This review stands in the larger framework of functional materials by focussing on heterostructures of rare-earth nickelates, described by the chemical formula RNiO where R is a trivalent rare-earth R = La, Pr, Nd, Sm, …, Lu. Nickelates are characterized by a rich phase diagram of structural and physical properties and serve as a benchmark for the physics of phase transitions in correlated oxides where electron-lattice coupling plays a key role. Much of the recent interest in nickelates concerns heterostructures, that is single layers of thin film, multilayers or superlattices, with the general objective of modulating their physical properties through strain control, confinement or interface effects. We will discuss the extensive studies on nickelate heterostructures as well as outline different approaches to tuning and controlling their physical properties and, finally, review application concepts for future devices.
The metal–insulator transition and the intriguing physical properties of rare-earth perovskite nickelates have attracted considerable attention in recent years. Nonetheless, a complete understanding of these materials remains elusive. Here we combine X-ray absorption and resonant inelastic X-ray scattering (RIXS) spectroscopies to resolve important aspects of the complex electronic structure of rare-earth nickelates, taking NdNiO3 thin film as representative example. The unusual coexistence of bound and continuum excitations observed in the RIXS spectra provides strong evidence for abundant oxygen holes in the ground state of these materials. Using cluster calculations and Anderson impurity model interpretation, we show that distinct spectral signatures arise from a Ni 3d8 configuration along with holes in the oxygen 2p valence band, confirming suggestions that these materials do not obey a conventional positive charge-transfer picture, but instead exhibit a negative charge-transfer energy in line with recent models interpreting the metal–insulator transition in terms of bond disproportionation.
ABSTRACT. The functional properties of oxide heterostructures ultimately rely on how the electronic and structural mismatches occurring at interfaces are accommodated by the chosen
Bulk NdNiO 3 and thin films grown along the pseudocubic (001) pc axis display a 1 st order metal to insulator transition (MIT) together with a Néel transition at T=200K. Here, we show that for NdNiO 3 films deposited on (111) pc NdGaO 3 the MIT occurs at T=335K and the Néel transition at T=230 K. By comparing transport and magnetic properties of layers grown on substrates with different symmetries and lattice parameters, we demonstrate a particularly large tuning when the epitaxy is realized on (111) pc surfaces. We attribute this effect to the specific lattice matching conditions imposed along this direction when using orthorhombic substrates.
Nucleation processes of mixed-phase states are an intrinsic characteristic of first-order phase transitions, typically related to local symmetry breaking. Direct observation of emerging mixed-phase regions in materials showing a first-order metal–insulator transition (MIT) offers unique opportunities to uncover their driving mechanism. Using photoemission electron microscopy, we image the nanoscale formation and growth of insulating domains across the temperature-driven MIT in NdNiO3 epitaxial thin films. Heteroepitaxy is found to strongly determine the nanoscale nature of the phase transition, inducing preferential formation of striped domains along the terraces of atomically flat stepped surfaces. We show that the distribution of transition temperatures is a local property, set by surface morphology and stable across multiple temperature cycles. Our data provide new insights into the MIT of heteroepitaxial nickelates and point to a rich, nanoscale phenomenology in this strongly correlated material.
approaches to controlling the MIT have been made, for example, by electric field effects [9] and through optical means. [10] Today, RNOs retain a strong focus, with recent work striving to understand their physics. [11][12][13][14][15] The R = La compound is the only RNO that does not have an MIT in bulk; it is metallic and paramagnetic at all temperatures. LaNiO 3 (LNO) may prove an ideal candidate as a base for engineering functional oxide heterostructures. For instance, it was suggested that specially engineered superlattices, based on single unit cells (u.c.) of LNO, may support superconductivity, [16] and it has been shown that this material is orbitally polarizable in specifically designed heterostructures. [17,18] Necessary to fine-tune the functionalities of LNO is a full understanding of the effects of heterostructuring on an atomic level, and the implications that the local structure, at this scale, has on the electronic properties. A close examination of the thin film structure at the boundaries with the substrate and the vacuum, as well as the effects of reducing the dimensionality on coexistence and, ultimately, competition between these local structures, is required.In reducing dimensionality, three conductivity regimes have previously been observed; thicker metallic films, intermediate thicknesses with a resistivity upturn, and insulating films under the ultrathin limit, which can be 3-6 u.c., depending upon the substrate. [19][20][21] In line with this, photoemission studies found drastic changes to the LNO Fermi surface as the thickness approaches a few u.c., indicating that there is a fundamental change in the electronic structure. [22,23] Here we report an intriguing thickness-dependent transport behavior in high-quality LNO films grown on a (001) LaAlO 3 (LAO) substrate, whereby conductivity is enhanced in films of 6-11 u.c. (2.3-4.3 nm). A maximum conductivity is also observed in ab initio calculations (for a thickness of 6-8 u.c.). In agreement with scanning transmission electron microscopy (STEM), the simulations further indicate that there are three characteristic local structures in the depth of the films. A three-element model of parallel conductors reproduces the thickness-dependent transport behavior well, and implies that conductivity enhancement derives from a struggle for dominance between the local structure of the surface and of the heterointerface.Both LNO and LAO are rhombohedral (R-3c) in bulk. LNO (pseudocubic lattice parameter 3.84 Å) deposited on LAO (pseudocubic lattice parameter 3.79 Å) is compressively strained by −1.3%.A marked conductivity enhancement is reported in 6-11 unit cell LaNiO 3 thin films. A maximal conductivity is also observed in ab initio calculations for films of the same thickness. In agreement with results from state of the art scanning transmission electron microscopy, the calculations also reveal a differentiated film structure comprising characteristic surface, interior, and heterointerface structures. Based on this observation, a three-element para...
Dimensionality is known to play an important role in many compounds for which ultrathin layers can behave very differently from the bulk. This is especially true for the paramagnetic metal LaNiO3, which can become insulating and magnetic when only a few monolayers thick. We show here that an induced antiferromagnetic order can be stabilized in the [111] direction by interfacial coupling to the insulating ferromagnet LaMnO3, and used to generate interlayer magnetic coupling of a nature that depends on the exact number of LaNiO3 monolayers. For 7-monolayer-thick LaNiO3/LaMnO3 superlattices, negative and positive exchange bias, as well as antiferromagnetic interlayer coupling are observed in different temperature windows. All three behaviours are explained based on the emergence of a (¼,¼,¼)-wavevector antiferromagnetic structure in LaNiO3 and the presence of interface asymmetry with LaMnO3. This dimensionality-induced magnetic order can be used to tailor a broad range of magnetic properties in well-designed superlattice-based devices.
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