Military Blood Supply and Distribution in USCENTCOM.

In expeditionary environments, the consistent availability of blood for casualty care is imperative yet challenging. Responding to evidence and the specific needs of its expeditionary context, the US Central Command (USCENTCOM) prioritized supplying stored low titer O whole blood (LTOWB) to its units from March, 2023 onward. A strategy was devised to set minimal LTOWB on-hand supply benchmarks, determined by the number of operating beds and point of injury teams. This transition led to a 54% reduction in orders for packed red blood cells. As a countermove, the Armed Services Blood Program (ASBP) enhanced LTOWB production at a conversion rate 2:1 from packed red blood cell to LTOWB. Consequently, there was a decline in expired blood products, and fulfillment rates for blood requests are projected to reach 100% consistently. This paper delves into the intricacies of the expeditionary blood supply, the rationale behind the LTOWB transition, the devised allocation strategy, and the subsequent impacts of this change.

The USCENTCOM Walking Blood Bank Performance Benchmark and Anticipated Benefit of Universal Low Titer Type O Screening.

The walking blood bank (WBB) is a system for emergency blood acquisition from nearby donors if a patient's blood needs exceed the immediate supply. USCENTCOM medical units will perform a walking blood bank if immediate blood requirements exceed the local supply. A benchmark WBB performance time was needed to provide a training goal for military WBB exercises. An expeditionary WBB performance time benchmark was created from prospective measurements of USCENTCOM medical unit performance times over 9 months. The mean total time, and new performance benchmark, for a WBB in USCENTCOM was 41.4 min +/- 13.2 min. USCENTCOM time from donor arrival to a transfusable unit mean time was 34.4 +/- 12.1 min. Expeditionary medical units conducting a WBB should expect to meet or exceed the provided benchmark.

Enhanced carrier densities in two-dimensional electron gas formed at BaSnO3/SrTaO3and SrSnO3/SrTaO3interfaces.

Two-dimensional electron gases (2DEGs) realized at perovskite oxide interfaces offer great promise for high charge carrier concentrations and low-loss charge transport. BaSnO3(BSO) and SrSnO3(SSO) are well-known wide bandgap semiconductors for their high mobility due to the Sn-5s-dominated conduction band minimum (CBM). Ta4+with a 5d1valence configuration in SrTaO3(STaO) injects thed1electron across the interface into the unoccupied Sn-5sstates in BSO and SSO. The present study uses ACBN0 density functional theory computations to explore charge transfer and 2DEG formation at BSO/STaO and SSO/STaO interfaces. The results of the ACBN0 computations confirm the Ta-5dto Sn-5scharge transfer. Moreover, the Sn-5s-dominated CBM is located ∼1.4 eV below the Fermi level, corresponding to an excess electron density in BSO of ∼1.5 × 1021cm-3, a ∼50% increase in electron density compared to the previously studied BSO/SrNbO3(SNO) interface. Similarly, the SSO/STaO interface shows an improvement in interface electron density by ∼20% compared to the BSO/SNO interface. The improved carrier density in SSO/STaO and BSO/STaO is further supported by ∼13% and ∼15% increase in electrical conductivities compared to BSO/SNO. In summary, BSO/STaO and SSO/STaO interfaces provide novel material platforms for 2DEGs formation and ultra-low-loss electron transport.

Engineering metal oxidation using epitaxial strain.

The oxides of platinum group metals are promising for future electronics and spintronics due to the delicate interplay of spin-orbit coupling and electron correlation energies. However, their synthesis as thin films remains challenging due to their low vapour pressures and low oxidation potentials. Here we show how epitaxial strain can be used as a control knob to enhance metal oxidation. Using Ir as an example, we demonstrate the use of epitaxial strain in engineering its oxidation chemistry, enabling phase-pure Ir or IrO2 films despite using identical growth conditions. The observations are explained using a density-functional-theory-based modified formation enthalpy framework, which highlights the important role of metal-substrate epitaxial strain in governing the oxide formation enthalpy. We also validate the generality of this principle by demonstrating epitaxial strain effect on Ru oxidation. The IrO2 films studied in our work further revealed quantum oscillations, attesting to the excellent film quality. The epitaxial strain approach we present could enable growth of oxide films of hard-to-oxidize elements using strain engineering.

High Mobility Two-Dimensional Electron Gas at the BaSnO3/SrNbO3 Interface.

Oxide two-dimensional electron gases (2DEGs) promise high charge carrier concentrations and low-loss electronic transport in semiconductors such as BaSnO3 (BSO). ACBN0 computations for BSO/SrNbO3 (SNO) interfaces show Nb-4d electron injection into extended Sn-5s electronic states. The conduction band minimum consists of Sn-5s states ∼1.2 eV below the Fermi level for intermediate thickness 6-unit cell BSO/6-unit cell SNO superlattices, corresponding to an electron density in BSO of ∼1021 cm-3. Experimental studies of analogous BSO/SNO interfaces grown by molecular beam epitaxy confirm significant charge transfer from SNO to BSO. In situ angle-resolved X-ray photoelectron spectroscopy studies show an electron density of ∼4 × 1021 cm-3. The consistency of theory and experiments show that BSO/SNO interfaces provide a novel materials platform for low loss electron transport in 2DEGs.

