An official website of the United States government
Abstract Mott metal–insulator transitions possess electronic, magnetic, and structural degrees of freedom promising next‐generation energy‐efficient electronics. A previously unknown, hierarchically ordered, and anisotropic supercrystal state is reported and its intrinsic formation characterized in‐situ during a Mott transition in a Ca2RuO4thin film. Machine learning‐assisted X‐ray nanodiffraction together with cryogenic electron microscopy reveal multi‐scale periodic domain formation at and below the film transition temperature (TFilm ≈ 200–250 K) and a separate anisotropic spatial structure at and aboveTFilm. Local resistivity measurements imply an intrinsic coupling of the supercrystal orientation to the material's anisotropic conductivity. These findings add a new degree of complexity to the physical understanding of Mott transitions, opening opportunities for designing materials with tunable electronic properties.
more »
« less
Real-space imaging of periodic nanotextures in thin films via phasing of diffraction data
New properties and exotic quantum phenomena can form due to periodic nanotextures, including Moire patterns, ferroic domains, and topologically protected magnetization and polarization textures. Despite the availability of powerful tools to characterize the atomic crystal structure, the visualization of nanoscale strain-modulated structural motifs remains challenging. Here, we develop nondestructive real-space imaging of periodic lattice distortions in thin epitaxial films and report an emergent periodic nanotexture in a Mott insulator. Specifically, we combine iterative phase retrieval with unsupervised machine learning to invert the diffuse scattering pattern from conventional X-ray reciprocal-space maps into real-space images of crystalline displacements. Our imaging in PbTiO3/SrTiO3superlattices exhibiting checkerboard strain modulation substantiates published phase-field model calculations. Furthermore, the imaging of biaxially strained Mott insulator Ca2RuO4reveals a strain-induced nanotexture comprised of nanometer-thin metallic-structure wires separated by nanometer-thin Mott-insulating-structure walls, as confirmed by cryogenic scanning transmission electron microscopy (cryo-STEM). The nanotexture in Ca2RuO4film is induced by the metal-to-insulator transition and has not been reported in bulk crystals. We expect the phasing of diffuse X-ray scattering from thin crystalline films in combination with cryo-STEM to open a powerful avenue for discovering, visualizing, and quantifying the periodic strain-modulated structures in quantum materials.
more »
« less
- PAR ID:
- 10488978
- Publisher / Repository:
- National Academy of Sciences
- Date Published:
- Journal Name:
- Proceedings of the National Academy of Sciences
- Volume:
- 120
- Issue:
- 28
- ISSN:
- 0027-8424
- Page Range / eLocation ID:
- e2303312120
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Cobalt oxides have long been understood to display intriguing phenomena known as spin-state crossovers, where the cobalt ion spin changes vs. temperature, pressure, etc. A very different situation was recently uncovered in praseodymium-containing cobalt oxides, where a first-order coupled spin-state/structural/metal-insulator transition occurs, driven by a remarkable praseodymium valence transition. Such valence transitions, particularly when triggering spin-state and metal-insulator transitions, offer highly appealing functionality, but have thus far been confined to cryogenic temperatures in bulk materials (e.g., 90 K in Pr1-xCaxCoO3). Here, we show that in thin films of the complex perovskite (Pr1-yYy)1-xCaxCoO3-δ, heteroepitaxial strain tuning enables stabilization of valence-driven spin-state/structural/metal-insulator transitions to at least 291 K, i.e., around room temperature. The technological implications of this result are accompanied by fundamental prospects, as complete strain control of the electronic ground state is demonstrated, from ferromagnetic metal under tension to nonmagnetic insulator under compression, thereby exposing a potential novel quantum critical point.more » « less
-
Abstract Electroactive polymer thin films undergo repeated reversible structural change during operation in electrochemical applications. While synchrotron X‐ray scattering is powerful for the characterization of stand‐alone and ex situ organic thin films, in situ/operando structural characterization has been underutilized—in large part due to complications arising from supporting electrolyte scattering. This has greatly hampered the development of application relevant structure property relationships. Therefore, a new methodology for in situ/operando X‐ray characterization that separates the incident and scattered X‐ray beam path from the electrolyte is developed. As a proof of concept, the operando structural characterization of weakly‐scattering, organic mixed conducting thin films in an aqueous electrolyte environment is demonstrated, accessing previously unexplored changes in the π‐π peak and diffuse scatter, while capturing the solvent swollen thin film structure which is inaccessible in previous ex situ studies. These in situ/operando measurements improve the sensitivity to structural changes, capturing minute changes not possible ex situ, and have multimodal potential such as combined Raman measurements that also serve to validate the true in situ/operando conditions of the cell. Finally, new directions enabled by this in situ/operando cell design are examined and state of the art measurements are compared.more » « less
-
Functional properties of transition-metal oxides strongly depend on crystallographic defects; crystallographic lattice deviations can affect ionic diffusion and adsorbate binding energies. Scanning x-ray nanodiffraction enables imaging of local structural distortions across an extended spatial region of thin samples. Yet, localized lattice distortions remain challenging to detect and localize using nanodiffraction, due to their weak diffuse scattering. Here, we apply an unsupervised machine learning clustering algorithm to isolate the low-intensity diffuse scattering in as-grown and alkaline-treated thin epitaxially strained SrIrO3 films. We pinpoint the defect locations, find additional strain variation in the morphology of electrochemically cycled SrIrO3, and interpret the defect type by analyzing the diffraction profile through clustering. Our findings demonstrate the use of a machine learning clustering algorithm for identifying and characterizing hard-to-find crystallographic defects in thin films of electrocatalysts and highlight the potential to study electrochemical reactions at defect sites in operando experiments.more » « less
-
Abstract Search for novel electronically ordered states of matter emerging near quantum phase transitions is an intriguing frontier of condensed matter physics. In ruthenates, the interplay between Coulomb correlations among the 4delectronic states and their spin-orbit interactions, lead to complex forms of electronic phenomena. Here we investigate the double layered Sr3(Ru1−xMnx)2O7and its doping-induced quantum phase transition from a metal to an antiferromagnetic Mott insulator. Using spectroscopic imaging with the scanning tunneling microscope, we visualize the evolution of the electronic states in real- and momentum-space. We find a partial-gap at the Fermi energy that develops with doping to form a weak Mott insulating state. Near the quantum phase transition, we discover a spatial electronic reorganization into a commensurate checkerboard charge order. These findings bear a resemblance to the universal charge order in the pseudogap phase of cuprates and demonstrate the ubiquity of charge order that emanates from doped Mott insulators.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1073/pnas.2303312120
