CN102910835A - Method for forming durable dual-layer antireflection film on surface of soda-lime glass - Google Patents
Method for forming durable dual-layer antireflection film on surface of soda-lime glass Download PDFInfo
- Publication number
- CN102910835A CN102910835A CN2012104166100A CN201210416610A CN102910835A CN 102910835 A CN102910835 A CN 102910835A CN 2012104166100 A CN2012104166100 A CN 2012104166100A CN 201210416610 A CN201210416610 A CN 201210416610A CN 102910835 A CN102910835 A CN 102910835A
- Authority
- CN
- China
- Prior art keywords
- film
- soda glass
- calcium soda
- weather resistance
- refractive index
- 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.)
- Pending
Links
Images
Abstract
The invention discloses a method for forming a durable dual-layer antireflection film on the surface of soda-lime glass. The method comprises the following steps of: 1) adding a precursor of metal oxide and water steam into a reaction cavity for reaction to obtain a reaction product, and depositing the reaction product on the two surfaces of a base of the soda-lime glass by adopting an atomic layer deposition method to obtain a high refractive index oxide film; 2) taking a silicon source, a solvent and a catalyst as raw materials to prepare silica sol; 3) coating the silica sol prepared in the step 2) to the surfaces of the base of the soda-lime glass obtained in the step 1) by adopting a coating technology so as to form an SiO2 film on the high refractive index oxide film; and 4) solidifying the high refractive index oxide film and the SiO2 film on the surface of the soda-lime glass to obtain the soda-lime glass with the durable dual-layer antireflection film. The method is low in cost and is suitable for large-scale application. The dual-layer film formed on the surface of the soda-lime glass by adopting the method is excellent in antireflection effect and durability.
Description
Technical field
The invention belongs to the glass coating technical field, be specifically related to a kind of method that forms the weather resistance double-layer reflection-decreasing film on calcium soda glass surface.
Background technology
The calcium soda glass is widely used in the various fields such as consumer electronics, photovoltaic device, buildings, automotive industry as the most frequently used type of glass.But the calcium soda glass also has its shortcoming and defect: on the one hand, because and the refractive index difference between the air, cause the reflection loss in its surface meeting generation about 8%, affect transmitance; On the other hand, in atmosphere especially in a humid environment, the H in the air in the moisture
+Ion can with the calcium soda glass in alkalimetal ion exchange, destroy simultaneously Si-O-Si network structure wherein, cause the calcium soda glass to be corroded, the life-span reduces.Therefore, be necessary to develop the calcium soda glass that has simultaneously anti-reflective effect and weather resistance, thereby further expand its Application Areas.
In order to reduce the reflection loss on calcium soda glass surface, settling mode commonly used is to apply one or more layers thin-film material on calcium soda glass surface as the antireflective coating film.Thomas I M(High laser damage threshold porous silica antireflective coating, Applied Optics, 1986,25:1481-1483) prepared individual layer porous SiO
2Antireflective film, transmitance has improved 7 ~ 8%, but the problem that the loose film of this high porosity exists is that endurance quality is relatively poor, is subject to simultaneously the pollution of outside atmosphere.Publication number is to mention in the Chinese invention patent application of CN101805135A adopting sol-gel process at the double-deck antireflective film of photovoltaic glass preparation, compare with individual layer porous antireflective film, to improving the useful visible light wave range of solar cell power higher transmitance is being arranged.For multilayer antireflective film system, anti-reflection effect and endurance quality are subjected to the design of film system and the deposition method of film to affect larger.
Summary of the invention
Technical problem to be solved by this invention is, for the deficiencies in the prior art, the method that forms the weather resistance double-layer reflection-decreasing film on calcium soda glass surface that a kind of cost is low, be fit to large-scale application is provided, adopts the method to have good anti-reflective effect and weather resistance at the bilayer film that calcium soda glass surface forms.
