CN106477914A - 一种复合透明导电薄膜玻璃的制备方法 - Google Patents
一种复合透明导电薄膜玻璃的制备方法 Download PDFInfo
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 63
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 40
- 239000002131 composite material Substances 0.000 claims abstract description 27
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- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 22
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical group OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 229910003978 SiClx Inorganic materials 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- UNRQTHVKJQUDDF-UHFFFAOYSA-N acetylpyruvic acid Chemical compound CC(=O)CC(=O)C(O)=O UNRQTHVKJQUDDF-UHFFFAOYSA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 235000014121 butter Nutrition 0.000 claims 1
- 239000013078 crystal Substances 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- 235000011194 food seasoning agent Nutrition 0.000 claims 1
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- 238000001935 peptisation Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 65
- 239000010409 thin film Substances 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
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- 239000004814 polyurethane Substances 0.000 description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 150000003378 silver Chemical class 0.000 description 3
- -1 silver halide Chemical class 0.000 description 3
- RTTFYYVFBVGCFC-UHFFFAOYSA-M silver;oxaldehydate Chemical compound [Ag+].[O-]C(=O)C=O RTTFYYVFBVGCFC-UHFFFAOYSA-M 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 239000000523 sample Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- CHACQUSVOVNARW-LNKPDPKZSA-M silver;(z)-4-oxopent-2-en-2-olate Chemical compound [Ag+].C\C([O-])=C\C(C)=O CHACQUSVOVNARW-LNKPDPKZSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- DCCXSCIRSRPUJX-UHFFFAOYSA-N 2-oxopropanoic acid;silver Chemical compound [Ag].CC(=O)C(O)=O DCCXSCIRSRPUJX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 1
