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Common belief is that the large band shifts observed in incommensurate misfit compounds, e.g. (LaSe)1.14(NbSe2)2, are due to interlayer charge transfer. In contrast, our analysis, based on both ARPES measurements and a specialized ab initio framework employing only quantities well defined in incommensurate materials, demonstrates that the large band shifts instead reflect changes in valence band hybridization and interlayer bonding. The strong alignment of our ab initio predictions and ARPES measurements confirms our understanding of the incommensurate electronic structure and charge transfer., Comment: 6 pages, 4 figures, Supplemental Materials included as pdf in LaTeX package

A key open question in the study of layered superconducting nickelate films is the role that hydrogen incorporation into the lattice plays in the appearance of the superconducting state. Due to the challenges of stabilizing highly crystalline square planar nickelate films, films are prepared by the deposition of a more stable parent compound which is then transformed into the target phase via a topotactic reaction with a strongly reducing agent such as CaH$_2$. Recent studies, both experimental and theoretical, have introduced the possibility that the incorporation of hydrogen from the reducing agent into the nickelate lattice may be critical for the superconductivity. In this work, we use secondary ion mass spectrometry to examine superconducting La$_{1-x}$X$_x$NiO$_2$ / SrTiO$_3$ (X = Ca and Sr) and Nd$_6$Ni$_5$O$_{12}$ / NdGaO$_3$ films, along with non-superconducting NdNiO$_2$ / SrTiO$_3$ and (Nd,Sr)NiO$_2$ / SrTiO$_3$. We find no evidence for extensive hydrogen incorporation across a broad range of samples, including both superconducting and non-superconducting films. Theoretical calculations indicate that hydrogen incorporation is broadly energetically unfavorable in these systems, supporting our conclusion that hydrogen incorporation is not generally required to achieve a superconducting state in layered square-planar nickelates., Comment: 23 pages, 21 figures (including supplemental information)

Charge order pervades the phase diagrams of many quantum materials where it competes with superconducting and magnetic phases, hosts electronic phase transitions and topological defects, and couples to the lattice generating intricate structural distortions. Incommensurate charge order is readily stabilized in manganese oxides where it is associated with anomalous electronic and magnetic properties, but its nanoscale structural inhomogeneity complicates precise characterization and understanding of these phases. Leveraging atomic-resolution variable temperature cryogenic scanning transmission electron microscopy (cryo-STEM), we characterize the thermal evolution of charge order in a model manganite system, finding that mobile networks of topological defects generate phase inhomogeneity and induce incommensuration in an otherwise lattice-locked modulation. The melting of charge order at high temperatures is accompanied by generation of additional defects which decouple large areas of the order from the lattice., Comment: 14 pages, 6 figures

Progress in the study of infinite-layer nickelates has always been highly linked to materials advances. In particular, the recent development of superconductivity via hole-doping was predicated on the controlled synthesis of Ni in a very high oxidation state, and subsequent topotactic reduction to a very low oxidation state, currently limited to epitaxial thin films. Here we demonstrate a process to combine these steps with a heterostructure which includes an epitaxial soluble buffer layer, enabling the release of freestanding membranes of (Nd,Sr)NiO2 encapsulated in SrTiO3, which serves as a protective layer. The membranes have comparable structural and electronic properties to that of optimized thin films, and range in lateral dimensions from millimeters to ~100 micron fragments, depending on the degree of strain released with respect to the initial substrate. The changes in the superconducting transition temperature associated with membrane release are quite similar to those reported for substrate and pressure variations, suggestive of a common underlying mechanism. These membranes structures should provide a versatile platform for a range of experimental studies and devices free from substrate constraints.

