Crystal-chemical origins of the ultrahigh conductivity of metallic delafossites.

Despite their highly anisotropic complex-oxidic nature, certain delafossite compounds (e.g., PdCoO2, PtCoO2) are the most conductive oxides known, for reasons that remain poorly understood. Their room-temperature conductivity can exceed that of Au, while their low-temperature electronic mean-free-paths reach an astonishing 20 µm. It is widely accepted that these materials must be ultrapure to achieve this, although the methods for their growth (which produce only small crystals) are not typically capable of such. Here, we report a different approach to PdCoO2 crystal growth, using chemical vapor transport methods to achieve order-of-magnitude gains in size, the highest structural qualities yet reported, and record residual resistivity ratios ( > 440). Nevertheless, detailed mass spectrometry measurements on these materials reveal that they are not ultrapure in a general sense, typically harboring 100s-of-parts-per-million impurity levels. Through quantitative crystal-chemical analyses, we resolve this apparent dichotomy, showing that the vast majority of impurities are forced to reside in the Co-O octahedral layers, leaving the conductive Pd sheets highly pure (∼1 ppm impurity concentrations). These purities are shown to be in quantitative agreement with measured residual resistivities. We thus conclude that a sublattice purification mechanism is essential to the ultrahigh low-temperature conductivity and mean-free-path of metallic delafossites.

Deconstructing magnetization noise: Degeneracies, phases, and mobile fractionalized excitations in tetris artificial spin ice.

Direct detection of spontaneous spin fluctuations, or "magnetization noise," is emerging as a powerful means of revealing and studying magnetic excitations in both natural and artificial frustrated magnets. Depending on the lattice and nature of the frustration, these excitations can often be described as fractionalized quasiparticles possessing an effective magnetic charge. Here, by combining ultrasensitive optical detection of thermodynamic magnetization noise with Monte Carlo simulations, we reveal emergent regimes of magnetic excitations in artificial "tetris ice." A marked increase of the intrinsic noise at certain applied magnetic fields heralds the spontaneous proliferation of fractionalized excitations, which can diffuse independently, without cost in energy, along specific quasi-1D spin chains in the tetris ice lattice.

Artificial Magnetic Tripod Ice.

We study the collective behavior of interacting arrays of nanomagnetic tripods. These objects have six discrete moment states, in contrast to the usual two states of an Ising-like moment. Our experimental data demonstrate that triangular lattice arrays form a "tripod ice" that exhibits charge ordering among the effective vertex magnetic charges, in direct analogy to artificial kagome spin ice. The results indicate that the interacting tripods have effective moments that act as emergent local variables, with strong connections to the well-studied Potts and clock models. In addition, the tripod moments display a tendency toward a nearest neighbor alignment in our thermalized samples that separates this system from kagome spin ice. Our results open a path toward the study of the collective behavior of nonbinary moments that is unavailable in other physical systems.

Topological kinetic crossover in a nanomagnet array.

Ergodic kinetics, which are critical to equilibrium thermodynamics, can be constrained by a system's topology. We studied a model nanomagnetic array in which such constraints visibly affect the behavior of the magnetic moments. In this system, magnetic excitations connect into thermally active one-dimensional strings whose motion can be imaged in real time. At high temperatures, our data showed the merging, breaking, and reconnecting of strings, resulting in the system transitioning between topologically distinct configurations. Below a crossover temperature, the string motion is dominated by simple changes in length and shape. In this low-temperature regime, the system is energetically stable because of its inability to explore all possible topological configurations. This kinetic crossover suggests a generalizable conception of topologically broken ergodicity and limited equilibration.

String Phase in an Artificial Spin Ice.

One-dimensional strings of local excitations are a fascinating feature of the physical behavior of strongly correlated topological quantum matter. Here we study strings of local excitations in a classical system of interacting nanomagnets, the Santa Fe Ice geometry of artificial spin ice. We measured the moment configuration of the nanomagnets, both after annealing near the ferromagnetic Curie point and in a thermally dynamic state. While the Santa Fe Ice lattice structure is complex, we demonstrate that its disordered magnetic state is naturally described within a framework of emergent strings. We show experimentally that the string length follows a simple Boltzmann distribution with an energy scale that is associated with the system's magnetic interactions and is consistent with theoretical predictions. The results demonstrate that string descriptions and associated topological characteristics are not unique to quantum models but can also provide a simplifying description of complex classical systems with non-trivial frustration.

Effect of Pore Structure on CO2 Adsorption Characteristics of Aminopolymer Impregnated MCM-36.

The CO2 adsorption characteristics of a pillared 2-dimensional porous silicate material impregnated with amine containing polymers have been investigated. It was determined that the introduction of amine polymer deteriorates the CO2 capture kinetics of the MCM-36 supported amine adsorbents compared to that of the bare material, due to the fact that with the addition of a higher loading of amine polymer the diffusion of CO2 through the 2-dimensional interlayer mesoporous channels of MCM-36 becomes greatly hindered. This pore blocking sets an upper limit to the CO2 capture performance of the polymer impregnated MCM-36 and greatly reduces the utility of using this sort of amine-solid adsorbent for carbon capture. Interestingly, these results suggest that for 2-D channel solid supports there is an optimal amine loading which is not likely to be equal to the maximum loading, and which can be determined and utilized to obtain the maximum improvement over the original materials. The study performed in this work for the MCM-36 material could therefore be applied to other porous supports to determine these optimum loadings and be used to more easily compare and contrast the alterations to capture characteristics which occur upon amine loading for a wide range of materials. It is believed this will make it more straightforward to determine which solid supports hold the promise for greatly improved capture characteristics upon amine loading and allow the field to more quickly determine avenues for fruitful development. These results also suggest the need for a new sort of support structure for amine loaded solids, one which can allow us to decouple amine loading from increasing diffusion resistance so that high amine efficiency can be maintained throughout the range of increased amine loadings.