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 1
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- 239000003638 chemical reducing agent Substances 0.000 description 1
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- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000002106 nanomesh Substances 0.000 description 1
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- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3642—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating containing a metal layer
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3668—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties
- C03C17/3671—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having electrical properties specially adapted for use as electrodes
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
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- General Chemical & Material Sciences (AREA)
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- Non-Insulated Conductors (AREA)
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Abstract
本发明涉及一种复合透明导电玻璃的制备方法，首先在溶胶‑凝胶法制备的二氧化硅过渡层龟裂缝隙中填充可溶性银盐，原位热分解生成纳米银粒子，进一步涂布掺氟氧化锡纳米溶胶，高温烧结得到纳米银网复合氧化锡透明导电薄膜。采取的技术方案包括龟裂的纳米二氧化硅过渡层制备、可溶性银盐填充、掺氟氧化锡凝胶薄膜制备和复合透明导电薄膜烧结四部分。本发明复合透明导电玻璃采用纳米银网复合掺氟氧化锡透明导电薄膜，具有透光率高和方块电阻低的特点，适合作为大面积薄膜太阳电池透明电极应用。
Description
技术领域
本发明涉及一种复合透明导电薄膜玻璃的制备方法，特别是一种在掺氟氧化锡导电玻璃的二氧化硅过渡层龟裂缝隙中原位生成纳米银粒子，进一步形成纳米银网复合氧化锡透明导电薄膜玻璃的制备方法，属于新能源材料和信息技术领域。
技术背景
导电玻璃通常是在玻璃表面通过物理或者化学方法均匀镀上一层透明导电氧化物（TCO）薄膜形成的。目前大量用作薄膜太阳电池的透明电极，还应用于液晶显示屏、触摸屏、光催化和建筑节能等领域，市场需求巨大。常见的TCO材料包括氧化铟基（ITO）、氧化锡基（FTO）和氧化锌基（AZO）三类，其中，ITO和FTO导电玻璃已商业化生产和应用，由于产品成本和电阻偏高限制了其应用推广。