We present an integrated procedure for the synthesis of infinite-layer nickelates using molecular-beam epitaxy with gas-phase reduction by atomic hydrogen. We first discuss challenges in the growth and characterization of perovskite NdNiO$_3$/SrTiO$_3$, arising from post growth crack formation in stoichiometric films. We then detail a procedure for fully reducing NdNiO$_3$ films to the infinite-layer phase, NdNiO$_2$, using atomic hydrogen; the resulting films display excellent structural quality, smooth surfaces, and lower residual resistivities than films reduced by other methods. We utilize the in situ nature of this technique to investigate of the role that SrTiO$_3$ capping layers play in the reduction process, illustrating their importance in preventing the formation of secondary phases at the exposed nickelate surface. A comparative bulk- and surface-sensitive study indicates formation of a polycrystalline crust on the film surface serves to limit the reduction process., Comment: Main text: 12 pages, 7 figures. Supplemental Materials: 11 pages, 11 figures

The charge density wave (CDW) material 1T-TaS$_2$ exhibits a pulse-induced insulator-to-metal transition, which shows promise for next-generation electronics such as memristive memory and neuromorphic hardware. However, the rational design of TaS$_2$ devices is hindered by a poor understanding of the switching mechanism, the pulse-induced phase, and the influence of material defects. Here, we operate a 2-terminal TaS$_2$ device within a scanning transmission electron microscope (STEM) at cryogenic temperature, and directly visualize the changing CDW structure with nanoscale spatial resolution and down to 300 {\mu}s temporal resolution. We show that the pulse-induced transition is driven by Joule heating, and that the pulse-induced state corresponds to nearly commensurate and incommensurate CDW phases, depending on the applied voltage amplitude. With our in operando cryo-STEM experiments, we directly correlate the CDW structure with the device resistance, and show that dislocations significantly impact device performance. This work resolves fundamental questions of resistive switching in TaS$_2$ devices critical for engineering reliable and scalable TaS$_2$ electronics.

Charge density waves are emergent quantum states that spontaneously reduce crystal symmetry, drive metal-insulator transitions, and precede superconductivity. In low-dimensions, distinct quantum states arise, however, thermal fluctuations and external disorder destroy long-range order. Here we stabilize ordered two-dimensional (2D) charge density waves through endotaxial synthesis of confined monolayers of 1T-TaS$_2$. Specifically, an ordered incommensurate charge density wave (oIC-CDW) is realized in 2D with dramatically enhanced amplitude and resistivity. By enhancing CDW order, the hexatic nature of charge density waves becomes observable. Upon heating via in-situ TEM, the CDW continuously melts in a reversible hexatic process wherein topological defects form in the charge density wave. From these results, new regimes of the CDW phase diagram for 1T-TaS$_2$ are derived and consistent with the predicted emergence of vestigial quantum order.

The layered square-planar nickelates, Nd$_{n+1}$Ni$_{n}$O$_{2n+2}$, are an appealing system to tune the electronic properties of square-planar nickelates via dimensionality; indeed, superconductivity was recently observed in Nd$_{6}$Ni$_{5}$O$_{12}$ thin films. Here, we investigate the role of epitaxial strain in the competing requirements for the synthesis of the $n=3$ Ruddlesden-Popper compound, Nd$_{4}$Ni$_{3}$O$_{10}$, and subsequent reduction to the square-planar phase, Nd$_{4}$Ni$_{3}$O$_{8}$. We synthesize our highest quality Nd$_{4}$Ni$_{3}$O$_{10}$ films under compressive strain on LaAlO$_{3}$ (001), while Nd$_{4}$Ni$_{3}$O$_{10}$ on NdGaO$_{3}$ (110) exhibits tensile strain-induced rock salt faults but retains bulk-like transport properties. A high density of extended defects forms in Nd$_{4}$Ni$_{3}$O$_{10}$ on SrTiO$_{3}$ (001). Films reduced on LaAlO$_{3}$ become insulating and form compressive strain-induced $c$-axis canting defects, while Nd$_{4}$Ni$_{3}$O$_{8}$ films on NdGaO$_{3}$ are metallic. This work provides a pathway to the synthesis of Nd$_{n+1}$Ni$_{n}$O$_{2n+2}$ thin films and sets limits on the ability to strain engineer these compounds via epitaxy.

