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Vanadium dioxide (VO2) manifests an abrupt metal–insulator transition (MIT) from monoclinic to rutile phases, with potential use for tunable electronic and optical properties and spiking neuromorphic devices. Understanding pathways to modulate electronic transport in VO2, as well as its response to irradiation (e.g., for space applications), is critical to better enable these applications. In this work, we investigate the selective modulation of electronic transport in VO2 films subject to different 10 keV helium ion (He+) fluences. Under these conditions, the resistivity in the individual monoclinic and rutile phases varied by 50%–200%, while the MIT transformation temperature remains constant within 4 °C independent of irradiation fluence. Importantly, different trends in the resistivity of the monoclinic and rutile phases were observed both as a function of total He fluence as well as in films grown on different substrates (amorphous SiO2/Si vs single crystal Al2O3). Through a combination of measurements including majority carrier sign via Seebeck, low frequency noise, and TEM, our investigation supports the presence of different kinds of point defects (V in; O in), which may arise due to grain boundary defect interactions. Our work suggests the utility of He irradiation for the selective modulation of VO2 transport properties for neuromorphic, in contrast to other established but non-selective methods, like doping. [ABSTRACT FROM AUTHOR]

A surrounding matrix is known to alter nanoparticle spin transitions, the solid state structural phase changes associated with transitions between high spin (HS) and low spin(LS) states. To better quantify how the spin transition solid and surrounding matrix interact, several series of core‐shell particles were prepared based on RbxCo[Fe(CN)6]z ⋅ nH2O, RbCoFe‐PBA, as spin transition core with isostructural shells of different compositions and thicknesses. Synchrotron PXRD through the thermal high HS to LS, the LS to photoexcited high spin (PXHS), and thermal PXHS to LS transitions, show the activation energy is lowered as shells become thicker and stiffer. Calorimetry data coupled with transition state theory analysis indicate the core stiffens in the core‐shell particles relative to the uncoated particles. The conclusion is supported by microstrain analysis that shows stiffer shells limit the extent to which the core distorts as individual sites transition, leading to the lower activation energy. Finally, differences in lattice mismatch with different shell materials are shown to alter the mechanism by which the transition progresses. [ABSTRACT FROM AUTHOR]

We report the compressibility of two Prussian blue analogs (PBAs) under hydrostatic pressure, one with small and one with a relatively large cubic unit cell among PBAs, and investigate the modification of their elastic properties when the two lattices are coupled within a heteroepitaxial core–shell structure. Bulk modulus (K0) values are derived from x-ray powder diffraction experiments using a diamond anvil cell with silicone oil as a pressure-transmitting medium. The pressure–volume curves fitted to Murnaghan equations of states show that K0 inversely scales with the crystal packing for the rubidium cobalt hexacyanoferrate and rubidium nickel hexacyanochromate samples (K0 ∼ 29 GPa for Co-Fe PBA, a0 = 9.95 Å and ∼20 GPa for Ni-Cr PBA, a0 = 10.48 Å with a0 being the lattice constant at ambient pressure). The two single-phase samples undergo a cubic-to-rhombohedral phase transition above ∼0.8 GPa, which correlates fairly well with the build-up of nonhydrostatic pressure contributions in the cell. Within the core–shell structure, the volume change observed for the core scales with that of the shell because of the configuration close to the case of a solid pressure-transmitting medium. The Ni-Cr PBA shell layer exhibits an increased rhombohedral distortion with respect to the single-phase reference possibly associated with shearing at the core–shell interface. Its bulk modulus is not significantly modified with respect to that of the single-phase sample despite the presence of defects associated with the growth mode, whereas the P-V curve of the core suggests a stiffening of the Co-Fe PBA lattice. [ABSTRACT FROM AUTHOR]

Strain is often used to alter material properties in applications ranging from bandgap tuning for semiconductor electronics to performing work through mechanical actuation. Spin transitions are accompanied by volume changes in the solid state and are being explored in actuation as a source of mechanical strain inducible by the many controllable stimuli known to trigger spin state changes. There is still much to understand, especially at small length scales, about how strain is transmitted from one material to another across a mechanically coupled interface. Theoretical efforts modeling spin-transition particles in a matrix provide significant insights, but this remains an area where systematic experimental studies are limited. This Perspective highlights the progress using cobalt hexacyanoferrate network solids, or Prussian blue analogues (CoFe-PBA), as a framework for investigating spin transition induced strain in nanometer scale and mesoscale heterostructures. Using a family of isostructural cyanometallate networks to form heterostructures with well-defined interfaces, measurements of the altered properties in response to strain generated by the thermally or optically induced spin state change of the CoFe-PBA provide the chance to experimentally interrogate factors that control interface transmitted strain. [ABSTRACT FROM AUTHOR]

