CN116180009A - 一种基于双光子3d打印的红外宽带吸波超材料及制备方法 - Google Patents
一种基于双光子3d打印的红外宽带吸波超材料及制备方法 Download PDFInfo
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Abstract
一种基于双光子3D打印的红外宽带吸波超材料及其制备方法，制备方法步骤如下：S1、通过双光子聚合3D打印技术制备具有类金字塔型凹槽的聚合物模板；S2、通过磁控溅射技术在步骤S1获得的具有类金字塔型凹槽的聚合物模板上覆盖TCOs材料，使得TCOs材料填满聚合物模板的凹槽形成TCOs材料谐振器，并继续磁控溅射形成TCOs材料基板；S3、通过酸洗技术去除聚合物模板，即完成红外宽带吸波超材料的制备。本发明解决了现有技术所制造的宽带多层超材料吸波结构加工困难及结构复杂问题，使用3D打印技术制备模板，一次成型TCOs吸波超材料，结合材料的选择和形状的优化设计，无需多层镀膜即可实现红外波段的宽带吸波，加工成本，制备效率、结构稳定性均优于现有技术。
Description
技术领域
本发明涉及吸波复合材料领域，属于基于3D打印工艺的超材料宽带吸波阵列的设计及其制备方法。
背景技术
随着电子科学技术的快速发展，电磁吸波超材料的应用范围越来越广，在战斗机、导弹、舰艇、消费电子、通讯、建筑、医院、民用机场等领域具有重要应用价值。人们对吸波材料的吸波性能的要求日益提高，寻求设计具有高吸收率、轻薄、稳定性强的吸波超材料的制备方法成为研究的热点和重点。而传统型的吸波器由于多层结构的设计存在厚度重量大、稳定性较差、耗材等问题，且多层镀膜在实际加工过程中会遇到表面粗糙，多层结构镀膜工艺复杂，加工困难，局部结构有变化或者不完整等问题，受到制造挑战和设计复杂性的影响。，
微纳结构超材料具有吸波效果好，性能稳定等优势，为吸波材料设计领域提供了一种全新的思路。但目前微纳超材料器件主要依赖聚焦离子束刻饰、电子束刻饰、光刻技术、纳米压印等设备进行制备。诸如此类技术都隶属于减材制造范畴，首先需要在基底上通过多层镀膜获得基材，然后再通过精密刻饰得到超材料结构，从而导致微纳结构超材料制造周期长，成本高，超材料层与层之间的粘合及机械性能低等问题。
发明内容
本发明的目的是提供基于双光子聚合3D打印，并具备纳米尺度分辨率的红外宽带吸波超材料结构及其制备方法，旨在解决现有技术所制造的宽带多层超材料吸波结构加工困难及结构复杂问题，同时双光子聚合技术能够实现其它3D打印技术不能达到的纳米级别加工精度技术瓶颈。
本发明实现其发明目的所采取的技术方案是：一种基于双光子3D打印的红外宽带吸波超材料及其制备方法，制备方法的制备步骤如下：
S1、通过双光子聚合3D打印技术制备具有类金字塔型凹槽的聚合物模板；
S2、通过磁控溅射技术在步骤S1获得的具有类金字塔型凹槽的聚合物模板上覆盖TCOs材料，使得TCOs材料填满聚合物模板的凹槽形成TCOs材料谐振器，并继续磁控溅射形成TCOs材料基板；
S3、通过酸洗技术去除聚合物模板，即完成红外宽带吸波超材料的制备。
进一步，本发明所述类金字塔型包括正四棱锥、正四棱台、圆锥或圆台。
进一步，本发明所述聚合物模板材料包括PDMS或PMMA。
进一步，本发明所述TCOs材料包括掺铝的氧化锌、掺镓的氧化锌或氧化铟锑。
进一步，本发明所述TCOs材料谐振器的高度为1.6-2μm。
更进一步，本发明所述类金字塔型为底面边长为的1μm正四棱锥或底面直径为1μm的圆锥。或者所述类金字塔型为底面边长为的1μm、顶面边长为0-0.1μm的正四棱台或底面直径为1μm、顶面直径为0-0.1μm的圆台。
再进一步，本发明所述TCOs材料基板的厚度为0.2-0.5μm。
与现有技术相比，本发明的有益效果是：
一、透明导电氧化物TCOs同时兼具金属导电特性和透明特性，既可以代替现有技术中MIM结构的金属层，又可以代替现有技术MIM结构的介质层。本发明选择单一TCOs材料金字塔结构实现宽带吸波，不用多层镀膜，同时也不用考虑每层厚度的影响，避免了传统一层金属/一层透明材料叠加的多层宽带吸波体多层镀膜的加工困难，而且简化了多层吸波结构层间的参数设计，结构简单，降低了制造难度，稳定性更好。
