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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 extensive hydrogen incorporation is not generally required to achieve a superconducting state in layered square-planar nickelates., (© 2024. This is a U.S. Government work and not under copyright protection in the US; foreign copyright protection may apply.)

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., (© 2024. The Author(s).)

The charge density wave 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 at cryogenic temperature, and directly visualize the changing charge density wave structure with nanoscale spatial resolution and down to 300 μs temporal resolution. We show that the pulse-induced transition is driven by Joule heating, and that the pulse-induced state corresponds to the nearly commensurate and incommensurate charge density wave phases, depending on the applied voltage amplitude. With our in operando cryogenic electron microscopy experiments, we directly correlate the charge density wave 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., (© 2023. The Author(s).)

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 ferroelectric Weyl semimetal T d phase and the higher-order topological insulator 1T' phase. However, in thin flakes of MoTe 2 , it is unclear if the layer stacking follows the T d , 1T', or an alternative stacking sequence. Here, we use atomic-resolution scanning transmission electron microscopy to directly visualize the MoTe 2 layer stacking. In thin flakes, we observe highly disordered stacking, with nanoscale 1T' and T d domains, as well as alternative stacking arrangements not found in the bulk. We attribute these findings to intrinsic confinement effects on the MoTe 2 stacking-dependent free energy. Our results are important for the understanding of exotic physics displayed in MoTe 2 flakes. More broadly, this work suggests c-axis confinement as a method to influence layer stacking in other 2D materials., (© 2023. Springer Nature Limited.)

Nickel-based superconductors provide a long-awaited experimental platform to explore possible cuprate-like superconductivity. Despite similar crystal structure and d electron filling, however, superconductivity in nickelates has thus far only been stabilized in thin-film geometry, raising questions about the polar interface between substrate and thin film. Here 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 polar discontinuity. We explore the effects of oxygen occupancy, hole doping and cation structure to disentangle the contributions of each for reducing interface charge density. Resolving the non-trivial interface structure will be instructive for future synthesis of nickelate films on other substrates and in vertical heterostructures., (© 2023. The Author(s), under exclusive licence to Springer Nature Limited.)

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., (© 2023. The Author(s).)

Spontaneous hierarchical self-organization of nanometre-scale subunits into higher-level complex structures is ubiquitous in nature. The creation of synthetic nanomaterials that mimic the self-organization of complex superstructures commonly seen in biomolecules has proved challenging due to the lack of biomolecule-like building blocks that feature versatile, programmable interactions to render structural complexity. In this study, highly aligned structures are obtained from an organic-inorganic mesophase composed of monodisperse Cd 37 S 18 magic-size cluster building blocks. Impressively, structural alignment spans over six orders of magnitude in length scale: nanoscale magic-size clusters arrange into a hexagonal geometry organized inside micrometre-sized filaments; self-assembly of these filaments leads to fibres that then organize into uniform arrays of centimetre-scale bands with well-defined surface periodicity. Enhanced patterning can be achieved by controlling processing conditions, resulting in bullseye and 'zigzag' stacking patterns with periodicity in two directions. Overall, we demonstrate that colloidal nanomaterials can exhibit a high level of self-organization behaviour at macroscopic-length scales., (© 2022. The Author(s), under exclusive licence to Springer Nature Limited.)

Since the discovery of high-temperature superconductivity in copper oxide materials 1 , there have been sustained efforts to both understand the origins of this phase and discover new cuprate-like superconducting materials 2 . 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 (ref. 3 ). 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 = ∞) 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 ~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 behaviour. In engineering a distinct superconducting nickelate, we identify the square-planar nickelates as a new family of superconductors that can be tuned via both doping and dimensionality., (© 2021. The Author(s), under exclusive licence to Springer Nature Limited.)

Compelling evidence suggests distinct correlated electron behavior may exist only in clean 2D materials such as 1T-TaS 2 . 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., (© 2022. The Author(s).)

The self-organization of strongly interacting electrons into superlattice structures underlies the properties of many quantum materials. How these electrons arrange within the superlattice dictates what symmetries are broken and what ground states are stabilized. Here we show that cryogenic scanning transmission electron microscopy (cryo-STEM) enables direct mapping of local symmetries and order at the intra-unit-cell level in the model charge-ordered system Nd 1/2 Sr 1/2 MnO 3 . In addition to imaging the prototypical site-centered charge order, we discover the nanoscale coexistence of an exotic intermediate state which mixes site and bond order and breaks inversion symmetry. We further show that nonlinear coupling of distinct lattice modes controls the selection between competing ground states. The results demonstrate the importance of lattice coupling for understanding and manipulating the character of electronic self-organization and that cryo-STEM can reveal local order in strongly correlated systems at the atomic scale.

