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Squeezed nanocrystals: equilibrium configuration of metal clusters embedded beneath the surface of a layered material

机译:挤压纳米晶体:均衡配置金属集群嵌入在表面之下的一个分层的材料

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摘要

Shapes of functional metallic nanocrystals, typically synthesized either free in solution or supported on surfaces, are key for controlling properties. Here, we consider a novel new class of metallic nanocrystals, copper clusters embedded near the surface of graphite, which can be considered a model system for metals embedded beneath surfaces of layered materials, or beneath supported membranes. We develop a continuum elasticity (CE) model for the equilibrium shape of these islands, and compare its predictions with experimental data. The CE model incorporates appropriate surface energy, adhesion energies, and strain energy. The agreement between the CE model and the data iswith one exceptionexcellent, both qualitatively and quantitatively, and is achieved with a single adjustable parameter. The model predicts that the embedded island shape is invariant with size, manifest both by constant side slope and by constant aspect ratio. This prediction is rationalized by dimensional analysis of the relevant energetic contributions. The aspect ratio (width:height) of an embedded Cu cluster is much larger than that of a supported but non-embedded Cu cluster, due to resistance of the graphene membrane to deformation. Experimental data diverge from the model predictions only in the case of the aspect ratio of small islands, below a critical height of approximate to 10 nm. The divergence may be due to bending strain, which is treated only approximately in the model. Strong support for the CE model and its interpretation is provided by additional data for embedded Fe clusters. Most of these observations and insights should be generally applicable to systems where a metal cluster is embedded beneath a layered material or supported membrane, provided that shape equilibration is possible.
机译:功能金属纳米晶体的形状,通常免费解决方案或合成支持表面,控制是关键属性。金属纳米晶体铜集群嵌入石墨的表面附近,可以被认为是金属嵌入模型系统下分层材料的表面,或下面支持膜。弹性(CE)模型的平衡形状这些岛屿,并比较其预测与实验数据。适当的表面能,附着力的能量,和应变能。模型和数据iswith exceptionexcellent之一,定性和定量,通过一个可调参数。模型预测,嵌入式岛形状与大小不变,清单通过常数边坡和恒定的长宽比。预测是由空间的合理化分析相关的积极贡献。高宽比(宽度:高度)的嵌入式铜集群是比这更大的支持但non-embedded铜集群,由于阻力石墨烯膜变形。实验数据偏离模型只在纵横比的情况下预测小岛,低于临界高度近似到10纳米。弯曲应变,这是治疗大约在模型中。CE模型及其解释通过额外的数据为嵌入式Fe集群。这样的观察和见解一般适用于系统的金属集群是嵌入在一个分层材料或支持膜,形状平衡是可能的。

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