Two-dimensional functional molecular nanoarchitectures – Complementary investigations with scanning tunneling microscopy and X-ray spectroscopy

IF 8.7 2区 工程技术 Q1 CHEMISTRY, PHYSICAL
Florian Klappenberger
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引用次数: 86

Abstract

Functional molecular nanoarchitectures (FMNs) are highly relevant for the development of future nanotechnology devices. Profound knowledge about the atomically controlled construction of such nanoscale assemblies is an indispensable requirement to render the implementation of such components into a real product successful. For exploiting their full potential the architectures’ functionalities have to be characterized in detail including the ways to tailor them. In recent years a plethora of sophisticated constructs were fabricated touching a wide range of research topics.

The present review summarizes important achievements of bottom-up fabricated, molecular nanostructures created on single crystal metal surfaces under ultra-high vacuum conditions. This selection focuses on examples where self-assembly mechanisms played a central role for their construction. Such systems, though typically quite complex, can be comprehensively understood by the STM+XS approach combining scanning tunneling microscopy (STM) with X-ray spectroscopy (XS) and being aided in the atomic interpretation by the appropriate theoretic analysis, often from density functional theory. The symbiosis of the techniques is especially fruitful because of the complementary character of the information accessed by the local microscopy and the space-averaging spectroscopy tools. STM delivers sub-molecular spatial-resolution, but suffers from limited sensitivity for the chemical and conformational states of the building-blocks. XS compensates these weaknesses with element- and moiety-specific data, which in turn would be hard to interpret with respect to structure formation without the topographic details revealed by STM. The united merit of this methodology allows detailed geometric information to be obtained and addresses both the electronic and chemical state of the complex organic species constituting such architectures. Thus, possible changes induced by the various processes such as surface interaction, thermal annealing, or molecular recognition can be followed with unprecedented level of detail.

The well-understood nanoarchitecture construction protocols often rely on the ‘classic’ supramolecular interactions, namely hydrogen bonding and metal-organic coordination. Further examples include rarely encountered special cases where substrate-mediated processes or repulsive forces drive the emergence of order. The demonstrated functionalities include tuning of the electronic structure by confining surface state electrons and atomically defined arrays of magnetic complexes. Moreover, the high-quality templates can be utilized for imposing novel thin film growth modes or act as basic constituents of nanoswitches. Finally, the aptitude of the STM+XS approach for the emerging field of creating nanoarchitectures by on-surface covalent coupling is addressed.

二维功能分子纳米结构。扫描隧道显微镜和x射线光谱学的补充研究
功能分子纳米结构(FMNs)与未来纳米技术器件的发展密切相关。要想成功地将这些组件实现为真正的产品,对这种纳米级组件的原子控制结构有深刻的了解是必不可少的。为了充分发挥其潜力,必须详细描述体系结构的功能,包括定制它们的方法。近年来,许多复杂的结构被制造出来,涉及广泛的研究课题。本文综述了在超高真空条件下在单晶金属表面自下而上制备分子纳米结构的重要进展。这一选择侧重于自组装机制在其建设中发挥核心作用的例子。这类系统虽然通常相当复杂,但可以通过STM+XS方法将扫描隧道显微镜(STM)与x射线光谱学(XS)相结合,并通过适当的理论分析(通常来自密度泛函理论)辅助原子解释,全面理解。由于局部显微镜和空间平均光谱工具获取的信息具有互补性,这两种技术的共生尤其富有成效。STM提供了亚分子的空间分辨率,但对构建块的化学和构象状态的灵敏度有限。XS用特定于元素和片段的数据弥补了这些缺陷,如果没有STM揭示的地形细节,这些数据反过来又很难解释结构形成。这种方法的统一优点是可以获得详细的几何信息,并解决了构成这种结构的复杂有机物种的电子和化学状态。因此,由表面相互作用、热退火或分子识别等各种过程引起的可能变化可以以前所未有的详细程度进行跟踪。众所周知的纳米结构构建方案通常依赖于“经典”的超分子相互作用,即氢键和金属-有机配位。进一步的例子包括很少遇到的特殊情况,即基质介导的过程或排斥力驱动秩序的出现。演示的功能包括通过限制表面态电子和磁性配合物的原子定义阵列来调整电子结构。此外,高质量的模板可用于施加新的薄膜生长模式或作为纳米开关的基本成分。最后,STM+XS方法在通过表面共价耦合创建纳米结构的新兴领域的能力得到了解决。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Progress in Surface Science
Progress in Surface Science 工程技术-物理:凝聚态物理
CiteScore
11.30
自引率
0.00%
发文量
10
审稿时长
3 months
期刊介绍: Progress in Surface Science publishes progress reports and review articles by invited authors of international stature. The papers are aimed at surface scientists and cover various aspects of surface science. Papers in the new section Progress Highlights, are more concise and general at the same time, and are aimed at all scientists. Because of the transdisciplinary nature of surface science, topics are chosen for their timeliness from across the wide spectrum of scientific and engineering subjects. The journal strives to promote the exchange of ideas between surface scientists in the various areas. Authors are encouraged to write articles that are of relevance and interest to both established surface scientists and newcomers in the field.
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