Solvent-mediated assembly of atom-precise gold–silver nanoclusters to semiconducting one-dimensional materials

• Published in: Nature communications Vol. 11; no. 1; pp. 2229 - 8
• Main Authors: Yuan, Peng, Zhang, Ruihua, Selenius, Elli, Ruan, Pengpeng, Yao, Yangrong, Zhou, Yang, Malola, Sami, Häkkinen, Hannu, Teo, Boon K., Cao, Yang, Zheng, Nanfeng
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 06.05.2020; Nature Publishing Group; Nature Portfolio
• Subjects: 119/118; 639/925/357/1016; 639/925/357/354; 639/925/357/995; Anisotropy; Atomic structure; Clusters; Crystal structure; Crystals; Density functional theory; Design; Field effect transistors; Gold; Hole mobility; Humanities and Social Sciences; multidisciplinary; Nanoclusters; Nanomaterials; Nanotechnology; P-type semiconductors; Polymerization; Polymers; Properties (attributes); Science; Science (multidisciplinary); Self-assembly; Semiconductor devices; Silver; Single crystals; Solvents; X-ray diffraction
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-020-16062-6

Bottom-up design of functional device components based on nanometer-sized building blocks relies on accurate control of their self-assembly behavior. Atom-precise metal nanoclusters are well-characterizable building blocks for designing tunable nanomaterials, but it has been challenging to achieve directed assembly to macroscopic functional cluster-based materials with highly anisotropic properties. Here, we discover a solvent-mediated assembly of 34-atom intermetallic gold–silver clusters protected by 20 1-ethynyladamantanes into 1D polymers with Ag–Au–Ag bonds between neighboring clusters as shown directly by the atomic structure from single-crystal X-ray diffraction analysis. Density functional theory calculations predict that the single crystals of cluster polymers have a band gap of about 1.3 eV. Field-effect transistors fabricated with single crystals of cluster polymers feature highly anisotropic p -type semiconductor properties with ≈1800-fold conductivity in the direction of the polymer as compared to cross directions, hole mobility of ≈0.02 cm 2 V −1 s −1 , and an ON/OFF ratio up to ≈4000. This performance holds promise for further design of functional cluster-based materials with highly anisotropic semiconducting properties. Bottom-up design of functional device components based on nanometer-sized building blocks relies on accurate control of their self-assembly behavior. Here, the authors demonstrate a solvent-mediated polymerization of atom-precise gold–silver nanoclusters into macroscopic single crystals with highly anisotropic p -type semiconducting characteristics.