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Enhanced thermoelectric performance of PbSe-graphene nanocomposite manufactured with acoustic cavitation induced defects

An order of magnitude rise in the thermoelectric (TE) performance of the PbSe, a scalable and easy-to-manufacture TE material, has been achieved by incorporating reduced graphene oxide (Gr) nanoplatelets in a PbSe/PbSeO 3 heterostructure formed by acoustic cavitation-assisted oxidation. The fabricated Gr/PbSe/PbSeO 3 nanocomposites exhibit high TE performance with an exceptionally high Seebeck coefficient coupled with low thermal conductivity. The variation in the Seebeck coefficient has been attributed to a reduction in charge carrier mobility due to the ferroelectric polarization effect. Furthermore, the increase in electrical resistivity is minimized by adding graphene. At an optimal weight fraction (0.2 wt%), graphene nano-inclusions lead to superior Seebeck coefficient values as high as ~2000 μV/K at ~500 K, providing high overall TE performance. This study shows substantial changes in the TE properties of PbSe through the incorporation of graphene and PbSeO 3 . The understanding and methodology developed in this study can be exploited for the scalable manufacturing of high-performance TE materials.

Structure-property correlations↗

Graphene oxide precursor effects on 3D-printed carbon scaffolds

Manganese oxide (MnO 2 ), an earth-abundant material, is a promising component for energy storage devices, with uses in both pseudocapacitors and batteries. However, high MnO 2 loading often leads to reduced performance due to poor ion diffusion. 3D printing, particularly using the direct ink writing (DIW) technique, offers a solution by enabling the fabrication of electrodes with hierarchical porous structures and open channels that enhance mass transport and ion diffusion. Previous work demonstrated that 3D-printed graphene aerogels with MnO 2 coatings exhibited excellent electrochemical performance, even with thick electrodes, due to their optimized structure. Building on this work, the current study investigates the performance differences between aerogels developed using graphene oxide (GO) and reduced graphene oxide (rGO) as carbon precursors. Both materials were incorporated into thixotropic inks, 3D-printed into lattice structures, and carbonized. Despite expected similarities between the final graphene aerogel, rGO-based aerogels exhibited superior areal capacitance, compared to GO-based aerogels. These differences are attributed to the lower oxygen content and defect density of rGO, which influence its interaction with cellulose viscosifiers in the ink formulation. Brunauer–Emmett–Teller (BET) surface area analysis revealed that rGO aerogels exhibit a larger surface area and mesoporous structure, further enhancing their performance. When coated with MnO 2 , rGO-based aerogels maintained their superior capacitive behavior over GO-based aerogels. This study highlights the effect of carbon precursor on the end performance of graphene aerogels.

Materials science↗

Oxygen stable isotopes in the nuclear fuel cycle: Assessment of the potential for determining the fabrication and provenance history of anhydrous and hydrous uranium oxides

Determining the origin and history of interdicted nuclear materials is a central challenge in nuclear forensics. The oxygen stable isotope composition of uranium oxide compounds has emerged as a promising forensic signature, attracting increasing attention since the early 2000s. This review examines analytical techniques for measuring oxygen isotope compositions in uranium oxides and evaluates how the nuclear fuel production cycle introduces or modifies these isotopic signatures. The potential for forensic geolocation is explored through workflows that calibrate the relationship between environmental water oxygen isotopes and those found in uranium oxides. Key strengths and limitations of this approach are assessed, including gaps in knowledge related to isotope fractionation during specific stages of the fuel cycle, and processing facility water inputs. The importance of proper sample handling and storage under inert atmospheres, as well as a deeper understanding of both intra-sample oxygen isotope heterogeneity, and hydrous uranium oxide phase formation, is highlighted for improving the reliability of forensic interpretations. In conclusion, the development of uranium oxide standards with well-characterized δ 18 O values and international collaboration toward consensus on their use are identified as essential steps for advancing the field.

