CN106634133A - Waterproof organic perovskite film and preparation method and application thereof - Google Patents
Waterproof organic perovskite film and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000463 material Substances 0.000 claims abstract description 31
- 239000010409 thin film Substances 0.000 claims abstract description 10
- 239000002105 nanoparticle Substances 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- -1 methylamine cation Chemical class 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 9
- 229910000077 silane Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N N-butylamine Natural products CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical group CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- KDSNLYIMUZNERS-UHFFFAOYSA-N isobutyl amine Natural products CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 claims description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 3
- WGYKZJWCGVVSQN-UHFFFAOYSA-N mono-n-propyl amine Natural products CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 3
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims 6
- 230000004048 modification Effects 0.000 claims 6
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical class CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims 2
- ONFRHRVYLPVAMA-UHFFFAOYSA-N C(CCCCCCCCC)[Si](OCC)(OCC)OCC.[F] Chemical class C(CCCCCCCCC)[Si](OCC)(OCC)OCC.[F] ONFRHRVYLPVAMA-UHFFFAOYSA-N 0.000 claims 1
- 239000004593 Epoxy Substances 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical group [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 claims 1
- 238000002454 metastable transfer emission spectrometry Methods 0.000 claims 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 23
- 239000002131 composite material Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 4
- 239000010703 silicon Substances 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 description 12
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 3
- 229960003493 octyltriethoxysilane Drugs 0.000 description 3
- KKYDYRWEUFJLER-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F KKYDYRWEUFJLER-UHFFFAOYSA-N 0.000 description 2
- WPTBEYMWFWQIJY-UHFFFAOYSA-N 2,2,3,5,5,5-hexafluoropentoxy-dimethoxy-propylsilane Chemical compound FC(C(F)(F)CO[Si](OC)(OC)CCC)CC(F)(F)F WPTBEYMWFWQIJY-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- CGUAVPURARJPSS-UHFFFAOYSA-N 10-fluorodecyl-dimethoxy-octadecoxysilane Chemical compound CCCCCCCCCCCCCCCCCCO[Si](OC)(OC)CCCCCCCCCCF CGUAVPURARJPSS-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- WPQJZUITFQDUQP-UHFFFAOYSA-N ethoxy(dipropyl)silane Chemical compound CCC[SiH](CCC)OCC WPQJZUITFQDUQP-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- PMQIWLWDLURJOE-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F PMQIWLWDLURJOE-UHFFFAOYSA-N 0.000 description 1
- BPCXHCSZMTWUBW-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F BPCXHCSZMTWUBW-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- C09D5/22—Luminous paints
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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Abstract
本发明公开了一种耐水性有机钙钛矿薄膜及其制备方法。该方法将有机钙钛矿材料纳米颗粒采用有机硅进行表面修饰，制备得到复合纳米溶胶，将其涂布成膜，干燥后，制备得到所述耐水性有机钙钛矿薄膜。本发明的制备方法简单，制备得到的耐水性有机钙钛矿薄膜耐水性好，可以作为LED光源的荧光材料。
The invention discloses a water-resistant organic perovskite film and a preparation method thereof. In the method, organic perovskite material nanoparticles are surface-modified with organic silicon to prepare a composite nano-sol, which is coated to form a film, and after drying, the water-resistant organic perovskite film is prepared. The preparation method of the invention is simple, and the prepared water-resistant organic perovskite thin film has good water resistance, and can be used as a fluorescent material of an LED light source.
Description
技术领域technical field
本发明涉及荧光材料制备领域，具体涉及耐水性有机钙钛矿荧光复合材料及其制备方法和应用。The invention relates to the field of fluorescent material preparation, in particular to a water-resistant organic perovskite fluorescent composite material and a preparation method and application thereof.
