CN106513284A - 一种利用铜纳米颗粒增强薄膜光子吸收的方法 - Google Patents
一种利用铜纳米颗粒增强薄膜光子吸收的方法 Download PDFInfo
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Abstract
本发明涉及一种利用铜纳米颗粒增强薄膜光子吸收的方法，属于光电材料领域。本发明是将高分子、无机物或表面活性剂等不同类型材料包覆的铜纳米颗粒和功能薄膜相结合，利用铜纳米颗粒的表面等离子激元共振性质提高薄膜的光子吸收强度。同时，利用此种方法，可以克服金或银等贵金属成本昂贵的缺点。
Description
技术领域
本发明涉及一种增强薄膜光子吸收的方法，具体涉及金属纳米颗粒共振增强薄膜光子吸收的方法。
背景技术
由于金属纳米颗粒尺度在纳米范围，因此具有突出的光学、电学和催化性能。近年来，其在薄膜太阳电池、光催化材料、发光材料、微电子、医药学以及生物学等领域的应用引起了广泛关注。上述这些潜在领域的应用都是基于金属纳米颗粒集体自由电子共振的金属局域表面等离子激元机制，因为利用这种特殊的性能可以在纳米尺度上对光进行操纵，并且决定了金属纳米颗粒的近场和远场特征。在光场的作用下，金属纳米颗粒中的自由电子由于受到核的库伦吸引力会引起电子的集体振荡，即形成金属局域表面等离子激元共振，进而引起强烈的光学吸收和散射。
贵金属银、金纳米颗粒是研究的最多的具有表面等离子激元共振的金属纳米颗粒。利用金或银纳米颗粒的表面等离子激元共振可以增强太阳能吸收的特点，在单晶硅PN或非晶硅P-I-N表面沉积金或银的纳米颗粒提高太阳能电池的短路电流和光电转换效率；利用金或银纳米颗粒的表面等离子激元共振增强光催化的性能，在TiO2，ZrO2，ZnO，SnO2，CeO2，Fe2O3，KNbO3等常见的具有催化性能的半导体纳米材料中引入金或银纳米颗粒提高紫外和可见光波段的光催化性能；利用金或银纳米颗粒的表面等离子激元共振增强提高激发光的吸收效率或荧光发射的强度，在稀土掺杂ZnO：Re、YVO4：Re、NaYF4：Re等常见的发光纳米材料中引入金或银纳米颗粒提高上转换和下转换的发光强度。另外，在这些应用中，光电转换效率、光催化以及发光性能的提高程度都和金、银等金属纳米颗粒的成分、尺寸、形状以及颗粒所处的介电环境等有密切关系。
考虑到金、银等贵金属纳米颗粒制作的成本因素，限制了金、银等贵金属纳米在表面等离子激元共振应用中的发展。因此，急需寻找金、银等贵金属纳米颗粒的替代品。由于铜纳米材料具有良好的延展性、优异的导热导电性，优异的表面等离子激元特性，而且抗电迁移能力强等性能。因此，为了降低金、银等贵金属纳米颗粒的成本以及相应器件的成本，提出采用资源更丰富、成本更廉价且高导电性的铜纳米颗粒代替金、银等贵金属纳米颗粒。
发明内容
鉴于前面所述背景技术，本发明的目的在于提供一种利用铜纳米颗粒的表面等离子激元共振增强薄膜光子吸收的方法，其克服了金或银等贵金属成本昂贵的缺点。该方法适用于不同类型材料包覆的铜纳米颗粒：高分子包覆的铜纳米颗粒包括不同分子量的聚吡咯烷酮、聚乙烯醇、聚乙二醇、聚丙烯酸钠、聚丙烯酸等；无机物包覆的铜纳米颗粒包括二氧化硅、碳、二氧化锡、氧化铜、银等；表面活性剂包覆的铜纳米颗粒包括十二烷基硫酸钠、十六烷基三甲基溴化铵、油酸、油胺、辛基酚聚氧乙烯醚等。