Attribution↗

The Development of a CO2 Test Capability in the NASA JSC ARCJet for Mars Reentry Simulation

The Atmospheric Reentry Materials and Structures Evaluation Facility (ARMSEF) located at NASA Johnson Space Center is used for simulating the extreme environment experienced upon reentry for the development and certification of thermal protection systems (TPS). The facility supports a large variety of programs and was heavily leveraged for the certification and operational support of the TPS for the Orbiter and, more recently, the development of the heat shield for CEV. This paper will provide more detail into the heritage of the facility. Unique attributes of the facility include a modular aerodynamically stabilized arc heater and independently controlled O2 and N2 for the test gases. When combining the O2 and N2 in a 23:77 mass ratio respectively the Earth s atmosphere is accurately simulated and via modification of this ratio the investigation of the effects of atomic oxygen on a material s response is possible. In the summer of 2010 a development effort was started to add CO2 as a third independently controlled test gas such that, when combined with N2, opens up the possibility of accurately simulating a Martian reentry environment. This paper will discuss the test facility, especially the arc heater, in more detail. Initial testing involved relatively low concentrations of CO2 combined with N2 for the primary purpose of gathering data to answer two pressing safety concerns. The first being the rate of production of carbon monoxide (CO) within the ejector vacuum system. The main concern was that CO can be flammable and possibly explosive at high enough concentrations and pressures. The hazard control during the development phase involved the use of injecting N2 inside the test chamber diffuser to dilute and reduce the concentration of any and all CO present. A residual gas analyzer (RGA) was used to determine the relative amount of CO in the exhaust gas and provide a conversion rate of CO2 to CO. This paper will discuss in more detail the results of the RGA data and the calculated conversion rate. The second safety concern addressed is the possible formation of hydrogen cyanide (HCN) and cyanide (CN). HCN would primarily be present in the cooling water while the CN would most probably condense onto the interior surfaces of the test chamber. Water samples and wipes of the test chamber surfaces were analyzed by an industrial hygienist for the presence of HCN and CN. His paper will discuss these results in more detail. Throughout this development effort measurements of the CO2:N2 flowfield were made with heat flux and pressure probes and with laser induced fluorescence (LIF) of the atomic oxygen. This paper will discuss these results

DelPapa, Steven V.↗

Combustion of metal powder with dinitrogen tetroxide

In this work, we present analysis of a novel reactive material system that employs dinitrogen tetroxide (N 2 O 4 ) as a liquid oxidizer with metal powder fuels. The oxidizer was added to micron scale aluminum and zirconium powders by a remote injection system. When ignited with a high voltage spark, the mixtures were observed to possess reactivity comparable to nanocomposite reactive materials, with open-tube flame expansion velocities from 500 to 1400 m/s depending on fuel/oxidizer ratio and tube diameter. Temperatures were observed to range from 3000 to 3500 K as measured with gray body fits to 16-channel time-resolved pyrometer and time-integrated spectrometer data. These values were significantly below calculated adiabatic flame temperatures, which we attribute to local deviations from stoichiometry and kinetic/energetic limitations similar to those observed in studies of particles burning in high pressures gaseous oxidizers. Al/N 2 O 4 reactivity was found to be most likely limited by the vaporization of the metal from the particle surface and Zr/N 2 O 4 was limited by slower burning and complex interactions involving the solubility of nitrogen and oxygen in the molten Zr. We also discuss the potential for these materials to be used to create an “on/off” reactive material, since N2O4 can be added remotely and driven to evaporate via vacuum or purge of inert gases to return it to a safe condition.