Exploiting the emerging nanoscale periodicities in epitaxial, single-crystal thin films is an exciting direction in quantum materials science: confinement and periodic distortions induce novel properties. The structural motifs of interest are ferroelastic, ferroelectric, multiferroic, and, more recently, topologically protected magnetization and polarization textures. A critical step towards heterostructure engineering is understanding their nanoscale structure, best achieved through real-space imaging. X-ray Bragg coherent diffractive imaging visualizes sub-picometer crystalline displacements with tens of nanometers spatial resolution. Yet, it is limited to objects spatially confined in all three dimensions and requires highly coherent, laser-like x-rays. Here we lift the confinement restriction by developing real-space imaging of periodic lattice distortions: we combine an iterative phase retrieval algorithm with unsupervised machine learning to invert the diffuse scattering in conventional x-ray reciprocal-space mapping into real-space images of polar and elastic textures in thin epitaxial films. We first demonstrate our imaging in PbTiO3/SrTiO3 superlattices to be consistent with published phase-field model calculations. We then visualize strain-induced ferroelastic domains emerging during the metal-insulator transition in Ca2RuO4 thin films. Instead of homogeneously transforming into a low-temperature structure (like in bulk), the strained Mott insulator splits into nanodomains with alternating lattice constants, as confirmed by cryogenic scanning transmission electron microscopy. Our study reveals the type, size, orientation, and crystal displacement field of the nano-textures. The non-destructive imaging of textures promises to improve models for their dynamics and enable advances in quantum materials and microelectronics.

The layer stacking order in 2D materials strongly affects functional properties and holds promise for next generation electronic devices. In bulk, octahedral MoTe$_2$ possesses two stacking arrangements, the Weyl semimetal T$_d$ phase, and the higher-order topological insulator 1T' phase; however, it remains unclear if thin exfoliated flakes of MoTe$_2$ follow the T$_d$, 1T', or an alternative stacking sequence. Here, we resolve this debate using atomic-resolution imaging within the transmission electron microscope. We find that the layer stacking in thin flakes of MoTe$_2$ is highly disordered and pseudo-random, which we attribute to intrinsic confinement effects. Conversely, WTe$_2$, which is isostructural and isoelectronic to MoTe$_2$, displays ordered stacking even for thin exfoliated flakes. Our results are important for understanding the quantum properties of MoTe$_2$ devices, and suggest that thickness may be used to alter the layer stacking in other 2D materials., Comment: 6 figures, 2 tables

The discrete Fourier transform is among the most routine tools used in high-resolution scanning / transmission electron microscopy (S/TEM). However, when calculating a Fourier transform, periodic boundary conditions are imposed and sharp discontinuities between the edges of an image cause a cross patterned artifact along the reciprocal space axes. This artifact can interfere with the analysis of reciprocal lattice peaks of an atomic resolution image. Here we demonstrate that the recently developed Periodic Plus Smooth Decomposition technique provides a simple, efficient method for reliable removal of artifacts caused by edge discontinuities. In this method, edge artifacts are reduced by subtracting a smooth background that solves Poisson's equation with boundary conditions set by the image's edges. Unlike the traditional windowed Fourier transforms, Periodic Plus Smooth Decomposition maintains sharp reciprocal lattice peaks from the image's entire field of view.

The Ruddlesden-Popper ($A_{n+1}B_{n}\text{O}_{3n+1}$) compounds are a highly tunable class of materials whose functional properties can be dramatically impacted by their structural phase $n$. The negligible energetic differences associated with forming a sample with a single value of $n$ versus a mixture of $n$ makes the growth of these materials difficult to control and can lead to local atomic-scale structural variation arising from small stoichiometric deviations. In this work, we present a Python analysis platform to detect, measure, and quantify the presence of different $n$-phases based on atomic-resolution scanning transmission electron microscopy (STEM) images in a statistically rigorous manner. We employ phase analysis on the 002 Bragg peak to identify horizontal Ruddlesden-Popper faults which appear as regions of high positive compressive strain within the lattice image, allowing us to quantify the local structure. Our semi-automated technique offers statistical advantages by considering effects of finite projection thickness, limited fields of view, and precise sampling rates. This method retains the real-space distribution of layer variations allowing for a spatial mapping of local $n$-phases, enabling both quantification of intergrowth occurrence as well as qualitative description of their distribution, opening the door to new insights and levels of control over a range of layered materials., Comment: 8 pages, 5 figures

