Ferroelectricity in Ultrathin HfO2-Based Films by Nanosecond Laser Annealing.

Nonvolatile memory devices based on ferroelectric HfxZr1-xO2 (HZO) show great promise for back-end integrable storage and for neuromorphic accelerators, but their adoption is held back by the inability to scale down the HZO thickness without violating the strict thermal restrictions of the Si CMOS back end of line. In this work, we overcome this challenge and demonstrate the use of nanosecond pulsed laser annealing (NLA) to locally crystallize areas of an ultrathin (3.6 nm) HZO film into the ferroelectric orthorhombic phase. Meanwhile, the heat induced by the pulsed laser is confined to the layers above the Si, allowing for back-end compatible integration. We use a combination of electrical characterization, nanofocused scanning X-ray diffraction (nano-XRD), and synchrotron X-ray photoelectron spectroscopy (SXPS) to gain a comprehensive view of the change in material and interface properties by systematically varying both laser energy and the number of laser pulses on the same sample. We find that NLA can provide remanent polarization up to 2Pr= 11.6 µC/cm2 in 3.6 nm HZO, albeit with a significant wake-up effect. The improved TiN/HZO interface observed by XPS explains why device endurance goes beyond 107 cycles, whereas an identical film processed by rapid thermal processing (RTP) breaks already after 106 cycles. All in all, NLA provides a promising approach to scale down the ferroelectric oxide thickness for emerging HZO ferroelectric devices, which is key for their integration in scaled process nodes.

Depth-Resolved X-Ray Photoelectron Spectroscopy Evidence of Intrinsic Polar States in HfO2-Based Ferroelectrics.

The discovery of ferroelectricity in nanoscale hafnia-based oxide films has spurred interest in understanding their emergent properties. Investigation focuses on the size-dependent polarization behavior, which is sensitive to content and movement of oxygen vacancies. Though polarization switching and electrochemical reactions is shown to co-occur, their relationship remains unclear. This study employs X-ray photoelectron spectroscopy with depth sensitivity to examine changes in electrochemical states occurring during polarization switching. Contrasting Hf0.5Zr0.5O2 (HZO) with Hf0.88La0.04Ta0.08O2 (HLTO), a composition with an equivalent structure and comparable average ionic radius, electrochemical states are directly observed for specific polarization directions. Lower-polarization films exhibit more significant electrochemical changes upon switching, suggesting an indirect relationship between polarization and electrochemical state. This research illuminates the complex interplay between polarization and electrochemical dynamics, providing evidence for intrinsic polar states in HfO2-based ferroelectrics.

Single Entity Electrocatalysis.

Making a measurement over millions of nanoparticles or exposed crystal facets seldom reports on reactivity of a single nanoparticle or facet, which may depart drastically from ensemble measurements. Within the past 30 years, science has moved toward studying the reactivity of single atoms, molecules, and nanoparticles, one at a time. This shift has been fueled by the realization that everything changes at the nanoscale, especially important industrially relevant properties like those important to electrocatalysis. Studying single nanoscale entities, however, is not trivial and has required the development of new measurement tools. This review explores a tale of the clever use of old and new measurement tools to study electrocatalysis at the single entity level. We explore in detail the complex interrelationship between measurement method, electrocatalytic material, and reaction of interest (e.g., carbon dioxide reduction, oxygen reduction, hydrazine oxidation, etc.). We end with our perspective on the future of single entity electrocatalysis with a key focus on what types of measurements present the greatest opportunity for fundamental discovery.

Biocontrol in built environments to reduce pathogen exposure and infection risk.

The microbiome of the built environment comprises bacterial, archaeal, fungal, and viral communities associated with human-made structures. Even though most of these microbes are benign, antibiotic-resistant pathogens can colonize and emerge indoors, creating infection risk through surface transmission or inhalation. Several studies have catalogued the microbial composition and ecology in different built environment types. These have informed in vitro studies that seek to replicate the physicochemical features that promote pathogenic survival and transmission, ultimately facilitating the development and validation of intervention techniques used to reduce pathogen accumulation. Such interventions include using Bacillus-based cleaning products on surfaces or integrating bacilli into printable materials. Though this work is in its infancy, early research suggests the potential to use microbial biocontrol to reduce hospital- and home-acquired multidrug-resistant infections. Although these techniques hold promise, there is an urgent need to better understand the microbial ecology of built environments and to determine how these biocontrol solutions alter species interactions. This review covers our current understanding of microbial ecology of the built environment and proposes strategies to translate that knowledge into effective biocontrol of antibiotic-resistant pathogens.

