CN102169195A - Method for manufacturing nanometer antireflection film or antireflection coating and optical or photoelectric device - Google Patents
Method for manufacturing nanometer antireflection film or antireflection coating and optical or photoelectric device Download PDFInfo
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Abstract
The invention relates to a method for manufacturing a nanometer antireflection film or antireflection coating and an optical or photoelectric device. The method comprises the step of assembling at least one layer of antireflection film or antireflection coating on at least one lighting window of the optical or photoelectric device by using transparent nanometer material, wherein the antireflection film or antireflection coating is of a nanometer array structure and an inclined angle between the antireflection film or antireflection coating and the surface structure layer of the lighting window is more than 0 degree. According to the method, by self-assembling a surface antireflection film or antireflection coating layer on the surface of the device by using the nanometer material and by utilizing the refraction and reflection comprehensive effect of light or electromagnetic wave in a nanometer structure layer, the purpose of reducing the loss of light or electromagnetic wave which enters into the structure layer of the device after being coupled many times is achieved and the structure layer of the device in which the light or electromagnetic wave enters is enhanced, thereby increasing the function of the device for absorbing the energy of the light or electromagnetic wave.
Description
Technical field
The present invention be more particularly directed to a kind of of optics, field of photoelectric technology has the anti-reflection film or the anti-reflection film of nanostructured and uses this nanometer to reduce to reflect or increase the preparation of devices method of transmission film.
Background technology
Along with the development of photoelectric technology is maked rapid progress, nano material has obtained significant progress, and shows wide application prospect.This development trend can find example from the research and development of nanometer technology progress, press for the introducing nanometer technology as the research and development of nano-device, utilizes nano effect and brand new ideas to design and make new unit.The progressively utilization of assemble method makes nanometer technology more obvious to the expansion of technique directions such as the infotech and the energy.
Particularly in recent years in the field of LED of all kinds such as luminescent device such as white light, green glow, blue light, ruddiness and light-detecting device such as infrared, far infrared, visible light, ultraviolet, deep ultraviolet radiation detection and monitoring device, the army and the people two aspects press for this type of luminous and semiconductor photoelectric device detecting that comprises nanometer technology of development.In addition, along with becoming increasingly conspicuous of energy crisis, people more and more pay close attention to and pay attention to more widely this device that directly conversion of solar energy is utilized of solar cell.The photoelectric device of all polymorphic types such as above-mentioned luminescent device, sensitive detection parts and solar cell all require device can be the highest photoelectricity or the conversion efficiency of electric light, the conversion efficiency of optimizing between light and the electricity is to improve the device performance key point.
The surface of above-mentioned device all is level and smooth semiconductor surface in general, and such semiconductor surface can reflect the incident light greater than 35%, and light or electromagnetic wave loss are very serious.For reducing light or reflection of electromagnetic wave, people can adopt two kinds of following methods usually at present: a kind of is to make antireflecting film or anti-reflection film, its ultimate principle is an optical path difference of utilizing light wave or electromagnetic wave to be produced in the reflection of antireflecting film upper and lower surface, making two bundle reflected light interfere disappears mutually, thereby diminished reflex increases transmission; Another kind is that semiconductor surface structure is handled, and the oblique angle by surface structuration makes light or electromagnetism wave energy be coupled to once more in the device architecture layer, and such restriction effect improves spectrum or electromagnetic utilization factor, thereby improves photoelectric conversion result.
Summary of the invention
One of purpose of the present invention is to propose the preparation method of a kind of nanometer anti-reflection film or anti-reflection film, it is applied in the device in fields such as optics, photoelectricity, especially in the time of on the smooth surface of the daylighting window of device, can significantly reduce the reflectivity of this smooth surface, reduce the loss of light or electromagnetic wave, thereby improve the actual service efficiency of device.
For achieving the above object, the present invention has adopted following technical scheme:
The preparation method of a kind of nanometer anti-reflection film or anti-reflection film, it is characterized in that this method is: on the daylighting window of optics or photoelectric device, adopt the assembling of transparent nano material to form one deck and daylighting window surface structural sheet at least at least and have anti-reflection film or anti-reflection film greater than the nano array structure of 0 ° of angle.