Incorporation of Ti in epitaxial Fe2TiO4thin films.

The titanomagnetites (Fe2-xTixO4,x⩽ 1) are a family of reducible spinel-structure oxides of interest for their favorable magnetic, catalytic, and electrical transport properties. To understand the stability of the system during low temperature deposition, epitaxial thin films of Fe2TiO4were deposited by molecular beam epitaxy (MBE) on MgO(001) at 250-375 °C. The homogeneous incorporation of Ti, Fe valence state, and film morphology were all found to be strongly dependent on the oxidation conditions at the low substrate temperatures employed. More oxidizing conditions led to phase separation into epitaxial, faceted Fe3O4and rutile TiO2. Less oxidizing conditions resulted in polycrystalline films that exhibited Ti segregation to the film surface, as well as mixed Fe valence (Fe3+, Fe2+, Fe0). A narrow window of intermediate oxygen partial pressure during deposition yielded nearly homogeneous Ti incorporation and a large fraction of Fe2+. However, these films were poorly crystallized, and no occupation of tetrahedral sites in the spinel lattice by Fe2+was detected by x-ray magnetic circular dichroism at the Fe L-edge. After vacuum annealing, a small fraction of Fe2+was found to occupy tetrahedral sites. Comparison of these results with previous work suggests that the low temperature deposition conditions imposed by use of MgO substrates limits the incorporation of Ti into the spinel lattice. This work suggests a path towards obtaining stoichiometric, well-crystallized Fe2TiO4by MBE by utilizing high substrate temperature and low oxygen partial pressure during deposition on thermally stable substrates.

Electronic and structural properties of single-crystal Jahn-Teller active Co1+x Mn2-x O4 thin films.

Recent investigations on spinel CoMn2O4 have shown its potential for applications in water splitting and fuel cell technologies as it exhibits strong catalytic behavior through oxygen reduction reactivity. To further understand this material, we report for the first time the synthesis of single-crystalline Co1+x Mn2-x O4 thin films using molecular beam epitaxy. By varying sample composition, we establish links between cation stoichiometry and material properties using in-situ x-ray photoelectron spectroscopy, x-ray diffraction, scanning transmission electron microscopy, x-ray absorption spectroscopy, and spectroscopic ellipsometry. Our results indicate that excess Co ions occupy tetrahedral interstitial sites at lower excess Co stoichiometries, and become substitutional for octahedrally-coordinated Mn at higher Co levels. We compare these results with density functional theory models of stoichiometric CoMn2O4 to understand how the Jahn-Teller distortion and hybridization in Mn-O bonds impact the ability to hole dope the material with excess Co. The findings provide important insights into CoMn2O4 and related spinel oxides that are promising candidates for inexpensive oxygen reduction reaction catalysts.

Electronic and Structural Properties of Single-crystal Jahn-Teller Active Co1+xMn2-xO4Thin Films.

Recent investigations on spinel CoMn2O4have shown its potential for applications in water splitting and fuel cell technologies as it exhibits strong catalytic behavior through oxygen reduction reactivity. To further understand this material, we report for the first time the synthesis of single-crystalline Co1+xMn2-xO4thin films using molecular beam epitaxy. By varying sample composition, we establish links between cation stoichiometry and material properties using in-situ x-ray photoelectron spectroscopy, x-ray diffraction, scanning transmission electron microscopy, x-ray absorption spectroscopy, and spectroscopic ellipsometry. Our results indicate that excess Co ions occupy tetrahedral interstitial sites at lower excess Co stoichiometries, and become substitutional for octahedrally-coordinated Mn at higher Co levels. We compare these results with density functional theory models of stoichiometric CoMn2O4to understand how the Jahn-Teller distortion and hybridization in Mn-O bonds impact the ability to hole dope the material with excess Co. The findings provide important insights into CoMn2O4and related spinel oxides that are promising candidates for inexpensive oxygen reduction reaction catalysts.

Tuning piezoelectric properties through epitaxy of La2Ti2O7 and related thin films.