The capacity of soil as a carbon (C) sink is mediated by interactions between organic matter and mineral phases. However, previously proposed layered accumulation of organic matter within aggregate organo-mineral microstructures has not yet been confirmed by direct visualization at the necessary nanometer-scale spatial resolution. Here, we identify disordered micrometer-size organic phases rather than previously reported ordered gradients in C functional groups. Using cryo-electron microscopy with electron energy loss spectroscopy (EELS), we show organo-organic interfaces in contrast to exclusively organo-mineral interfaces. Single-digit nanometer-size layers of C forms were detected at the organo-organic interface, showing alkyl C and nitrogen (N) enrichment (by 4 and 7%, respectively). At the organo-mineral interface, 88% (72-92%) and 33% (16-53%) enrichment of N and oxidized C, respectively, indicate different stabilization processes than at organo-organic interfaces. However, N enrichment at both interface types points towards the importance of N-rich residues for greater C sequestration.

Electrochemical cells that utilize lithium and sodium anodes are under active study for their potential to enable high-energy batteries. Liquid and solid polymer electrolytes based on ether chemistry are among the most promising choices for rechargeable lithium and sodium batteries. However, uncontrolled anionic polymerization of these electrolytes at low anode potentials and oxidative degradation at working potentials of the most interesting cathode chemistries have led to a quite concession in the field that solid-state or flexible batteries based on polymer electrolytes can only be achieved in cells based on low- or moderate-voltage cathodes. Here, we show that cationic chain transfer agents can prevent degradation of ether electrolytes by arresting uncontrolled polymer growth at the anode. We also report that cathode electrolyte interphases composed of preformed anionic polymers and supramolecules provide a fundamental strategy for extending the high voltage stability of ether-based electrolytes to potentials well above conventionally accepted limits.

In charge-ordered phases, broken translational symmetry emerges from couplings between charge, spin, lattice, or orbital degrees of freedom, giving rise to remarkable phenomena such as colossal magnetoresistance and metal-insulator transitions. The role of the lattice in charge-ordered states remains particularly enigmatic, soliciting characterization of the microscopic lattice behavior. Here we directly map picometer scale periodic lattice displacements at individual atomic columns in the room temperature charge-ordered manganite Bi 0.35 Sr 0.18 Ca 0.47 MnO 3 using aberration-corrected scanning transmission electron microscopy. We measure transverse, displacive lattice modulations of the cations, distinct from existing manganite charge-order models. We reveal locally unidirectional striped domains as small as ~5 nm, despite apparent bidirectionality over larger length scales. Further, we observe a direct link between disorder in one lattice modulation, in the form of dislocations and shear deformations, and nascent order in the perpendicular modulation. By examining the defects and symmetries of periodic lattice displacements near the charge ordering phase transition, we directly visualize the local competition underpinning spatial heterogeneity in a complex oxide.

Secondary batteries based on earth-abundant sodium metal anodes are desirable for both stationary and portable electrical energy storage. Room-temperature sodium metal batteries are impractical today because morphological instability during recharge drives rough, dendritic electrodeposition. Chemical instability of liquid electrolytes also leads to premature cell failure as a result of parasitic reactions with the anode. Here we use joint density-functional theoretical analysis to show that the surface diffusion barrier for sodium ion transport is a sensitive function of the chemistry of solid-electrolyte interphase. In particular, we find that a sodium bromide interphase presents an exceptionally low energy barrier to ion transport, comparable to that of metallic magnesium. We evaluate this prediction by means of electrochemical measurements and direct visualization studies. These experiments reveal an approximately three-fold reduction in activation energy for ion transport at a sodium bromide interphase. Direct visualization of sodium electrodeposition confirms large improvements in stability of sodium deposition at sodium bromide-rich interphases.The chemistry at the interface between electrolyte and electrode plays a critical role in determining battery performance. Here, the authors show that a NaBr enriched solid-electrolyte interphase can lower the surface diffusion barrier for sodium ions, enabling stable electrodeposition.

Considerable progress in the fabrication of quasicrystals demonstrates that they can be realized in a broad range of materials. However, the development of chemistries enabling direct experimental observation of early quasicrystal growth pathways remains challenging. Here, we report the synthesis of four surfactant-directed mesoporous silica nanoparticle structures, including dodecagonal quasicrystalline nanoparticles, as a function of micelle pore expander concentration or stirring rate. We demonstrate that the early formation stages of dodecagonal quasicrystalline mesoporous silica nanoparticles can be preserved, where precise control of mesoporous silica nanoparticle size down to <30 nm facilitates comparison between mesoporous silica nanoparticles and simulated single-particle growth trajectories beginning with a single tiling unit. Our results reveal details of the building block size distributions during early growth and how they promote quasicrystal formation. This work identifies simple synthetic parameters, such as stirring rate, that may be exploited to design other quasicrystal-forming self-assembly chemistries and processes.Probing the growth pathways of quasicrystalline materials, where tiling units arrange with local but no long-range order, remains challenging. Here, the authors demonstrate that dodecagonal tiling of mesoporous silica nanoparticles occurs via irreversible packing of micelles with non-uniform size distribution.