Say further, in this method, be to adopt the method for physics or chemogenic deposit to form nano array structure in the daylighting window assembling of device, the method for described physics or chemogenic deposit comprises any one or the two or more combinations in evaporation, sputter, laser deposition, spin coating, printing, spraying, CVD, PVD, VPD, chemical hydro-thermal, chemical microemulsion, chemical solution glue gel, the chemical liquid deposition.
Say that further described transparent nano material is zinc paste, titanium dioxide, silicon nitride, monox, tantalum oxide, zirconia, aluminium oxide, indium oxide, tin oxide, gallium oxide, tin-doped indium oxide, fluoridize tin-doped indium oxide, mix any one or two or more combinations in fluorine indium oxide, fluorine doped tin oxide, Al-Doped ZnO, gallium-doped zinc oxide, zinc sulphide, zinc selenide and the magnesium fluoride.
Preferably, described anti-reflection film or anti-reflection film mainly are made up of the nanometer zinc oxide array structure with refraction gradient.
Preferably, described anti-reflection film is compound anti-reflection film or anti-reflection film, and it comprises by the anti-reflection membrane structure formed of nanometer zinc oxide array structure with refraction gradient and by titanium dioxide, silicon nitride, monox, tantalum oxide, zirconia, aluminium oxide, indium oxide, tin oxide, gallium oxide, tin-doped indium oxide, fluoridize tin-doped indium oxide, mix any one or the two or more anti-reflection of one deck at least membrane structures that is combined to form in fluorine indium oxide, fluorine doped tin oxide, Al-Doped ZnO, gallium-doped zinc oxide, zinc paste, zinc sulphide, zinc selenide and the magnesium fluoride.
The preparation method of a kind of optics or photoelectric device, it is characterized in that, this method is: on the daylighting window of described device, adopts the assembling of transparent nano material to form one deck and daylighting window surface structural sheet at least at least and has anti-reflection film or anti-reflection film greater than the nano array structure of 0 ° of angle, thus zone and/or incident ratio that raising incident light or electromagnetic wave enter the device architecture layer.
Say further, in this method, be to adopt the method for physics or chemogenic deposit to form nano array structure in the daylighting window assembling of device, the method for described physics or chemogenic deposit comprises any one or the two or more combinations in evaporation, sputter, laser deposition, spin coating, printing, spraying, CVD, PVD, VPD, chemical hydro-thermal, chemical microemulsion, chemical solution glue gel, the chemical liquid deposition
Say that further described transparent nano material is zinc paste, titanium dioxide, monox, silicon nitride, tantalum oxide, zirconia, aluminium oxide, indium oxide, zinc paste, tin oxide, gallium oxide, tin-doped indium oxide, fluoridize tin-doped indium oxide, mix any one or two or more combinations in fluorine indium oxide, fluorine doped tin oxide, Al-Doped ZnO, gallium-doped zinc oxide, zinc sulphide, zinc selenide and the magnesium fluoride.
Preferably, described anti-reflection film or anti-reflection film mainly are made up of the nanometer zinc oxide array structure with refraction gradient.
Preferably, described anti-reflection film is compound anti-reflection film or anti-reflection film, and it comprises by the anti-reflection membrane structure formed of nanometer zinc oxide array structure with refraction gradient and by titanium dioxide, silicon nitride, monox, tantalum oxide, zirconia, aluminium oxide, indium oxide, zinc paste, tin oxide, gallium oxide, tin-doped indium oxide, fluoridize tin-doped indium oxide, mix any one or the two or more anti-reflection of one deck at least membrane structures that is combined to form in fluorine indium oxide, fluorine doped tin oxide, Al-Doped ZnO, gallium-doped zinc oxide, zinc sulphide, zinc selenide and the magnesium fluoride.
Description of drawings
Fig. 1 adopts the preceding InP surface reflectivity curve map of nanometer anti-reflection film;
Fig. 2 is the InP surface reflectivity curve map behind the employing nanometer anti-reflection film of the present invention;
Fig. 3 adopts the forward and backward InP surface reflectivity curve map of nanometer anti-reflection film;
Fig. 4 adopts the forward and backward AlInP surface reflectivity curve map of nanometer anti-reflection film of the present invention.