二、TCOs材料微纳结构加工困难，为了构筑大规模TCOs材料微结构且精确控制微结构的精度，本发明首先借助双光子聚合3D打印技术获得大面积的金字塔凹槽聚合物模板，在此模板上通过磁控溅射技术覆盖TCOs材料于3D打印模板上，酸洗之后即可获得具有金字塔微结构的TCOs吸波超材料，制备工艺简单，生产成本低。
三、本发明制备的具有金字塔微结构的TCOs吸波超材料在近红外波段表现出明显的宽度吸波响应，三维有限差分时域(FDTD)全波模拟仿真验证该结构材料在近红外波段表现出明显的宽度吸波响应，并且吸波率在宽频带内高达90％以上，且在1.2-5μm波段范围内有完美100％吸波。
四、由于金字塔结构沿传播反向是4次旋转轴对称结构，因此吸波性能对偏振不敏感，本发明制备的具有金字塔微结构的TCOs吸波超材料的吸波性能对偏振和角度均不敏感，吸波性能稳定。
总之，现有技术要想在同样的红外波段加工实现宽带的红外吸波超材料必须使用多层镀膜技术和昂贵的高精度微纳加工技术。而本发明提出使用3D打印技术制备模板，一次成型TCOs吸波超材料，结合材料的选择和形状的优化设计，可以使结构的吸波能力最大化，无需多层镀膜即可实现红外波段的宽带吸波。本发明的加工成本，制备效率、结构稳定性均优于现有技术。
附图说明
图1为本发明实施例一基于双光子3D打印的红外宽带吸波超材料的三维结构图。
图2为本发明实施例一基于双光子3D打印的红外宽带吸波超材料单胞尺寸示意图。
图3为本发明实施例一基于双光子3D打印的红外宽带吸波超材料的红外1-5um波段的宽带吸波曲线。
图4为本发明实施例一基于双光子3D打印的红外宽带吸波超材料的制备方法技术路线图。
图5为本发明实施例一基于双光子3D打印的红外宽带吸波超材料的电子显微镜下的实物图。
具体实施方式
实施例一
一种基于双光子3D打印的红外宽带吸波超材料及其制备方法，制备方法的制备步骤如下：
S1、通过双光子聚合3D打印技术制备具有类金字塔型凹槽的聚合物模板；
S2、通过磁控溅射技术在步骤S1获得的具有类金字塔型凹槽的聚合物模板上覆盖TCOs材料，使得TCOs材料填满聚合物模板的凹槽形成TCOs材料谐振器，并继续磁控溅射形成TCOs材料基板；
S3、通过酸洗技术去除聚合物模板，即完成红外宽带吸波超材料的制备。
本例中所述类金字塔型为底面边长为的1μm正四棱锥，所述TCOs材料谐振器的高度为1.6μm，所述TCOs材料基板的厚度为0.2μm。图1为本实施例基于双光子3D打印的红外宽带吸波超材料的三维结构图。图2为本实施例基于双光子3D打印的红外宽带吸波超材料单胞尺寸示意图。
本例中所述聚合物模板材料为PDMS，所述TCOs材料为氧化铟锡。
采用三维有限差分时域(FDTD)全波模拟对本实施例红外宽带吸波超材料进行吸波模拟，平面波从-z方向入射。x和y方向均采用周期性边界条件，z方向采用完全匹配层边界条件，所有方向的网格尺寸都设置为5nm。图3为本实施例基于双光子3D打印的红外宽带吸波超材料的红外1-5um波段的宽带吸波曲线，图中可以看出，本实施例红外宽带吸波超材料在近红外波段1-5um表现出明显的宽度吸波响应，并且吸波率在宽频带内90％以上，曲线平滑没有抖动，实现了超宽带吸波性能。这是由于在水平方向，类金字塔的任意位置可以当做某一固定波长的红外ITO吸收层，任意两相邻的ITO层电流形成环流，环形电流形成磁偶极子。在整个TCOs吸波超材料中，每个波长的信号都有与之对应的电偶极子、磁偶极子共振，最后每层的共振效应叠加在一起形成宽带吸波。
图4为本实施例基于双光子3D打印的红外宽带吸波超材料的制备方法技术路线图，图中底部为3D打印金字塔凹槽聚合物模板，顶部为磁控溅射后的TCOs金字塔吸波超材料结构阵列。
图5为本实施例基于双光子3D打印的红外宽带吸波超材料的实物图。
实施例二
一种基于双光子3D打印的红外宽带吸波超材料及其制备方法，制备方法的制备步骤如下：
S1、通过双光子聚合3D打印技术制备具有类金字塔型凹槽的聚合物模板；
S2、通过磁控溅射技术在步骤S1获得的具有类金字塔型凹槽的聚合物模板上覆盖TCOs材料，使得TCOs材料填满聚合物模板的凹槽形成TCOs材料谐振器，并继续磁控溅射形成TCOs材料基板；
S3、通过酸洗技术去除聚合物模板，即完成红外宽带吸波超材料的制备。