The present invention solves the problems of the technologies described above the technical scheme that adopts: a kind of method that forms the weather resistance double-layer reflection-decreasing film on calcium soda glass surface may further comprise the steps:
1) passing into the presoma of metal oxide and water vapour in reaction chamber reacts and obtains reaction product, adopt atomic layer deposition method that two surfaces that reaction product is deposited on the substrate of calcium soda glass are simultaneously obtained the high refractive index oxide film, the temperature of calcium soda glass substrate is 25 ~ 300 ℃ in the deposition process, and the air pressure of sediment chamber is 100 ~ 150Pa in the reaction chamber;
2) take silicon source, solvent and catalyzer as raw material, prepare silicon colloidal sol;
3) adopt paint-on technique with step 2) in the silicon sol that obtains of preparation be coated on the surface of the calcium soda glass substrate that obtains in the step 1), thereby on the high refractive index oxide film, form again SiO
2Film;
4) at last to high refractive index oxide film and the SiO on calcium soda glass surface
2Film is cured processing, obtains having the calcium soda glass of weather resistance double-layer reflection-decreasing film.
Preferably, in step 1), the presoma of described metal oxide is a kind of in titanium isopropylate, zinc methide, zirconium tetrachloride, the trimethyl aluminium.
Preferably, in step 1) and step 3), described high refractive index oxide is TiO
2, ZnO, ZrO
2, Al
2O
3In a kind of.
Preferably, in step 2) in, described silicon source is one or both in methyl silicate, the tetraethoxy, and described solvent is one or more in ethanol, Virahol, ethylene glycol, thanomin, the diethanolamine, and described catalyzer is a kind of in hydrochloric acid, the ammoniacal liquor.
Preferably, in step 2) in, the mol ratio of described silicon source, solvent and catalyzer is 1: 40 ~ 90: 0.005 ~ 0.01.
Preferably, in step 3), the temperature of described solidification treatment is 150 ~ 350 ℃, and the time is 0.5 ~ 2 hour.
Preferably, in step 3), described paint-on technique is a kind of in crystal pulling method, spin coating, spraying, the roller coat.
Preferably, in step 1), the thickness of described high refractive index oxide film is 10 ~ 50nm.
Preferably, in step 3), described SiO
2The thickness of film is 80 ~ 150nm.
Compared with prior art, the present invention has following advantage:
1, the calcium soda glass after employing the inventive method is processed has by high refractive index oxide film and SiO
2The double-layer reflection-decreasing film that film forms, the thickness of high refractive index oxide film is 10 ~ 50nm, SiO
2The thickness of film is 80 ~ 150nm, at the substrate of calcium soda glass and SiO
2Be formed with the high refractive index oxide film between the film, double-layer reflection-decreasing film that can Effective Regulation calcium soda glass surface is in the anti-reflection characteristic of visible light wave range.
2, by forming the ultra-thin high refractive index oxide film of one deck on calcium soda glass surface, its thickness only has 10 ~ 50nm, can greatly improve the endurance quality of calcium soda glass, in addition because this high refractive index oxide film is very thin, therefore can effectively control preparation cost, be fit to large-scale application.
3, the high refractive index oxide film adopts the atomic layer deposition method preparation, can realize layer by layer deposition, accurately controls thickness and the homogeneity of film, reduces the defective in the film, thereby obtains high-quality thin film.
4, the average transmittances of calcium soda glass in 400 ~ 700nm scope with weather resistance double-layer reflection-decreasing film that the inventive method makes can reach 95.71%, compares with the calcium soda glass that does not form the weather resistance double-layer reflection-decreasing film and improved 6.32%; Simultaneously, this calcium soda glass with weather resistance double-layer reflection-decreasing film is carried out height accelerate hot and humid stress test (Highly-Accelerated Temperature and Humidity Stress Test, be called for short Hast), after 121 ℃ of temperature, humidity are carried out test in 180 hours for 97% time, still has excellent weather resistance.
