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1. Large Polarization and Susceptibilities in Artificial Morphotropic Phase Boundary PbZr 1− x Ti x O 3 Superlattices

   https://doi.org/10.1002/aelm.201901395  

   Lupi, Eduardo ; Ghosh, Anirban ; Saremi, Sahar ; Hsu, Shang‐Lin ; Pandya, Shishir ; Velarde, Gabriel ; Fernandez, Abel ; Ramesh, Ramamoorthy ; Martin, Lane W. ( January 2020 , Advanced Electronic Materials)

   The ability to produce atomically precise, artificial oxide heterostructures allows for the possibility of producing exotic phases and enhanced susceptibilities not found in parent materials. Typical ferroelectric materials either exhibit large saturation polarization away from a phase boundary or large dielectric susceptibility near a phase boundary. Both large ferroelectric polarization and dielectric permittivity are attained wherein fully epitaxial (PbZr_0.8Ti_0.2O₃)_n/(PbZr_0.4Ti_0.6O₃)_2n(n= 2, 4, 6, 8, 16 unit cells) superlattices are produced such that the overall film chemistry is at the morphotropic phase boundary, but constitutive layers are not. Long‐ (n≥ 6) and short‐period (n= 2) superlattices reveal large ferroelectric saturation polarization (P_s= 64 µC cm⁻²) and small dielectric permittivity (ε_r≈ 400 at 10 kHz). Intermediate‐period (n= 4) superlattices, however, exhibit both large ferroelectric saturation polarization (P_s= 64 µC cm⁻²) and dielectric permittivity (ε_r= 776 at 10 kHz). First‐order reversal curve analysis reveals the presence of switching distributions for each parent layer and a third, interfacial layer wherein superlattice periodicity modulates the volume fraction of each switching distribution and thus the overall material response. This reveals that deterministic creation of artificial superlattices is an effective pathway for designing materials with enhanced responses to applied bias.

    

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2. Stranger than metals

   https://doi.org/10.1126/science.abh4273  

   Phillips, Philip W. ; Hussey, Nigel E. ; Abbamonte, Peter ( July 2022 , Science)

   BACKGROUND Landau’s Fermi liquid theory provides the bedrock on which our understanding of metals has developed over the past 65 years. Its basic premise is that the electrons transporting a current can be treated as “quasiparticles”—electron-like particles whose effective mass has been modified, typically through interactions with the atomic lattice and/or other electrons. For a long time, it seemed as though Landau’s theory could account for all the many-body interactions that exist inside a metal, even in the so-called heavy fermion systems whose quasiparticle mass can be up to three orders of magnitude heavier than the electron’s mass. Fermi liquid theory also lay the foundation for the first successful microscopic theory of superconductivity. In the past few decades, a number of new metallic systems have been discovered that violate this paradigm. The violation is most evident in the way that the electrical resistivity changes with temperature or magnetic field. In normal metals in which electrons are the charge carriers, the resistivity increases with increasing temperature but saturates, both at low temperatures (because the quantized lattice vibrations are frozen out) and at high temperatures (because the electron mean free path dips below the smallest scattering pathway defined by the lattice spacing). In “strange metals,” by contrast, no saturation occurs, implying that the quasiparticle description breaks down and electrons are no longer the primary charge carriers. When the particle picture breaks down, no local entity carries the current. ADVANCES A new classification of metallicity is not a purely academic exercise, however, as strange metals tend to be the high-temperature phase of some of the best superconductors available. Understanding high-temperature superconductivity stands as a grand challenge because its resolution is fundamentally rooted in the physics of strong interactions, a regime where electrons no longer move independently. Precisely what new emergent phenomena one obtains from the interactions that drive the electron dynamics above the temperature where they superconduct is one of the most urgent problems in physics, attracting the attention of condensed matter physicists as well as string theorists. One thing is clear in this regime: The particle picture breaks down. As particles and locality are typically related, the strange metal raises the distinct possibility that its resolution must abandon the basic building blocks of quantum theory. We review the experimental and theoretical studies that have shaped our current understanding of the emergent strongly interacting physics realized in a host of strange metals, with a special focus on their poster-child: the copper oxide high-temperature superconductors. Experiments are highlighted that attempt to link the phenomenon of nonsaturating resistivity to parameter-free universal physics. A key experimental observation in such materials is that removing a single electron affects the spectrum at all energy scales, not just the low-energy sector as in a Fermi liquid. It is observations of this sort that reinforce the breakdown of the single-particle concept. On the theoretical side, the modern accounts that borrow from the conjecture that strongly interacting physics is really about gravity are discussed extensively, as they have been the most successful thus far in describing the range of physics displayed by strange metals. The foray into gravity models is not just a pipe dream because in such constructions, no particle interpretation is given to the charge density. As the breakdown of the independent-particle picture is central to the strange metal, the gravity constructions are a natural tool to make progress on this problem. Possible experimental tests of this conjecture are also outlined. OUTLOOK As more strange metals emerge and their physical properties come under the scrutiny of the vast array of experimental probes now at our disposal, their mysteries will be revealed and their commonalities and differences cataloged. In so doing, we should be able to understand the universality of strange metal physics. At the same time, the anomalous nature of their superconducting state will become apparent, offering us hope that a new paradigm of pairing of non-quasiparticles will also be formalized. The correlation between the strength of the linear-in-temperature resistivity in cuprate strange metals and their corresponding superfluid density, as revealed here, certainly hints at a fundamental link between the nature of strange metallicity and superconductivity in the cuprates. And as the gravity-inspired theories mature and overcome the challenge of projecting their powerful mathematical machinery onto the appropriate crystallographic lattice, so too will we hope to build with confidence a complete theory of strange metals as they emerge from the horizon of a black hole. Curved spacetime with a black hole in its interior and the strange metal arising on the boundary. This picture is based on the string theory gauge-gravity duality conjecture by J. Maldacena, which states that some strongly interacting quantum mechanical systems can be studied by replacing them with classical gravity in a spacetime in one higher dimension. The conjecture was made possible by thinking about some of the fundamental components of string theory, namely D-branes (the horseshoe-shaped object terminating on a flat surface in the interior of the spacetime). A key surprise of this conjecture is that aspects of condensed matter systems in which the electrons interact strongly—such as strange metals—can be studied using gravity. 

