CN102584024A - Preparation method of efficient increased-transmission and antireflection glass - Google Patents
Preparation method of efficient increased-transmission and antireflection glass Download PDFInfo
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- CN102584024A CN102584024A CN2012100168361A CN201210016836A CN102584024A CN 102584024 A CN102584024 A CN 102584024A CN 2012100168361 A CN2012100168361 A CN 2012100168361A CN 201210016836 A CN201210016836 A CN 201210016836A CN 102584024 A CN102584024 A CN 102584024A
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- 239000011521 glass Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000004793 Polystyrene Substances 0.000 claims abstract description 12
- 239000004816 latex Substances 0.000 claims abstract description 11
- 229920000126 latex Polymers 0.000 claims abstract description 11
- 229920002223 polystyrene Polymers 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 7
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- -1 catalyzer Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000010408 film Substances 0.000 abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000010409 thin film Substances 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 2
- 239000002105 nanoparticle Substances 0.000 abstract 2
- 230000001276 controlling effect Effects 0.000 abstract 1
- 238000002310 reflectometry Methods 0.000 abstract 1
- 230000003667 anti-reflective effect Effects 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000006117 anti-reflective coating Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical class F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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Abstract
The invention discloses a preparation method of efficient increased-transmission and antireflection glass, which comprises the steps as follows: (1) the molar ratio of raw materials comprising silicon sources to deionized water to catalysts to solvents is 1:0.05 to 10:0.01 to 10: 10 to 300, the deionized water, the catalysts and the solvents are firstly mixed, heated and stirred at a uniform speed, when an obtained mixture is heated to 20 to 50 DEG C, the silicon sources are added to the mixture and stirred with the mixture for 2 to 40 hours at a maintained constant temperature and a uniform speed, and then silica nano-particle dispersion liquid is obtained; (2) polystyrene latex spheres are used as templates to be mixed with the silica nano-particle dispersion liquid obtained in the step (1) at a volume ratio of 1:5 to 5:1, and then a blended solution is obtained; (3) the blended solution obtained in the step (2) is coated on the surface of a photovoltaic glass substrate; and (4) the film-coated photovoltaic glass substrate is placed in a temperature condition of 300 to 700 DEG C to be sintered for 5 to 30 minutes, and then the efficient increased-transmission and antireflection glass is obtained. The preparation method has the advantages that the binding force between an antireflection film and the substrate is strengthened, and the durability of the thin film is improved; and besides, through controlling the diameter and the mixing proportion of the polystyrene latex sphere templates, the reflectivity of the thin film is accurately regulated, so that an obvious increased-transmission effect is achieved.
Description
Technical field
The invention belongs to used for solar batteries photovoltaic glass field, particularly a kind of preparation method of efficient anti-reflection anti-reflection glass.
Background technology
Worldwide energy shortage and environmental protection pressure have greatly promoted research and development, the application of people to the solar photovoltaic assembly technology.Along with people's is continued to optimize the solar cell photovoltaic assembly; The transformation efficiency of crystalline silicon or thin film solar cell sheet is near ultimate value in the solar photovoltaic assembly; Continue to rely on improve the efficient of battery sheet own and improve battery sheet efficient and improve the photovoltaic module real output very difficulty that becomes, but can raise the efficiency through increasing other modes such as light intensity.Used ultra-white photovoltaic glass has higher transmittance at visible light wave range at present; Its transmitance is about 91.5%, but owing to the refractive index difference between photovoltaic glass and the air, still there is about reflection of about 8% in photovoltaic glass to visible light; This luminous energy of about 8% causes the on the low side of solar conversion efficiency; Use cost increases, and therefore, the utilization ratio that improves this 8% left and right sides luminous energy is significant; Usually be coated with the transmitance that one or more layers anti-reflection film can effectively improve light at photovoltaic glass surface, thereby improve the output rating of solar cell photovoltaic assembly.According to the test of European Studies mechanism, if the solar energy glass transmitance increases by 5%, the efficient of plate solar collector will improve 6-10%, and the photoelectric transformation efficiency of photovoltaic solar cell will improve 3-6%.
