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通过迭代嵌段共聚物自组装制备大面积氧化铝-金覆盆子状纳米团簇

Large area AlO-Au raspberry-like nanoclusters from iterative block-copolymer self-assembly.

作者信息

Alvarez-Fernandez Alberto, Nallet Frédéric, Fontaine Philippe, Cummins Cian, Hadziioannou Georges, Barois Philippe, Fleury Guillaume, Ponsinet Virginie

机构信息

CNRS, Univ. Bordeaux, Centre de Recherche Paul Pascal, UMR 5031 115 Avenue Schweitzer 33600 Pessac France.

CNRS, Univ. Bordeaux, Bordeaux INP, LCPO, UMR 5629 F-33600 Pessac France

出版信息

RSC Adv. 2020 Nov 11;10(67):41088-41097. doi: 10.1039/d0ra08730k. eCollection 2020 Nov 9.

Abstract

In the field of functional nanomaterials, core-satellite nanoclusters have recently elicited great interest due to their unique optoelectronic properties. However, core-satellite synthetic routes to date are hampered by delicate and multistep reaction conditions and no practical method has been reported for the ordering of these structures onto a surface monolayer. Herein we show a reproducible and simplified thin film process to fabricate bimetallic raspberry nanoclusters using block copolymer (BCP) lithography. The fabricated inorganic raspberry nanoclusters consisted of a ∼36 nm alumina core decorated with ∼15 nm Au satellites after infusing multilayer BCP nanopatterns. A series of cylindrical BCPs with different molecular weights allowed us to dial in specific nanodot periodicities (from 30 to 80 nm). Highly ordered BCP nanopatterns were then selectively infiltrated with alumina and Au species to develop multi-level bimetallic raspberry features. Microscopy and X-ray reflectivity analysis were used at each fabrication step to gain further mechanistic insights and understand the infiltration process. Furthermore, grazing-incidence small-angle X-ray scattering studies of infiltrated films confirmed the excellent order and vertical orientation over wafer scale areas of AlO/Au raspberry nanoclusters. We believe our work demonstrates a robust strategy towards designing hybrid nanoclusters since BCP blocks can be infiltrated with various low cost salt-based precursors. The highly controlled nanocluster strategy disclosed here could have wide ranging uses, in particular for metasurface and optical based sensor applications.

摘要

在功能纳米材料领域,核 - 卫星纳米团簇因其独特的光电特性最近引起了极大的关注。然而,迄今为止,核 - 卫星合成路线受到精细且多步骤反应条件的限制,并且尚未报道将这些结构有序排列到表面单层上的实用方法。在此,我们展示了一种可重现且简化的薄膜工艺,利用嵌段共聚物(BCP)光刻技术制备双金属覆盆子纳米团簇。在注入多层BCP纳米图案后,制备的无机覆盆子纳米团簇由一个约36纳米的氧化铝核和装饰在其表面的约15纳米金卫星组成。一系列具有不同分子量的圆柱形BCP使我们能够设定特定的纳米点周期(从30到80纳米)。然后,用氧化铝和金物种选择性地渗透高度有序的BCP纳米图案,以形成多级双金属覆盆子特征。在每个制造步骤中都使用显微镜和X射线反射率分析,以获得进一步的机理见解并了解渗透过程。此外,对渗透膜的掠入射小角X射线散射研究证实了在AlO/Au覆盆子纳米团簇的晶圆级区域上具有出色的有序性和垂直取向。我们相信我们的工作展示了一种设计混合纳米团簇的强大策略,因为BCP嵌段可以用各种低成本的盐基前驱体进行渗透。这里公开的高度可控的纳米团簇策略可能有广泛的用途,特别是在超表面和基于光学的传感器应用中。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/6843/9057902/d0b918014ba8/d0ra08730k-f1.jpg

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