Description of drawings
Fig. 1 is the structural representation of the calcium soda glass with weather resistance double-layer reflection-decreasing film of the inventive method acquisition;
Fig. 2 is the transmitance correlation curve figure that calcium soda glass surface forms weather resistance double-layer reflection-decreasing film front and back (being before the plated film and behind the plated film) in the embodiment of the invention 1;
Fig. 3 is that calcium soda glass surface forms the durability line figure of (before being plated film) before the weather resistance double-layer reflection-decreasing film in the embodiment of the invention 1;
Fig. 4 is that calcium soda glass surface forms the durability line figure of (after being plated film) behind the weather resistance double-layer reflection-decreasing film in the embodiment of the invention 1.
Embodiment
Embodiment is described in further detail the present invention below in conjunction with accompanying drawing.
Embodiment 1: pass into trimethyl aluminium and water vapour and react and obtain reaction product in reaction chamber, the temperature of calcium soda glass substrate is 250 ℃, the air pressure of sediment chamber is set as 100Pa in the reaction chamber, and two surfaces of adopting atomic layer deposition method that reaction product is deposited on the substrate of calcium soda glass simultaneously obtain the high refractive index Al of 50nm thickness
2O
3Film; Tetraethoxy (TEOS), dehydrated alcohol and the ratio of hydrochloric acid take mol ratio as 1:49:0.007 are at room temperature mixed, stirred 8 hours, obtain the silicon sol of stable transparent, aging 3 days stand-by; Silicon sol after aging is coated on the high refractive index Al that above-mentioned deposition obtains with crystal pulling method
2O
3The surface of film, pull rate 1.6mm/s lifts number of times 1 time, thereby at high refractive index Al
2O
3Form again SiO on the film
2Film is at last to the high refractive index Al on calcium soda glass surface
2O
3Film and SiO
2Film with 300 ℃ of solidification treatment 0.5 hour, obtains SiO in air
2The thickness of film is 110nm's and have that transmissivity is high, the Al of good endurance
2O
3/ SiO
2The calcium soda glass of double-layer reflection-decreasing film.
The transmitance correlation curve figure of calcium soda glass surface formation weather resistance double-layer reflection-decreasing film front and back (being before the plated film and behind the plated film) sees Fig. 2 in the present embodiment, the durability line figure of (before being plated film) sees Fig. 3 before the formation weather resistance double-layer reflection-decreasing film, and the durability line figure of (after being plated film) sees Fig. 4 behind the formation weather resistance double-layer reflection-decreasing film.
Embodiment 2: pass into trimethyl aluminium and water vapour and react and obtain reaction product in reaction chamber, the temperature of calcium soda glass substrate is 250 ℃, the air pressure of sediment chamber is set as 100Pa in the reaction chamber, and two surfaces of adopting atomic layer deposition method that reaction product is deposited on the substrate of calcium soda glass simultaneously obtain the high refractive index Al of 25nm thickness
2O
3Film; Tetraethoxy (TEOS), dehydrated alcohol and the ratio of hydrochloric acid take mol ratio as 1:49:0.01 are at room temperature mixed, stirred 8 hours, obtain the silicon sol of stable transparent, aging 3 days stand-by; Silicon sol after aging is coated on the high refractive index Al that above-mentioned deposition obtains with crystal pulling method
2O
3The surface of film, pull rate 1.6mm/s lifts number of times 1 time, thereby at high refractive index Al
2O
3Form again SiO on the film
2Film is at last to the high refractive index Al on calcium soda glass surface
2O
3Film and SiO
2Film with 300 ℃ of solidification treatment 1 hour, obtains SiO in air
2The thickness of film is 110nm's and have that transmissivity is high, the Al of good endurance
2O
3/ SiO
2The calcium soda glass of double-layer reflection-decreasing film.