The rare-earth nickelates possess a diverse set of collective phenomena including metal-to-insulator transitions, magnetic phase transitions, and, upon chemical reduction, superconductivity. Here, we demonstrate epitaxial stabilization of layered nickelates in the Ruddlesden-Popper form, Nd$_{n+1}$Ni$_n$O$_{3n+1}$, using molecular beam epitaxy. By optimizing the stoichiometry of the parent perovskite NdNiO$_3$, we can reproducibly synthesize the $n = 1 - 5$ member compounds. X-ray absorption spectroscopy at the O $K$ and Ni $L$ edges indicate systematic changes in both the nickel-oxygen hybridization level and nominal nickel filling from 3$d^8$ to 3$d^7$ as we move across the series from $n = 1$ to $n = \infty$. The $n = 3 - 5$ compounds exhibit weakly hysteretic metal-to-insulator transitions with transition temperatures that depress with increasing order toward NdNiO$_3$ ($n = \infty)$., Comment: 11 pages, 4 figures with Supplemental Information

Nickel-based superconductors provide a long-awaited experimental platform to explore possible cuprate-like superconductivity. Despite similar crystal structure and $d$ electron filling, these systems exhibit several differences. Nickelates are the most polar layered oxide superconductor, raising questions about the interface between substrate and thin film -- thus far the only sample geometry to successfully stabilize superconductivity. We conduct a detailed experimental and theoretical study of the prototypical interface between Nd$_{1-x}$Sr$_x$NiO$_2$ and SrTiO$_3$. Atomic-resolution electron energy loss spectroscopy in the scanning transmission electron microscope reveals the formation of a single intermediate Nd(Ti,Ni)O$_3$ layer. Density functional theory calculations with a Hubbard $U$ term show how the observed structure alleviates the strong polar discontinuity. We explore effects of oxygen occupancy, hole doping, and cation structure to disentangle the contributions of each for reducing interface charge density. Resolving the nontrivial interface structure will be instructive for future synthesis of nickelate films on other substrates and in vertical heterostructures.

Since the discovery of high-temperature superconductivity in the copper oxide materials, there have been sustained efforts to both understand the origins of this phase and discover new cuprate-like superconducting materials. One prime materials platform has been the rare-earth nickelates and indeed superconductivity was recently discovered in the doped compound Nd$_{0.8}$Sr$_{0.2}$NiO$_2$. Undoped NdNiO$_2$ belongs to a series of layered square-planar nickelates with chemical formula Nd$_{n+1}$Ni$_n$O$_{2n+2}$ and is known as the 'infinite-layer' ($n = \infty$) nickelate. Here, we report the synthesis of the quintuple-layer ($n = 5$) member of this series, Nd$_6$Ni$_5$O$_{12}$, in which optimal cuprate-like electron filling ($d^{8.8}$) is achieved without chemical doping. We observe a superconducting transition beginning at $\sim$13 K. Electronic structure calculations, in tandem with magnetoresistive and spectroscopic measurements, suggest that Nd$_6$Ni$_5$O$_{12}$ interpolates between cuprate-like and infinite-layer nickelate-like behavior. In engineering a distinct superconducting nickelate, we identify the square-planar nickelates as a new family of superconductors which can be tuned via both doping and dimensionality., Comment: 21 pages, 4 figures

The observation of superconductivity in infinite layer nickelate (Nd,Sr)NiO$_{2}$ thin films has led to rapid theoretical and experimental investigations of these copper-oxide-analogue systems [1-15]. Superconductivity has also been found in (Pr,Sr)NiO$_{2}$ [16,17], but not previously in (La,Sr)NiO$_{2}$ [2], raising a fundamental question whether superconductivity is associated with the presence of rare-earth moments [18,19]. Here we show that with significant materials optimization, substantial portions of the La$_{1-x}$Sr$_{x}$NiO$_{2}$ phase diagram can enter the regime of coherent low-temperature transport ($x$ = 0.14 - 0.20), with subsequent superconducting transitions and a maximum onset of ~ 9 K at $x$ = 0.20. Additionally, we observe the unexpected indication of a superconducting ground state in undoped LaNiO$_{2}$, which likely reflects the self-doped nature of the electronic structure. Combining the results of (La/Pr/Nd)$_{1-x}$Sr$_{x}$NiO$_{2}$ reveals a generalized superconducting dome, characterized by systematic shifts in the unit cell volume and in the relative electron-hole populations across the lanthanides., Comment: 23 pages, 4 figures

