Photonically active bowtie nanoassemblies with chirality continuum.

Chirality is a geometrical property described by continuous mathematical functions1-5. However, in chemical disciplines, chirality is often treated as a binary left or right characteristic of molecules rather than a continuity of chiral shapes. Although they are theoretically possible, a family of stable chemical structures with similar shapes and progressively tuneable chirality is yet unknown. Here we show that nanostructured microparticles with an anisotropic bowtie shape display chirality continuum and can be made with widely tuneable twist angle, pitch, width, thickness and length. The self-limited assembly of the bowties enables high synthetic reproducibility, size monodispersity and computational predictability of their geometries for different assembly conditions6. The bowtie nanoassemblies show several strong circular dichroism peaks originating from absorptive and scattering phenomena. Unlike classical chiral molecules, these particles show a continuum of chirality measures2 that correlate exponentially with the spectral positions of the circular dichroism peaks. Bowtie particles with variable polarization rotation were used to print photonically active metasurfaces with spectrally tuneable positive or negative polarization signatures for light detection and ranging (LIDAR) devices.

Magnetic anisotropy reversal driven by structural symmetry-breaking in monolayer α-RuCl3.

Layered α-RuCl3 is a promising material to potentially realize the long-sought Kitaev quantum spin liquid with fractionalized excitations. While evidence of this state has been reported under a modest in-plane magnetic field, such behaviour is largely inconsistent with theoretical expectations of spin liquid phases emerging only in out-of-plane fields. These predicted field-induced states have been largely out of reach due to the strong easy-plane anisotropy of bulk crystals, however. We use a combination of tunnelling spectroscopy, magnetotransport, electron diffraction and ab initio calculations to study the layer-dependent magnons, magnetic anisotropy, structure and exchange coupling in atomically thin samples. Due to picoscale distortions, the sign of the average off-diagonal exchange changes in monolayer α-RuCl3, leading to a reversal of spin anisotropy to easy-axis anisotropy, while the Kitaev interaction is concomitantly enhanced. Our work opens the door to the possible exploration of Kitaev physics in the true two-dimensional limit.

The mesoscale order of nacreous pearls.

A pearl's distinguished beauty and toughness are attributable to the periodic stacking of aragonite tablets known as nacre. Nacre has naturally occurring mesoscale periodicity that remarkably arises in the absence of discrete translational symmetry. Gleaning the inspiring biomineral design of a pearl requires quantifying its structural coherence and understanding the stochastic processes that influence formation. By characterizing the entire structure of pearls (∼3 mm) in a cross-section at high resolution, we show that nacre has medium-range mesoscale periodicity. Self-correcting growth mechanisms actively remedy disorder and topological defects of the tablets and act as a countervailing process to long-range disorder. Nacre has a correlation length of roughly 16 tablets (∼5.5 µm) despite persistent fluctuations and topological defects. For longer distances (>25 tablets , ∼8.5 µm), the frequency spectrum of nacre tablets follows [Formula: see text] behavior, suggesting that growth is coupled to external stochastic processes-a universality found across disparate natural phenomena, which now includes pearls.

Autonomous Electron Tomography Reconstruction with Machine Learning.

Modern electron tomography has progressed to higher resolution at lower doses by leveraging compressed sensing (CS) methods that minimize total variation (TV). However, these sparsity-emphasized reconstruction algorithms introduce tunable parameters that greatly influence the reconstruction quality. Here, Pareto front analysis shows that high-quality tomograms are reproducibly achieved when TV minimization is heavily weighted. However, in excess, CS tomography creates overly smoothed three-dimensional (3D) reconstructions. Adding momentum to the gradient descent during reconstruction reduces the risk of over-smoothing and better ensures that CS is well behaved. For simulated data, the tedious process of tomography parameter selection is efficiently solved using Bayesian optimization with Gaussian processes. In combination, Bayesian optimization with momentum-based CS greatly reduces the required compute time-an 80% reduction was observed for the 3D reconstruction of SrTiO3 nanocubes. Automated parameter selection is necessary for large-scale tomographic simulations that enable the 3D characterization of a wider range of inorganic and biological materials.

Atomically engineered ferroic layers yield a room-temperature magnetoelectric multiferroic.