Microbiology of the built environment: harnessing human-associated built environment research to inform the study and design of animal nests and enclosures.

SUMMARYOver the past decade, hundreds of studies have characterized the microbial communities found in human-associated built environments (BEs). These have focused primarily on how the design and use of our built spaces have shaped human-microbe interactions and how the differential selection of certain taxa or genetic traits has influenced health outcomes. It is now known that the more removed humans are from the natural environment, the greater the risk for the development of autoimmune and allergic diseases, and that indoor spaces can be harsh, selective environments that can increase the emergence of antimicrobial-resistant and virulent phenotypes in surface-bound communities. However, despite the abundance of research that now points to the importance of BEs in determining human-microbe interactions, only a fraction of non-human animal structures have been comparatively explored. It is here, in the context of human-associated BE research, that we consider the microbial ecology of animal-built natural nests and burrows, as well as artificial enclosures, and point to areas of primary interest for future research.

Thin-film design of amorphous hafnium oxide nanocomposites enabling strong interfacial resistive switching uniformity.

A design concept of phase-separated amorphous nanocomposite thin films is presented that realizes interfacial resistive switching (RS) in hafnium oxide-based devices. The films are formed by incorporating an average of 7% Ba into hafnium oxide during pulsed laser deposition at temperatures ≤400°C. The added Ba prevents the films from crystallizing and leads to ∼20-nm-thin films consisting of an amorphous HfOx host matrix interspersed with ∼2-nm-wide, ∼5-to-10-nm-pitch Ba-rich amorphous nanocolumns penetrating approximately two-thirds through the films. This restricts the RS to an interfacial Schottky-like energy barrier whose magnitude is tuned by ionic migration under an applied electric field. Resulting devices achieve stable cycle-to-cycle, device-to-device, and sample-to-sample reproducibility with a measured switching endurance of ≥104 cycles for a memory window ≥10 at switching voltages of ±2 V. Each device can be set to multiple intermediate resistance states, which enables synaptic spike-timing-dependent plasticity. The presented concept unlocks additional design variables for RS devices.

Ferroelectric Orthorhombic ZrO2 Thin Films Achieved Through Nanosecond Laser Annealing.

A new approach for the stabilization of the ferroelectric orthorhombic ZrO2 films is demonstrated through nanosecond laser annealing (NLA) of as-deposited Si/SiOx /W(14 nm)/ZrO2 (8 nm)/W(22 nm), grown by ion beam sputtering at low temperatures. The NLA process optimization is guided by COMSOL multiphysics simulations. The films annealed under the optimized conditions reveal the presence of the orthorhombic phase, as confirmed by X-ray diffraction, electron backscatter diffraction, and transmission electron microscopy. Macroscopic polarization-electric field hysteresis loops show ferroelectric behavior, with saturation polarization of 12.8 µC cm-2 , remnant polarization of 12.7 µC cm-2 and coercive field of 1.2 MV cm-1 . The films exhibit a wake-up effect that is attributed to the migration of point defects, such as oxygen vacancies, and/or a transition from nonferroelectric (monoclinic and tetragonal phase) to the ferroelectric orthorhombic phase. The capacitors demonstrate a stable polarization with an endurance of 6.0 × 105 cycles, demonstrating the potential of the NLA process for the fabrication of ferroelectric memory devices with high polarization, low coercive field, and high cycling stability.

Converting Commodity Polyolefins to Electronic Materials through Borane-Catalyzed Alkene Isomerization.

Novel approaches to the functionalization of commodity polymers could provide avenues for the synthesis of materials for next-generation electronic devices. Herein, we present a catalytic method for the conversion of common unsaturated polymers such as polybutadiene, polyisoprene, and styrene-butadiene copolymers [e.g., polystyrene-block-polybutadiene-block-polystyrene and poly(styrene-stat-butadiene)] to poly(acetylene) (PA)-based multiblock copolymers with conjugation lengths of up to ∼20, making them potentially suitable for electronics applications. Additionally, we demonstrate the application of this method to the formal conversion of polyethylene─the most widely produced thermoplastic─into PA-containing multiblock materials.

3D Bragg Coherent Diffraction Imaging of Extended Nanowires: Defect Formation in Highly Strained InGaAs Quantum Wells.