The ability to create and manipulate materials in two-dimensional (2D) form has repeatedly had transformative impact on science and technology. In parallel with the exfoliation and stacking of intrinsically layered crystals, atomic-scale thin film growth of complex materials has enabled the creation of artificial 2D heterostructures with novel functionality and emergent phenomena, as seen in perovskite heterostructures. However, separation of these layers from the growth substrate has proved challenging, limiting the manipulation capabilities of these heterostructures with respect to exfoliated materials. Here we present a general method to create freestanding perovskite membranes. The key is the epitaxial growth of water-soluble Sr 3 Al 2 O 6 on perovskite substrates, followed by in situ growth of films and heterostructures. Millimetre-size single-crystalline membranes are produced by etching the Sr 3 Al 2 O 6 layer in water, providing the opportunity to transfer them to arbitrary substrates and integrate them with heterostructures of semiconductors and layered compounds.

Epitaxial attachment of quantum dots into ordered superlattices enables the synthesis of quasi-two-dimensional materials that theoretically exhibit features such as Dirac cones and topological states, and have major potential for unprecedented optoelectronic devices. Initial studies found that disorder in these structures causes localization of electrons within a few lattice constants, and highlight the critical need for precise structural characterization and systematic assessment of the effects of disorder on transport. Here we fabricated superlattices with the quantum dots registered to within a single atomic bond length (limited by the polydispersity of the quantum dot building blocks), but missing a fraction (20%) of the epitaxial connections. Calculations of the electronic structure including the measured disorder account for the electron localization inferred from transport measurements. The calculations also show that improvement of the epitaxial connections will lead to completely delocalized electrons and may enable the observation of the remarkable properties predicted for these materials.

The concept 'the interface is the device' is embodied in a wide variety of interfacial electronic phenomena and associated applications in oxide materials, ranging from catalysts and clean energy systems to emerging multifunctional devices. Many device properties are defined by the band alignment, which is often influenced by interface dipoles. On the other hand, the ability to purposefully create and control interface dipoles is a relatively unexplored degree of freedom for perovskite oxides, which should be particularly effective for such ionic materials. Here we demonstrate tuning the band alignment in perovskite metal-semiconductor heterojunctions over a broad range of 1.7 eV. This is achieved by the insertion of positive or negative charges at the interface, and the resultant dipole formed by the induced screening charge. This approach can be broadly used in applications where decoupling the band alignment from the constituent work functions and electron affinities can enhance device functionality.

Electronic changes at polar interfaces between transition metal oxides offer the tantalizing possibility to stabilize novel ground states yet can also cause unintended reconstructions in devices. The nature of these interfacial reconstructions should be qualitatively different for metallic and insulating films as the electrostatic boundary conditions and compensation mechanisms are distinct. Here we directly quantify with atomic-resolution the charge distribution for manganite-titanate interfaces traversing the metal-insulator transition. By measuring the concentration and valence of the cations, we find an intrinsic interfacial electronic reconstruction in the insulating films. The total charge observed for the insulating manganite films quantitatively agrees with that needed to cancel the polar catastrophe. As the manganite becomes metallic with increased hole doping, the total charge build-up and its spatial range drop substantially. Direct quantification of the intrinsic charge transfer and spatial width should lay the framework for devices harnessing these unique electronic phases.

The interplay between antagonistic superconductivity and ferromagnetism has been a interesting playground to explore the interaction between competing ground states. Although this effect in systems of conventional superconductors is better understood, the framework of the proximity effect at complex-oxide-based superconductor/ferromagnet interfaces is not so clear. The main difficulty originates from the lack of experimental tools capable of probing the interfaces directly with high spatial resolution. Here we harness cross-sectional scanning tunnelling microscopy and spectroscopy together with atomic-resolution electron microscopy to understand the buried interfaces between cuprate and manganite layers. The results show that the fundamental length scale of the electronic evolution between YBa2Cu3O(7-δ) (YBCO) and La2/3Ca1/3MnO3 (LCMO) is confined to the subnanometre range. Our findings provide a complete and direct microscopic picture of the electronic transition across the YBCO/LCMO interfaces, which is an important step towards understanding the competition between ferromagnetism and superconductivity in complex-oxide heterostructures.