另一类导电玻璃是将低电阻金属银镀在玻璃上形成透明导电玻璃。第一种方法是热蒸镀或磁控溅射金属银，在玻璃表面形成10-20nm的透明导电银膜；第二种方式是将银络合物涂覆在玻璃上，热处理分解形成透明导电银膜；第三种方式是将纳米银线涂布在玻璃上形成透明导电银膜；第四种方式是将卤化银乳剂涂布在玻璃上，曝光和显影形成金属银导电网格。韩国印可得公司发明专利CN101678658（2010-03-24）公开将银络合物涂布在玻璃上，120℃热处理形成银导电玻璃，透光率80%，方块电阻20-30Ω，可用于显示屏、电磁屏蔽和透明电极。蚌埠玻璃工业设计院发明专利CN104332215（2015-02-04）公开低电阻率透明导电膜的制备方法，发明专利CN103979802（2014-08-13）公开一种纳米银线透明导电玻璃的生产方法。将纳米银线印刷在玻璃上制备高透光率和低电阻导电玻璃已取得技术突破，大日本印刷公司已能提供纳米银线导电膜中试产品，应用于液晶显示屏和触摸屏方面。乐凯集团公司发明专利CN101577148（2009-11-11）公开在玻璃上涂布卤化银乳剂，采用卤化银乳剂曝光和显影技术形成纳米银网格，进一步化学镀铜或镍形成导电玻璃，导电金属网开孔率大于80%，透光率80%以上，方块电阻0.1-30Ω，可应用于液晶显示屏和触摸屏方面。
银金属具有良好的导电性，其电阻率比透明氧化物低二个数量级，但只有在金属薄膜厚度小于20nm 时才具有良好的透光性能，而极薄的金属膜层往往以岛状形式存在，导致大面积薄膜具有很高的电阻和反射率。将FTO导电薄膜与银金属复合是一种降低FTO导电薄膜方块电阻的有效途径。
中国专利CN103151394(2013-06-12)公开一种薄膜太阳能电池及其制作方法，在TCO导电薄膜上涂覆10-20nm厚度的纳米银薄膜，得到了低电阻的纳米银复合透明导电薄膜，提高了薄膜太阳电池效率，但需要采用技术复杂和高成本的磁控溅射技术和热蒸镀技术。中国专利CN101515602(2009-08-26)公开一种透明导电膜玻璃，在FTO导电薄膜上印刷银栅电极，从而降低导电基底的欧姆损失，但印刷制备的银栅线一般宽度和厚度都比较大，宽银栅线的光遮挡使透光率降低，厚银栅线也不利于后续光吸收材料均匀涂覆。
钙钛矿薄膜太阳电池颠覆性技术突破带动了导电玻璃市场发展，扩大了高透光率低电阻和低成本的导电玻璃的市场需求。
发明内容
本发明的目的是提供一种复合透明导电薄膜玻璃制备方法，其特征是首先在溶胶-凝胶法制备的二氧化硅过渡层龟裂缝隙中填充可溶性银盐，原位热分解生成纳米银粒子，进一步涂布掺氟氧化锡纳米溶胶，高温烧结得到纳米银网复合氧化锡透明导电薄膜玻璃，采取的技术方案包括龟裂的纳米二氧化硅过渡层制备、可溶性银盐填充、掺氟氧化锡凝胶薄膜制备、复合透明导电薄膜烧结四部分。
在太阳电池玻璃基体上涂覆二氧化硅过渡层，用于阻滞高温下钠钙玻璃中钠钙离子向导电薄膜中扩散，同时作为减反射层增大玻璃基体透光率和提高掺氟氧化锡薄膜在玻璃基体上的附着力。为实现这一目标，通常采用正硅酸乙酯在乙醇水溶液中碱性水解得到的粒径为20-40nm纳米二氧化硅溶胶，并添加一些溶剂挥发控制剂，以防止二氧化硅凝胶膜干燥时溶剂挥发过快引起的膜层应力开裂，形成的膜层具有较高的孔隙率。
本发明采用的纳米二氧化硅溶胶与现有市售二氧化硅溶胶产品不同，要求二氧化硅膜层致密，二氧化硅膜层龟裂程度可以通过二氧化硅纳米溶胶组成和膜层制备工艺控制，当二氧化硅溶胶聚合度过低、凝胶膜层过厚和凝胶膜层干燥速度过快时，太阳电池玻璃上涂布的二氧化硅纳米溶胶在凝胶固化时会因为表面收缩和内应力过大，而发生膜层表面大面积龟裂，但龟裂的二氧化硅膜层并不发生剥离脱落。
龟裂的纳米二氧化硅过渡层制备方法为：（1）将正硅酸乙酯、水和硝酸水溶液混合，控制原料摩尔比为：正硅酸乙酯：水：硝酸=1:20-50:0.01-0.1，在25-40℃下搅拌反应1-4 h，使正硅酸乙酯完全水解形成纳米二氧化硅水溶胶，纳米二氧化硅水溶胶的质量百分浓度为5%-10%；（2）纳米二氧化硅水溶胶在室温下放置12-24 h，使纳米二氧化硅聚合度增大，直到溶胶能够在玻璃片上提拉成膜，纳米二氧化硅粒子直径为5-10nm；（3）在洁净的太阳电池玻璃上涂布纳米二氧化硅水溶胶过渡层，采用热风烘干；（4）再在150℃下干燥3-5分钟，二氧化硅凝胶膜表面形成大量规则的多边形龟裂缝隙，裂缝宽度20-200nm，裂缝面积占膜层面积的2%-20%，膜层厚度为100-300nm。