At present; Being used for producing photovoltaic glass has chemical corrosion method, sol-gel method, magnetron sputtering method, U.S. Pat 4019884 to disclose a kind of U.S. Coning company prepares antireflective coating through chemical milling at glass surface technology with the major technique of anti-reflection film; Can the reflection of glass surface rate be reduced to 0.5%, in addition, U.S. Pat 45355026 discloses on substrate deposition one deck SiO earlier
2Film is realized antireflecting effect thereby adopt chemical etching to form hole then, and Denmark SurarcTechnologyA/S company utilizes this method to realize that on the photovoltaic glass two sides transmitance increases by 5% optics antireflective coating.But, the complex process of chemical corrosion method, cost is high, and use is the hydrofluoric acid class chemical reagent that is prone to contaminate environment.
Sol-gel method also is a kind of technology for preparing silicon oxide antireflective coating comparative maturity; Publication number be in the one Chinese patent application of CN1263354A through in nano SiO 2 particle cross-linked network or particle network, infiltrating organic additive and silane coupling agent, utilize the two-step acid-alkali method to prepare antireflection coatings; It is catalyzer with the mineral acid that the Chinese invention patent of patent ZL200510016828.7 discloses a kind of, and cohydrolysis titanic acid ester, silicon ester and silane coupling agent obtain colloidal sol in Virahol, obtain antireflection coatings through filming.Sol-gel method exists the specific refractory power control of film inaccurate, and bonding force is poor, and film is prone to come off and defective such as performance degradation.Therefore, the further research and development of anti-reflection antireflective film technology seem very necessary and urgent.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of efficient anti-reflection anti-reflection glass, present method had not only strengthened bonding force between film and the substrate, but also had significantly improved antireflective effect.
A kind of preparation method of efficient anti-reflection anti-reflection glass is characterized in that, comprises the following steps:
(1) preparation nano SiO 2 particle dispersion liquid: raw material is counted in molar ratio; Silicon source: deionized water: catalyzer: solvent=1:0.05~10:0.01~10:10~300; With deionized water, catalyzer, solvent, heating is also at the uniform velocity stirred, and is heated to 20~50 ℃ earlier; Add the silicon source and keep constant temperature at the uniform velocity to stir 2~40 hours, obtain the nano SiO 2 particle dispersion liquid;
(2) be that 1:5~5:1 mixes with the polystyrene latex ball by volume as the nano SiO 2 particle dispersion liquid that obtains in template and the step (1), obtain blend solution;
(3) film: the blend solution that obtains in the step (2) is coated on the photovoltaic glass substrate surface;
(4) rete intensified process: the photovoltaic glass substrate of filming was placed under 300~700 ℃ of temperature condition sintering 5~30 minutes, obtain efficient anti-reflection anti-reflection glass.
Said silicon source is one or both mixtures in tetraethoxy (TEOS) or the methyl silicate (TMOS); Said catalyzer is one or more mixtures in hydrochloric acid, ammoniacal liquor or the sodium hydroxide, and said solvent is one or more mixtures in ethanol, methyl alcohol, propyl alcohol, the terepthaloyl moietie.
The diameter of polystyrene latex ball is 10~200nm described in the step (2).
Filming described in the step (3) to dipping lifts, spin coating, roller coat or spraying.
Compared with prior art, the invention has the beneficial effects as follows: through control rational heat treatment temperature and time sintered film, strengthen the bonding force between antireflective film and the substrate, improved the weather resistance of film; Porosity and the hole size of accurately having controlled rete through the diameter and the blending ratio of control PS ball template, thus the specific refractory power of accurately having regulated film makes antireflective effect obvious; Manufacture craft of the present invention is simple simultaneously, cost is low, be fit to industrialized mass production.
Description of drawings
Fig. 1 is the sem photograph of anti-reflection anti-reflection glass among the embodiment 1;
Fig. 2 is anti-reflection anti-reflection glass antireflective effect correlation curve figure among the embodiment 1.
Embodiment
Embodiment 1:
0.12mol water, 0.04mol ammoniacal liquor and 3mol absolute ethyl alcohol are mixed stirring heating, treat that temperature reaches 35 ℃ of design temperatures, add the 0.04mol tetraethoxy; Keep constant temperature, continue to stir 21 hours, obtain the nano SiO 2 particle dispersion liquid; Be that the polystyrene latex ball of 105nm slowly adds in the nano SiO 2 particle dispersion liquid and stirs with diameter then; Volume ratio is 2.6:1, obtains blend solution, and is for use.
