Evolution of Cu-Bi-Zn-S colloidal nanorods via in situ generated metal-semiconductor heterostructures

Nilotpal Kapuria^a, Michele Conroy^b, Vasily A. Lebedev^d, Esther Adegoke^a, Yu Zhang^c, Ibrahim Saana Aminu^a, Andreu Cabot^c, Ursel Bangert^b, Shalini Singh^a, Kevin M. Ryan^a

^aDepartment of Chemical Sciences and Bernal Institute, University of Limerick, V94 T9PX, Limerick, Ireland

^bDepartment of Physics and Bernal Institute, University of Limerick, V94 T9PX, Limerick, Ireland

^cCatalonia Institute for Energy Research−IREC, Jardins de les Dones de Negre 1, 2ª pl., Sant Adrià de Besòs, Spain

^dBernal Institute, University of Limerick, V94 T9PX, Limerick, Ireland

Proceedings of Internet NanoGe Conference on Nanocrystals (iNCNC)

Online, Spain, 2021 June 28th - July 2nd

Organizers: Maksym Kovalenko, Maria Ibáñez, Peter Reiss and Quinten Akkerman

Oral, Nilotpal Kapuria, presentation 019
DOI: https://doi.org/10.29363/nanoge.incnc.2021.019
Publication date: 8th June 2021

1D heterostructure NCs are typically synthesized through colloidal methods, solution-liquid-solid growth (SLS), solution-solid-solid growth (SSS), and cation exchange processes. However, the transformation of 1D heterostructures to alloyed multi-element NCs requires cation diffusion in NC templates or seeds using complex ligand-cation interactions and high annealing temperatures. A facile approach and mechanistic insights into the transformation of heterostructures especially for metal-semiconductor heterostructure to alloyed multi-element NCs is needed. Here we demonstrate the combination of metallic seeded (SLS) and cationic diffusion mediated growth in a conventional hot-injection system for colloidal Cu-Bi-Zn-S nanorods (NRs) formation from Bi-Cu_2-xS heterostructures. The transformation of the Bi seed and Cu_2-xS stem into ternary metal sulfides and materialization of a transitional segment at the heterointerface lead to the formation of the tri-segmented heterostructure NCs with Bi_xCu_yS_z phases. The NR evolution is driven by the dissolution of the Bi-rich seed and recrystallization of the Cu-rich stem into the transitional segment, followed by the incorporation of Zn²⁺ to form the quaternary Cu-Bi-Zn-S NRs. This study highlights the importance of the integration of seeded growth into colloidal chemistry to access new multi-element alloyed NRs. The present study also revealed the variation of Zn concentration in the NRs modulates the aspect ratio and affects the nature of majority charge carriers. The NRs exhibit promising thermoelectric properties with significantly low thermal conductivity values of 0.45 W/mK and 0.65 W/mK at 775 K and 605 K respectively for Zn poor and Zn rich NRs.

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