可溶性银盐填充方法是在二氧化硅过渡层上涂布可溶性银盐的乙醇水溶液2-3次，使可溶性银盐浸渍填充到二氧化硅膜龟裂缝隙中，再涂布乙醇溶液使龟裂缝隙填充均匀密实，控制原料的摩尔比为Sn：Ag =1：0.02-0.1，在150℃下烘干，使可溶性银盐原位还原为银粒子，所述可溶性银盐是乙醛酸银、丙酮酸银和乙酰丙酮酸银，它们能够在较低的温度下热分解形成纳米银粒子。
掺氟氧化锡凝胶薄膜制备方法为：（1）向四氯化锡水溶液中加入氨水使锡盐水解，将形成的沉淀洗涤至无氯离子；（2）将水合氧化锡沉淀物悬浮在去离子水中，加入含氟掺杂剂氟化铵或氢氟酸，再加入饱和草酸水溶液，使水合氧化锡沉淀在50-60℃下完全胶溶，生成掺氟氧化锡纳米溶胶的pH为0.8-1.5，掺氟氧化锡纳米溶胶的组成摩尔比为Sn(OH)4：F：H2C2O4=1：0.2-0.6：0.1-0.4；（3）向掺氟氧化锡纳米溶胶中加入质量百分浓度为0.01%-0.2%的聚氨酯乳液，以改善掺氟氧化锡溶胶稳定性、涂布均匀性和防止膜层干燥时开裂，掺氟氧化锡纳米溶胶中二氧化锡质量百分浓度为4%-5%;（4）在太阳电池玻璃过渡层上涂覆掺氟氧化锡溶胶2-3遍，使凝胶薄膜厚度400-600nm，在150℃下烘干得到掺氟氧化锡凝胶薄膜。
复合氧化锡透明导电薄膜烧结方法是将镀膜玻璃基体加热到400℃，在400-450℃时升温速度降低到3-5℃/min，最后在500℃高温下烧结30分钟，使有机物完全分解，使氟原子掺杂进入氧化锡晶格中形成掺氟氧化锡，并使掺氟氧化锡结晶长大形成透明导电薄膜，原位生成的纳米银网与二氧化硅和氧化锡烧结在一起使过渡层龟裂缝隙填平，形成复合透明导电薄膜玻璃的可见光透光率为81%-85%，薄膜方块电阻为0.2-5Ω
本发明能够降低复合薄膜方块电阻的原因包括几个方面：（1）二氧化硅过渡层龟裂缝隙中原位还原生成的纳米银自身连接形成低电阻的纳米银网，从而降低了复合透明导电薄膜方块电阻；（2）原位还原生成的纳米银网与掺氟氧化锡半导体电阻并联，从而降低了复合透明导电薄膜方块电阻（3）掺氟氧化锡薄膜高温处理使纳米银掺杂形成银锡合金，从而降低掺氟氧化锡薄膜方块电阻。
本发明所用的实验原料正硅酸乙酯溶胶、四氯化锡、氨水、氟化铵、草酸、硝酸银、硝酸、乙醇、聚氨酯乳液均为市售化学纯试剂；太阳电池玻璃为市售商品。
复合氧化锡透明导电薄膜玻璃的透光率用 Lambda 920 型分光光度计测试样品在400-760nm可见光范围的透过率计算；复合氧化锡透明导电薄膜玻璃的方块电阻用ST2258C型四探针方阻计测试；龟裂的纳米二氧化硅过渡层缝隙面积通过显微图像截面计算。
本发明的有益效果体现在：
（1）本发明复合透明导电薄膜玻璃采用银纳米网复合掺氟氧化锡薄膜，具有透光率高和方块电阻低的特点，适合作为大面积薄膜太阳电池透明电极应用；
（2）本发明在FTO导电玻璃的纳米二氧化硅龟裂过渡层中原位热分解形成纳米银网，是降低FTO导电薄膜电阻简便易行的技术措施，具有产业化应用前景。
具体实施方式
实施例1
龟裂的纳米二氧化硅过渡层制备:将正硅酸乙酯21g(0.1mol)、水90g(5mol)和硝酸溶液0.6g(0.01mol)混合，在室温下搅拌反应2h，溶液温度最高上升到35℃，正硅酸乙酯完全水解形成透明的纳米二氧化硅水溶胶，纳米二氧化硅水溶胶的质量百分浓度为5%；在室温下放置一天，使二氧化硅聚合度增大至溶胶能够在玻璃片上提拉成膜；在清洗干净的100mm×100 mm×1mm的太阳电池玻璃上涂布二氧化硅纳米溶胶过渡层，热风烘干，再在150℃下干燥3-5分钟，玻璃上涂布的二氧化硅凝胶膜表面形成大量规则的多边形龟裂缝隙，裂缝宽度100nm，裂缝面积占膜层面积的8%，膜层厚度200nm。镀膜前后玻璃在400-760nm波长范围的透光率分别为91.6%和92.5%。
可溶性银盐填充：在二氧化硅过渡层上涂布乙醛酸银的乙醇水溶液2-3次，使可溶性银盐浸渍填充到二氧化硅薄膜龟裂缝隙和薄膜孔隙中，再涂布乙醇溶液使可溶性银盐填充均匀密实，控制原料的摩尔比为Sn：Ag =1：0.05，在150℃下烘干，使可溶性银盐原位还原为银粒子。
