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Significant advances in colloidal synthesis made in the past two decades have enabled the preparation of high quality nanoparticles with well-controlled sizes, shapes, and compositions. It has recently been realized that such nanoparticles can be utilized as ‘artificial atoms’ for building new materials which not only combine the size- and shape-dependent properties of individual nanoparticles but also create new collective properties by taking advantage of their electromagnetic interactions. The controlled clustering of nanoparticle building blocks into defined geometric arrangements opens a new research area in materials science and as a result much interest has been paid to the creation of secondary structures of nanoparticles, either by direct solution growth or self-assembly methods. In this tutorial review, we introduce recently developed strategies for the creation and surface modification of colloidal nanoparticle clusters, demonstrate the new collective properties resulting from their secondary structures, and highlight several of their many important technological applications ranging from photonics, separation, and detection, to multimodal imaging, energy storage and transformation, and catalysis.
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