背景技术Background technique
近年来，有机钙钛矿材料由于其在太阳能光电转换、OLED、LED等领域的广泛应用前景，而引起了广泛的研究兴趣，但由于该材料对水极度敏感，而大大限制了其实际的应用，最近，H.J.Bolink等人报道了有机钙钛矿和纳米氧化铝混合的复合材料(J.Mater.Chem.C,2015,3,11286)具有较好的耐水功能，将纳米有机钙钛矿颗粒采用长链胺进行功能化也可以延长有机钙钛矿材料的稳定性(ACS Nano,2015,9,4533)，但这些材料，虽然在湿度不太大的条件下，具有一定的稳定性，但是当其遇水时，其晶体结构会被破坏，因此发展出对水稳定的有机钙钛矿材料是目前该材料研究的难点和热点。In recent years, organic perovskite materials have attracted extensive research interest due to their wide application prospects in solar photoelectric conversion, OLED, LED, etc., but their practical applications are greatly limited due to the extreme sensitivity of the material to water. , recently, H.J.Bolink et al. reported that the composite material (J.Mater.Chem.C, 2015,3,11286) mixed with organic perovskite and nano-alumina has good water resistance, and the nano-organic perovskite particles Functionalization with long-chain amines can also prolong the stability of organic perovskite materials (ACS Nano, 2015, 9, 4533), but these materials, although they have certain stability under the condition of not too high humidity, but When it encounters water, its crystal structure will be destroyed, so the development of water-stable organic perovskite materials is the difficulty and focus of current material research.
发明内容Contents of the invention
针对现有技术的上述缺陷，本发明提出了一种耐水性有机钙钛矿薄膜及其制备方法。将有机钙钛矿材料的表面采用有机硅进行修饰，制备得到混合溶胶，将其涂布成膜，干燥后，制备得到耐水性有机钙钛矿荧光复合材料。本发明的制备方法简单，制备得到的耐水性有机钙钛矿薄膜耐水性好，可以作为LED光源的荧光材料。Aiming at the above-mentioned defects of the prior art, the present invention proposes a water-resistant organic perovskite film and a preparation method thereof. The surface of the organic perovskite material is modified with organic silicon to prepare a mixed sol, which is coated to form a film and dried to prepare a water-resistant organic perovskite fluorescent composite material. The preparation method of the invention is simple, and the prepared water-resistant organic perovskite thin film has good water resistance, and can be used as a fluorescent material of an LED light source.
本发明的耐水性有机钙钛矿薄膜制备方法包括如下步骤：The preparation method of the water-resistant organic perovskite film of the present invention comprises the following steps:
(1)有机硅修饰有机钙钛矿溶胶的制备(1) Preparation of organosilicon-modified organic perovskite sol
将有机钙钛矿材料分散在有机溶剂中，形成有机钙钛矿分散液；在搅拌下向所述有机钙钛矿分散液加入二氧化硅纳米溶胶，搅拌均匀后，加入硅烷进行反应，得到有机硅修饰的有机钙钛矿溶胶。Disperse the organic perovskite material in an organic solvent to form an organic perovskite dispersion; add silica nano-sol to the organic perovskite dispersion under stirring, and after stirring evenly, add silane to react to obtain an organic perovskite dispersion. Silicon-modified organic perovskite sols.
(2)耐水性有机钙钛矿薄膜的制备(2) Preparation of water-resistant organic perovskite films
将步骤(1)制备得到的所述有机硅修饰的有机钙钛矿溶胶涂布在洁净物体表面，并在空气中干燥固化，得到所述耐水性有机钙钛矿薄膜。The organic silicon-modified organic perovskite sol prepared in step (1) is coated on the surface of a clean object, and dried and solidified in air to obtain the water-resistant organic perovskite film.
其中，步骤(1)中，Among them, in step (1),
所述的有机溶剂选自丙酮、丁酮、戊酮、环己酮、甲苯、二甲苯、氯苯中的一种或多种。The organic solvent is selected from one or more of acetone, methyl ethyl ketone, pentanone, cyclohexanone, toluene, xylene, and chlorobenzene.