Current piezoelectric sensors and actuators are limited to operating temperatures less than ~200 °C due to the low Curie temperature of the piezoelectric material. Strengthening the piezoelectric coupling of high-temperature piezoelectric materials, such as La2Ti2O7 (LTO), would allow sensors to operate across a broad temperature range. The crystalline orientation and piezoelectric coupling direction of LTO thin films can be controlled by epitaxial matching to SrTiO3(001), SrTiO3(110), and rutile TiO2(110) substrates via pulsed laser deposition. The structure and phase purity of the films are investigated by x-ray diffraction and scanning transmission electron microscopy. Piezoresponse force microscopy is used to measure the in-plane and out-of-plane piezoelectric coupling in the films. The strength of the out-of-plane piezoelectric coupling can be increased when the piezoelectric direction is rotated partially out-of-plane via epitaxy. The strongest out-of-plane coupling is observed for LTO/STO(001). Deposition on TiO2(110) results in epitaxial La2/3TiO3, an orthorhombic perovskite of interest as a microwave dielectric material and an ion conductor. La2/3TiO3 can be difficult to stabilize in bulk form, and epitaxial stabilization on TiO2(110) is a promising route to realize La2/3TiO3 for both fundamental studies and device applications. Overall, these results confirm that control of the crystalline orientation of epitaxial LTO-based materials can govern the resulting functional properties.

Influence of LaFeO3 Surface Termination on Water Reactivity.

The polarity of oxide surfaces can dramatically impact their surface reactivity, in particular, with polar molecules such as water. The surface species that result from this interaction change the oxide electronic structure and chemical reactivity in applications such as photoelectrochemistry but are challenging to probe experimentally. Here, we report a detailed study of the surface chemistry and electronic structure of the perovskite LaFeO3 in humid conditions using ambient-pressure X-ray photoelectron spectroscopy. Comparing the two possible terminations of the polar (001)-oriented surface, we find that the LaO-terminated surface is more reactive toward water, forming hydroxyl species and adsorbing molecular water at lower relative humidity than its FeO2-terminated counterpart. However, the FeO2-terminated surface forms more hydroxyl species during water adsorption at higher humidity, suggesting that adsorbate-adsorbate interactions may impact reactivity. Our results demonstrate how the termination of a complex oxide can dramatically impact its reactivity, providing insight that can aid in the design of catalyst materials.

Interface Structure, Band Alignment, and Built-In Potentials at LaFeO_{3}/n-SrTiO_{3} Heterojunctions.

Interface structure at polar-nonpolar interfaces has been shown to be a key factor in controlling emergent behavior in oxide heterostructures, including the LaFeO_{3}/n-SrTiO_{3} system. We demonstrate via high-energy-resolution x-ray photoemission that epitaxial LaFeO_{3}/n-SrTiO_{3}(001) heterojunctions engineered to have opposite interface polarities exhibit very similar band offsets and potential gradients within the LaFeO_{3} films. However, differences in the potential gradient within the SrTiO_{3} layer depending on polarity may promote hole diffusion into LaFeO_{3} for applications in photocatalysis.

Predictive Control over Charge Density in the Two-Dimensional Electron Gas at the Polar-Nonpolar NdTiO_{3}/SrTiO_{3} Interface.

Through systematic control of the Nd concentration, we show that the carrier density of the two-dimensional electron gas (2DEG) in SrTiO_{3}/NdTiO_{3}/SrTiO_{3}(001) can be modulated over a wide range. We also demonstrate that the NdTiO_{3} in heterojunctions without a SrTiO_{3} cap is degraded by oxygen absorption from air, resulting in the immobilization of donor electrons that could otherwise contribute to the 2DEG. This system is, thus, an ideal model to understand and control the insulator-to-metal transition in a 2DEG based on both environmental conditions and film-growth processing parameters.

Infrared optical absorption in low-spin Fe(2+)-doped SrTiO3.

Band gap engineering in SrTiO3 and related titanate perovskites has long been explored due to the intriguing properties of the materials for photocatalysis and photovoltaic applications. A popular approach in the materials chemistry community is to substitutionally dope aliovalent transition metal ions onto the B site in the lattice to alter the valence band. However, in such a scheme there is limited control over the dopant valence, and compensating defects often form. Here we demonstrate a novel technique to controllably synthesize Fe(2+)- and Fe(3+)-doped SrTiO3 thin films without formation of compensating defects by co-doping with La(3+) ions on the A site. We stabilize Fe(2+)-doped films by doping with two La ions for every Fe dopant, and find that the Fe ions exhibit a low-spin electronic configuration, producing optical transitions in the near infrared regime and degenerate doping. The novel electronic states observed here offer a new avenue for band gap engineering in perovskites for photocatalytic and photovoltaic applications.

Directed self-assembly of epitaxial CoFe2O(4)-BiFeO3 multiferroic nanocomposites.

CoFe(2)O(4) (CFO)-BiFeO(3) (BFO) nanocomposites are an intriguing option for future memory and logic technologies due to the magnetoelectric properties of the system. However, these nanocomposites form with CFO pillars randomly located within a BFO matrix, making implementation in devices difficult. To overcome this, we present a technique to produce patterned nanocomposites through self-assembly. CFO islands are patterned on Nb-doped SrTiO(3) to direct the self-assembly of epitaxial CFO-BFO nanocomposites, producing square arrays of CFO pillars.