36 MATERIALS SCIENCE↗

Ionic Dopant-Induced Ordering Enhances the Thermoelectric Properties of a Polythiophene-Based Block Copolymer

Conjugated polymer-based block copolymers (CP-BCPs) are an unexplored class of materials for organic thermoelectrics. In this study, the authors report on the electronic conductivity (σ) and Seebeck coefficient (α) of a newly synthesized CP-BCP, poly(3-hexylthiophene)-block-poly (oligo-oxyethylene methacrylate) (P3HT-b-POEM), upon solution co-processing with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and subsequently vapor-doping with a molecular dopant, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ). It is found that the addition of the hydrophilic block POEM greatly enhances the processability of P3HT, enabling homogeneous solution-mixing with LiTFSI. Notably, interactions between P3HT-b-POEM with ionic species significantly improve molecular order and unexpectedly cause electrical oxidizing doping of P3HT block both in solution and solid-states, a phenomenon that has not been previously observed in Li-salt containing P3HT. Vapor doping of P3HT-b-POEM-LiTFSI thin films with F4TCNQ further enhances σ and yields a thermoelectric power factor PF = α 2 σ of 13.0 μW m -1 K -2 , which is more than 20 times higher than salt-free P3HT-b-POEM sample. Through modeling thermoelectric behaviors of P3HT-b-POEM with the Kang-Snyder transport model, the improvement in PF is attributed to higher electronic charge mobility originating from the enhanced molecular ordering of P3HT. The results demonstrate that solution co-processing CP-BCPs with a salt is a powerful method to control structure and performance of organic thermoelectric materials.

36 MATERIALS SCIENCE↗

Will high-entropy carbides and borides be enabling materials for extreme environments?

Abstract The concept of multi-principal component has created promising opportunities for the development of novel high-entropy ceramics for extreme environments encountered in advanced turbine engines, nuclear reactors, and hypersonic vehicles, as it expands the compositional space of ceramic materials with tailored properties within a single-phase solid solution. The unique physical properties of some high-entropy carbides and borides, such as higher hardness, high-temperature strength, lower thermal conductivity, and improved irradiation resistance than the constitute ceramics, have been observed. These promising properties may be attributed to the compositional complexity, atomic-level disorder, lattice distortion, and other fundamental processes related to defect formation and phonon scattering. This manuscript serves as a critical review of the recent progress in high-entropy carbides and borides, focusing on synthesis and evaluations of their performance in extreme high-temperature, irradiation, and gaseous environments.

36 MATERIALS SCIENCE↗

First-results from the Perseverance SHERLOC Investigation: Aqueous Alteration Processes and Implications for Organic Geochemistry in Jezero Crater, Mars

