning by attracting paramagnetic strong oxidizing group to the surface of graphene through a magnetic field. The method relates to the adoption of a complex vacuum cavity system and the design of magnetic field intensity, is not suitable for processing large-area material workpieces, prolongs the process time due to vacuum acquisition and is inconvenient for the flow operation of a production line.
Chinese patent CN104752156A discloses a method for patterning a nano-carbon material film, which decomposes ozone generated by an external ozone generator into active atomic oxygen by ultraviolet rays, and simultaneously breaks the covalent bond of the carbon material by the ultraviolet rays to generate active carbon atoms, so that the carbon atoms and the active carbon atoms react to generate gaseous carbon oxide, thereby realizing the purpose of patterning the surface by etching. The method mainly indirectly generates active oxygen atoms by decomposing ozone, the generated active oxygen atoms move on the surface of a material to be treated in a disordered way, the treatment efficiency is poor, the efficiency can be improved only by heating the material at high temperature, and the method is not beneficial to large-area surface treatment.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to overcome the defects of the prior art and provide a method for surface treatment of materials.
Meanwhile, the invention also discloses a special device suitable for the material surface treatment method.
The technical scheme is as follows: in order to achieve the above object, the present invention is specifically realized as follows: the method for treating the surface of the material comprises the steps of irradiating reaction gas by ultraviolet rays to generate strong oxidizing active groups, and guiding the strong oxidizing active groups to the surface of the material for treatment.
Preferably, the material is a material capable of being oxidized.
Preferably, the reactive gases are oxygen and water vapor.
Preferably, the strongly oxidizing reactive group is an active oxygen group O (3p) or an active intermediate HO.
Preferably, the process of treating the surface of the material comprises cleaning, oxidizing, modifying or etching the surface of the material.
Preferably, the reaction gas is oxygen, the oxygen content is less than or equal to 0.01V/V% under the protection of nitrogen or argon, and the gas is at normal pressure and one atmosphere.
Preferably, the reaction gas is water vapor, the nitrogen or argon is used for protection, the water vapor content is less than or equal to 0.2V/V%, and the gas has normal pressure and one atmosphere pressure.
Preferably, the gas is passed through the UV irradiation region in the form of a gas stream, and the resulting strongly oxidizing radicals are directed with the gas stream to the surface of the material perpendicular to the gas stream for treatment.
Preferably, ultraviolet light having a wavelength of 126nm, 146nm, 175nm, 193nm, or any combination thereof is used. The optical absorption coefficient of oxygen and water molecules at these several ultraviolet wavelengths is as high as 107And/m, reactive groups are easily generated. While the highly transparent materials required for the fabrication of light sources of these several wavelengths are still available on the market. Light source systems with wavelengths shorter than 126nm are complex and expensive, and cannot use simple and convenient high-light-transmittance material windows to lead out ultraviolet light, so that the light source systems do not haveThe method is used for the flow production of industrial production lines.
The strongly oxidizing reactive groups are obtained in particular by the following reaction:
O2+hν→O(3p)+O(3p), h v refers to ultraviolet photon energy, and the vacuum ultraviolet wavelength lambda of the ultraviolet photon energy is ultraviolet rays with any combination of 126, 146, 175 and 193 nm;
H2o + H v → HO + H, H v refers to ultraviolet photon energy, and the vacuum ultraviolet wavelength lambda is ultraviolet ray of any combination of 126, 146, 175 and 193 nm.
The method for treating the surface of the material can adopt a special device for treatment, and comprises a reactor, wherein the inside of the reactor is divided into three parts by a group of parallel flow equalizing plates, a gas mixing area at the top, an ultraviolet light irradiation area between the two flow equalizing plates and an oxidation reaction area at the bottom; the reactor part corresponding to the mixing zone is provided with a reaction gas inlet and a protective gas inlet, a group of ultraviolet lamps are clamped and fixed in the ultraviolet irradiation zone through a flow equalizing plate, a workbench is arranged in the oxidation reaction zone, and the bottom of the corresponding reactor is provided with a tail gas outlet.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) the treatment process of the invention is a soft photochemical reaction, does not damage the material of the material substrate, and has no redundant treatment steps;
(2) the method leads the active groups to the surface of the material for reaction, has controllable processing result, good repeatability and high efficiency, and is suitable for large-area high-precision surfaces;
(3) the equipment adopted by the invention has simple structure and low investment cost, and is easy to be upgraded into large-scale large-area treatment equipment.