InGaAs quantum wells embedded in GaAs nanowires can serve as compact near-infrared emitters for direct integration onto Si complementary metal oxide semiconductor technology. While the core-shell geometry in principle allows for a greater tuning of composition and emission, especially farther into the infrared, the practical limits of elastic strain accommodation in quantum wells on multifaceted nanowires have not been established. One barrier to progress is the difficulty of directly comparing the emission characteristics and the precise microstructure of a single nanowire. Here we report an approach to correlating quantum well morphology, strain, defects, and emission to understand the limits of elastic strain accommodation in nanowire quantum wells specific to their geometry. We realize full 3D Bragg coherent diffraction imaging (BCDI) of intact quantum wells on vertically oriented epitaxial nanowires, which enables direct correlation with single-nanowire photoluminescence. By growing In0.2Ga0.8As quantum wells of distinct thicknesses on different facets of the same nanowire, we identified the critical thickness at which defects are nucleated. A correlation with a traditional transmission electron microscopy analysis confirms that BCDI can image the extended structure of defects. Finite element simulations of electron and hole states explain the emission characteristics arising from strained and partially relaxed regions. This approach, imaging the 3D strain and microstructure of intact nanowire core-shell structures with application-relevant dimensions, can aid the development of predictive models that enable the design of new compact infrared emitters.

Comparative analysis of fetal pig decomposition processes in burials of variable depths and wrapping.

This research examined the effects that the variables of burial depth and presence of plastic wrapping had on the decomposition rate of fetal pig (Sus scrofa) remains in a New England environment. The decomposition of 56 fetal pigs was observed in four independent variable groups: 20 cm depth unwrapped, 20 cm wrapped, 60 cm unwrapped, and 60 cm wrapped, with exhumation at months 1, 2, 3, 6, 9, 12, and 18. The authors hypothesized that the rate of decay would be slower for wrapped remains and/or for remains at a greater burial depth. Analysis of these remains consisted of preburial and postburial mass, adipocere coverage, skeletal exposure, and decomposition quantified as Total Body Score (TBS). The difference between preburial and postburial mass was reported as a loss percentage to account for varying preburial masses. Wrapping was a significant influencer of mass loss percentage, with p = 0.0298 but not for the TBS, with p = 0.17565. Burial depth did not have a significant effect on either mass loss percentage or TBS, with p = 0.1956 and 0.08969, respectively. This study suggests that wrapping has a greater influence on decomposition patterns than burial depth in this environment, particularly the mass loss percentage. It is suggested that there are limitations with the use of TBS in Postmortem Interval (PMI) estimation, such as variable burial conditions and body characteristics.

Migrating Type 2 Dendritic Cells Prime Mucosal Th17 Cells Specific to Small Intestinal Commensal Bacteria.

Dendritic cells (DCs) are professional APCs equipped with MHC-restricted Ags, costimulations, and cytokines that effectively prime and differentiate naive T cells into distinct functional subsets. The immune signals that DCs carry reflect the route of Ag uptake and the innate stimuli they received. In the mucosal tissues, owing to the great variety of foreign Ags and inflammatory cues, DCs are predominantly activated and migratory. In the small intestine, CD4 Th17 cells are abundant and have been shown to be regulated by DCs and macrophages. Using a mouse commensal bacteria experimental model, we identified that the early priming step of commensal-driven Th17 cells is controlled by bona fide Zbtb46-expressing DCs. CCR7-dependent migration of type 2 DCs (DC2s) from the small intestine to the mesenteric lymph nodes (MLNs) is essential for the activation of naive CD4 T cells. The migratory DC2 population in the MLNs is almost exclusively Esam+ cells. Single-cell RNA sequencing highlighted the abundance of costimulatory markers (CD40 and OX40) and chemokines (Ccl22 and Cxcl16) on MLN migratory DCs. Further resolution of MLN migratory DC2s revealed that the Th17-polarizing cytokine IL-6 colocalizes with DC2s expressing CD40, Ccl17, and Ccl22. Thus, early Th17 cell differentiation is initiated by a small subset of migratory DC2s in the gut-draining lymph nodes.

Accelerating amorphous polymer electrolyte screening by learning to reduce errors in molecular dynamics simulated properties.

