Colloidal Anisotropic ZnO-Fe@FexOy Nanoarchitectures with Interface-Mediated Exchange-Bias and Band-Edge Ultraviolet Fluorescence

TL;DR

This paper reports the synthesis of hybrid ZnO nanorods decorated with magnetic Fe-based domains, demonstrating interface-mediated exchange bias and enhanced ultraviolet fluorescence, revealing structure-property relationships in these nanocrystals.

Contribution

It introduces a colloidal seeded-growth method to create hybrid nanocrystals with tunable magnetic and optical properties, highlighting the role of nanodomain size and distribution.

Findings

Large number of small Fe@FexOy domains induce exchange bias.

Larger Fe@FexOy domains suppress exchange coupling.

Ultraviolet fluorescence is blue-shifted in hybrid nanocrystals.

Abstract

Hybrid nanocrystals (HNCs), based on ZnO nanorods (NRs) decorated with magnetic Fe-based domains, were synthesized via a colloidal seeded-growth method. The approach involved heterogeneous nucleation of Fe nanocrystals on size-tailored ZnO nanorod seeds in a noncoordinating solvent, followed by partial surface oxidation of the former to the corresponding Fe@FexOy core@shell domains. HNCs with variable population and size of the Fe-based nanodomains could be synthesized depending on the surface reactivity of the ZnO seeds. The structure-property relationships in these HNCs were carefully studied. In HNCs characterized by a large number of small Fe@FexOy core@shell nanodomains on the ZnO seed surface, the interfacial communication across the Fe-core and FexOy-shell generated a sizeable exchange-bias effect mediated by frozen interfacial spins. On the other hand, in HNCs carrying a lower density of comparatively larger Fe@FexOy domains, partial removal of the Fe core created an inner void in-between that led to suppressed exchange coupling anisotropy. As a further proof of functionality, the HNCs exhibited pronounced band-edge ultraviolet fluorescence. The latter was blue-shifted compared to the parent ZnO NRs, inferring coupling of the semiconductor and magnet sections.