Embodiment 3: pass into titanium isopropylate and water vapour and react and obtain reaction product in reaction chamber, the temperature of calcium soda glass substrate is 200 ℃, the air pressure of sediment chamber is set as 100Pa in the reaction chamber, and two surfaces of adopting atomic layer deposition method that reaction product is deposited on the substrate of calcium soda glass simultaneously obtain the high refractive index TiO of 10nm thickness
2Film; Methyl silicate, Virahol and the hydrochloric acid ratio take mol ratio as 1:75:0.005 is at room temperature mixed, stirred 8 hours, obtain the silicon sol of stable transparent, aging 3 days stand-by; Silicon sol after aging is coated on the high refractive index TiO that above-mentioned deposition obtains with spraying method
2The surface of film, thereby at high refractive index TiO
2Form again SiO on the film
2Film is at last to the high refractive index TiO on calcium soda glass surface
2Film and SiO
2Film with 300 ℃ of solidification treatment 1 hour, obtains SiO in air
2The thickness of film is 100nm's and have that transmissivity is high, the TiO of good endurance
2/ SiO
2The calcium soda glass of double-layer reflection-decreasing film.
Embodiment 4: pass into zinc methide and water vapour and react and obtain reaction product in reaction chamber, the temperature of calcium soda glass substrate is 200 ℃, the air pressure of sediment chamber is set as 100Pa in the reaction chamber, and two surfaces of adopting atomic layer deposition method that reaction product is deposited on the substrate of calcium soda glass simultaneously obtain the high refractive index ZnO film of 20nm thickness; Methyl silicate, Virahol and the ammoniacal liquor ratio take mol ratio as 1:75:0.007 is at room temperature mixed, stirred 8 hours, obtain the silicon sol of stable transparent, aging 3 days stand-by; Silicon sol after aging is coated on the surface of the high refractive index ZnO film that above-mentioned deposition obtains with spraying method, thereby on the high refractive index ZnO film, forms again SiO
2Film is at last to high refractive index ZnO film and the SiO on calcium soda glass surface
2Film with 300 ℃ of solidification treatment 1 hour, obtains SiO in air
2The thickness of film is 100nm's and have that transmissivity is high, the ZnO/SiO of good endurance
2The calcium soda glass of double-layer reflection-decreasing film.
Embodiment 5: pass into zirconium tetrachloride and water vapour and react and obtain reaction product in reaction chamber, the temperature of calcium soda glass substrate is 200 ℃, the air pressure of sediment chamber is set as 100Pa in the reaction chamber, and two surfaces of adopting atomic layer deposition method that reaction product is deposited on the substrate of calcium soda glass simultaneously obtain the high refractive index ZrO of 10nm thickness
2Film; Tetraethoxy (TEOS), dehydrated alcohol and the ratio of hydrochloric acid take mol ratio as 1:49:0.005 are at room temperature mixed, stirred 8 hours, obtain the silicon sol of stable transparent, aging 3 days stand-by; Silicon sol after aging is coated on the high refractive index ZrO that above-mentioned deposition obtains with rolling method
2The surface of film, thereby at high refractive index ZrO
2Form again SiO on the film
2Film is at last to the high refractive index ZrO on calcium soda glass surface
2Film and SiO
2Film with 300 ℃ of solidification treatment 1 hour, obtains SiO in air
2The thickness of film is 100nm's and have that transmissivity is high, the ZrO of good endurance
2/ SiO
2The calcium soda glass of double-layer reflection-decreasing film.
After testing, the average transmittances of calcium soda glass in 400 ~ 700nm scope with bilayer film that the inventive method makes can reach 95.71%, compares with the calcium soda glass that does not form the weather resistance double-layer reflection-decreasing film and improved 6.32%; Simultaneously, this calcium soda glass with weather resistance double-layer reflection-decreasing film is carried out height accelerate hot and humid stress test, after 121 ℃ of temperature, humidity are carried out test in 180 hours for 97% time, still have excellent weather resistance.
Claims (9)
1. method that forms the weather resistance double-layer reflection-decreasing film on calcium soda glass surface is characterized in that may further comprise the steps:
1) passing into the presoma of metal oxide and water vapour in reaction chamber reacts and obtains reaction product, adopt atomic layer deposition method that two surfaces that reaction product is deposited on the substrate of calcium soda glass are simultaneously obtained the high refractive index oxide film, the temperature of calcium soda glass substrate is 25 ~ 300 ℃ in the deposition process, and the air pressure of sediment chamber is 100 ~ 150Pa in the reaction chamber;
2) take silicon source, solvent and catalyzer as raw material, prepare silicon colloidal sol;
3) adopt paint-on technique with step 2) in the silicon sol that obtains of preparation be coated on the surface of the calcium soda glass substrate that obtains in the step 1), thereby on the high refractive index oxide film, form again SiO
2Film;
4) at last to high refractive index oxide film and the SiO on calcium soda glass surface
2Film is cured processing, obtains having the calcium soda glass of weather resistance double-layer reflection-decreasing film.