Compelling evidence suggests distinct correlated electron behavior may exist only in clean 2D materials such as 1T-TaS2. Unfortunately, experiment and theory suggest that extrinsic disorder in free standing 2D layers disrupts correlation-driven quantum behavior. Here we demonstrate a route to realizing fragile 2D quantum states through endotaxial polytype engineering of van der Waals materials. The true isolation of 2D charge density waves (CDWs) between metallic layers stabilizes commensurate long-range order and lifts the coupling between neighboring CDW layers to restore mirror symmetries via interlayer CDW twinning. The twinned-commensurate charge density wave (tC-CDW) reported herein has a single metal--insulator phase transition at ~350 K as measured structurally and electronically. Fast in-situ transmission electron microscopy and scanned nanobeam diffraction map the formation of tC-CDWs. This work introduces endotaxial polytype engineering of van der Waals materials to access latent 2D ground states distinct from conventional 2D fabrication.

The recent observation of superconductivity in thin film infinite-layer nickelates$^{1-3}$ offers a different angle to investigate superconductivity in layered oxides$^{4}$. A wide range of candidate models have been proposed$^{5-10}$, emphasizing single- or multi-orbital electronic structure, Kondo or Hund's coupling, and analogies to cuprates. Clearly, further experimental characterization of the superconducting state is needed to develop a full understanding of the nickelates. Here we use magnetotransport measurements to probe the superconducting anisotropy in Nd$_{0.775}$Sr$_{0.225}$NiO$_{2}$. We find that the upper critical field is surprisingly isotropic at low temperatures despite the layered crystal structure. In a magnetic field the superconductivity is strongly Pauli-limited, such that the paramagnetic effect dominates over orbital de-pairing. Underlying this isotropic response is a substantial anisotropy in the superconducting coherence length, which is at least four times longer in-plane than out-of-plane. A prominent low-temperature upturn in the upper critical field indicates the presence of an unconventional ground state., Comment: 9 pages, 4 figures, 1 supplementary info

We demonstrate a-axis YBa2Cu3O7-x/PrBa2Cu3O7-x/YBa2Cu3O7-x trilayers grown on (100) LaAlO3 substrates with improved interface smoothness. The trilayers are synthesized by ozone-assisted molecular-beam epitaxy. The thickness of the PrBa2Cu3O7-x layer is held constant at 8 nm and the thickness of the YBa2Cu3O7-x layers is varied from 24 nm to 100 nm. X-ray diffraction measurements show all trilayers to have >95% a-axis content. The rms roughness of the thinnest trilayer is < 0.7 nm and this roughness increases with the thickness of the YBa2Cu3O7-x layers. The thickness of the YBa2Cu3O7-x layers also affects the transport properties: while all samples exhibit an onset of the superconducting transition at and above 85 K, the thinner samples show wider transition widths, {\Delta}Tc. High-resolution scanning transmission electron microscopy reveals coherent and chemically sharp interfaces, and that growth begins with a cubic (Y,Ba)CuO3-x perovskite phase that transforms into a-axis oriented YBa2Cu3O7-x as the substrate temperature is ramped up., Comment: Manuscript: 21 pages, 5 figures; supplementary materials: 12 pages, 1 table, 10 supplementary figures

Transition-metal dichalcogenides containing tellurium anions show remarkable charge-lattice modulated structures and prominent interlayer character. Using cryogenic scanning transmission electron microscopy (STEM), we map the atomic-scale structures of the high temperature (HT) and low temperature (LT) modulated phases in 1T'-TaTe$_{2}$. At HT, we directly show in-plane metal distortions which form trimerized clusters and staggered, three-layer stacking. In the LT phase at 93 K, we visualize an additional trimerization of Ta sites and subtle distortions of Te sites by extracting structural information from contrast modulations in plan-view STEM data. Coupled with density functional theory calculations and image simulations, this approach opens the door for atomic-scale visualizations of low temperature phase transitions and complex displacements in a variety of layered systems.