所述的有机钙钛矿材料分子式为ABX3，其中A为甲胺、乙胺、丙胺、丁胺、异丙胺、异丁胺或叔丁胺正离子，B为铅(Pb)，X为F-、Cl-、Br-或I-。The molecular formula of the organic perovskite material is ABX 3 , wherein A is methylamine, ethylamine, propylamine, butylamine, isopropylamine, isobutylamine or tert-butylamine positive ion, B is lead (Pb), X is F - , Cl − , Br − or I − .
所述有机钙钛矿材料的纳米颗粒的颗粒大小为1纳米-5微米，优选为5纳米-2微米，进一步优选为10纳米-1微米。The particle size of the nanoparticles of the organic perovskite material is 1 nanometer to 5 micrometers, preferably 5 nanometers to 2 micrometers, and more preferably 10 nanometers to 1 micrometer.
所述的二氧化硅纳米溶胶尺寸为2-150纳米，优选为5-80纳米，进一步优选为10-30纳米。可以直接从市场购买，如阿克苏诺贝尔的Levasil系列硅溶胶，扶桑化学工业集团或南京海泰纳米材料有限公司的纳米硅溶胶。The size of the silica nano-sol is 2-150 nm, preferably 5-80 nm, more preferably 10-30 nm. It can be purchased directly from the market, such as AkzoNobel's Levasil series of silica sol, Fuso Chemical Industry Group or Nanjing Haitai Nano Materials Co., Ltd.'s nano-silica sol.
本发明可以在磁力搅拌下向所述有机钙钛矿分散液加入二氧化硅纳米溶胶。In the present invention, silicon dioxide nano-sol can be added to the organic perovskite dispersion under magnetic stirring.
所述硅烷选自甲基三乙氧基硅烷、二甲基二乙氧基硅烷、乙基聚硅酸酯、3-环氧丙醇三甲氧基硅烷、γ-丙基三乙氧基硅烷、辛基三乙氧基硅烷、辛基三甲氧基硅烷、苯基三乙氧基硅烷、十八烷基三甲氧基硅烷、十六烷基三甲氧基硅烷、十二氟庚基丙基三甲氧基硅烷、六氟丁基丙基三甲氧基硅烷、十七氟癸基三甲氧基硅烷、十三氟辛基三甲氧基硅烷、十二氟庚基丙基三乙氧基硅烷、六氟丁基丙基乙氧基硅烷、十七氟癸基三乙氧基硅烷、十三氟辛基三乙氧基硅烷中的任意一种或多种。The silane is selected from methyltriethoxysilane, dimethyldiethoxysilane, ethyl polysilicate, 3-glycidyl trimethoxysilane, γ-propyl triethoxysilane, Octyltriethoxysilane, Octyltrimethoxysilane, Phenyltriethoxysilane, Octadecyltrimethoxysilane, Hexadecyltrimethoxysilane, Dodecafluoroheptylpropyltrimethoxy Hexafluorobutylpropyltrimethoxysilane, Hexafluorobutylpropyltrimethoxysilane, Heptadecylfluorodecyltrimethoxysilane, Tridecafluorooctyltrimethoxysilane, Dodecafluoroheptylpropyltriethoxysilane, Hexafluorobutyl Any one or more of propylpropylethoxysilane, heptadecafluorodecyltriethoxysilane, and tridecafluorooctyltriethoxysilane.
所述耐水性有机钙钛矿薄膜，有机硅为二氧化硅纳米溶胶和硅烷的混合物；该方法将有机钙钛矿材料纳米颗粒采用有机硅进行表面修饰，制备得到复合纳米溶胶，将其涂布成膜，干燥后，制备得到所述耐水性有机钙钛矿薄膜。In the water-resistant organic perovskite film, the organic silicon is a mixture of silica nano-sol and silane; in this method, the surface of organic perovskite material nanoparticles is modified with organic silicon to prepare a composite nano-sol, which is coated After film formation and drying, the water-resistant organic perovskite film is prepared.
所述有机钙钛矿材料占有机钙钛矿分散液的质量百分比为5％～85％；优选地，为15～50％，进一步优选地为25～35％。The mass percentage of the organic perovskite material in the organic perovskite dispersion is 5%-85%, preferably 15-50%, more preferably 25-35%.