Materials that exhibit simultaneous order in their electric and magnetic ground states hold promise for use in next-generation memory devices in which electric fields control magnetism. Such materials are exceedingly rare, however, owing to competing requirements for displacive ferroelectricity and magnetism. Despite the recent identification of several new multiferroic materials and magnetoelectric coupling mechanisms, known single-phase multiferroics remain limited by antiferromagnetic or weak ferromagnetic alignments, by a lack of coupling between the order parameters, or by having properties that emerge only well below room temperature, precluding device applications. Here we present a methodology for constructing single-phase multiferroic materials in which ferroelectricity and strong magnetic ordering are coupled near room temperature. Starting with hexagonal LuFeO3-the geometric ferroelectric with the greatest known planar rumpling-we introduce individual monolayers of FeO during growth to construct formula-unit-thick syntactic layers of ferrimagnetic LuFe2O4 (refs 17, 18) within the LuFeO3 matrix, that is, (LuFeO3)m/(LuFe2O4)1 superlattices. The severe rumpling imposed by the neighbouring LuFeO3 drives the ferrimagnetic LuFe2O4 into a simultaneously ferroelectric state, while also reducing the LuFe2O4 spin frustration. This increases the magnetic transition temperature substantially-from 240 kelvin for LuFe2O4 (ref. 18) to 281 kelvin for (LuFeO3)9/(LuFe2O4)1. Moreover, the ferroelectric order couples to the ferrimagnetism, enabling direct electric-field control of magnetism at 200 kelvin. Our results demonstrate a design methodology for creating higher-temperature magnetoelectric multiferroics by exploiting a combination of geometric frustration, lattice distortions and epitaxial engineering.

Ultrafast Modulations and Detection of a Ferro-Rotational Charge Density Wave Using Time-Resolved Electric Quadrupole Second Harmonic Generation.

We show the ferro-rotational nature of the commensurate charge density wave (CCDW) in 1T-TaS_{2} and track its dynamic modulations by temperature-dependent and time-resolved electric quadrupole rotation anisotropy-second harmonic generation (EQ RA-SHG), respectively. The ultrafast modulations manifest as the breathing and the rotation of the EQ RA-SHG patterns at three frequencies around the reported single CCDW amplitude mode frequency. A sudden shift of the triplet frequencies and a dramatic increase in the breathing and rotation magnitude further reveal a photoinduced transient CDW phase across a critical pump fluence of ∼0.5 mJ/cm^{2}.

Nature and evolution of incommensurate charge order in manganites visualized with cryogenic scanning transmission electron microscopy.

Incommensurate charge order in hole-doped oxides is intertwined with exotic phenomena such as colossal magnetoresistance, high-temperature superconductivity, and electronic nematicity. Here, we map, at atomic resolution, the nature of incommensurate charge-lattice order in a manganite using scanning transmission electron microscopy at room temperature and cryogenic temperature ([Formula: see text]93 K). In diffraction, the ordering wave vector changes upon cooling, a behavior typically associated with incommensurate order. However, using real space measurements, we discover that the ordered state forms lattice-locked regions over a few wavelengths interspersed with phase defects and changing periodicity. The cations undergo picometer-scale ([Formula: see text]6 pm to 11 pm) transverse displacements, suggesting that charge-lattice coupling is strong. We further unearth phase inhomogeneity in the periodic lattice displacements at room temperature, and emergent phase coherence at 93 K. Such local phase variations govern the long-range correlations of the charge-ordered state and locally change the periodicity of the modulations, resulting in wave vector shifts in reciprocal space. These atomically resolved observations underscore the importance of lattice coupling and phase inhomogeneity, and provide a microscopic explanation for putative "incommensurate" order in hole-doped oxides.

Atomic and electronic reconstruction at the van der Waals interface in twisted bilayer graphene.

Control of the interlayer twist angle in two-dimensional van der Waals (vdW) heterostructures enables one to engineer a quasiperiodic moiré superlattice of tunable length scale1-8. In twisted bilayer graphene, the simple moiré superlattice band description suggests that the electronic bandwidth can be tuned to be comparable to the vdW interlayer interaction at a 'magic angle'9, exhibiting strongly correlated behaviour. However, the vdW interlayer interaction can also cause significant structural reconstruction at the interface by favouring interlayer commensurability, which competes with the intralayer lattice distortion10-16. Here we report atomic-scale reconstruction in twisted bilayer graphene and its effect on the electronic structure. We find a gradual transition from an incommensurate moiré structure to an array of commensurate domains with soliton boundaries as we decrease the twist angle across the characteristic crossover angle, θc ≈ 1°. In the solitonic regime (θ < θc) where the atomic and electronic reconstruction become significant, a simple moiré band description breaks down and the secondary Dirac bands appear. On applying a transverse electric field, we observe electronic transport along the network of one-dimensional topological channels that surround the alternating triangular gapped domains. Atomic and electronic reconstruction at the vdW interface provide a new pathway to engineer the system with continuous tunability.

Optimal STEM Convergence Angle Selection Using a Convolutional Neural Network and the Strehl Ratio.

The selection of the correct convergence angle is essential for achieving the highest resolution imaging in scanning transmission electron microscopy (STEM). The use of poor heuristics, such as Rayleigh's quarter-phase rule, to assess probe quality and uncertainties in the measurement of the aberration function results in the incorrect selection of convergence angles and lower resolution. Here, we show that the Strehl ratio provides an accurate and efficient way to calculate criteria for evaluating the probe size for STEM. A convolutional neural network trained on the Strehl ratio is shown to outperform experienced microscopists at selecting a convergence angle from a single electron Ronchigram using simulated datasets. Generating tens of thousands of simulated Ronchigram examples, the network is trained to select convergence angles yielding probes on average 85% nearer to optimal size at millisecond speeds (0.02% of human assessment time). Qualitative assessment on experimental Ronchigrams with intentionally introduced aberrations suggests that trends in the optimal convergence angle size are well modeled but high accuracy requires a high number of training datasets. This near-immediate assessment of Ronchigrams using the Strehl ratio and machine learning highlights a viable path toward the rapid, automated alignment of aberration-corrected electron microscopes.