2. according to claim 1 a kind of in the surperficial method that forms the weather resistance double-layer reflection-decreasing film of calcium soda glass, it is characterized in that: in step 1), the presoma of described metal oxide is a kind of in titanium isopropylate, zinc methide, zirconium tetrachloride, the trimethyl aluminium.
3. according to claim 1 a kind of in the surperficial method that forms the weather resistance double-layer reflection-decreasing film of calcium soda glass, it is characterized in that: in step 1) and step 3), described high refractive index oxide is TiO
2, ZnO, ZrO
2, Al
2O
3In a kind of.
4. according to claim 1 a kind of in the surperficial method that forms the weather resistance double-layer reflection-decreasing film of calcium soda glass, it is characterized in that: in step 2) in, described silicon source is one or both in methyl silicate, the tetraethoxy, described solvent is one or more in ethanol, Virahol, ethylene glycol, thanomin, the diethanolamine, and described catalyzer is a kind of in hydrochloric acid, the ammoniacal liquor.
5. a kind of method that forms the weather resistance double-layer reflection-decreasing film on calcium soda glass surface according to claim 1 is characterized in that: in step 2) in, the mol ratio of described silicon source, solvent and catalyzer is 1: 40 ~ 90: 0.005 ~ 0.01.
6. according to claim 1 a kind of in the surperficial method that forms the weather resistance double-layer reflection-decreasing film of calcium soda glass, it is characterized in that: in step 3), the temperature of described solidification treatment is 150 ~ 350 ℃, and the time is 0.5 ~ 2 hour.
7. a kind of method that forms the weather resistance double-layer reflection-decreasing film on calcium soda glass surface according to claim 1 is characterized in that: in step 3), described paint-on technique is a kind of in crystal pulling method, spin coating, spraying, the roller coat.
8. each described a kind of method that forms the weather resistance double-layer reflection-decreasing film on calcium soda glass surface according to claim 1 ~ 7, it is characterized in that: in step 1), the thickness of described high refractive index oxide film is 10 ~ 50nm.
9. each described a kind of method that forms the weather resistance double-layer reflection-decreasing film on calcium soda glass surface according to claim 1 ~ 7 is characterized in that: in step 3), and described SiO
2The thickness of film is 80 ~ 150nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104166100A CN102910835A (en) | 2012-10-25 | 2012-10-25 | Method for forming durable dual-layer antireflection film on surface of soda-lime glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012104166100A CN102910835A (en) | 2012-10-25 | 2012-10-25 | Method for forming durable dual-layer antireflection film on surface of soda-lime glass |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102910835A true CN102910835A (en) | 2013-02-06 |
Family
ID=47609442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012104166100A Pending CN102910835A (en) | 2012-10-25 | 2012-10-25 | Method for forming durable dual-layer antireflection film on surface of soda-lime glass |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102910835A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105789340A (en) * | 2016-05-18 | 2016-07-20 | 广东爱康太阳能科技有限公司 | Method for preparing high strength double-layer anti-reflection film |
| CN108445567A (en) * | 2018-03-30 | 2018-08-24 | 苏州沛斯仁光电科技有限公司 | A kind of high-reflecting film and preparation method of high damage threshold |
| CN113788631A (en) * | 2021-10-11 | 2021-12-14 | 上海西源新能源技术有限公司 | ZnO-SiO2Double-coating down-conversion antireflection film and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5496621A (en) * | 1993-04-16 | 1996-03-05 | Central Glass Company, Limited | Glass pane with reflectance reducing coating and combiner of head-up display system |