Embodiment
At optics, photoelectric device in the prior art, surface such as semiconductor devices etc., especially the high problem of smooth surface reflectivity of its daylighting window, the special proposition of this case inventor is a kind of by forming nanometer anti-reflection film or anti-reflection film on optics, photoelectric device surface, thereby reduction surface reflectivity, increase light or electromagnetic wave and enter the device inside structural sheet,, realize higher light or electromagnetic wave output power or light detection sensitivity so that improve device to spectrum or electromagnetic utilization ratio.
The method of aforementioned formation nanometer anti-reflection film is specially: on the surface of device, particularly it all or utilize the transparent material assembling to form nanostructured on the local light window area makes it have the function that reduces light or reflection of electromagnetic wave.
Further, described nanostructured preferably adopts the array structure with refraction gradient.
Described nano array structure preferably adopts the array structure of non-parallel device surface.
Aforementioned transparent material can be selected from but be not limited to titanium dioxide, silicon nitride, monox, tantalum oxide, zirconia, indium oxide, aluminium oxide, zinc paste, tin oxide, gallium oxide, tin-doped indium oxide (ITO), fluoridize tin-doped indium oxide, mix in fluorine indium oxide, fluorine doped tin oxide, Al-Doped ZnO, gallium-doped zinc oxide, zinc sulphide, zinc selenide and the magnesium fluoride any one or multiple.
Preferably, described nanometer anti-reflection film is mainly formed by the nano zine oxide assembling.
More preferred, described nanometer anti-reflection film is a composite structure, its comprise the nano array structure layer formed by zinc paste and by titanium dioxide, silicon nitride, monox, tantalum oxide, zirconia, indium oxide, aluminium oxide, zinc paste, tin oxide, gallium oxide, tin-doped indium oxide (ITO), fluoridize tin-doped indium oxide, mix in fluorine indium oxide, fluorine doped tin oxide, Al-Doped ZnO, gallium-doped zinc oxide, zinc sulphide, zinc selenide and the magnesium fluoride one or more single or multiple lift nano array structure layers of forming.
Nanometer anti-reflection film of the present invention can be by chemistry or physical deposition mode preparation, technologies such as for example, the evaporation of those skilled in the art's indication, sputter, laser deposition, spin coating, printing, spraying, CVD, PVD, VPD, chemical hydro-thermal, chemical microemulsion, chemical solution glue gel, chemical liquid deposition.
Below in conjunction with accompanying drawing one preferred embodiment technical scheme of the present invention is elaborated.
This embodiment relates to a class opto-electronic conversion or a photoelectric detector, and such device preparing process is with reference to following method, comprises the steps but not only for following example order:
Step 1: on epitaxial wafer, carry out the surface and or other table tops handle the back and make required conductive electrode, form print;
Step 2: the print of finishing electro-deposition is carried out high temperature alloy or annealing in process, make it satisfy the requirement of device ohm or Schottky contacts;
Step 3: utilize transparent material (particularly ZnO) to prepare nano array structure to the optical window oral region of print and reached the effect that reduces spectrum or reflection of electromagnetic wave, or the surface-assembled nano array structure combined with individual layer or the above deposit film of individual layer constitute compound antireflection structure and reach the effect that reduces to reflect in surface-assembled; Enumerate wherein several chemical liquid phase surface-assembled and prepare the method for nano array structure, method may further comprise the steps:
Method one: solution preparation: will contain zincate or zinc compound such as zinc acetate, zinc acetate two water, zinc nitrate, zinc sulfate, zinc chloride etc. and be prepared into solution, adding reductive agent such as aqua ammonia, NaOH, potassium hydroxide are not limited only to these akaline liquids, regulate pH value simultaneously to suitable numerical value preferred 9～11, stir, obtain aaerosol solution, finish the solution preparation.
The nano array structure assembling of surface oxidation zinc: sample is put into reaction vessel, can select for use but be not limited to autoclave, the solution for preparing is poured into wherein, be placed under the proper temperature environment, as 30 ℃～600 ℃, the wait regular hour makes chemical reaction fully carry out, and allows the print surface-assembled to constitute the ZnO nanostructured.