The Perseverance rover landed in Jezero crater, a site selected to fulfill the Mars-2020 mission goals of characterizing the geology of habitable environments and searching for signs of life while collecting samples for return to Earth [1]. Jezero hosted an open-basin lake during the late Noachian/early Hesperian (~3.7 Ga) [1-2], has units associated with the largest carbonate deposit identified on Mars [3-4], and has a well-preserved delta with clay and carbonate-bearing sediments, well-suited to preservation of organics [1,3-4]. Investigating the nature of organics and aqueous environments within their geologic con-text allows us to understand important aqueous processes and determine habitability within Jezero crater. Previous in situ landed measurements of organics could not resolve their spatial and mineralogical con-text [5-6]. Although Martian meteorites lack geological context, the spatial distribution of organic compounds in Martian meteorites have allowed recognition of an association between aqueous processes and organics [7-8]. Here, we show for the first time in-situ associations between carbonate-forming ultramafic alteration process, later stage aqueous sulfate and perchlorate formation, and organics on the Martian surface. Methodology and geological context: We use the Perseverance rover’s SHERLOC instrument (Scanning Habitable Environments with Raman and Lumines-ence of Organics and Chemicals), a deep-ultraviolet fluorescence and Raman scattering spectrometer capable of mapping the organic and mineral composition with a spatial resolution of 100 μm resolution to report the presence of organics and aqueously formed minerals at Jezero crater [9]. These spectral detections were compared with co-located images obtained with the autofocus context imager (ACI) and the WATSON camera for textural analysis [9]. As of writing, the Per-severance rover has abraded five targets that were measured with the SHERLOC instrument. The five targets are located in two different orbitally-identified geological units within the floor of Jezero crater; the Crater Floor Fractured Rough unit (CF-Fr) and the Séítah region within the Crater Floor Fractured 1 unit (CF-F1) [10]. In orbital infrared spectroscopic data, the CF-Fr unit is associated with pyroxene spectral signatures and minor alteration, while the Séítah region is associated with olivine and minor Mg-rich carbonates and clays [3-4,10]. Carbonation of ultramafic protolith recorded within Jezero crater: All scans of abraded targets within the Séítah region reveal strong peaks at 1080–1090 cm−1 consistent with carbonate and peak singlets or doublets at 820–840 cm−1 attributed to olivine (Fig. 1), consistent with orbital infrared observations. Our detailed micron-scale petrographic and spectroscopic evidence shows that these carbonates formed through carbonation of an ultramafic protolith. The supporting observations include: (1) Carbonate cation compositions match those of olivine, suggesting mixed Fe- and Mg-olivine gave rise to mixed Fe- and Mg-carbonates, similar to observations of ultramafic systems on Earth and within Martian meteorites [3-4,7-8]. (2) The ob-served carbonates co-occur with hydrated materials, gypsum, and potentially aqueously-formed phases, amorphous silicates and phosphate. (3) The spectral and textural variation of olivine and carbonate dominated zones and olivine-carbonate mixtures within both primary grains and interstitial zones are expected for carbonated ultramafic protoliths. (4) These mineral associations and textures closely resemble those observed within the ALH84001 and Nakhlite meteorites attributed to olivine carbonation on Mars [6-7]. Taken together, micron-scale SHERLOC documentation of these phenomena bridge previous orbital and meteorite observations and demonstrate in-situ regionally extensive (~106 km2) ultramafic alteration resulting in geo-logical deposition of carbonates. Furthermore, we observe that olivine carbonation was involved in preserving and possibly synthesizing organics, which makes this environment potentially habitable, as previously suggested in [1,3-4] (Fig. 1). Late-stage aqueous perchlorate and sulfate in Jezero crater: An abrasion target within the CF-Fr unit contains combinations of high intensity 950-955 cm−1 peaks and minor 1090-1095 cm−1 and 1150-1155 cm−1 peaks that are spectral fits to anhydrous perchlorate (Fig. 1). Some spectra show a combination of 950-955 cm−1 peaks with equally strong 1010-1020 cm−1 peaks, low intensity broad features at 1120 cm−1, and occasional broad 3450 cm−1 hydration (-OH) features, indicating a mixture of Ca-sulfate and perchlorate that is minimally hydrated (Fig. 1). The detections of per-chlorates within Jezero crater differ from previous measurements (e.g. Phoenix lander, Curiosity rover, Tissint meteorite [7,11]) because they are observed to be intimately related to aqueous processes including sulfate formation, they present as a secondary white void-fill occurring within the interior of the rock, and they are found to likely be Na-perchlorate. implications for their formation: Three different types of organics embedded within three different lithologies were observed within the abraded targets. Organics associated with low intensity ~340 nm fluorescence were widespread within targets with no apparent association to particular minerals (Fig. 1). Organics associated with ~305 nm and ~275 nm fluorescence correlated with sulfates within the Bellegarde target in the CF-Fr unit, while organics associated with high intensity ~340 nm fluorescence correlated with carbonate, phosphate, and amorphous silicate mixtures within the Garde target in the Séítah region (Fig. 1). Although assignment of fluorescence signatures to specific organic compounds is not conclusive, ~340 nm fluorescence is generally more consistent with 2-ring aromatic organics, ~275 nm fluorescence is more consistent with 1-ring aromatic organics, and ~305 nm fluorescence can be created by either 2- or 1-ring aromatics [12]. These observations indicate that the strongest fluorescence signatures interpreted as organics were found in materials associated with aqueous processes, i.e. sulfate- and carbonate-bearing materials, suggesting both brines and ultramafic carbonation aqueous environments were capable of preserving organics on ancient Mars. In Martian meteorites, simple aromatic organics proposed to have been synthesized through aqueous processes can be found within minerals associated with olivine carbonation and in spatial association with perchlorate and sulfate materials [7-8], similar to SHERLOC observations. Hence, we advance an abiotic aqueous synthesis origin for the organics although we cannot rule out the presence of organics from meteoritic in-fall or putative organic biosignatures. Detailed analyses will be required upon return of these materials to Earth.