Polymer electrolytes are promising candidates for the next generation lithium-ion battery technology. Large scale screening of polymer electrolytes is hindered by the significant cost of molecular dynamics (MD) simulation in amorphous systems: the amorphous structure of polymers requires multiple, repeated sampling to reduce noise and the slow relaxation requires long simulation time for convergence. Here, we accelerate the screening with a multi-task graph neural network that learns from a large amount of noisy, unconverged, short MD data and a small number of converged, long MD data. We achieve accurate predictions of 4 different converged properties and screen a space of 6247 polymers that is orders of magnitude larger than previous computational studies. Further, we extract several design principles for polymer electrolytes and provide an open dataset for the community. Our approach could be applicable to a broad class of material discovery problems that involve the simulation of complex, amorphous materials.

Bone dispersal by vertebrate taxa in an urban park environment in New England, USA.

The questions of the frequency, distance, and maximum size of the bones that carnivores, rodents, and other common taxa can disperse have been little addressed, especially in the later phases of skeletonization when individual bones are more subject to transport and loss. The present research utilized a sample of dry white-tailed deer (Odocoileus virginianus) bones in two locations in a forested urban environment dense with eastern gray squirrels (Sciurus carolinensis), chipmunks (Tamias striatus), coyotes (Canis latrans), raccoons (Procyon lotor), and other potential scavenging taxa. Game cameras were used to document their dispersal behavior. A total of 1731 visits were recorded, by a minimum of 12 mammalian and 9 avian taxa. Small amounts of dispersal impacted the bone samples continuously throughout the observation period, with 52.2% of all movement in the range of 1-5 cm. The bones were dispersed a maximum distance of 1252 cm, and the largest bone moved had an initial mass of 194.6 g. Rodent dry-bone gnawing behavior affected 72.7% of the sample. The project also assessed a smaller sample of Tile Mate® tracking chips for their utility in dispersal research, and these were found to have a useful potential though were not pivotal in acquiring the data presented here. Forensic surface search methods and interpretations of skeletal recovery patterns should take into consideration the ability of these common species to disperse even dry bones away from their initial locations, and this behavior may continue years after the time of initial deposition.

Type 2 dendritic cells mediate control of cytotoxic T cell resistant tumors.

Type 2 DCs (DC2s) comprise the majority of conventional DCs within most tumors; however, little is known about their ability to initiate and sustain antitumor immunity, as most studies have focused on antigen cross-presenting DC1s. Here, we report that DC2 infiltration identified by analysis of multiple human cancer data sets showed a significant correlation with survival across multiple human cancers, with the benefit being seen in tumors resistant to cytotoxic T cell control. Characterization of DC subtype infiltration into an immunotherapy-resistant model of breast cancer revealed that impairment of DC1s through 2 unique models resulted in enhanced DC2 functionality and improved tumor control. BATF3 deficiency depleted intratumoral DC1s, which led to increased DC2 lymph node migration and CD4+ T cell activation. Enhancing DC2 stimulatory potential by genetic deletion of Hsp90b1 (encoding molecular chaperon GP96) led to a similar enhancement of T cell immunity and improved survival in a spontaneous breast cancer model. These data highlight the therapeutic and prognostic potential of DC2s within checkpoint blockade-resistant tumors.

Clip Chemistry: Diverse (Bio)(macro)molecular and Material Function through Breaking Covalent Bonds.

In the two decades since the introduction of the "click chemistry" concept, the toolbox of "click reactions" has continually expanded, enabling chemists, materials scientists, and biologists to rapidly and selectively build complexity for their applications of interest. Similarly, selective and efficient covalent bond breaking reactions have provided and will continue to provide transformative advances. Here, we review key examples and applications of efficient, selective covalent bond cleavage reactions, which we refer to herein as "clip reactions." The strategic application of clip reactions offers opportunities to tailor the compositions and structures of complex (bio)(macro)molecular systems with exquisite control. Working in concert, click chemistry and clip chemistry offer scientists and engineers powerful methods to address next-generation challenges across the chemical sciences.

Molecular Chaperone GRP94/GP96 in Cancers: Oncogenesis and Therapeutic Target.

During tumor development and progression, intrinsic and extrinsic factors trigger endoplasmic reticulum (ER) stress and the unfolded protein response, resulting in the increased expression of molecular chaperones to cope with the stress and maintain tumor cell survival. Heat shock protein (HSP) GRP94, also known as GP96, is an ER paralog of HSP90 and has been shown to promote survival signaling during tumor-induced stress and modulate the immune response through its multiple clients, including TLRs, integrins, LRP6, GARP, IGF, and HER2. Clinically, elevated expression of GRP94 correlates with an aggressive phenotype and poor clinical outcome in a variety of cancers. Thus, GRP94 is a potential molecular marker and therapeutic target in malignancies. In this review, we will undergo deep molecular profiling of GRP94 in tumor development and summarize the individual roles of GRP94 in common cancers, including breast cancer, colon cancer, lung cancer, liver cancer, multiple myeloma, and others. Finally, we will briefly review the therapeutic potential of selectively targeting GRP94 for the treatment of cancers.