| CN101560653A (en) * | 2009-05-14 | 2009-10-21 | 浙江大学 | Method for preparing gradient-index film |
| CN101805135A (en) * | 2010-04-19 | 2010-08-18 | 中国科学院宁波材料技术与工程研究所 | Photovoltaic glass plated with double-layer antireflection film and preparation method thereof |
-
2012
- 2012-10-25 CN CN2012104166100A patent/CN102910835A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5496621A (en) * | 1993-04-16 | 1996-03-05 | Central Glass Company, Limited | Glass pane with reflectance reducing coating and combiner of head-up display system |
| CN101560653A (en) * | 2009-05-14 | 2009-10-21 | 浙江大学 | Method for preparing gradient-index film |
| CN101805135A (en) * | 2010-04-19 | 2010-08-18 | 中国科学院宁波材料技术与工程研究所 | Photovoltaic glass plated with double-layer antireflection film and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105789340A (en) * | 2016-05-18 | 2016-07-20 | 广东爱康太阳能科技有限公司 | Method for preparing high strength double-layer anti-reflection film |
| CN108445567A (en) * | 2018-03-30 | 2018-08-24 | 苏州沛斯仁光电科技有限公司 | A kind of high-reflecting film and preparation method of high damage threshold |
| CN113788631A (en) * | 2021-10-11 | 2021-12-14 | 上海西源新能源技术有限公司 | ZnO-SiO2Double-coating down-conversion antireflection film and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101805135B (en) | Photovoltaic glass plated with double-layer antireflection film and preparation method thereof | |
| US20130163087A1 (en) | Glass substrate coated with an anti-reflective layer | |
| Li et al. | A scratch-resistant and hydrophobic broadband antireflective coating by sol–gel method | |
| Wu et al. | A novel route to control refractive index of sol-gel derived nano-porous silica films used as broadband antireflective coatings | |
| CN103770404B (en) | Weather-resistant solar glass surface anti-reflective film and preparation method thereof | |
| TWI491506B (en) | Anti-reflective coatings and methods of making the same | |
| CN110002767B (en) | Preparation method of high-transmittance hydrophobic coating film for photovoltaic glass | |
| KR101194257B1 (en) | Transparent substrate for solar cell having a broadband anti-reflective multilayered coating thereon and method for preparing the same | |
| Xin et al. | A novel route to prepare weather resistant, durable antireflective films for solar glass | |
| CN102222704B (en) | Crystalline silicon solar battery three-layer antireflection film and preparation method thereof | |
| CN103771727A (en) | Anti-reflection glass substrate as well as preparation method and application thereof | |
| CN102838288A (en) | Antireflection coated glass with self-cleaning effect and preparation method thereof | |
| CN106966603A (en) | A kind of preparation method of high transmission rate photovoltaic coated glass | |
| CN103524049A (en) | Preparation method of monolayer SiO2 antireflection film | |
| CN103613283A (en) | Preparation method of SiO2-TiO2 inorganic anti-reflection film | |
| CN102910835A (en) | Method for forming durable dual-layer antireflection film on surface of soda-lime glass | |
| CN103066161B (en) | Preparation method for solar cell composite antireflection coating | |
| CN105837052A (en) | Preparation method of fluorine-containing coated glass with high light transmittance and weatherability | |
| CN103524048A (en) | Preparation method of multi-layer SiO2 inorganic anti-reflection film | |
| JP2015229614A (en) | Window glass for vehicle | |
| KR101456220B1 (en) | Transparent substrate having an anti-reflective multilayered coating thereon and method for preparing the same | |
| CN206616149U (en) | A kind of high transmission rate photovoltaic coated glass | |
| CN109052981B (en) | Preparation method of high-hardness super-wear-resistant hydrophobic self-cleaning anti-reflection film | |
| CN105541123A (en) | Photovoltaic glass-based high antireflection composite nanometer film | |
| CN111718129B (en) | PEG-modified SiO2-TiO2Composite self-cleaning antireflection film and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130206 |