Drawings
Fig. 1 is a schematic structural diagram of an apparatus suitable for surface treatment of a material.
Detailed Description
Example 1:
introducing oxygen and nitrogen into the reactor, controlling the oxygen content to be less than or equal to 0.01V/V%, and controlling the gas to have one atmosphere at normal pressure; the mixed gas passes through an ultraviolet irradiation area (the ultraviolet wavelength is 126nm) in the form of gas flow to generate strong oxidizing radicals, and the strong oxidizing radicals are guided to the surface of a material vertical to the gas flow along with the gas flow to be treated, for example, organic pollutants on the surface of the liquid crystal display glass can be oxidized into carbon dioxide and water vapor within 0.5 minute, and the carbon dioxide and the water vapor are gasified and escaped to leave a clean glass surface, thereby meeting the requirements of the manufacturing process.
Example 2:
introducing water vapor and argon into a reactor, controlling the water vapor content to be less than or equal to 0.2V/V%, and controlling the gas to have one atmospheric pressure at normal pressure; the mixed gas passes through an ultraviolet irradiation area (the ultraviolet wavelength is 146nm) in the form of gas flow to generate strong oxidizing groups, and the strong oxidizing groups are guided to the surface of a material perpendicular to the gas flow along with the gas flow to be treated, for example, the surface of a crystalline silicon can be oxidized within 30 minutes to generate the silicon dioxide of an insulating layer required by wafer manufacturing.
Example 3:
introducing oxygen and argon into the reactor, controlling the oxygen content to be less than or equal to 0.01V/V%, and controlling the gas to have one atmosphere at normal pressure; the mixed gas passes through an ultraviolet irradiation area (the ultraviolet wavelength is 175nm) in the form of gas flow to generate strong oxidizing groups, and the strong oxidizing groups are guided to the surface of the material perpendicular to the gas flow along with the gas flow to be treated, for example, the surface energy of the plastic surface can be changed after being oxidized within 60 minutes, so that the adhesiveness of the plastic surface with the surface printing ink is improved.
Example 4:
introducing water vapor and nitrogen into a reactor, controlling the water vapor content to be less than or equal to 0.2V/V%, and controlling the gas to have one atmospheric pressure at normal pressure; the mixed gas passes through an ultraviolet irradiation area (the ultraviolet wavelength is 146nm) in the form of gas flow to generate strong oxidizing groups, the strong oxidizing groups are guided to the surface of the material perpendicular to the gas flow along with the gas flow for treatment, such as graphite or carbon surface is covered with a mask so that the uncovered part can be oxidized within 30 minutes, and the generated carbon dioxide is gasified and escaped, and a microstructure required by the process is left.
Example 5:
the special device for material surface treatment as shown in fig. 1 comprises a reactor 1, the reactor 1 is divided into three parts by a group of parallel flow equalizing plates 2, a gas mixing area 3 at the top, an ultraviolet light irradiation area 4 between the two flow equalizing plates, and an oxidation reaction area 5 at the bottom; the reactor part corresponding to the mixing zone 3 is provided with a reaction gas inlet 6 and a protective gas inlet 7, a group of ultraviolet lamps 8 are clamped and fixed in the ultraviolet irradiation zone 4 through a flow equalizing plate 2, a workbench 9 is arranged in the oxidation reaction zone 5, and a tail gas outlet 10 is arranged at the bottom of the corresponding reactor 1. In the specific operation process, a workpiece to be treated is placed on a workbench of an oxidation reaction zone through an opening in the side wall of the reactor, the workbench can also be a heatable workbench to increase the oxidation speed of strong oxidizing groups and the workpiece to be reacted, then a reaction gas inlet and a protective gas inlet are opened to control the content of reaction gas, the reaction gas and the protective gas are oxidized by an ultraviolet lamp under the control of pressure to generate the strong oxidizing groups, and then the strong oxidizing groups pass through a flow equalizing plate under the control of pressure and are uniformly irradiated on the surface of the workpiece to be treated to be cleaned, oxidized, modified or etched.