Method two:
Sample is prepared: makes up surperficial guide layer, is not limited only to these catalyzer, after treatment, finish the structure of sample surfaces inducing layer at surface deposition catalyzer gold, cobalt, tin, copper, the zinc of specimen in use, and stand-by.
Solution preparation: will contain zincate or zinc compound such as zinc acetate, zinc acetate two water, zinc nitrate, zinc sulfate, zinc chloride etc. and be prepared into solution, adding reductive agent such as aqua ammonia, NaOH, potassium hydroxide are not limited only to these akaline liquids, regulate pH value simultaneously to suitable numerical value preferred 9～11, stir, obtain aaerosol solution, finish the solution preparation.
The nano array structure assembling of surface oxidation zinc: the sample that will have the spatial induction layer is put into reaction vessel, as autoclave but be not limited only to autoclave, the solution for preparing is poured into wherein, be placed under the proper temperature environment, as 30 ℃～600 ℃, or accompanying by agitation as appropriate, the wait regular hour makes chemical reaction fully carry out, and allows the print surface-assembled to constitute the ZnO nanostructured.
Method three:
Sample is prepared: makes up surperficial Seed Layer, contains the volatile solvent soln of zinc salt, after the drying, after bakingout process, finish the structure of Seed Layer at the sample surfaces coated with multiple layer, and stand-by.
Solution preparation: will contain zincate or zinc compound such as zinc acetate, zinc acetate two water, zinc nitrate, zinc sulfate, zinc chloride etc. and be prepared into solution, adding reductive agent such as aqua ammonia, NaOH, potassium hydroxide are not limited only to these akaline liquids, regulate pH value simultaneously to suitable numerical value preferred 9～11, stir, obtain aaerosol solution, finish the solution preparation.
The nano array structure assembling of surface oxidation zinc: the sample that will finish Seed Layer is put into reaction vessel, as autoclave but not only limit the use of autoclave, the solution for preparing is poured into wherein, be placed under the proper temperature environment, as 30 ℃～600 ℃, or accompanying by agitation as appropriate, the wait regular hour makes chemical reaction fully carry out, and allows the print surface-assembled to constitute the ZnO nanostructured.
Step 4: the device of finishing above-mentioned technology preparation is cut apart, gone between and encapsulates.
The reflectance spectrum curve of preparation test is respectively as Fig. 1, Fig. 2 and shown in Figure 3, as can be observed from Figure, adopt nanostructured layers back reflection rate obviously to reduce, its reflectivity R is lower than 5% from original being reduced to more than 30% behind InP material preparation nano structure of zinc oxide layer, and table 1 has shown the amplitude of the change of different wave length.About its reflectivity behind the AlInP material preparation nano structure of zinc oxide layer hangs down approximately to 10% from original being reduced to more than 30% (consulting Fig. 4).Formula according to photocurrent:
And the relational expression of quantum efficiency and reflectivity: η ∝ (1-R), can learn the reduction of reflectivity R after, quantum efficiency η improves, photoelectric current increases, the conversion between light and the electricity will be improved.
Table 1
| Wavelength (nanometer) | 400 | 500 | 600 | 700 |
| Adopt the preceding reflectivity R of nanostructured Before(％) | 45.2 | 34.8 | 32 | 31 |
| Reflectivity R after the employing nanostructured After(％) | 0.4 | 3.3 | 4.9 | 5 |
| Reduction amplitude (R Before-R After)/R Before(％) | 99.1 | 90.5 | 84.6 | 83.8 |
Have diversity in process recipes of the present invention and the selection, more than only be the representational several embodiment that has much in the numerous concrete exemplary applications of the present invention, protection scope of the present invention is not constituted any limitation.The all employing equivalents or the simple replacement of material and the technical scheme that forms, the device for preparing so long as adopt anti-anti-membrane material of the present invention all drops within the rights protection scope of the present invention.
Claims (10)
1. the preparation method of nanometer anti-reflection film or anti-reflection film, it is characterized in that this method is: on the daylighting window of optics or photoelectric device, adopt the assembling of transparent nano material to form one deck and daylighting window surface structural sheet at least at least and have anti-reflection film or anti-reflection film greater than the nano array structure of 0 ° of angle.