Utilize rolling method to carry out plated film at the photovoltaic glass surface that cleans up, obtain transparent film.The photovoltaic glass that has plated film is placed under 500 ℃ of temperature condition sintering processes 18 minutes, obtain efficient anti-reflection anti reflection glass.
Fig. 1 shows that prepared film is the silica membrane with porous cavity pattern, and thin-film refractive index is controlled; Analysis 2, we find that anti-reflection glass transmitance increases by 3%, has tangible wide spectrum antireflective effect.
Embodiment 2:
0.4mol water, 0.4mol hydrochloric acid and 12mol terepthaloyl moietie are mixed stirring heating, treat that temperature reaches 20 ℃ of design temperatures, add the 0.04mol methyl silicate; Keep constant temperature, continue to stir 2 hours, obtain the nano SiO 2 particle dispersion liquid; Be that the polystyrene latex ball of 10nm slowly adds in the nano SiO 2 particle dispersion liquid and stirs with diameter then; Volume ratio is 1:5, obtains blend solution, and is for use.
Utilize rolling method to carry out plated film at the photovoltaic glass surface that cleans up, obtain transparent film.The photovoltaic glass that has plated film was placed under 700 ℃ of temperature condition sintering processes 5 minutes, obtain efficient anti-reflection anti reflection glass, through detecting, anti-reflection glass transmitance increases by 2.6%.
Embodiment 3:
0.004mol water, 0.002mol sodium hydroxide and 0.4mol propyl alcohol are mixed stirring heating, treat that temperature reaches 50 ℃ of design temperatures, add the 0.04mol methyl silicate; Keep constant temperature, continue to stir 40 hours, obtain the nano SiO 2 particle dispersion liquid; Be that the polystyrene latex ball of 200nm slowly adds in the nano SiO 2 particle dispersion liquid and stirs with diameter then; Volume ratio is 5:1, obtains blend solution, and is for use.
Utilize spraying method to carry out plated film at the photovoltaic glass surface that cleans up, obtain transparent film.The photovoltaic glass that has plated film was placed under 300 ℃ of temperature condition sintering processes 30 minutes, obtain efficient anti-reflection anti reflection glass, through detecting, anti-reflection glass transmitance increases by 2.5%.
Embodiment 4:
With 0.2mol water, 0.2mol ammoniacal liquor and 6.2mol methanol mixed stirring heating, treat that temperature reaches 30 ℃ of design temperatures, add the 0.04mol methyl silicate; Keep constant temperature, continue to stir 10 hours, obtain the nano SiO 2 particle dispersion liquid; Be that the polystyrene latex ball of 80nm slowly adds in the nano SiO 2 particle dispersion liquid and stirs with diameter then; Volume ratio is 1:1, obtains blend solution, and is for use.
Lift at the photovoltaic glass surface utilization that cleans up dipping and to carry out plated film, obtain transparent film.The photovoltaic glass that has plated film was placed under 610 ℃ of temperature condition sintering processes 15 minutes, obtain efficient anti-reflection anti reflection glass, through detecting, anti-reflection glass transmitance increases by 2.8%.
Embodiment 5:
0.04mol water, 0.02mol ammoniacal liquor, 2mol ethanol and 1mol propyl alcohol are mixed stirring heating, treat that temperature reaches 28 ℃ of design temperatures, add the 0.04mol methyl silicate; Keep constant temperature, continue to stir 6 hours, obtain the nano SiO 2 particle dispersion liquid; Be that the polystyrene latex ball of 150nm slowly adds in the nano SiO 2 particle dispersion liquid and stirs with diameter then; Volume ratio is 2:3, obtains blend solution, and is for use.
Utilize spin-coating method to carry out plated film at the photovoltaic glass surface that cleans up, obtain transparent film.The photovoltaic glass that has plated film was placed under 480 ℃ of temperature condition sintering processes 23 minutes, obtain efficient anti-reflection anti reflection glass, through detecting, anti-reflection glass transmitance increases by 2.9%.
The foregoing description only is a preferred embodiments of the present invention; Technical conceive of the present invention and essential implementation have been specified; Be not to be that protection scope of the present invention is limited; All any simple modification that spirit is done according to the present invention and equivalent structure transformation or modification all should be encompassed within protection scope of the present invention.