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3. Extreme Ultraviolet Reflection-Absorption (XUV-RA) Spectroscopy: Probing Dynamics at Surfaces from a Molecular Perspective

   https://doi.org/https://doi.org/10.1021/acs.accounts.1c00765  

   Biswas, Somnath ; Baker, L. Robert ( March 2022 , Accounts of chemical research)

   Extreme ultraviolet (XUV) light sources based on high harmonic generation are enabling the development of novel spectroscopic methods to help advance the frontiers of ultrafast science and technology. In this account we discuss the development of XUV-RA spectroscopy at near grazing incident reflection geometry and highlight recent applications of this method to study ultrafast electron dynamics at surfaces. Measuring core-to-valence transitions with broadband, femtosecond pulses of XUV light extends the benefits of x-ray absorption spectroscopy to a laboratory tabletop by providing a chemical fingerprint of materials, including the ability to resolve individual elements with sensitivity to oxidation state, spin state, carrier polarity, and coordination geometry. Combining this chemical state sensitivity with femtosecond time resolution provides new insight into the material properties that govern charge carrier dynamics in complex materials. It is well known that surface dynamics differ significantly from equivalent processes in bulk materials, and that charge separation, trapping, transport, and recombination occurring uniquely at surfaces governs the efficiency of numerous technologically relevant processes spanning photocatalysis, photovoltaics, and information storage and processing. Importantly, XUV-RA spectroscopy at near grazing angle is also surface sensitive with a probe depth of 3 nm, providing a new window into electronic and structural dynamics at surfaces and interfaces. Here we highlight the unique capabilities and recent applications of XUVRA spectroscopy to study photo-induced surface dynamics in metal oxide semiconductors, including photocatalytic oxides (Fe2O3, Co3O4 NiO, and CuFeO2) as well as photoswitchable magnetic oxide (CoFe2O4). We first compare the ultrafast electron self-trapping rates via small polaron formation at the surface and bulk of Fe2O3 where we note that the energetics and kinetics of this process differ significantly at the surface. Additionally, we demonstrate the ability to systematically tune this kinetics by molecular functionalization, thereby, providing a route to control carrier transport at surfaces. We also measure the spectral signatures of charge transfer excitons with site specific localization of both electrons and holes in a series of transition metal oxide semiconductors (Fe2O3, NiO, Co3O4). The presence of valence band holes probed at the oxygen L1-edge confirms a direct relationship between the metal-oxygen bond covalency and water oxidation efficiency. For a mixed metal oxide CuFeO2 in the layered delafossite structure, XUV-RA reveals that the sub-picosecond hole thermalization from O 2p to Cu 3d states of CuFeO2 leads to the spatial separation of electrons and holes, resulting in exceptional photocatalytic performance for H2 evolution and CO2 reduction of this material. Finally, we provide an example to show the ability of XUV-RA to probe spin state specific dynamics in a the photo-switchable ferrimagnet, cobalt ferrite (CoFe2O4). This study provides a detailed understating of ultrafast spin switching in a complex magnetic material with site-specific resolution. In summary, the applications of XUV-RA spectroscopy demonstrated here illustrate the current abilities and future promise of this method to extend molecule-level understanding from well-defined photochemical complexes to complex materials so that charge and spin dynamics at surfaces can be tuned with the precision of molecular photochemistry. 