2. the preparation method of nanometer anti-reflection film according to claim 1 or anti-reflection film, it is characterized in that, in this method, be to adopt the method for physics or chemogenic deposit to form nano array structure in the daylighting window assembling of device, the method for described physics or chemogenic deposit comprises any one or the two or more combinations in evaporation, sputter, laser deposition, spin coating, printing, spraying, CVD, PVD, VPD, chemical hydro-thermal, chemical microemulsion, chemical solution glue gel, the chemical liquid deposition.
3. the preparation method of nanometer anti-reflection film according to claim 1 or anti-reflection film, it is characterized in that described transparent nano material is zinc paste, titanium dioxide, silicon nitride, monox, tantalum oxide, zirconia, aluminium oxide, indium oxide, tin oxide, gallium oxide, tin-doped indium oxide, fluoridize tin-doped indium oxide, mix any one or two or more combinations in fluorine indium oxide, fluorine doped tin oxide, Al-Doped ZnO, gallium-doped zinc oxide, zinc sulphide, zinc selenide and the magnesium fluoride.
4. the preparation method of nanometer anti-reflection film according to claim 1 or anti-reflection film is characterized in that, described anti-reflection film mainly is made up of the nanometer zinc oxide array structure with refraction gradient.
5. the preparation method of nanometer anti-reflection film according to claim 1, it is characterized in that, described anti-reflection film is compound anti-reflection film or anti-reflection film, and it comprises by the anti-reflection film formed of nanometer zinc oxide array structure with refraction gradient or anti-reflection film structure and by titanium dioxide, silicon nitride, monox, tantalum oxide, zirconia, aluminium oxide, indium oxide, tin oxide, gallium oxide, tin-doped indium oxide, fluoridize tin-doped indium oxide, mix the fluorine indium oxide, fluorine doped tin oxide, Al-Doped ZnO, gallium-doped zinc oxide, zinc paste, zinc sulphide, in zinc selenide and the magnesium fluoride any one or the two or more anti-reflection film of one deck at least or the anti-reflection film structures that are combined to form.
6. the preparation method of optics or photoelectric device, it is characterized in that, this method is: on the daylighting window of described device, adopts the assembling of transparent nano material to form one deck and daylighting window surface structural sheet at least at least and has anti-reflection film or anti-reflection film greater than the nano array structure of 0 ° of angle, thus zone and/or incident ratio that the raising incident electromagnetic wave enters the device architecture layer.
7. the preparation method of optics according to claim 6 or photoelectric device, it is characterized in that, in this method, be to adopt the method for physics or chemogenic deposit to form nano array structure in the daylighting window assembling of device, the method for described physics or chemogenic deposit comprises any one or the two or more combinations in evaporation, sputter, laser deposition, spin coating, printing, spraying, CVD, PVD, VPD, chemical hydro-thermal, chemical microemulsion, chemical solution glue gel, the chemical liquid deposition
8. the preparation method of optics according to claim 6 or photoelectric device, it is characterized in that described transparent nano material is zinc paste, titanium dioxide, monox, silicon nitride, tantalum oxide, zirconia, aluminium oxide, indium oxide, zinc paste, tin oxide, gallium oxide, tin-doped indium oxide, fluoridize tin-doped indium oxide, mix any one or two or more combinations in fluorine indium oxide, fluorine doped tin oxide, Al-Doped ZnO, gallium-doped zinc oxide, zinc sulphide, zinc selenide and the magnesium fluoride.
9. the preparation method of optics according to claim 6 or photoelectric device is characterized in that, described anti-reflection film or anti-reflection film mainly are made up of the nanometer zinc oxide array structure with refraction gradient.