The psychology of bio-banding: a Vygotskian perspective.

CONTEXT: Bio-banding is the process of grouping players by their maturational status rather than chronological age. It is designed to limit the impact of maturational timing on talent identification and development and expose early and late maturing players to new learning experiences and challenges. A common criticism of bio-banding is that it does not consider age related differences in psychosocial and behaviour development. OBJECTIVE: The purpose of this case study is to describe how theory and research pertaining to the design and delivery of mixed-aged classrooms can be used to prepare early and late maturing players for bio-banding and optimise the benefits of this practice. METHOD: After placing the players in their bio-banded groups, one Elite Premier League Academy provided bespoke group psychology sessions for early and late maturing players for six weeks. RESULTS: Providing bespoke psychology sessions for players maturation age allows for the cognitive processes of both early and late maturity status to work within the zone of proximal development. CONCLUSION: Pedagogical practice associated with mixed age classrooms can be used in bio-banded contexts to benefit both early and late maturing players. Delivering psychological sessions alongside bio-banding permits learning and development to both ends of the maturity spectrum.

Remote Doping of Scalable Nanowire Branches.

Selective-area epitaxy provides a path toward high crystal quality, scalable, complex nanowire networks. These high-quality networks could be used in topological quantum computing as well as in ultrafast photodetection schemes. Control of the carrier density and mean free path in these devices is key for all of these applications. Factors that affect the mean free path include scattering by surfaces, donors, defects, and impurities. Here, we demonstrate how to reduce donor scattering in InGaAs nanowire networks by adopting a remote-doping strategy. Low-temperature magnetotransport measurements indicate weak anti-localization-a signature of strong spin-orbit interaction-across a nanowire Y-junction. This work serves as a blueprint for achieving remotely doped, ultraclean, and scalable nanowire networks for quantum technologies.

Relative age and maturation selection biases in academy football.

This study examined the simultaneous effects of relative age and biological maturity status upon player selection in an English professional soccer academy. A total of 202 players from the U9 to U16 age groups, over an eight-year period (total of 566 observations), had their relative age (birth quarter) and biological maturity (categorised as late, on-time or early maturing based upon the Khamis-Roche method of percentage of predicted adult height at time of observation) recorded. Players born in the first birth quarter of the year (54.8%) were over-represented across all age groups. A selection bias towards players advanced in maturity status for chronological age emerged in U12 players and increased with age; 0% of players in the U15 and U16 age group were categorised as late maturing. A clear maturity selection bias for early maturing players was, however, only apparent when the least conservative criterion for estimating maturity status was applied (53.8% early and 1.9% late maturing in the U16 age group). Professional football academies need to recognise relative age and maturation as independent constructs that exist and operate independently. Thus, separate strategies should perhaps be designed to address the respective selection biases, to better identify, retain and develop players.

Metabolites produced by Batrachochytrium dendrobatidis alter development in tadpoles, but not growth or mortality.

The mass decline of amphibian populations poses a serious threat to global biodiversity and ecosystem stability. The pathogenic fungus Batrachochytrium dendrobatidis (Bd) has contributed to the extirpation and extinction of hundreds of amphibian species worldwide. Bd produces potentially damaging metabolites during the host infection process that may affect amphibian growth and development, even in the absence of infection. In this experiment, Cuban tree frog Osteopilus septentrionalis tadpoles and adults were exposed once to either artificial spring water (ASW) or Bd metabolites (n = 31 tadpoles per treatment and n = 30 and 20 adults per treatment, respectively). Tadpoles exposed to Bd metabolites alone developed faster than those exposed to ASW; however, there was no difference in tadpole length, weight change, or mortality between treatments. Despite the faster developmental speed, metabolite exposure did not reduce tadpole weight or length (compared at Gosner stages 27, 29, and 31). There was no effect of treatment on adult size or mortality. These results indicate that both tadpole and adult O. septentrionalis do not appear to be negatively impacted by exposure to non-infectious Bd-contaminated water. In fact, tadpoles developed faster when exposed to metabolites and were of equal size as those in their stage cohort, implying a potential long-term benefit if faster development allows them to leave Bd-infected waters sooner.