Spectroscopic mapping by scanning transmission electron microscopy coupled with electron energy loss spectroscopy (STEM-EELS) is a powerful technique for determining the structure and chemistry of a wide range of materials and interfaces. The extension of this technique to cryogenic temperatures opens the door to new experiments across many fields including materials physics, energy storage and conversion, and biology. Such experiments, however, often face signal limitations due to sample sensitivity or the need for rapid data acquisition under less stable cryogenic conditions. Compared to traditional indirect detection systems such as charge coupled devices (CCDs), direct electron detectors (DEDs) offer improved detective quantum efficiencies, narrower point spread functions, and superior signal-to-noise ratios. Here, we compare the performance of a Gatan K2 Summit DED to an UltraScan 1000 CCD for use in signal-limited atomic-resolution STEM-EELS experiments. Due to its improved point spread function, the DED's energy resolution remains comparable to that of the CCD at a 5 times lower dispersion, providing simultaneous access to a much broader total energy range without sacrificing spectral resolution. More importantly, the benefits of direct detection enable a variety of low-signal experiments, including atomic-resolution mapping of minor and high energy edges such as the La-M$_{2,3}$ edge at 1123 eV and the Bi-M$_{4,5}$ edge at 2580 eV. For rapid acquisitions at 400 spectra per second, elemental maps recorded with the DED show an up to 40 percent increase in atomic lattice fringe contrast compared to those acquired with the CCD. Taking advantage of these performance improvements and the fast readout of the K2 DED, we use direct detection STEM-EELS to demonstrate atomic-resolution elemental mapping at cryogenic temperatures., Comment: 6 figures

A variety of nickel oxide compounds have long been studied for their manifestation of various correlated electron phenomena. Recently, superconductivity was observed in nanoscale infinite layer nickelate thin films of Nd$_{0.8}$Sr$_{0.2}$NiO$_2$, epitaxially stabilized on SrTiO$_3$ substrates via topotactic reduction from the perovskite precursor phase. Here we present the synthesis and properties of PrNiO$_2$ thin films on SrTiO$_3$. Upon doping in Pr$_{0.8}$Sr$_{0.2}$NiO$_2$, we observe superconductivity with a transition temperature of 7-12 K, and robust critical current density at 2 K of 334 kA/cm$^2$. These findings indicate that superconductivity in the infinite layer nickelates is relatively insensitive to the details of the rare earth 4$f$ configuration. Furthermore, they motivate the exploration of a broader family of compounds based on two-dimensional NiO$_2$ planes, which will enable systematic investigation of the superconducting and normal state properties and their underlying mechanisms., Comment: 19 pages, 4 figures

Superconductivity is among the most fascinating and well-studied quantum states of matter. Despite over 100 years of research, a detailed understanding of how features of the normal-state electronic structure determine superconducting properties has remained elusive. For instance, the ability to deterministically enhance the superconducting transition temperature by design, rather than by serendipity, has been a long sought-after goal in condensed matter physics and materials science, but achieving this objective may require new tools, techniques and approaches. Here, we report the first instance of the transmutation of a normal metal into a superconductor through the application of epitaxial strain. We demonstrate that synthesizing RuO$_{2}$ thin films on (110)-oriented TiO$_{2}$ substrates enhances the density of states near the Fermi level, which stabilizes superconductivity under strain, and suggests that a promising strategy to create new transition-metal superconductors is to apply judiciously chosen anisotropic strains that redistribute carriers within the low-energy manifold of $d$ orbitals., Comment: 30 pages, 20 figures (including supplemental information)

The recent observation of superconductivity in Nd$_{0.8}$Sr$_{0.2}$NiO$_2$ has raised fundamental questions about the hierarchy of the underlying electronic structure. Calculations suggest that this system falls in the Mott-Hubbard regime, rather than the charge-transfer configuration of other nickel oxides and the superconducting cuprates. Here, we use state-of-the-art, locally-resolved electron energy loss spectroscopy to directly probe the Mott-Hubbard character of Nd$_{1-x}$Sr$_x$NiO$_2$. Upon doping, we observe emergent hybridization reminiscent of the Zhang-Rice singlet via the oxygen-projected states, modification of the Nd 5$d$ states, and the systematic evolution of Ni 3$d$ hybridization and filling. These results clearly evidence the multiband nature of this system and the distinct electronic landscape for infinite-layer nickelates despite their formal similarity to the cuprates.