10. the preparation method of optics according to claim 6 or photoelectric device, it is characterized in that, described anti-reflection film is compound anti-reflection film or anti-reflection film, and it comprises by the anti-reflection membrane structure formed of nanometer zinc oxide array structure with refraction gradient and by titanium dioxide, silicon nitride, monox, tantalum oxide, zirconia, aluminium oxide, indium oxide, zinc paste, tin oxide, gallium oxide, tin-doped indium oxide, fluoridize tin-doped indium oxide, mix the fluorine indium oxide, fluorine doped tin oxide, Al-Doped ZnO, gallium-doped zinc oxide, zinc sulphide, in zinc selenide and the magnesium fluoride any one or the two or more anti-reflection film of one deck at least or the anti-reflection film structures that are combined to form.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102723378A (en) * | 2012-07-17 | 2012-10-10 | 东方电气集团(宜兴)迈吉太阳能科技有限公司 | Laminated antireflective film for single-crystalline-silicon-like solar cell |
| CN102838288A (en) * | 2012-08-16 | 2012-12-26 | 浙江格拉威宝玻璃技术有限公司 | Antireflection coated glass with self-cleaning effect and preparation method thereof |
| CN102888585A (en) * | 2012-10-28 | 2013-01-23 | 梧州奥卡光学仪器有限公司 | Process for producing reflection reducing coating |
| CN103214030A (en) * | 2013-04-24 | 2013-07-24 | 中国科学院物理研究所 | Liquid deposition method of stannic oxide |
| CN104561907A (en) * | 2014-12-31 | 2015-04-29 | 西南技术物理研究所 | Preparation method of antireflection film allowing wide-angle incidence of infrared optical waveband in silicon or germanium base |
| CN105524566A (en) * | 2015-09-23 | 2016-04-27 | 合肥炜烨光学科技有限公司 | PET-based protection film with function of blue light adjustment |
| CN106086791A (en) * | 2016-06-04 | 2016-11-09 | 浙江星星科技股份有限公司 | A kind of manufacture method of the windows be protected panel with AG+AR+AF plated film |
| US10139532B2 (en) | 2015-07-24 | 2018-11-27 | Huawei Technologies Co., Ltd. | Camera module and terminal |
| CN110204981A (en) * | 2019-06-13 | 2019-09-06 | 天津市朗威柏丽科技有限公司 | The transparent water-repellent paint of delustring |
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| CN101858995A (en) * | 2009-04-09 | 2010-10-13 | 通用电气公司 | Nanostructured anti-reflection coatings and correlation technique and device |
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| CN101858995A (en) * | 2009-04-09 | 2010-10-13 | 通用电气公司 | Nanostructured anti-reflection coatings and correlation technique and device |
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| CN102723378A (en) * | 2012-07-17 | 2012-10-10 | 东方电气集团(宜兴)迈吉太阳能科技有限公司 | Laminated antireflective film for single-crystalline-silicon-like solar cell |
| CN102838288A (en) * | 2012-08-16 | 2012-12-26 | 浙江格拉威宝玻璃技术有限公司 | Antireflection coated glass with self-cleaning effect and preparation method thereof |
| CN102888585A (en) * | 2012-10-28 | 2013-01-23 | 梧州奥卡光学仪器有限公司 | Process for producing reflection reducing coating |
| CN102888585B (en) * | 2012-10-28 | 2014-11-26 | 梧州奥卡光学仪器有限公司 | Process for producing reflection reducing coating |
| CN103214030A (en) * | 2013-04-24 | 2013-07-24 | 中国科学院物理研究所 | Liquid deposition method of stannic oxide |
| CN103214030B (en) * | 2013-04-24 | 2015-04-29 | 中国科学院物理研究所 | Liquid deposition method of stannic oxide |
| CN104561907A (en) * | 2014-12-31 | 2015-04-29 | 西南技术物理研究所 | Preparation method of antireflection film allowing wide-angle incidence of infrared optical waveband in silicon or germanium base |
| US10139532B2 (en) | 2015-07-24 | 2018-11-27 | Huawei Technologies Co., Ltd. | Camera module and terminal |
| CN105524566A (en) * | 2015-09-23 | 2016-04-27 | 合肥炜烨光学科技有限公司 | PET-based protection film with function of blue light adjustment |
| CN106086791A (en) * | 2016-06-04 | 2016-11-09 | 浙江星星科技股份有限公司 | A kind of manufacture method of the windows be protected panel with AG+AR+AF plated film |
| CN106086791B (en) * | 2016-06-04 | 2018-08-10 | 浙江星星科技股份有限公司 | A kind of manufacturing method of the windows be protected panel with AG+AR+AF plated films |
| CN110204981A (en) * | 2019-06-13 | 2019-09-06 | 天津市朗威柏丽科技有限公司 | The transparent water-repellent paint of delustring |
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Application publication date: 20110831 |