掺氟氧化锡凝胶薄膜制备:将无水四氯化锡26.1g(0.1mol)溶于500ml去离子水中，在搅拌下加入2mol/l的氨水，直到不再有沉淀析出和溶液pH为8-9，将水解形成的沉淀过滤，用去离子水洗涤至无氯离子。将沉淀物悬浮在200ml去离子水中，加入饱和草酸水溶液37g(0.03mol)，使水合氧化锡沉淀在50-60℃下完全胶溶，加入氟化铵0.37g(0.01mol)作为掺杂氟源，加入聚氨酯乳液0.5g，得到二氧化锡质量百分浓度为5%的掺氟氧化锡纳米溶胶，溶胶pH为1.1。在填充后的太阳电池玻璃过渡层上涂覆掺氟氧化锡溶胶3次，使凝胶薄膜厚度为500-600nm，在150℃下烘干得到掺氟氧化锡凝胶薄膜。
复合氧化锡透明导电薄膜制备:将镀膜玻璃基体加热到400℃，在400-450℃时升温速度降低到3-5℃/min，最后在500℃高温下烧结30分钟，使有机物完全分解，使氟原子掺杂进入氧化锡晶格中形成掺氟氧化锡，并使掺氟氧化锡结晶长大形成透明导电薄膜，原位生成的纳米银网与二氧化硅和氧化锡烧结在一起，复合导电玻璃可见光透光率83.8%，方块电阻1.8Ω。
实施例2
龟裂的纳米二氧化硅过渡层制备:将正硅酸乙酯21g(0.1mol)、水36g(2mol)和硝酸溶液0.6g(0.01mol)混合，在室温下搅拌反应，溶液温度最高上升到40℃，搅拌反应1 h，正硅酸乙酯完全水解形成透明的纳米二氧化硅溶胶，纳米二氧化硅溶胶的质量百分浓度为9.8%；在室温下放置一天，使溶胶聚合度增大，溶胶能够在玻璃片上提拉成膜；在清洗干净的100mm×100 mm×1mm太阳电池玻璃上涂布二氧化硅纳米溶胶过渡层，热风烘干，再在150℃下干燥3-5分钟，玻璃上的凝胶膜表面形成大量规则的多边形龟裂缝隙，膜层厚度300nm，裂缝宽度150nm，裂缝面积占膜层面积的15%。镀膜前后玻璃在400-760nm波长范围的透光率分别为91.6%和92.1%。
填充可溶性银盐和还原剂：在二氧化硅过渡层上涂布乙酰丙酮银的乙酰丙酮溶液2-3次，使可溶性银盐浸渍填充到二氧化硅薄膜龟裂缝隙和薄膜孔隙中，再涂布乙酰丙酮溶剂使可溶性银盐填充均匀密实，控制原料的摩尔比为Sn：Ag =1：0.1，在150℃下烘干，使可溶性银盐原位还原为银粒子。
掺氟氧化锡凝胶薄膜制备:将无水四氯化锡26.1g(0.1mol)溶于500ml去离子水中，在搅拌下加入2mol/l的氨水，直到不再有沉淀析出和溶液pH为8-9，将水解形成的沉淀过滤，用去离子水洗涤至无氯离子。将沉淀物悬浮在200ml去离子水中，加入饱和草酸水溶液37g(0.03mol)，使水合氧化锡沉淀在50-60℃下完全胶溶，加入氟化铵0.37g(0.01mol)作为掺杂氟源，加入聚氨酯乳液0.5g，得到二氧化锡质量百分浓度为5%的掺氟氧化锡纳米溶胶，溶胶pH为1.1。在填充后的太阳电池玻璃过渡层上涂覆掺氟氧化锡溶胶3次，使凝胶薄膜厚度为500-600nm，在150℃下烘干得到掺氟氧化锡凝胶薄膜。
复合氧化锡透明导电薄膜制备:将镀膜玻璃基体加热到400℃，在400-450℃时升温速度降低到3-5℃/min，最后在500℃高温下烧结30分钟，使有机物完全分解，使氟原子掺杂进入氧化锡晶格中形成掺氟氧化锡，并使掺氟氧化锡结晶长大形成透明导电薄膜，原位生成的纳米银网与二氧化硅和氧化锡烧结在一起，复合导电玻璃可见光透光率80.2%，方块电阻0.8Ω。
Claims (5)
1.一种复合透明导电薄膜玻璃的制备方法，其特征是首先在溶胶-凝胶法制备的二氧化硅过渡层龟裂缝隙中填充可溶性银盐，原位热分解生成纳米银粒子，进一步涂布掺氟氧化锡纳米溶胶，高温烧结得到纳米银网复合氧化锡透明导电薄膜，采取的技术方案包括龟裂的纳米二氧化硅过渡层制备、可溶性银盐填充、掺氟氧化锡凝胶薄膜制备、复合透明导电薄膜烧结四部分。
2.如权利要求1所述复合透明导电薄膜玻璃的制备方法，其特征是龟裂的纳米二氧化硅过渡层制备方法为：
（1）将正硅酸乙酯、水和硝酸水溶液混合，控制原料摩尔比为：正硅酸乙酯：水：硝酸=1：20-50：0.01-0.1，在25-40℃下搅拌反应1-4 h，使正硅酸乙酯完全水解形成纳米二氧化硅水溶胶，纳米二氧化硅水溶胶的质量百分浓度为5%-10%；
（2）纳米二氧化硅水溶胶在室温下放置12-24 h，使纳米二氧化硅聚合度增大，直到溶胶能够在玻璃片上提拉成膜，纳米二氧化硅粒子直径为5-10nm；
（3）在洁净的太阳电池玻璃上涂布纳米二氧化硅水溶胶过渡层，采用热风烘干；
（4）再在150℃下干燥3-5分钟，二氧化硅凝胶膜表面形成大量规则的多边形龟裂缝隙，裂缝宽度20-200nm，裂缝面积占膜层面积的2%-20%，膜层厚度为100-300nm。
