title: Uncoupled surface spin induced exchange bias in α-MnO2 nanowires.
abstract: We have studied the microstructure, surface states, valence fluctuations, magnetic properties, and exchange bias effect in MnO2 nanowires. High purity α-MnO2 rectangular nanowires were synthesized by a facile hydrothermal method with microwave-assisted procedures. The microstructure analysis indicates that the nanowires grow in the [0 0 1] direction with the (2 1 0) plane as the surface. Mn(3+) and Mn(2+) ions are not found in the system by X-ray photoelectron spectroscopy. The effective magnetic moment of the manganese ions fits in with the theoretical and experimental values of Mn(4+) very well. The uncoupled spins in 3d(3) orbitals of the Mn(4+) ions in MnO6 octahedra on the rough surface are responsible for the net magnetic moment. Spin glass behavior is observed through magnetic measurements. Furthermore, the exchange bias effect is observed for the first time in pure α-MnO2 phase due to the coupling of the surface spin glass with the antiferromagnetic α-MnO2 matrix. These α-MnO2 nanowires, with a spin-glass-like behavior and with an exchange bias effect excited by the uncoupled surface spins, should therefore inspire further study concerning the origin, theory, and applicability of surface structure induced magnetism in nanostructures.
authors.affiliation: 1] School of Materials Science and Engineering, Shanghai University, Shanghai 200072, PR China [2] Institute for Superconducting and Electronic Materials, University of Wollongong, NSW 2522, Australia.
authors.forename: Wenxian
authors.initials: W
authors.lastname: Li
authors.affiliation: Institute for Superconducting and Electronic Materials, University of Wollongong, NSW 2522, Australia.
authors.forename: Rong
authors.initials: R
authors.lastname: Zeng
authors.affiliation: Institute for Superconducting and Electronic Materials, University of Wollongong, NSW 2522, Australia.
authors.forename: Ziqi
authors.initials: Z
authors.lastname: Sun
authors.affiliation: 1] Institute for Superconducting and Electronic Materials, University of Wollongong, NSW 2522, Australia [2] Key Laboratory of Bio-Inspired Smart Interfacial Science and Technology of Ministry of Education, School of Chemistry and Environment, Beihang University, Beijing, PR China.
authors.forename: Dongliang
authors.initials: D
authors.lastname: Tian
authors.affiliation: Institute for Superconducting and Electronic Materials, University of Wollongong, NSW 2522, Australia.
authors.forename: Shixue
authors.initials: S
authors.lastname: Dou