本发明所采用的方法是将具有表面等离子激元共振性质的铜纳米颗粒和功能性薄膜相结合，提高薄膜的光子吸收强度。本发明解决其技术问题所采用的技术方案是：一种利用铜纳米颗粒的表面等离子激元共振增强薄膜光子吸收的方法。具体包括：
(1)、选择不同尺寸的球形铜纳米颗粒，铜纳米颗粒的直径为10nm-1um，优选10nm-700nm；铜纳米颗粒可以为不同类型材料包覆的铜纳米颗粒。
(2)、将步骤(1)中选择好尺寸的球形铜纳米颗粒用不同的方法涂覆在具有不同功能特性的薄膜表面或分散在薄膜内部。涂覆的方法包括旋涂法、刮刀法或浸渍法。不同功能的薄膜包括染料敏化太阳能电池或钙钛矿太阳能电池中的吸收层、半导体光催化薄膜、稀土纳米颗粒、稀土配合物纳米颗粒或染料杂化发光薄膜。
本发明提供的方法中，利用铜纳米颗粒的表面等离子激元共振增强提高薄膜的光子吸收，通过调节铜纳米颗粒的尺寸控制近场和远场，即控制吸收和散射占比，通过这种方式提高薄膜的光子吸收。
本发明提供的方法中，利用铜纳米颗粒的吸收增强提高薄膜的光子吸收，铜纳米颗粒的直径优选10nm-160nm。光子主要局限在铜纳米颗粒的表面，即铜纳米颗粒和介质环境的界面。
本发明提供的方法中，利用铜纳米颗粒的散射增强提高薄膜的光子吸收，铜纳米颗粒的直径优选160nm-700nm。铜纳米颗粒尺寸越大，远场成分占比越大，光子受到铜纳米颗粒的散射越强，增长了光子在薄膜中的运动长度，即提高了薄膜的光子吸收。
本发明的利用铜纳米颗粒的表面等离子激元共振增强薄膜光子吸收的方法，只需将金或银等贵金属纳米颗粒用铜纳米颗粒替代，无需其他的步骤，与现有的太阳能工艺、光催化薄膜工艺以及发光薄膜工艺等有着良好的兼容性，克服了背景技术所存在的不足，具有如下效果：成本低、易实现。
附图说明
图1为聚吡咯烷酮包覆的不同尺寸的铜纳米颗粒的扫描电镜照片。
图2利用铜纳米颗粒的表面等离子激元共振增强提高薄膜的光子吸收的原型器件结构。(a)、吸收增强型；(b)散射增强型。
图3是利用不同直径的铜纳米颗粒的吸收增强提高薄膜的光子吸收方案中铜纳米颗粒的散射、吸收、消光光谱。(a)、10nm；(b)、20nm；(c)、40nm；(d)、80nm。
图4是利用不同直径的铜纳米颗粒的散射增强提高薄膜的光子吸收方案中铜纳米颗粒的散射、吸收、消光光谱。(a)、120nm；(b)、160nm；(c)、320nm；(d)、640nm。
具体实施方式
下面结合附图和实施例对本发明作进一步说明。
图1为合成的聚吡咯烷酮包覆的不同尺寸的铜纳米颗粒的扫描电镜照片。对于不同的尺寸有不同的处理方法。
实施例1：利用铜纳米颗粒的吸收增强提高薄膜的光子吸收的方法，包括：
步骤1，选择涂覆功能性薄膜的基板；本实施例中，该基板可以为ITO玻璃、FTO玻璃、载波片。
步骤2，将铜纳米颗粒和组成薄膜的材料均匀混合；本实施例中，铜纳米颗粒的尺寸位于10nm-80nm。
步骤3，将步骤2得到的材料涂覆在基板表面。
其原型器件的结构如图2(a)所示。本实施例之中，该步骤2中混合的方法例如由高分子有机溶液和铜纳米颗粒超声混合方法，或者硅烷偶联剂和铜纳米颗粒水解混合方法，但并不以此为限，根据需要可采用其他方法。
步骤3中的涂覆的方法例如由旋涂法，浸渍法或者刮刀法，但并不以此为限，根据需要可采用其他方法。