3.如权利要求1所述复合透明导电薄膜玻璃的制备方法，其特征是可溶性银盐填充方法是在二氧化硅过渡层上涂布可溶性银盐的乙醇水溶液2-3次，使可溶性银盐浸渍填充到二氧化硅膜龟裂缝隙中，再涂布乙醇溶液使龟裂缝隙填充均匀密实，控制原料的摩尔比为Sn：Ag =1：0.02-0.1，在150℃下烘干，使可溶性银盐原位还原为银粒子，所述可溶性银盐是乙醛酸银、丙酮酸银和乙酰丙酮酸银。
4.如权利要求1所述复合透明导电薄膜玻璃的制备方法，其特征是掺氟氧化锡凝胶薄膜制备方法为：
（1）向四氯化锡水溶液中加入氨水使锡盐水解，将形成的沉淀洗涤至无氯离子；
（2）将水合氧化锡沉淀物悬浮在去离子水中，加入含氟掺杂剂氟化铵或氢氟酸，再加入饱和草酸水溶液，使水合氧化锡沉淀在50-60℃下完全胶溶，生成掺氟氧化锡纳米溶胶pH为0.8-1.5，掺氟氧化锡纳米溶胶的组成摩尔比为Sn(OH)4：F：H2C2O4=1：0.2-0.6：0.1-0.4；
（3）向掺氟氧化锡纳米溶胶中加入聚氨酯乳液，使其质量百分浓度为0.01%-0.2%的，以改善掺氟氧化锡溶胶稳定性、涂布均匀性和防止膜层干燥时开裂，掺氟氧化锡纳米溶胶中二氧化锡质量百分浓度为4%-5%；
（4）在太阳电池玻璃过渡层上涂覆掺氟氧化锡溶胶2-3遍，使凝胶薄膜厚度400-600nm，在150℃下烘干得到掺氟氧化锡凝胶薄膜。
5.如权利要求1所述复合透明导电薄膜玻璃的制备方法，其特征是复合氧化锡透明导电薄膜烧结方法为将镀膜玻璃基体加热到400℃，在400-450℃时升温速度降低到3-5℃/min，最后在500℃高温下烧结30分钟，使有机物完全分解，使氟原子掺杂进入氧化锡晶格中形成掺氟氧化锡，并使掺氟氧化锡结晶长大形成透明导电薄膜，原位生成的纳米银网与二氧化硅和氧化锡烧结在一起使过渡层龟裂缝隙填平，形成复合导电玻璃的可见光透光率为81%-85%，方块电阻为0.2-5Ω。
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108766627A (zh) * | 2018-05-15 | 2018-11-06 | 华南理工大学 | 一种银纳米网格柔性透明电极及其制备方法 |
| CN109524170A (zh) * | 2018-10-30 | 2019-03-26 | 天津市职业大学 | 一种石墨烯和氟共掺杂氧化锡透明导电薄膜的制备方法 |
| CN109872834A (zh) * | 2019-04-18 | 2019-06-11 | 东北大学 | 一种透明导电银网格薄膜及其制备方法 |
| CN110655331A (zh) * | 2019-11-05 | 2020-01-07 | 河北小草新材料科技有限公司 | 一种玻璃镀膜液及功能膜制备方法 |
| CN110944418A (zh) * | 2019-11-28 | 2020-03-31 | 宁波材料所杭州湾研究院 | 一种高温透明柔性的电加热膜及其制备方法 |
| CN113808781A (zh) * | 2021-08-23 | 2021-12-17 | 湖南兴威新材料有限公司 | 一种薄膜电极及其制备方法和应用 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100166948A1 (en) * | 2007-06-15 | 2010-07-01 | Inktec Co., Ltd. | Transparent Conductive Layer and Preparation Method Thereof |
| CN103151394A (zh) * | 2012-12-14 | 2013-06-12 | 广东志成冠军集团有限公司 | 薄膜太阳能电池及其制作方法 |
| CN103227240A (zh) * | 2013-04-10 | 2013-07-31 | 华南师范大学 | 一种基于龟裂模板法制备多孔金属薄膜透明导电电极的方法 |
| US20130333752A1 (en) * | 2009-12-21 | 2013-12-19 | Ppg Industries Ohio, Inc. | Photovoltaic Solar Cell With High-Haze Substrate |