所述的有机钙钛矿分散液与二氧化硅溶胶及硅烷的质量比为85～55：15～35：15～35；优选地，为75～65：15～25：15～25。The mass ratio of the organic perovskite dispersion to the silica sol and silane is 85-55:15-35:15-35; preferably, 75-65:15-25:15-25.
所述步骤(1)中，反应的温度为10-90℃；优选地，为20-60℃；进一步优选地，为25-45℃。In the step (1), the reaction temperature is 10-90°C; preferably, 20-60°C; more preferably, 25-45°C.
所述步骤(1)中，反应的时间为0.5小时-24小时；优选地，为2小时～10小时；进一步优选地，为2小时～4小时。In the step (1), the reaction time is 0.5 hours to 24 hours; preferably, 2 hours to 10 hours; more preferably, 2 hours to 4 hours.
其中，步骤(2)中，Among them, in step (2),
优选地，在空气中干燥固化。Preferably, it is dried and cured in air.
所述干燥固化的温度为25-70℃；优选地，为40-60℃。The drying and curing temperature is 25-70°C; preferably, 40-60°C.
所述干燥固化的时间为5-120分钟，优选地，为20-60分钟。The drying and curing time is 5-120 minutes, preferably 20-60 minutes.
本发明还提出了由上述制备方法制备得到的有机硅修饰的有机钙钛矿溶胶，该溶胶分散均匀，不发生分层现象，发光性能稳定The present invention also proposes the organosilicon-modified organic perovskite sol prepared by the above-mentioned preparation method, the sol is uniformly dispersed, no delamination phenomenon occurs, and the luminescent performance is stable
本发明还提出了所述有机硅修饰的有机钙钛矿溶胶在制备LED光源荧光涂层中的应用。The invention also proposes the application of the organosilicon-modified organic perovskite sol in preparing fluorescent coatings for LED light sources.
本发明还提出了一种由上述方法得到的耐水性有机钙钛矿薄膜；该耐水性有机钙钛矿薄膜耐水性好，在潮湿的环境中具有稳定的荧光性能，如图1所示，将水滴滴到薄膜上，薄膜不受水的影响，正常发光，具有很好的稳定性。The present invention also proposes a water-resistant organic perovskite film obtained by the above method; the water-resistant organic perovskite film has good water resistance and has stable fluorescent properties in a humid environment, as shown in Figure 1. Water droplets drip onto the film, and the film is not affected by water, normally glows, and has good stability.
本发明还提出了所述耐水性有机钙钛矿薄膜在制备LED光源荧光涂层中的应用。The invention also proposes the application of the water-resistant organic perovskite thin film in preparing fluorescent coatings for LED light sources.
本发明还提出了所述耐水性有机钙钛矿薄膜在用于LED光源调色中的应用。The invention also proposes the application of the water-resistant organic perovskite thin film in LED light source color matching.
本发明的有益效果包括：本发明制备得到的耐水性有机钙钛矿薄膜(耐水性有机钙钛矿荧光材料)的制备方法简单，耐水性好，可以作为LED光源的荧光材料。The beneficial effects of the invention include: the water-resistant organic perovskite film (water-resistant organic perovskite fluorescent material) prepared by the invention has a simple preparation method and good water resistance, and can be used as a fluorescent material for an LED light source.
附图说明Description of drawings
图1为本发明实施例1制备得到的耐水性有机钙钛矿薄膜，其中液滴为水滴，薄膜对水具有很好的稳定性。Figure 1 shows the water-resistant organic perovskite film prepared in Example 1 of the present invention, in which the liquid droplets are water droplets, and the film has good stability to water.
图2为制备得到的采用耐水性有机钙钛矿荧光材料为荧光剂的LED灯珠。Fig. 2 is a prepared LED lamp bead using a water-resistant organic perovskite fluorescent material as a fluorescent agent.