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4. Florida mangrove saltmarsh reference surface soils

   https://doi.org/10.6073/pasta/0e08cbe07c84488cb7b9dd16669946d0  

   Lewis, David Bruce ( January 2021 , Environmental Data Initiative)

   Site description. This data package consists of data obtained from sampling surface soil (the 0-7.6 cm depth profile) in black mangrove (Avicennia germinans) dominated forest and black needlerush (Juncus roemerianus) saltmarsh along the Gulf of Mexico coastline in peninsular west-central Florida, USA. This location has a subtropical climate with mean daily temperatures ranging from 15.4 °C in January to 27.8 °C in August, and annual precipitation of 1336 mm. Precipitation falls as rain primarily between June and September. Tides are semi-diurnal, with 0.57 m median amplitudes during the year preceding sampling (U.S. NOAA National Ocean Service, Clearwater Beach, Florida, station 8726724). Sea-level rise is 4.0 ± 0.6 mm per year (1973-2020 trend, mean ± 95 % confidence interval, NOAA NOS Clearwater Beach station). The A. germinans mangrove zone is either adjacent to water or fringed on the seaward side by a narrow band of red mangrove (Rhizophora mangle). A near-monoculture of J. roemerianus is often adjacent to and immediately landward of the A. germinans zone. The transition from the mangrove to the J. roemerianus zone is variable in our study area. An abrupt edge between closed-canopy mangrove and J. roemerianus monoculture may extend for up to several hundred meters in some locations, while other stretches of ecotone present a gradual transition where smaller, widely spaced trees are interspersed into the herbaceous marsh. Juncus roemerianus then extends landward to a high marsh patchwork of succulent halophytes (including Salicornia bigellovi, Sesuvium sp., and Batis maritima), scattered dwarf mangrove, and salt pans, followed in turn by upland vegetation that includes Pinus sp. and Serenoa repens. Field design and sample collection. We established three study sites spaced at approximately 5 km intervals along the western coastline of the central Florida peninsula. The sites consisted of the Salt Springs (28.3298°, -82.7274°), Energy Marine Center (28.2903°, -82.7278°), and Green Key (28.2530°, -82.7496°) sites on the Gulf of Mexico coastline in Pasco County, Florida, USA. At each site, we established three plot pairs, each consisting of one saltmarsh plot and one mangrove plot. Plots were 50 m^2 in size. Plots pairs within a site were separated by 230-1070 m, and the mangrove and saltmarsh plots composing a pair were 70-170 m apart. All plot pairs consisted of directly adjacent patches of mangrove forest and J. roemerianus saltmarsh, with the mangrove forests exhibiting a closed canopy and a tree architecture (height 4-6 m, crown width 1.5-3 m). Mangrove plots were located at approximately the midpoint between the seaward edge (water-mangrove interface) and landward edge (mangrove-marsh interface) of the mangrove zone. Saltmarsh plots were located 20-25 m away from any mangrove trees and into the J. roemerianus zone (i.e., landward from the mangrove-marsh interface). Plot pairs were coarsely similar in geomorphic setting, as all were located on the Gulf of Mexico coastline, rather than within major sheltering formations like Tampa Bay, and all plot pairs fit the tide-dominated domain of the Woodroffe classification (Woodroffe, 2002, "Coasts: Form, Process and Evolution", Cambridge University Press), given their conspicuous semi-diurnal tides. There was nevertheless some geomorphic variation, as some plot pairs were directly open to the Gulf of Mexico while others sat behind keys and spits or along small tidal creeks. Our use of a plot-pair approach is intended to control for this geomorphic variation. Plot center elevations (cm above mean sea level, NAVD 88) were estimated by overlaying the plot locations determined with a global positioning system (Garmin GPS 60, Olathe, KS, USA) on a LiDAR-derived bare-earth digital elevation model (Dewberry, Inc., 2019). The digital elevation model had a vertical accuracy of ± 10 cm (95 % CI) and a horizontal accuracy of ± 116 cm (95 % CI). Soil samples were collected via coring at low tide in June 2011. From each plot, we collected a composite soil sample consisting of three discrete 5.1 cm diameter soil cores taken at equidistant points to 7.6 cm depth. Cores were taken by tapping a sleeve into the soil until its top was flush with the soil surface, sliding a hand under the core, and lifting it up. Cores were then capped and transferred on ice to our laboratory at the University of South Florida (Tampa, Florida, USA), where they were combined in plastic zipper bags, and homogenized by hand into plot-level composite samples on the day they were collected. A damp soil subsample was immediately taken from each composite sample to initiate 1 y incubations for determination of active C and N (see below). The remainder of each composite sample was then placed in a drying oven (60 °C) for 1 week with frequent mixing of the soil to prevent aggregation and liberate water. Organic wetland soils are sometimes dried at 70 °C, however high drying temperatures can volatilize non-water liquids and oxidize and decompose organic matter, so 50 °C is also a common drying temperature for organic soils (Gardner 1986, "Methods of Soil Analysis: Part 1", Soil Science Society of America); we accordingly chose 60 °C as a compromise between sufficient water removal and avoidance of non-water mass loss. Bulk density was determined as soil dry mass per core volume (adding back the