Sulfur-deficient polycrystalline two-dimensional (2D) molybdenum disulfide (MoS2) memtransistors exhibit gate-tunable memristive switching to implement emerging memory operations and neuromorphic computing paradigms. Grain boundaries and sulfur vacancies are critical for memristive switching; however, the underlying physical mechanisms are not fully understood. Furthermore, the adsorption of water and gaseous species strongly perturbs electronic transport in monolayer MoS2, and little work has been done to explore the influence of surface interactions on defect-related kinetics that produces memristive switching. Here, we study the switching kinetics of back-gated MoS2 memtransistors using current transient measurements in a controlled atmosphere chamber. We observe that adsorbed water molecules lead to suppression of the electronic trap-filling processes concomitant with the resistive switching process, resulting in altered kinetics of the resistive switching. Additionally, using the transient response from "bunched" drain voltage pulse trains performed as a function of temperature, we extract the energy of the affected trap state and find that it places the trap roughly midgap [ E T = E C – 0.7 (± 0.4) eV]. Our results highlight the importance of controlling for surface interactions that may affect switching kinetics in 2D memtransistors, synaptic transistors, and related memory devices. [ABSTRACT FROM AUTHOR]

New nanometer scale heterostructure particles of the two-dimensional Hofmann-like Fe(ii) spin-crossover network, Fe(phpy)2[Ni(CN)4]·0.5H2O {phpy = 4-phenylpyridine}, and the Prussian blue analogue K0.4Ni1.0[Cr(CN)6]0.8·nH2O (NiCr-PBA) have been developed, exhibiting synergistic photomagnetic effects, whereby the LIESST (light-induced electron spin-state trapping) effect in the Hofmann-like material induces a magnetization change in the NiCr-PBA. A variety of microscopic and spectroscopic techniques demonstrate the heterogeneous growth of the NiCr-PBA on the Hofmann seed particles and show the Hofmann compound retains its thermal and photoinduced spin transition properties in the heterostructure. The photoinduced magnetization change in the NiCr-PBA network arises from coupling of the two lattices despite dissimilar structure types. Isothermal magnetization minor hysteresis loop studies at 5 K show light absorption leads to changes in the local anisotropy of NiCr-PBA magnetic domains, providing direct evidence for a general magnetomechanical mechanism of light-switchable magnetism in coordination polymer heterostructures combining a photoactive material with a magnet. [ABSTRACT FROM AUTHOR]

The [Mn12O12(O2CR)16(L4)] family (R = various; L = terminal ligand) of clusters holds a special place in molecular magnetism; they are the most well-studied single-molecule magnets (SMMs). Targeted linkage of these SMMs has now been achieved for the first time. The resulting chain structures have been confirmed crystallographically, and the magnetic properties, up to 1.14 GPa, and high-field electron paramagnetic resonance spectra have been collected and analyzed. [ABSTRACT FROM AUTHOR]

Soil maps provide a tool for rapid, low-cost delineation of river flood plains, based on the difference in morphology between soils frequently flooded and soils free of flooding. Very rare floods along the Mississippi River inundated over 99% of the soils that would be expected to flood but in addition flooded 7% of the terrace soils. Flooding predicted with soils information was compared with flooding predicted with an engineering study for small streams in a mature landscape in southwestern Wisconsin. For a 100-year synthetic flood an agreement of ±4.5% was obtained. Comparison of flooding with soil types for a small stream in a recently glaciated landscape in southeastern Wisconsin indicated that alluvial soils flood frequently and, in addition, that soils with restricted drainage and soils of fluvial origin also flood frequently. Some of the data are inconclusive, owing to the lack of precise flooding information to serve as a basis of comparison. In areas where man-made works do not appreciably alter the stream regimen and where extensive flood plain areas must be delineated, it appears that accurate soil maps, properly interpreted, will give a good estimate of areas subject to flooding. [ABSTRACT FROM AUTHOR]

Inconsistent interface control in devices based on two-dimensional materials (2DMs) has limited technological maturation. Astounding variability of 2D/three-dimensional (2D/3D) interface properties has been reported, which has been exacerbated by the lack of direct investigations of buried interfaces commonly found in devices. Herein, we demonstrate a new process that enables the assembly and isolation of device-relevant heterostructures for buried interface characterization. This is achieved by implementing a water-soluble substrate (GeO 2 ), which enables deposition of many materials onto the 2DM and subsequent heterostructure release by dissolving the GeO 2 substrate. Here, we utilize this novel approach to compare how the chemistry, doping, and strain in monolayer MoS 2 heterostructures fabricated by direct deposition vary from those fabricated by transfer techniques to show how interface properties differ with the heterostructure fabrication method. Direct deposition of thick Ni and Ti films is found to react with the monolayer MoS 2 . These interface reactions convert 50% of MoS 2 into intermetallic species, which greatly exceeds the 10% conversion reported previously and 0% observed in transfer-fabricated heterostructures. We also measure notable differences in MoS 2 carrier concentration depending on the heterostructure fabrication method. Direct deposition of thick Au, Ni, and Al 2 O 3 films onto MoS 2 increases the hole concentration by >10 12 cm -2 compared to heterostructures fabricated by transferring MoS 2 onto these materials. Thus, we demonstrate a universal method to fabricate 2D/3D heterostructures and expose buried interfaces for direct characterization.