We report the phase diagram of Nd$_{1-x}$Sr$_x$NiO$_2$ infinite layer thin films grown on SrTiO$_3$. A superconducting dome spanning $0.125 < x < 0.25$ is found, remarkably similar to cuprates, albeit over a narrower doping window. However, while cuprate superconductivity is bounded by an insulator for underdoping and a metal for overdoping, here we observe weakly insulating behavior on either side of the dome. Furthermore, the normal state Hall coefficient is always small and proximate to a continuous zero crossing in doping and in temperature, in contrast to the $\sim 1/x$ dependence observed for cuprates. This suggests the presence of both electron- and hole-like bands, consistent with band structure calculations., Comment: 18 pages (including Supplemental Material), 7 figures (including 4 supplemental figure)

The recent observation of superconductivity in Nd$_{0.8}$Sr$_{0.2}$NiO$_{2}$ calls for further investigation and optimization of the synthesis of this metastable infinite-layer nickelate structure. Here, we present our current understanding of important aspects of the growth of the parent perovskite compound via pulsed laser deposition on SrTiO$_{3}$ (001) substrates, and the subsequent topotactic reduction. We find that to achieve single-crystalline, single-phase superconducting Nd$_{0.8}$Sr$_{0.2}$NiO$_{2}$, it is essential that the precursor perovskite Nd$_{0.8}$Sr$_{0.2}$NiO$_{3}$ thin film is stabilized with high crystallinity and no impurity phases; in particular, a Ruddlesden-Popper-type secondary phase is often observed. We have further investigated the evolution of the soft-chemistry topotactic reduction conditions to realize full transformation to the infinite-layer structure with no film decomposition or formation of other phases. We find that capping the nickelate film with a subsequent SrTiO$_{3}$ layer provides an epitaxial template to the top region of the nickelate film, much like the substrate. Thus, for currently optimized growth conditions, we can stabilize superconducting single-phase Nd$_{0.8}$Sr$_{0.2}$NiO$_{2}$ (001) epitaxial thin films up to ~ 10 nm.

Incorporating magnetism into two dimensional (2D) van der Waals (VdW) heterostrutures is crucial for the development of functional electronic and magnetic devices. Here we show that Nb3X8 (X = Cl, Br) is a family of 2D layered trimerized kagom\'e magnets that are paramagnetic at high temperatures and undergo a first order phase transition on cooling to a singlet magnetic state. X-ray diffraction shows that a rearrangement of the VdW stacking accompanies the magnetic transition, with high and low temperature phases consistent with STEM images of the end members {\alpha}-Nb3Cl8 and \b{eta}-Nb3Br8. The temperature of this transition is systematically varied across the solid solution Nb3Cl8-xBrx (x = 0-8), with x = 6 having transitions near room temperature. The solid solution also varies the optical properties, which are further modulated by the phase transition. As such, they provide a platform on which to understand and exploit the interplay between dimensionality, magnetism, and optoelectronic behavior in VdW materials.

Dielectric capacitors hold a tremendous advantage for energy storage due to their fast charge/discharge times and stability in comparison to batteries and supercapacitors. A key limitation to today's dielectric capacitors, however, is the low storage capacity of conventional dielectric materials. To mitigate this issue, antiferroelectric materials have been proposed, but relatively few families of antiferroelectric materials have been identified to date. Here, we propose a new design strategy for the construction of lead-free antiferroelectric materials using interfacial electrostatic engineering. We begin with a ferroelectric material with one of the highest known bulk polarizations, BiFeO3. We show that by confining atomically-precise thin layers of BiFeO3 in a dielectric matrix that we can induce a metastable antiferroelectric structure. Application of an electric field reversibly switches between this new phase and a ferroelectric state, in addition, tuning of the dielectric layer causes coexistence of the ferroelectric and antiferroelectric states. Precise engineering of the structure generates an antiferroelectric phase with energy storage comparable to that of the best lead-based materials. The use of electrostatic confinement provides a new pathway for the design of engineered antiferroelectric materials with large and potentially coupled responses., Comment: 17 pages, 4 figures

