Abstract

This work presents pulsed laser deposition as a method to obtain unoxidized LaNi5 nanoscale films and describes their temperature and thickness dependent electrical conductivity and the spectral dispersions of some optical properties. AB5-type rare earth element (REE)-nickel compounds are currently studied from both theoretical and practical points of view. Special challenges are posed during the preparation of these nanomaterials, which can be overcome using finely tuned parameters in a preparation process that always involves the use of high energies. Film deposition was made by laser—induced vaporization, with short and modulated impulses and electro–optical tuning of the quality factor, mainly on glass and one SiO2 substrate. Deposition geometry dependent linear thickness increase, between 1.5–2.5 nm per laser burst, was achieved. Film structures and phase compositions were determined using XRD and discussed in comparison with films obtained by similar deposition procedures. Temperature and scale dependent properties were determined by studying electrical conductivity and optical properties. Electrical conductivity was measured using the four-probe method. The observed semiconductor-like conductivity for film thicknesses up to 110 nm can be explained by thermal activation of electrons followed by inter-insular hopping or quantum tunneling, which, on the other hand, modulates the material’s native metallic conductance. Films with thicknesses above this value can be considered essentially metallic and bulk-like. The spectral behaviors of the refractive index and absorption coefficient were deduced from differential reflectance spectroscopy data acquired on a broad ultraviolet, visible, near- and mid-infrared (UV-VIS-NIR-MIR) domain, processed using the Kramers-Krönig formalism. Their study led to the identification of the allowed interband transitions. Electronic behavior in the energy bands near the Fermi level and in the surface and interface-states was described, discussing the differences between experimental data and the classical free-electron theoretical model applied for the bulk intermetallic alloy, in correlation with theoretical optical properties or experimental X-ray photoelectron spectroscopy (XPS) results from references. However, the dielectric-like shape of the reflectance of the thinnest film was in accordance with the Lorentz–Drude model.

Highlights

  • The importance of rare earth element (REE) compounds is undeniable in modern technologies, proven by the number of studies published for both their theoretical description and practicalMaterials 2018, 11, 1475; doi:10.3390/ma11081475 www.mdpi.com/journal/materialsMaterials 2018, 11, 1475 applications

  • In this work we report successful deposition and study of electrical conductivity and optical properties of polycrystalline nanometer thickness LaNi5 films on mainly glass and a single SiO2 substrate

  • A crystallite size of 17 nm and a micro-strain below 0.5% was evaluated for the 68 nm film

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Summary

Introduction

The importance of rare earth element (REE) compounds is undeniable in modern technologies, proven by the number of studies published for both their theoretical description and practicalMaterials 2018, 11, 1475; doi:10.3390/ma11081475 www.mdpi.com/journal/materialsMaterials 2018, 11, 1475 applications. Its compounds with cations like Boron are semiconductors; as such, they can be used to construct thin film transistors [1], or as a plasmonic material when partially replaced by Eu, because of wide band near-infrared (NIR). Its best known application is hydrogen storage in its AB5 -type alloy with Ni. Early studies of RNi5 type compounds—where R is a REE like La or Gd, and where Ni can be replaced in a certain amount by some other metal—were made to link theoretically computed electron energy band structures to the observed calorimetric [7,8] and magnetic properties [9,10,11]. Most of the Ni-metal hydride batteries use this type of compound in the cathode, while cutting-edge research methods are applied to enhance storage capacity

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