| CN105355675A (zh) * | 2015-11-13 | 2016-02-24 | 华南师范大学 | 一种高雾度复合透明导电电极的制备方法 |
-
2016
- 2016-10-09 CN CN201610879736.XA patent/CN106477914B/zh not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100166948A1 (en) * | 2007-06-15 | 2010-07-01 | Inktec Co., Ltd. | Transparent Conductive Layer and Preparation Method Thereof |
| US20130333752A1 (en) * | 2009-12-21 | 2013-12-19 | Ppg Industries Ohio, Inc. | Photovoltaic Solar Cell With High-Haze Substrate |
| CN103151394A (zh) * | 2012-12-14 | 2013-06-12 | 广东志成冠军集团有限公司 | 薄膜太阳能电池及其制作方法 |
| CN103227240A (zh) * | 2013-04-10 | 2013-07-31 | 华南师范大学 | 一种基于龟裂模板法制备多孔金属薄膜透明导电电极的方法 |
| CN105355675A (zh) * | 2015-11-13 | 2016-02-24 | 华南师范大学 | 一种高雾度复合透明导电电极的制备方法 |
Non-Patent Citations (2)
| Title |
|---|
| HAN BING等: "Uniform Self-Forming Metallic Network as a High-Performance Transparent Conductive Electrode", 《ADVANCED MATERIALS》 * |
| S. KIRUTHIKA等: "Fabrication of Oxidation-Resistant Metal Wire Network-Based Transparent Electrodes by a Spray-Roll Coating Process", 《ACS APPLIED MATERIALS&INTERFACES》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108766627A (zh) * | 2018-05-15 | 2018-11-06 | 华南理工大学 | 一种银纳米网格柔性透明电极及其制备方法 |
| CN109524170A (zh) * | 2018-10-30 | 2019-03-26 | 天津市职业大学 | 一种石墨烯和氟共掺杂氧化锡透明导电薄膜的制备方法 |
| CN109872834A (zh) * | 2019-04-18 | 2019-06-11 | 东北大学 | 一种透明导电银网格薄膜及其制备方法 |
| CN109872834B (zh) * | 2019-04-18 | 2020-08-28 | 东北大学 | 一种透明导电银网格薄膜及其制备方法 |
| CN110655331A (zh) * | 2019-11-05 | 2020-01-07 | 河北小草新材料科技有限公司 | 一种玻璃镀膜液及功能膜制备方法 |
| CN110944418A (zh) * | 2019-11-28 | 2020-03-31 | 宁波材料所杭州湾研究院 | 一种高温透明柔性的电加热膜及其制备方法 |
| CN110944418B (zh) * | 2019-11-28 | 2021-12-21 | 宁波材料所杭州湾研究院 | 一种高温透明柔性的电加热膜及其制备方法 |
| CN113808781A (zh) * | 2021-08-23 | 2021-12-17 | 湖南兴威新材料有限公司 | 一种薄膜电极及其制备方法和应用 |
| CN113808781B (zh) * | 2021-08-23 | 2023-11-21 | 湖南兴威新材料有限公司 | 一种薄膜电极及其制备方法和应用 |
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