实施例1中的利用铜纳米颗粒的吸收增强提高薄膜的光子吸收的方法中，直径分别为10nm、20nm、40nm、80nm的铜纳米颗粒的吸收、散射、消光光谱图如图3所示。从图3中的光谱图结果可以看出铜纳米颗粒的散射相比吸收来讲要弱很多，主要是铜纳米颗粒的共振吸收。所以为了利用铜纳米颗粒的吸收增强提高薄膜中光子的吸收，采用实例1中的原型器件结构。
实施例2：利用铜纳米颗粒的散射增强提高薄膜的光子吸收的方法，包括：
步骤1，选择涂覆功能性薄膜的基板；本实施例中，该基板可以为ITO玻璃、FTO玻璃、载波片。
步骤2，将铜纳米颗粒涂覆在功能薄膜的表面或者功能性薄膜和基板的界面之中。
其原型器件的结构如图2(b)所示。本实施例之中，该步骤2中涂覆的方法例如由旋涂法，浸渍法或者刮刀法，但并不以此为限，根据需要可采用其他方法。涂覆溶液的配置例如由铜纳米颗粒的乙醇等有机溶剂分散液产生。
步骤2中铜纳米颗粒层的位置处于涂覆在功能性薄膜和基板的界面，然后在铜纳米颗粒薄膜表面通过不同的方法形成薄膜；铜纳米颗粒层的位置处于薄膜的表面，则在基板表面先通过不同的方法形成薄膜，然后在薄膜的表面涂覆铜纳米颗粒。
实施例2中，对光源的照射方向有一定的要求，见图2(b)所示。
实施例2中的利用铜纳米颗粒的散射增强提高薄膜的光子吸收的方法中，直径分别为120nm、160nm、320nm、640nm的铜纳米颗粒的吸收、散射、消光光谱图如图4所示。从图4中的光谱图结果可以看出铜纳米颗粒的直径增加到120nm，散射的贡献和吸收的贡献可以相比拟，铜纳米颗粒直径在160nm以后，散射相比吸收来讲要强很多，主要是铜纳米颗粒的共振散射。所以为了利用铜纳米颗粒的散射增强来提高薄膜中光子的吸收，采用实例2中的原型器件结构。
以上所述，仅为本发明的实施例而已，依据本发明专利范围及说明书内容所做的等效变化与修饰，皆属本发明涵盖的范围内。
Claims (5)
1.一种利用铜纳米颗粒增强薄膜光子吸收的方法，其特征在于包括如下步骤：
步骤1，制备铜纳米颗粒的涂覆液；
步骤2，将步骤1制得的涂覆液涂在基板或薄膜表面，或薄膜和基板之间的界面。
2.根据权利要求1所述的一种利用铜纳米颗粒增强薄膜光子吸收的方法，其特征在于：所述步骤1中的涂覆液由铜纳米颗粒和组成薄膜的材料均匀混合，或者由铜纳米颗粒的乙醇分散液配置。
3.根据权利要求1所述的一种利用铜纳米颗粒增强薄膜光子吸收的方法，其特征在于：所述步骤1中的铜纳米颗粒为聚吡咯烷酮、聚乙烯醇、聚乙二醇、聚丙烯酸钠、聚丙烯酸，二氧化硅、碳、二氧化锡、氧化铜、银、十二烷基硫酸钠、十六烷基三甲基溴化铵、油酸、油胺、辛基酚聚氧乙烯醚等材料包覆的铜纳米颗粒的一种。
4.根据权利要求1所述的一种利用铜纳米颗粒增强薄膜光子吸收的方法，其特征在于：所述步骤2中铜纳米颗粒尺寸在10nm-160nm之间的，涂覆在基板表面；铜纳米颗粒尺寸在160nm-1um之间的，涂覆在薄膜表面或薄膜和基板之间的界面。
5.根据权利要求2所述的一种利用铜纳米颗粒增强薄膜光子吸收的方法，其特征在于：铜纳米颗粒和组成薄膜的材料均匀混合的涂覆液适用于直径在10nm-160nm之间的铜纳米颗粒，铜纳米颗粒的乙醇分散液适用于直径在160nm-1um之间的铜纳米颗粒。
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