Engineering the Electronic Properties of Strongly Correlated Metal Thin Films

Open Access
Eaton, Craig Ernest
Graduate Program:
Materials Science and Engineering
Doctor of Philosophy
Document Type:
Date of Defense:
October 08, 2015
Committee Members:
  • Roman Engel Herbert, Dissertation Advisor
  • Susan E Trolier Mckinstry, Committee Member
  • Suman Datta, Committee Member
  • Venkatraman Gopalan, Committee Member
  • MBE
  • SrVO3
  • CaVO3
  • epitaxy
  • Hybrid
This dissertation reports on advances in synthesis and characterization of high quality perovskite metals with strong electron correlation. These materials have attracted considerable attention for their potential application as an active electronic material in logic applications utilizing the Mott type metal-to-insulator transition. CaVO3 and SrVO3 correlated metal oxide films have been grown by hybrid-molecular beam epitaxy (MBE), where alkaline earth cations are supplied using a conventional effusion cell and the transition metal vanadium is supplied using the metal-organic precursor vanadium (V) oxytriisopropoxide. Oxygen is available in both molecular and remote plasma activated forms. Titanate-based band insulators, namely SrTiO3 and CaTiO3, have also been grown using titanium tetra-isopropoxide as metal-organic precursor. The grown films have been characterized using reflection high energy electron diffraction (RHEED), X-ray diffraction (XRD), atomic force microscopy (AFM), transition electron microscopy (TEM), and electrical properties have been determined using temperature dependent resistivity and Hall measurements. Optimized films exhibit high quality Kiessig fringes, with substrate limited rocking curve widths of 8 arc seconds in the case of CaVO3 and 17 arc seconds in the case of SrVO3. Both vanadate films grew in a step-flow mode with atomic steps visible after growth by AFM. In SrVO3, the perovskite phase remained present with a gradual lattice expansion away from the optimal cation flux ratio. For CaVO3, the films remained phase pure and with little change in lattice parameter throughout a growth window that spanned a 30% range in cation flux ratios. While an abrupt increase of lattice parameter was found for CaVO3 films grown under Ca-rich conditions, films grown under V-rich conditions revealed a gradual reduction in lattice parameter, in contrast to SrVO3 where all defects have been shown to increase unit cell volume. Low resistivity and high residual resistivity ration complex vanadate thin films have been demonstrated. Methods for growing minimally strained SrVO3 films on (LaAlO3)0.3(Sr2AlTaO6)0.7 substrates (0.7% tensile) were expanded to other substrates with different lattice mismatches, namely SrTiO3 (1.8% tensile) and LaAlO3 (1.3% compressive). Varying strain modifies bond angles or overlap, and can give rise to an insulating ground state. Changes in the film surface morphology derived from atomic force microscopy (AFM) was used to discriminate optimal growth conditions on each substrate. Films grown at each strain state remain strongly metallic at 10 nm thickness. Low temperature resistivity measurements, which demonstrates a marked increase in low temperature resistivity with respect to those films grown at optimized growth parameters, were found to be substrate dependent. The thickness of films grown on SrTiO3 are optimized for maximum thickness without cracking. Use of epitaxial strain as a mechanism for enabling a Mott transition was not demonstrated at strains and conditions attempted within this study. The experimental support of this hypothesis could not be experimentally confirmed within the range of strains studied here. Finally, high quality epitaxial SrTiO3-SrVO3-SrTiO3 heterostructures are grown on (LaAlO3)0.3(Sr2AlTaO6)0.7 substrates by hybrid MBE. RHEED, XRD, and TEM showed that these structures are of high structural quality, with atomically and chemically abrupt interfaces. By fixing the thickness of the SrTiO3 confinement layers to be 15 nm and decreasing the thickness of the SrVO3 from 50 nm down to 1.2 nm, it has been demonstrated that the system transitions from a strongly-correlated metal to an insulating state, as shown by temperature dependent resistivity and carrier concentration measurements. For films with thickness larger than 1.2 nm, the resistivity versus temperature is described by Fermi liquid behavior. Below this critical thickness the material undergoes an electronic phase transition into a variable-range hopping insulating phase. The results of this dissertation show that high quality vanadate thin films can be grown by hybrid MBE. Their electronic ground state, metallic in the bulk phase, can be effectively changed using geometrical confinement, while epitaxial strain was found to have a negligible effect. The ability to grow CaVO3 in a self-regulated fashion holds promise that the favorable growth kinetics in hybrid MBE might be a general characteristic of the metalorganic precursor employed.