Contamination of TEM Holders Quantified and Mitigated With the Open-Hardware, High-Vacuum Bakeout System.

Hydrocarbon contamination plagues high-resolution and analytical electron microscopy by depositing carbonaceous layers onto surfaces during electron irradiation, which can render carefully prepared specimens useless. Increased specimen thickness degrades resolution with beam broadening alongside loss of contrast. The large inelastic cross-section of carbon hampers accurate atomic species detection. Oxygen and water molecules pose problems of lattice damage by chemically etching the specimen during imaging. These constraints on high-resolution and spectroscopic imaging demand clean, high-vacuum microscopes with dry pumps. Here, we present an open-hardware design of a high-vacuum manifold for transmission electron microscopy (TEM) holders to mitigate hydrocarbon and residual species exposure. We quantitatively show that TEM holders are inherently dirty and introduce a range of unwanted chemical species. Overnight storage in our manifold reduces contaminants by one to two orders of magnitude and promotes two to four times faster vacuum recovery. A built-in bakeout system further reduces contaminants partial pressure to below 10−10 hPa (Torr) (approximately four orders of magnitude down from ambient storage) and alleviates monolayer adsorption during a typical TEM experiment. We determine that bakeout of TEM holder with specimen held therein is the optimal cleaning method. Our high-vacuum manifold design is published with open-source blueprints, parts, and cost list.

Deep Ultraviolet Luminescence Due to Extreme Confinement in Monolayer GaN/Al(Ga)N Nanowire and Planar Heterostructures.

We present experimental results confirming extreme quantum confinement in GaN/AlxGa1-xN (x = 0.65 and 1.0) nanowire and planar heterostructures, where the GaN layer thickness is of the order of a monolayer. The results were obtained from temperature- and excitation-dependent and time-resolved photoluminescence measurements. In the GaN/AlN nanowire heterostructure array sample, the measured emission peak at 300 K is ∼5.18-5.28 eV. This is in excellent agreement with the calculated optical gap of 5.23 eV and 160-260 meV below the calculated electronic gap of 5.44 eV, suggesting that the observed emission is excitonic in nature with an exciton binding energy of ∼160-260 meV. Similarly, in the monolayer GaN/Al0.65Ga0.35N planar heterostructure, the measured emission peak at 300 K is 4.785 eV and in good agreement with the calculated optical gap of 4.68 eV and 95 meV below the calculated electronic gap of 4.88 eV. The estimated exciton binding energy is 95 meV and in close agreement with our theoretical calculations. Excitation-dependent and time-resolved photoluminescence data support the presence of excitonic transitions. Our results indicate that deep-ultraviolet excitonic light sources and microcavity devices can be realized with heterostructures incorporating monolayer-thick GaN.

Atomic lattice disorder in charge-density-wave phases of exfoliated dichalcogenides (1T-TaS2).

Charge-density waves (CDWs) and their concomitant periodic lattice distortions (PLDs) govern the electronic properties in several 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.

Removing Stripes, Scratches, and Curtaining with Nonrecoverable Compressed Sensing.

Highly-directional image artifacts such as ion mill curtaining, mechanical scratches, or image striping from beam instability degrade the interpretability of micrographs. These unwanted, aperiodic features extend the image along a primary direction and occupy a small wedge of information in Fourier space. Deleting this wedge of data replaces stripes, scratches, or curtaining, with more complex streaking and blurring artifacts-known within the tomography community as "missing wedge" artifacts. Here, we overcome this problem by recovering the missing region using total variation minimization, which leverages image sparsity-based reconstruction techniques-colloquially referred to as compressed sensing (CS)-to reliably restore images corrupted by stripe-like features. Our approach removes beam instability, ion mill curtaining, mechanical scratches, or any stripe features and remains robust at low signal-to-noise. The success of this approach is achieved by exploiting CS's inability to recover directional structures that are highly localized and missing in Fourier Space.

Structure and control of charge density waves in two-dimensional 1T-TaS2.

The layered transition metal dichalcogenides host a rich collection of charge density wave phases in which both the conduction electrons and the atomic structure display translational symmetry breaking. Manipulating these complex states by purely electronic methods has been a long-sought scientific and technological goal. Here, we show how this can be achieved in 1T-TaS2 in the 2D limit. We first demonstrate that the intrinsic properties of atomically thin flakes are preserved by encapsulation with hexagonal boron nitride in inert atmosphere. We use this facile assembly method together with transmission electron microscopy and transport measurements to probe the nature of the 2D state and show that its conductance is dominated by discommensurations. The discommensuration structure can be precisely tuned in few-layer samples by an in-plane electric current, allowing continuous electrical control over the discommensuration-melting transition in 2D.