| dc.description.abstract | Rare-earth nickelates (RENiO3), a family of transition metal oxides, exhibit a complex phase diagram involving electronic, magnetic, and structural phase transitions. While LaNiO3 remains paramagnetic, metallic down to very low temperature, RENiO3 members with RE=Nd, Pr exhibit simultaneous metal-insulator transition (MIT), paramagnetic to antiferromagnetic transition, structural phase transition and a bond disproportionation (BD) transition as a function of temperature. The other members of the series such as EuNiO3, SmNiO3, etc. first undergo simultaneous MIT, BD, and structural phase transition and further becomes antiferromagnetic upon lowering the temperature. Understanding the origin of the MIT in this family remains a challenging problem and has attracted a lot of attention in recent times. The MIT temperature can be tuned by a variety of parameters such as chemical doping, pressure, epitaxial strain, light, etc. In this thesis, we have grown epitaxial thin films of doped rare-earth nickelates and investigated their electronic and magnetic behavior using several experimental techniques, including synchrotron-based measurements.
In the first part, we have investigated Ca2+ (divalent) and Ce4+ (tetravalent) doped NdNiO3 thin films. Doping with divalent ions at the Nd sites introduces holes, whereas doping with tetravalent ions introduces electrons, resulting in a change in the formal valence of Ni. Both electron and hole doping suppress the insulating phases with asymmetric suppression rates for the metal-insulator phase transition. We have shown that the effective charge transfer energy changes with carrier doping and the formation of the BD phase is not favored above a critical doping, suppressing the insulating phase. Our research clearly shows that the appearance of BD mode is critical for the appearance of MIT in RENiO3 family.
In the second part, we have investigated rare-earth nickelate in high entropy oxide (HEO) form. HEOs are defined as a class of materials containing equimolar or nearly equimolar portions of five or more elements stabilizing in a single phase. HEOs have been explored in recent years to achieve tunable properties in unexplored parts of the complex phase diagram. However, epitaxial stabilization of such multi-element systems is challenging, and it is unknown how epitaxial strain will affect the electronic and magnetic behavior of HEO. We have been able to grow (LaPrNdSmEu)0.2NiO3 [(LPNSE)NO] thin films on different substrates having different epitaxial strains. We have shown that, in spite of having multi-element and strong disorder at the RE site, the average tolerance factor determines the electronic and magnetic properties. We further studied the strain effect on MIT of those HEO thin films. We have observed that (LPNSE)NO film grown under tensile strain (substrates: NdGaO3 and SrTiO3) exhibits a metal-insulator transition. We have found that this transition can be completely suppressed by compressive strain exerted by SrLaAlO4 substrate. Surprisingly, HEO film, grown on SrPrGaO4 substrate, where the strain is almost negligible, does not exhibit any MIT. We have further demonstrated that the octahedral rotation pattern of the substrate governs the octahedral rotation and Ni-O-Ni bond angle of the epitaxial thin films, which in turn controls the MIT.
In the third part, we have explored (LPNSE)NO thin films as electrocatalysts. Oxygen evolution reaction (OER) is a key process in several alternative energy generation platforms such as solar and electric driven water splitting, fuel cells, rechargeable metal-air batteries, etc. We have investigated the thickness dependent OER of (LPNSE)NO thin films and found that the increase of film thickness results in higher OER activity. X-ray absorption spectroscopy measurements find an increase in Ni d-O p covalency and a decrease in charge transfer energy with the increase in film thickness. These facilitate higher charge transfer between Ni and surface adsorbates, resulting in higher OER activity. | en_US |