具体实施方式detailed description
结合以下具体实施例和附图，对本发明作进一步的详细说明，本发明的保护内容不局限于以下实施例。在不背离发明构思的精神和范围下，本领域技术人员能够想到的变化和优点都被包括在本发明中，并且以所附的权利要求书为保护范围。实施本发明的过程、条件、试剂、实验方法等，除以下专门提及的内容之外，均为本领域的普遍知识和公知常识，本发明没有特别限制内容。The present invention will be described in further detail in conjunction with the following specific examples and accompanying drawings, and the protection content of the present invention is not limited to the following examples. Without departing from the spirit and scope of the inventive concept, changes and advantages conceivable by those skilled in the art are all included in the present invention, and the appended claims are the protection scope. The process, conditions, reagents, experimental methods, etc. for implementing the present invention are general knowledge and common knowledge in the art except for the content specifically mentioned below, and the present invention has no special limitation content.
实施例1Example 1
将0.5克CH3NH4PbBr3材料分散在1.0克丙酮中，搅拌均匀，滴加入0.4克LevasilS200硅溶胶，继续搅拌反应30分钟。Disperse 0.5 g of CH 3 NH 4 PbBr 3 material in 1.0 g of acetone, stir evenly, add 0.4 g of LevasilS200 silica sol dropwise, and continue stirring for 30 minutes.
将0.1克甲基三乙氧基硅烷和0.1克辛基三乙氧基硅烷混合均匀，然后滴加到上述溶液中，在40-60℃的温度下反应4小时，得到有机硅修饰的有机钙钛矿溶胶。将材料采用旋涂方法涂布于2×2cm玻璃片上，在50℃下烘烤60分钟，制备得到耐水性有机钙钛矿薄膜。Mix 0.1 gram of methyltriethoxysilane and 0.1 gram of octyltriethoxysilane evenly, then add it dropwise to the above solution, and react at a temperature of 40-60°C for 4 hours to obtain organosilicon-modified organocalcium Titanium Sol. The material was coated on a 2×2 cm glass sheet by spin coating, and baked at 50° C. for 60 minutes to prepare a water-resistant organic perovskite film.
实施例2Example 2
将1.0克CH3NH4PbBr3材料分散在3.0克丁酮中，搅拌均匀，滴加入0.5克扶桑化学工业集团ST-O硅溶胶，继续搅拌反应30分钟。Disperse 1.0 g of CH 3 NH 4 PbBr 3 material in 3.0 g of butanone, stir evenly, add 0.5 g of Fuso Chemical Industry Group ST-O silica sol dropwise, and continue stirring for 30 minutes.
将0.2克甲基三乙氧基硅烷和0.2克十七氟癸基三甲氧基硅烷混合均匀，然后滴加到上述溶液中，在40-60℃的温度下反应2小时，得到有机硅修饰的有机钙钛矿溶胶。将溶胶采用旋涂法涂布于2×2cm玻璃片上，得到耐水性有机钙钛矿薄膜。Mix 0.2 g of methyltriethoxysilane and 0.2 g of heptadecafluorodecyltrimethoxysilane evenly, then dropwise add them to the above solution, and react at a temperature of 40-60°C for 2 hours to obtain silicone-modified Organic perovskite sol. The sol was coated on a 2×2 cm glass sheet by spin coating to obtain a water-resistant organic perovskite film.
实施例3Example 3
将0.5克C4H9NH4PbBr3材料分散在3.0克氯苯中，搅拌均匀，滴加入0.2克扶桑化学工业集团IPA-30硅溶胶，继续搅拌反应30分钟。Disperse 0.5 g of C 4 H 9 NH 4 PbBr 3 material in 3.0 g of chlorobenzene, stir evenly, add 0.2 g of Fuso Chemical Industry Group IPA-30 silica sol dropwise, and continue stirring for 30 minutes.
