Design Rules, Accurate Enthalpy Prediction, and Synthesis of Stoichiometric Eu3+ Quantum Memory Candidates.

Stoichiometric Eu3+ compounds have recently shown promise for building dense, optically addressable quantum memory as the cations' long nuclear spin coherence times and shielded 4f electron optical transitions provide reliable memory platforms. Implementing such a system, though, requires ultranarrow, inhomogeneous linewidth compounds. Finding this rare linewidth behavior within a wide range of potential chemical spaces remains difficult, and while exploratory synthesis is often guided by density functional theory (DFT) calculations, lanthanides' 4f electrons pose unique challenges for stability predictions. Here, we report DFT procedures that reliably reproduce known phase diagrams and correctly predict two experimentally realized quantum memory candidates. We are the first to synthesize the double perovskite halide Cs2NaEuF6. It is an air-stable compound with a calculated band gap of 5.0 eV that surrounds Eu3+ with mononuclidic elements, which are desirable for avoiding inhomogeneous linewidth broadening. We also analyze computational database entries to identify phosphates and iodates as the next generation of chemical spaces for stoichiometric quantum memory system studies. This work identifies new candidate platforms for exploring chemical effects on quantum memory candidates' inhomogeneous linewidth while also providing a framework for screening Eu3+ compound stability with DFT.

Formation and impact of nanoscopic oriented phase domains in electrochemical crystalline electrodes.

Electrochemical phase transformation in ion-insertion crystalline electrodes is accompanied by compositional and structural changes, including the microstructural development of oriented phase domains. Previous studies have identified prevailingly transformation heterogeneities associated with diffusion- or reaction-limited mechanisms. In comparison, transformation-induced domains and their microstructure resulting from the loss of symmetry elements remain unexplored, despite their general importance in alloys and ceramics. Here, we map the formation of oriented phase domains and the development of strain gradient quantitatively during the electrochemical ion-insertion process. A collocated four-dimensional scanning transmission electron microscopy and electron energy loss spectroscopy approach, coupled with data mining, enables the study. Results show that in our model system of cubic spinel MnO2 nanoparticles their phase transformation upon Mg2+ insertion leads to the formation of domains of similar chemical identity but different orientations at nanometre length scale, following the nucleation, growth and coalescence process. Electrolytes have a substantial impact on the transformation microstructure ('island' versus 'archipelago'). Further, large strain gradients build up from the development of phase domains across their boundaries with high impact on the chemical diffusion coefficient by a factor of ten or more. Our findings thus provide critical insights into the microstructure formation mechanism and its impact on the ion-insertion process, suggesting new rules of transformation structure control for energy storage materials.

Exfoliable Transition Metal Chalcogenide Semiconductor NbSe2I2.

As the field of exfoliated van der Waals electronics grows to include complex heterostructures, the variety of available in-plane symmetries and geometries becomes increasingly valuable. In this work, we present an efficient chemical vapor transport synthesis of NbSe2I2 with the triclinic space group P1̅. This material contains Nb-Nb dimers and an in-plane crystallographic angle γ = 61.3°. We show that NbSe2I2 can be exfoliated down to few-layer and monolayer structures and use Raman spectroscopy to test the preservation of the crystal structure of exfoliated thin films. The crystal structure was verified by single-crystal and powder X-ray diffraction methods. Density functional theory calculations show triclinic NbSe2I2 to be a semiconductor with a band gap of around 1 eV, with similar band structure features for bulk and monolayer crystals. The physical properties of NbSe2I2 have been characterized by transport, thermal, optical, and magnetic measurements, demonstrating triclinic NbSe2I2 to be a diamagnetic semiconductor that does not exhibit any phase transformation below room temperature.

Quasi-One-Dimensional Transition-Metal Chalcogenide Semiconductor (Nb4Se15I2)I2.

The discovery of new low-dimensional transition-metal chalcogenides is contributing to the already prosperous family of these materials. In this study, needle-shaped single crystals of a quasi-one-dimensional (1D) material, (Nb4Se15I2)I2, were grown by chemical vapor transport, and the structure was solved by single-crystal X-ray diffraction (XRD). The structure has 1D (Nb4Se15I2)n chains along the [101] direction, with two I- ions per formula unit directly bonded to Nb5+. The other two I- ions are loosely coordinated and intercalated between the chains. Individual chains are chiral and stack along the b axis in opposing directions, giving space group P21/c. The phase purity and crystal structure were verified by powder XRD. Density functional theory calculations show (Nb4Se15I2)I2 to be a semiconductor with a direct band gap of around 0.6 eV. Resistivity measurements of bulk crystals and micropatterned devices demonstrate that (Nb4Se15I2)I2 has an activation energy of around 0.1 eV, and no anomaly or transition was seen upon cooling. Low-temperature XRD shows that (Nb4Se15I2)I2 does not undergo a structural phase transformation from room temperature to 8.2 K, unlike related compounds (NbSe4)nI (n = 2, 3, or 3.33), which all exhibit charge-density waves. This compound represents a well-characterized and valence-precise member of a diverse family of anisotropic transition-metal chalcogenides.

Capillary RheoSANS: measuring the rheology and nanostructure of complex fluids at high shear rates.

Complex fluids containing micelles, proteins, polymers and inorganic nanoparticles are often processed and used in high shear environments that can lead to structural changes at the nanoscale. Here, capillary rheometry is combined with small-angle neutron scattering (SANS) to simultaneously measure the viscosity and nanostructure of model complex fluids at industrially-relevant high shear rates. Capillary RheoSANS (CRSANS) uses pressure-driven flow through a long, flexible, silica capillary to generate wall shear rates up to 106 s-1 and measure pressure drops up to 500 bar. Sample volumes as small as 2 mL are required, which allow for measurement of supply-limited biological and deuterated materials. The device design, rheology and scattering methodologies, and broad sample capabilities are demonstrated by measuring a variety of model systems including silica nanoparticles, NIST monoclonal antibodies, and surfactant worm-like micelles. For a shear-thinning suspension of worm-like micelles, CRSANS measurements are in good agreement with traditional RheoSANS measurements. Collectively, these techniques provide insight into relationships between nanostructure and steady-shear viscosity over eight orders of magnitude in shear rate. Overall, CRSANS expands the capabilities of traditional RheoSANS instruments toward higher shear rates, enabling in situ structural measurements of soft materials at shear rates relevant to extrusion, coating, lubrication, and spraying applications.