Interfaces between complex oxides constitute a unique playground for 2D electron systems (2DES), where superconductivity and magnetism can arise from combinations of bulk insulators. The 2DES at the LaAlO3/SrTiO3 interface is one of the most studied in this regard, and its origin is determined by both the presence of a polar field in LaAlO3 and the insurgence of point defects, such as oxygen vacancies and intermixed cations. These defects usually reside in the conduction channel and are responsible for a decreased electronic mobility. In this work we use an amorphous WO3 overlayer to control the defect formation and obtain an increased electron mobility and effective mass in WO3/LaAlO3/SrTiO3 heterostructures. The studied system shows a sharp insulator-to-metal transition as a function of both LaAlO3 and WO3 layer thickness. Low-temperature magnetotransport reveals a strong magnetoresistance reaching 900% at 10 T and 1.5 K, the presence of multiple conduction channels with carrier mobility up to 80 000 cm2/Vs and an unusually high effective mass of 5.6 me. The amorphous character of the WO3 overlayer makes this a versatile approach for defect control at oxide interfaces, which could be applied to other heterestrostures disregarding the constraints imposed by crystal symmetry.

Charge density waves (CDW) and their concomitant periodic lattice distortions (PLD) govern the electronic properties in many layered transition-metal dichalcogenides. In particular, 1T-TaS2 undergoes a metal-to-insulator phase transition as the PLD becomes commensurate with the crystal lattice. Here we directly image PLDs of the nearly-commensurate (NC) and commensurate (C) phases in thin exfoliated 1T-TaS2 using atomic resolution scanning transmission electron microscopy at room and cryogenic temperature. At low temperatures, we observe commensurate PLD superstructures, suggesting ordering of the CDWs both in- and out-of-plane. In addition, we discover stacking transitions in the atomic lattice that occur via one bond length shifts. Interestingly, the NC PLDs exist inside both the stacking domains and their boundaries. Transitions in stacking order are expected to create fractional shifts in the CDW between layers and may be another route to manipulate electronic phases in layered dichalcogenides., Comment: 4 figures in Proceedings of the National Academy of Sciences of the United States of America, 2016

We report the growth of thin films of the mixed valence compound YbAl$_{3}$ on MgO using molecular-beam epitaxy. Employing an aluminum buffer layer, epitaxial (001) films can be grown with sub-nm surface roughness. Using x-ray diffraction, in situ low-energy electron diffraction and aberration-corrected scanning transmission electron microscopy we establish that the films are ordered in the bulk as well as at the surface. Our films show a coherence temperature of 37 K, comparable to that reported for bulk single crystals. Photoelectron spectroscopy reveals contributions from both $\textit{f}^{13}$ and $\textit{f}^{12}$ final states establishing that YbAl$_{3}$ is a mixed valence compound and shows the presence of a Kondo Resonance peak near the Fermi-level., Comment: 4 pages, 6 figures

Complex oxide heterostructures display some of the most chemically abrupt, atomically precise interfaces, which is advantageous when constructing new interface phases with emergent properties by juxtaposing incompatible ground states. One might assume that atomically precise interfaces result from stoichiometric growth, but here we show that the most precise control is obtained for non-stoichiometric growth where differing surface energies can be compensated by surfactant-like effects. For the precise growth of Sr$_{n+1}$Ti$_n$O$_{3n+1}$ Ruddlesden-Popper (RP) phases, stoichiometric deposition leads to the loss of the first RP rock-salt double layer, but growing with a strontium-rich surface layer restores the bulk stoichiometry and ordering of the subsurface RP structure. Our results dramatically expand the materials that can be prepared in epitaxial heterostructures with precise interface control---from just the $n=\infty$ end members (perovskites) to the entire RP family---enabling the exploration of novel quantum phenomena at a richer variety of oxide interfaces., Comment: 9 pages, 5 figures

With nearly complete spin polarization, the ferromagnetic semiconductor europium monoxide could enable next-generation spintronic devices by providing efficient ohmic spin injection into silicon. Spin injection is greatly affected by the quality of the interface between the injector and silicon. Here, we use atomic-resolution scanning transmission electron microscopy in conjunction with electron energy loss spectroscopy to directly image and chemically characterize a series of EuO|Si and EuO|YAlO3 interfaces fabricated using different growth conditions. We identify the presence of europium silicides and regions of disorder at the EuO|Si interfaces, imperfections that could significantly reduce spin injection efficiencies via spin-flip scattering.