dry mass equivalent of the damp subsample removed prior to drying). Dried subsamples were obtained for determination of soil organic matter (SOM), mineral texture composition, and extractable and total carbon (C) and nitrogen (N) within the following week. Sample analyses. A dried subsample was apportioned from each composite sample to determine SOM as mass loss on ignition at 550 °C for 4 h. After organic matter was removed from soil via ignition, mineral particle size composition was determined using a combination of wet sieving and density separation in 49 mM (3 %) sodium hexametaphosphate ((NaPO_3)_6) following procedures in Kettler et al. (2001, Soil Science Society of America Journal 65, 849-852). The percentage of dry soil mass composed of silt and clay particles (hereafter, fines) was calculated as the mass lost from dispersed mineral soil after sieving (0.053 mm mesh sieve). Fines could have been slightly underestimated if any clay particles were burned off during the preceding ignition of soil. An additional subsample was taken from each composite sample to determine extractable N and organic C concentrations via 0.5 M potassium sulfate (K_2SO_4) extractions. We combined soil and extractant (ratio of 1 g dry soil:5 mL extractant) in plastic bottles, reciprocally shook the slurry for 1 h at 120 rpm, and then gravity filtered it through Fisher G6 (1.6 μm pore size) glass fiber filters, followed by colorimetric detection of nitrite (NO_2^-) + nitrate (NO_3^-) and ammonium (NH_4^+) in the filtrate (Hood Nowotny et al., 2010,Soil Science Society of America Journal 74, 1018-1027) using a microplate spectrophotometer (Biotek Epoch, Winooski, VT, USA). Filtrate was also analyzed for dissolved organic C (referred to hereafter as extractable organic C) and total dissolved N via combustion and oxidation followed by detection of the evolved CO_2 and N oxide gases on a Formacs HT TOC/TN analyzer (Skalar, Breda, The Netherlands). Extractable organic N was then computed as total dissolved N in filtrate minus extractable mineral N (itself the sum of extractable NH_4-N and NO_2-N + NO_3-N). We determined soil total C and N from dried, milled subsamples subjected to elemental analysis (ECS 4010, Costech, Inc., Valencia, CA, USA) at the University of South Florida Stable Isotope Laboratory. Median concentration of inorganic C in unvegetated surface soil at our sites is 0.5 % of soil mass (Anderson, 2019, Univ. of South Florida M.S. thesis via methods in Wang et al., 2011, Environmental Monitoring and Assessment 174, 241-257). Inorganic C concentrations are likely even lower in our samples from under vegetation, where organic matter would dilute the contribution of inorganic C to soil mass. Nevertheless, the presence of a small inorganic C pool in our soils may be counted in the total C values we report. Extractable organic C is necessarily of organic C origin given the method (sparging with HCl) used in detection. Active C and N represent the fractions of organic C and N that are mineralizable by soil microorganisms under aerobic conditions in long-term soil incubations. To quantify active C and N, 60 g of field-moist soil were apportioned from each composite sample, placed in a filtration apparatus, and incubated in the dark at 25 °C and field capacity moisture for 365 d (as in Lewis et al., 2014, Ecosphere 5, art59). Moisture levels were maintained by frequently weighing incubated soil and wetting them up to target mass. Daily CO_2 flux was quantified on 29 occasions at 0.5-3 week intervals during the incubation period (with shorter intervals earlier in the incubation), and these per day flux rates were integrated over the 365 d period to compute an estimate of active C. Observations of per day flux were made by sealing samples overnight in airtight chambers fitted with septa and quantifying headspace CO_2 accumulation by injecting headspace samples (obtained through the septa via needle and syringe) into an infrared gas analyzer (PP Systems EGM 4, Amesbury, MA, USA). To estimate active N, each incubated sample was leached with a C and N free, 35 psu solution containing micronutrients (Nadelhoffer, 1990, Soil Science Society of America Journal 54, 411-415) on 19 occasions at increasing 1-6 week intervals during the 365 d incubation, and then extracted in 0.5 M K_2SO_4 at the end of the incubation in order to remove any residual mineral N. Active N was then quantified as the total mass of mineral N leached and extracted. Mineral N in leached and extracted solutions was detected as NH_4-N and NO_2-N + NO_3-N via colorimetry as above. This incubation technique precludes new C and N inputs and persistently leaches mineral N, forcing microorganisms to meet demand by mineralizing existing pools, and thereby directly assays the potential activity of soil organic C and N pools present at the time of soil sampling. Because this analysis commences with disrupting soil physical structure, it is biased toward higher estimates of active fractions. Calculations. Non-mobile C and N fractions were computed as total C and N concentrations minus the extractable and active fractions of each element. This data package reports surface-soil constituents (moisture, fines, SOM, and C and N pools and fractions) in both gravimetric units (mass constituent / mass soil) and areal units (mass constituent / soil surface area integrated through 7.6 cm soil depth, the depth of sampling). Areal concentrations were computed as X × D × 7.6, where X is the gravimetric concentration of a soil constituent, D is soil bulk density (g dry soil / cm^3), and 7.6 is the sampling depth in cm. 