将0.1克甲基三乙氧基硅烷和0.1克十七氟癸基三甲氧基硅烷混合均匀，然后滴加到上述溶液中，在40-60℃的温度下反应2小时，得到有机硅修饰的有机钙钛矿溶胶。将溶胶采用旋涂法涂布于2×2cm玻璃片上，在50℃下烘烤60分钟，制备得到耐水性有机钙钛矿薄膜。Mix 0.1 gram of methyltriethoxysilane and 0.1 gram of heptadecafluorodecyltrimethoxysilane evenly, then add dropwise to the above solution, and react at a temperature of 40-60°C for 2 hours to obtain silicone-modified Organic perovskite sol. The sol was coated on a 2×2 cm glass sheet by spin coating, and baked at 50° C. for 60 minutes to prepare a water-resistant organic perovskite film.
实施例4Example 4
将0.5克C3H7NH4PbCl3材料分散在3.0克甲苯中，搅拌均匀，滴加入0.1克扶桑化学工业集团MEK-30硅溶胶，继续搅拌反应30分钟。Disperse 0.5 g of C 3 H 7 NH 4 PbCl 3 material in 3.0 g of toluene, stir evenly, add 0.1 g of Fuso Chemical Industry Group MEK-30 silica sol dropwise, and continue stirring for 30 minutes.
将0.1克二甲基二乙氧基硅烷和0.1克十三氟辛基三甲氧基硅烷混合均匀，然后滴加到上述溶液中，在40-60℃的温度下反应2小时，得到有机硅修饰的有机钙钛矿溶胶。将溶胶采用旋涂法涂布于2×2cm玻璃片上，在40℃下烘烤40分钟，得到耐水性有机钙钛矿薄膜。Mix 0.1 gram of dimethyldiethoxysilane and 0.1 gram of tridecafluorooctyltrimethoxysilane evenly, then add dropwise to the above solution, and react at a temperature of 40-60°C for 2 hours to obtain silicone modified organic perovskite sols. The sol was coated on a 2×2 cm glass sheet by spin coating, and baked at 40° C. for 40 minutes to obtain a water-resistant organic perovskite film.
实施例5Example 5
将0.2克C3H7NH4PbI3材料分散在1.0克甲苯中，搅拌均匀，滴加入0.1克扶桑化学工业集团MEK-30硅溶胶，在60℃下烘烤90分钟，继续搅拌反应30分钟。Disperse 0.2 g of C 3 H 7 NH 4 PbI 3 material in 1.0 g of toluene, stir evenly, add dropwise 0.1 g of Fuso Chemical Industry Group MEK-30 silica sol, bake at 60°C for 90 minutes, and continue stirring for 30 minutes .
将0.1克辛基三乙氧基硅烷和0.1克六氟丁基丙基乙氧基硅烷混合均匀，然后滴加到上述溶液中，在40-60℃的温度下反应2小时，得到有机硅修饰的有机钙钛矿溶胶。将溶胶采用旋涂法涂布于2×2cm玻璃片上，在70℃下烘烤30分钟，得到耐水性有机钙钛矿薄膜。Mix 0.1 gram of octyltriethoxysilane and 0.1 gram of hexafluorobutylpropylethoxysilane evenly, then add dropwise to the above solution, and react at a temperature of 40-60°C for 2 hours to obtain silicone modified organic perovskite sols. The sol was coated on a 2×2 cm glass slide by spin coating, and baked at 70° C. for 30 minutes to obtain a water-resistant organic perovskite film.
实施例6Example 6
将实施例2中制备得到有机硅修饰的有机钙钛矿溶胶刷涂到GaN芯片上，GaN芯片的发光波长为410纳米，在50℃下烘烤进行干燥固化60分钟，在荧光涂层的作用下，将GaN发出的410纳米的光，调制到绿光范围，制备得到绿光LED光源，样品如图2所示；(涂层本身不会发光，在荧光涂层的作用下，将GaN发出的410纳米的光，调制到绿光范围)。Brush the organosilicon-modified organic perovskite sol prepared in Example 2 onto the GaN chip. The GaN chip has an emission wavelength of 410 nanometers, and bake it at 50°C for 60 minutes to dry and cure. In this case, the 410nm light emitted by GaN is modulated to the green light range to prepare a green LED light source, the sample is shown in Figure 2; (the coating itself does not emit light, under the action of the fluorescent coating, the GaN emits light 410 nm light, modulated into the green range).
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