化学研究报告2013-09-05 2:58 AM

Screw Dislocation Driven Growth of Nanomaterials - Accounts of Chemical Research (ACS Publications)

Nanoscience and nanotechnology impact our lives in many ways, from electronic and photonic devices to biosensors. They also hold the promise of tackling the renewable energy challenges facing us. However, one limiting scientific challenge is the effective and efficient bottom-up synthesis of nanomaterials. We can approach this core challenge in nanoscience and nanotechnology from two perspectives: (a) how to controllably grow high-quality nanomaterials with desired dimensions, morphologies, and material compositions and (b) how to produce them in a large quantity at reasonable cost. Because many chemical and physical properties of nanomaterials are size- and shape-dependent, rational syntheses of nanomaterials to achieve desirable dimensionalities and morphologies are essential to exploit their utilities. In this Account, we show that the dislocation-driven growth mechanism, where screw dislocation defects provide self-perpetuating growth steps to enable the anisotropic growth of various nanomaterials at low supersaturation, can be a powerful and versatile synthetic method for a wide variety of nanomaterials. Despite significant progress in the last two decades, nanomaterial synthesis has often remained an “art”, and except for a few well-studied model systems, the growth mechanisms of many anisotropic nanostructures remain poorly understood. We strive to go beyond the empirical science (“cook-and-look”) and adopt a fundamental and mechanistic perspective to the anisotropic growth of nanomaterials by first understanding the kinetics of the crystal growth process. Since most functional nanomaterials are in single-crystal form, insights from the classical crystal growth theories are crucial. We pay attention to how screw dislocations impact the growth kinetics along different crystallographic directions and how the strain energy of defected crystals influences their equilibrium shapes. Furthermore, such inquiries are supported by detailed structural investigation to identify the evidence of dislocations. The dislocation-driven growth mechanism not only can unify the various explanations behind a wide variety of exotic nanoscale morphologies but also allows the rational design of catalyst-free solution-phase syntheses that could enable the scalable and low cost production of nanomaterials necessary for large scale applications, such as solar and thermoelectric energy conversions, energy storage, and nanocomposites. In this Account, we discuss the fundamental theories of the screw dislocation driven growth of various nanostructures including one-dimensional nanowires and nanotubes, two-dimensional nanoplates, and three-dimensional hierarchical tree-like nanostructures. We then introduce the transmission electron microscopy (TEM) techniques to structurally characterize the dislocation-driven nanomaterials for future searching and identifying purposes. We summarize the guidelines for rationally designing the dislocation-driven growth and discuss specific examples to illustrate how to implement the guidelines. By highlighting our recent discoveries in the last five years, we show that dislocation growth is a general and versatile mechanism that can be used to grow a variety of nanomaterials via distinct reaction chemistry and synthetic methods. These discoveries are complemented by selected examples of anisotropic crystal growth from other researchers. The fundamental investigation and development of dislocation-driven growth of nanomaterials will create a new dimension to the rational design and synthesis of increasingly complex nanomaterials.

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