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5. Radical chemistry in oxidation flow reactors for atmospheric chemistry research

   https://doi.org/10.1039/C9CS00766K  

   Peng, Zhe ; Jimenez, Jose L. ( May 2020 , Chemical Society Reviews)

   Environmental chambers have been playing a vital role in atmospheric chemistry research for seven decades. In last decade, oxidation flow reactors (OFR) have emerged as a promising alternative to chambers to study complex multigenerational chemistry. OFR can generate higher-than-ambient concentrations of oxidants via H 2 O, O 2 and O 3 photolysis by low-pressure-Hg-lamp emissions and reach hours to days of equivalent photochemical aging in just minutes of real time. The use of OFR for volatile-organic-compound (VOC) oxidation and secondary-organic-aerosol formation has grown very rapidly recently. However, the lack of detailed understanding of OFR photochemistry left room for speculation that OFR chemistry may be generally irrelevant to the troposphere, since its initial oxidant generation is similar to stratosphere. Recently, a series of studies have been conducted to address important open questions on OFR chemistry and to guide experimental design and interpretation. In this Review, we present a comprehensive picture connecting the chemistries of hydroxyl (OH) and hydroperoxy radicals, oxidized nitrogen species and organic peroxy radicals (RO 2 ) in OFR. Potential lack of tropospheric relevance associated with these chemistries, as well as the physical conditions resulting in it will also be reviewed. When atmospheric oxidation is dominated by OH, OFR conditions can often be similar to ambient conditions, as OH dominates against undesired non-OH effects. One key reason for tropospherically-irrelevant/undesired VOC fate is that under some conditions, OH is drastically reduced while non-tropospheric/undesired VOC reactants are not. The most frequent problems are running experiments with too high precursor concentrations, too high UV and/or too low humidity. On other hand, another cause of deviation from ambient chemistry in OFR is that some tropospherically-relevant non-OH chemistry ( e.g. VOC photolysis in UVA and UVB) is not sufficiently represented under some conditions. In addition, the fate of RO 2 produced from VOC oxidation can be kept relevant to the troposphere. However, in some cases RO 2 lifetime can be too short for atmospherically-relevant RO 2 chemistry, including its isomerization. OFR applications using only photolysis of injected O 3 to generate OH are less preferable than those using both 185 and 254 nm photons (without O 3 injection) for several reasons. When a relatively low equivalent photochemical age (<∼1 d) and high NO are needed, OH and NO generation by organic-nitrite photolysis in the UVA range is preferable. We also discuss how to achieve the atmospheric relevance for different purposes in OFR experimental planning. 

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