本例中所述类金字塔型为底面边长为的1μm正四棱锥，所述TCOs材料谐振器的高度为2μm，所述TCOs材料基板的厚度为0.5μm。
本例中所述聚合物模板材料为PMMA，所述TCOs材料为掺镓的氧化锌。
实施例三
一种基于双光子3D打印的红外宽带吸波超材料及其制备方法，制备方法的制备步骤如下：
S1、通过双光子聚合3D打印技术制备具有类金字塔型凹槽的聚合物模板；
S2、通过磁控溅射技术在步骤S1获得的具有类金字塔型凹槽的聚合物模板上覆盖TCOs材料，使得TCOs材料填满聚合物模板的凹槽形成TCOs材料谐振器，并继续磁控溅射形成TCOs材料基板；
S3、通过酸洗技术去除聚合物模板，即完成红外宽带吸波超材料的制备。
本例中所述类金字塔型为底面直径为1μm的圆锥，所述TCOs材料谐振器的高度为2μm，所述TCOs材料基板的厚度为0.5μm。
本例中所述聚合物模板材料为PDMS，所述TCOs材料为掺铝的氧化锌。
实施例四
一种基于双光子3D打印的红外宽带吸波超材料及其制备方法，制备方法的制备步骤如下：
S1、通过双光子聚合3D打印技术制备具有类金字塔型凹槽的聚合物模板；
S2、通过磁控溅射技术在步骤S1获得的具有类金字塔型凹槽的聚合物模板上覆盖TCOs材料，使得TCOs材料填满聚合物模板的凹槽形成TCOs材料谐振器，并继续磁控溅射形成TCOs材料基板；
S3、通过酸洗技术去除聚合物模板，即完成红外宽带吸波超材料的制备。
本例中所述类金字塔型为底面边长为的1μm、顶面边长为0-0.1μm的正四棱台。
本例中所述聚合物模板材料为PMMA，所述TCOs材料为氧化铟锡。
实施例五
一种基于双光子3D打印的红外宽带吸波超材料及其制备方法，制备方法的制备步骤如下：
S1、通过双光子聚合3D打印技术制备具有类金字塔型凹槽的聚合物模板；
S2、通过磁控溅射技术在步骤S1获得的具有类金字塔型凹槽的聚合物模板上覆盖TCOs材料，使得TCOs材料填满聚合物模板的凹槽形成TCOs材料谐振器，并继续磁控溅射形成TCOs材料基板；
S3、通过酸洗技术去除聚合物模板，即完成红外宽带吸波超材料的制备。
本例中所述类金字塔型为底面直径为1μm、顶面直径为0-0.1μm的圆台。
本例中所述聚合物模板材料为PMMA，所述TCOs材料为氧化铟锡。
Claims (9)
1.一种基于双光子3D打印的红外宽带吸波超材料的制备方法，其制备步骤如下：
S1、通过双光子聚合3D打印技术制备具有类金字塔型凹槽的聚合物模板；
S2、通过磁控溅射技术在步骤S1获得的具有类金字塔型凹槽的聚合物模板上覆盖TCOs材料，使得TCOs材料填满聚合物模板的凹槽形成TCOs材料谐震器，并继续磁控溅射形成TCOs材料基板；
S3、通过酸洗技术去除聚合物板，即完成红外宽带吸波超材料的制备。
2.根据权利要求1所述的一种基于双光子3D打印的红外宽带吸波超材料的制备方法，其特征在于：所述类金字塔型包括正四棱锥、正四棱台、圆锥或圆台。
3.根据权利要求1所述的一种基于双光子3D打印的红外宽带吸波超材料的制备方法，其特征在于：所述聚合物模板材料包括PDMS或PMMA。
4.根据权利要求1所述的一种基于双光子3D打印的红外宽带吸波超材料的制备方法，其特征在于：所述TCOs材料包括掺铝的氧化锌、掺镓的氧化锌或氧化铟锑。
5.根据权利要求1所述的一种基于双光子3D打印的红外宽带吸波超材料的制备方法，其特征在于：所述TCOs材料谐振器的高度为1.6-2μm。
6.根据权利要求5所述的一种基于双光子3D打印的红外宽带吸波超材料的制备方法，其特征在于：所述类金字塔型为底面边长为的1μm正四棱锥或底面直径为1μm的圆锥。
7.根据权利要求5所述的一种基于双光子3D打印的红外宽带吸波超材料的制备方法，其特征在于：所述类金字塔型为底面边长为的1μm、顶面边长为0-0.1μm的正四棱台或底面直径为1μm、顶面直径为0-0.1μm的圆台。
8.根据权利要求5所述的一种基于双光子3D打印的红外宽带吸波超材料的制备方法，其特征在于：所述TCOs材料基板的厚度为0.2-0.5μm。
9.一种基于双光子3D打印的红外宽带吸波超材料，其特征在于：所述红外宽带吸波超材料通过权利要求1-8任一制备方法制备而成。
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