Structure and Reactivity of II–VI and III–V Magic-Sized Clusters: Understanding and Expanding the Scope of Accessible Form and Function,Accounts of Materials Research

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Structure and Reactivity of II–VI and III–V Magic-Sized Clusters: Understanding and Expanding the Scope of Accessible Form and Function
Accounts of Materials Research ( IF 14.0 ) Pub Date : 2024-05-03 , DOI: 10.1021/accountsmr.4c00064
Hunter H. Ripberger ₁ , Soren F. Sandeno ₁ , Forrest W. Eagle ₁ , Hao A. Nguyen ₁ , Brandi M. Cossairt ₁

Affiliation

In nanoscale chemistry, magic-sized clusters (MSCs) stand out for their precise atomic configurations and privileged stability, offering unprecedented insights into the atomic-level structure of ligand-capped nanocrystals and a gateway to new synthesis and functionality. This article explores our efforts to shed light on the structure and reactivity of II–VI and III–V semiconductor MSCs. We have specifically been interested in the synthesis, isolation, and characterization of MSCs implicated as key intermediates in the synthesis of semiconductor quantum dots. Our exploration into their synthesis, structure, transformation, and reactivity provides a roadmap to expand the scope of accessible semiconductor clusters with diverse structures and properties. It paves the way for tailor-made nanomaterials with unprecedented atom-level control. In these studies, atomic level structure has been deduced through advanced characterization methods, including single-crystal and powder X-ray diffraction, complemented by pair distribution function analysis, nuclear magnetic resonance spectroscopy, and vibrational spectroscopy. We have identified two distinct families of CdSe MSCs with zincblende and wurtzite-like structures. We have also characterized two members of the wurtzite-like family of InP clusters and a related InAs cluster. Our research has revealed intriguing structural homologies between II–VI and III–V MSCs. These findings contribute to our fundamental understanding of semiconductor MSCs and hint at broader implications for phase control at the nanoscale and the synthesis of novel nanomaterials. We have also explored three distinct pathways of cluster reactivity, including cluster interconversion mediated by controlling the chemical potential of the reaction environment, both seeded and single source precursor growth mechanisms to convert MSCs into larger nanostructures, and cation exchange to access new cluster compositions that are precursors to nanocrystals that may be challenging or impossible to access from traditional bottom-up nucleation and growth. Together with the collective efforts of other researchers in the field of semiconductor cluster chemistry, our work establishes a strong foundation for predicting and controlling the form and function of semiconductor MSCs. By highlighting the role of surface chemistry, stoichiometry, and dopant incorporation in determining cluster properties, our work opens exciting possibilities for the design and synthesis of new materials. The insights gained through these efforts could significantly impact the future of nanotechnology, particularly in areas like photonics, electronics, and catalysis.

中文翻译：

II-VI 和 III-V 魔法大小团簇的结构和反应性：理解和扩展可访问形式和功能的范围

在纳米级化学中，神奇大小的簇（MSC）因其精确的原子构型和优越的稳定性而脱颖而出，为配体封端的纳米晶体的原子级结构提供了前所未有的见解，并为新的合成和功能提供了途径。本文探讨了我们为阐明 II-VI 和 III-V 半导体 MSC 的结构和反应性所做的努力。我们特别感兴趣的是作为半导体量子点合成中关键中间体的 MSC 的合成、分离和表征。我们对它们的合成、结构、转化和反应性的探索为扩大具有不同结构和性质的可访问半导体簇的范围提供了路线图。它为具有前所未有的原子级控制的定制纳米材料铺平了道路。在这些研究中，通过先进的表征方法（包括单晶和粉末 X 射线衍射）推导出原子级结构，并辅以对分布函数分析、核磁共振光谱和振动光谱。我们已经鉴定出两个不同的 CdSe MSC 家族，它们具有闪锌矿和类纤锌矿结构。我们还对类纤锌矿族 InP 团簇的两个成员以及相关的 InAs 团簇进行了表征。我们的研究揭示了 II-VI 型和 III-V 型 MSC 之间有趣的结构同源性。这些发现有助于我们对半导体间充质干细胞的基本理解，并暗示对纳米尺度的相控制和新型纳米材料的合成具有更广泛的影响。我们还探索了簇反应性的三种不同途径，包括通过控制反应环境的化学势介导的簇相互转化、将 MSC 转化为更大的纳米结构的种子和单源前体生长机制，以及阳离子交换以获得新的簇组合物，这些组合物是纳米晶体的前体可能具有挑战性或不可能通过传统的自下而上的成核和生长来获得。与半导体簇化学领域其他研究人员的共同努力，我们的工作为预测和控制半导体间充质干细胞的形态和功能奠定了坚实的基础。通过强调表面化学、化学计量和掺杂剂掺入在确定簇特性中的作用，我们的工作为新材料的设计和合成开辟了令人兴奋的可能性。通过这些努力获得的见解可能会对纳米技术的未来产生重大影响，特别是在光子学、电子学和催化等领域。

更新日期：2024-05-03

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