Claims (4)
1. the preparation method of an efficient anti-reflection anti-reflection glass is characterized in that, comprises the following steps:
(1) preparation nano SiO 2 particle dispersion liquid: raw material is counted in molar ratio; Silicon source: deionized water: catalyzer: solvent=1:0.05~10:0.01~10:10~300; With deionized water, catalyzer, solvent, heating is also at the uniform velocity stirred, and is heated to 20~50 ℃ earlier; Add the silicon source and keep constant temperature at the uniform velocity to stir 2~40 hours, obtain the nano SiO 2 particle dispersion liquid;
(2) be that 1:5~5:1 mixes with the polystyrene latex ball by volume as the nano SiO 2 particle dispersion liquid that obtains in template and the step (1), obtain blend solution;
(3) film: the blend solution that obtains in the step (2) is coated on the photovoltaic glass substrate surface;
(4) rete intensified process: the photovoltaic glass substrate of filming was placed under 300~700 ℃ of temperature condition sintering 5~30 minutes, obtain efficient anti-reflection anti-reflection glass.
2. the preparation method of a kind of efficient anti-reflection anti-reflection glass according to claim 1; It is characterized in that; Said silicon source is one or both mixtures in tetraethoxy or the methyl silicate; Said catalyzer is one or more mixtures in hydrochloric acid, ammoniacal liquor or the sodium hydroxide, and said solvent is one or more mixtures in ethanol, methyl alcohol, propyl alcohol, the terepthaloyl moietie.
3. the preparation method of a kind of efficient anti-reflection anti-reflection glass according to claim 1 is characterized in that, the diameter of polystyrene latex ball is 10~200nm described in the step (2).
4. the preparation method of a kind of efficient anti-reflection anti-reflection glass according to claim 1 is characterized in that, filming to dipping lifts, spin coating, roller coat or spraying described in the step (3).
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Cited By (14)
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CN103022252A (en) * | 2012-12-22 | 2013-04-03 | 蚌埠玻璃工业设计研究院 | Preparation method for antireflection film of solar cell |
CN103219454A (en) * | 2013-04-25 | 2013-07-24 | 易美芯光(北京)科技有限公司 | Film coating method capable of improving luminous efficiency of light-emitting diode (LED) package device and LED package device |
CN103434215A (en) * | 2013-08-12 | 2013-12-11 | 广东南亮玻璃科技有限公司 | Super-hydrophilic anti-reflection coated glass and preparation method thereof |
CN103951279A (en) * | 2014-05-04 | 2014-07-30 | 江南大学 | Hydrophobic and oleophobic silica-based translucent coating film and preparation method thereof |
CN104860546A (en) * | 2014-02-26 | 2015-08-26 | 上海西源节能材料有限公司 | Wide-spectrum omnidirectional photovoltaic glass antireflection film and its preparation method and use |
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CN103219454A (en) * | 2013-04-25 | 2013-07-24 | 易美芯光(北京)科技有限公司 | Film coating method capable of improving luminous efficiency of light-emitting diode (LED) package device and LED package device |
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CN109502987A (en) * | 2018-12-17 | 2019-03-22 | 常州大学 | A method of high rigidity antireflective film is prepared based on hollow silica |
CN109502987B (en) * | 2018-12-17 | 2021-09-28 | 常州大学 | Method for preparing high-hardness anti-reflection film based on hollow silicon oxide |
CN110734561A (en) * | 2019-10-28 | 2020-01-31 | 中国工程物理研究院激光聚变研究中心 | frequency doubling element matching film of strong laser device and preparation method thereof |
CN110734561B (en) * | 2019-10-28 | 2022-02-11 | 中国工程物理研究院激光聚变研究中心 | Frequency doubling element matching film of intense laser device and preparation method thereof |
CN113912303A (en) * | 2021-11-02 | 2022-01-11 | 常州亚玛顿股份有限公司 | A kind of preparation method of high quality and high bending strength double-sided coated glass |
CN114890681A (en) * | 2022-04-02 | 2022-08-12 | 深圳市秉兴光电技术有限公司 | Moth-eye-like structure antireflection glass and preparation method and application thereof |
CN114890681B (en) * | 2022-04-02 | 2023-12-01 | 深圳市秉兴光电技术有限公司 | Moth-eye-like structure anti-reflection and anti-reflection glass and preparation method and application thereof |
CN115010380A (en) * | 2022-08-09 | 2022-09-06 | 中国华能集团清洁能源技术研究院有限公司 | Preparation method of photovoltaic glass based on disordered photonic crystals |
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Application publication date: 20120718 |