Claims (10)
1. The method for treating the surface of the material is characterized in that reaction gas is irradiated by ultraviolet rays to generate strong oxidizing active groups, and the strong oxidizing active groups are oriented to the surface of the material for treatment.
2. The method for the surface treatment of a material according to claim 1, characterized in that the material is a material capable of being oxidized.
3. The method for the surface treatment of materials according to claim 1, characterized in that the reactive gas is oxygen and water vapor.
4. The method for the surface treatment of materials according to claim 1, characterized in that said strongly oxidizing reactive groups are reactive oxygen groups O (O: (a) (b))3 p) Or an active intermediate HO.
5. The method for material surface treatment according to claim 1, wherein the material surface treatment process comprises cleaning, oxidizing, modifying or etching the material surface.
6. The method as claimed in claim 1, wherein the reaction gas is oxygen protected with nitrogen or argon, the oxygen content is less than or equal to 0.01V/V%, and the gas is at normal pressure and one atmosphere.
7. The method as claimed in claim 1, wherein the reaction gas is water vapor, the reaction gas is protected by nitrogen or argon, the water vapor content is less than or equal to 0.2V/V%, and the gas has a normal pressure of one atmosphere.
8. The method according to claim 1, wherein the reactive gas is passed through the ultraviolet irradiation region in the form of a forced gas flow, and the generated strongly oxidizing radicals are guided with the gas flow to the surface of the material perpendicular to the direction of the gas flow for treatment.
9. The method for the surface treatment of materials according to claim 1, characterized in that uv light with a wavelength of 126nm, 146nm, 175nm, 193nm or any combination thereof is used.
10. A special device suitable for the method for surface treatment of materials according to any one of claims 1 to 9, comprising a reactor, wherein the reactor is divided into three parts by a group of parallel flow equalizing plates, a gas mixing area at the top, an ultraviolet light irradiation area between the two flow equalizing plates, and an oxidation reaction area at the bottom; the reactor part corresponding to the mixing zone is provided with a reaction gas inlet and a protective gas inlet, a group of ultraviolet lamps are clamped and fixed in the ultraviolet irradiation zone through a flow equalizing plate, a workbench is arranged in the oxidation reaction zone, and the bottom of the corresponding reactor is provided with a tail gas outlet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110594926.8A CN113275331B (en) | 2021-05-28 | 2021-05-28 | Method and special device for material surface treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110594926.8A CN113275331B (en) | 2021-05-28 | 2021-05-28 | Method and special device for material surface treatment |
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| Publication Number | Publication Date |
|---|---|
| CN113275331A true CN113275331A (en) | 2021-08-20 |
| CN113275331B CN113275331B (en) | 2023-05-12 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202110594926.8A Active CN113275331B (en) | 2021-05-28 | 2021-05-28 | Method and special device for material surface treatment |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11236460A (en) * | 1998-02-20 | 1999-08-31 | Dainippon Printing Co Ltd | Treatment of surface of plastic film |
| US5967156A (en) * | 1994-11-07 | 1999-10-19 | Krytek Corporation | Processing a surface |
| JP2001015472A (en) * | 1999-06-28 | 2001-01-19 | Hoya Schott Kk | Method and device for projecting ultraviolet ray |
| CN104852001A (en) * | 2014-02-14 | 2015-08-19 | 丰田自动车株式会社 | Surface treatment apparatus and surface treatment method |
| CN207628166U (en) * | 2017-10-30 | 2018-07-20 | 佛山五合精密科技有限公司 | A kind of gas sampling filter device |
-
2021
- 2021-05-28 CN CN202110594926.8A patent/CN113275331B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5967156A (en) * | 1994-11-07 | 1999-10-19 | Krytek Corporation | Processing a surface |
| JPH11236460A (en) * | 1998-02-20 | 1999-08-31 | Dainippon Printing Co Ltd | Treatment of surface of plastic film |
| JP2001015472A (en) * | 1999-06-28 | 2001-01-19 | Hoya Schott Kk | Method and device for projecting ultraviolet ray |
| CN104852001A (en) * | 2014-02-14 | 2015-08-19 | 丰田自动车株式会社 | Surface treatment apparatus and surface treatment method |
| CN207628166U (en) * | 2017-10-30 | 2018-07-20 | 佛山五合精密科技有限公司 | A kind of gas sampling filter device |
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| CN113275331B (en) | 2023-05-12 |
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