E L Scheller↗

Photochemical Decomposition of Y‐Series Non‐Fullerene Acceptors Is Responsible for Degradation of High‐Efficiency Organic Solar Cells

Abstract Organic photovoltaic cells that employ Y‐series non‐fullerene acceptors (NFAs) have recently achieved impressive power‐conversion efficiencies (>18%). To fulfill their commercial promise, it is important to quantify their operational lifetimes and understand their degradation mechanisms. In this work, the spectral‐dependent photostability of films and solar cells comprising several Y‐series acceptors and the donor polymer PM6 is investigated systematically. By applying longpass filters during aging, it is shown that UV/near‐UV photons are responsible for the photochemical decomposition of Y‐series acceptors; this degradation is the primary driver of early solar cell performance losses. Using mass spectrometry, the vinylene linkage between the core and electron‐accepting moieties of Y‐series acceptors is identified as the weak point susceptible to cleavage under UV‐illumination. Employing a series of device characterization, along with numerical simulations, the efficiency losses in organic photovoltaic cells are attributed to the formation of traps, which reduces charge extraction efficiency and facilitates non‐radiative recombination as the Y‐series acceptors degrade. This study provides new insights for molecular degradation of organic photovoltaic absorber materials and highlights the importance of future molecular design and strategies for improved solar cell stability.

14 SOLAR ENERGY↗

Controlling Valley-Specific Light Emission from Monolayer MoS 2 with Achiral Dielectric Metasurfaces

Excitons in two-dimensional transition metal dichalcogenides have a valley degree of freedom that can be optically manipulated for quantum information processing. Here, we integrate MoS 2 monolayers with achiral silicon disk array metasurfaces to enhance and control valley-specific absorption and emission. Through the coupling to the metasurface electric and magnetic Mie modes, the intensity and lifetime of the emission of neutral excitons, trions, and defect bound excitons can be enhanced and shortened, respectively, while the spectral shape can be modified. Additionally, the degree of polarization (DOP) of exciton and trion emission from the valley can be symmetrically enhanced at 100 K. The DOP increase is attributed to both the metasurface-enhanced chiral absorption of light and the metasurface-enhanced exciton emission from the Purcell effect. Finally, combining Si-compatible photonic design with large-scale 2D materials integration, our work makes an important step toward on-chip valleytronic applications approaching room-temperature operation.

2D materials↗

Yttrium-based Double Perovskite Nanorods for Electrocatalysis

In this work, we investigate the effect of chemical composition of double perovskite nanorods on their versatile electrocatalytic activity not only as supports for the oxidation of small organic molecules but also as catalysts for the oxygen evolution reaction. Specifically, Y 2 CoMnO 6 and Y 2 NiMnO 6 nanorods with average diameters of 300 nm were prepared by a two-step hydrothermal method, in which the individual effects of synthetic parameters, such as the pH, annealing temperature, and precursor ratios on both the composition and morphology, were systematically investigated. When used as supports for Pt nanoparticles, Y 2 CoMnO 6 /Pt catalysts exhibited an electrocatalytic activity for the methanol oxidation reaction, which is 2.1 and 1.3 times higher than that measured for commercial Pt/C and Y 2 NiMnO 6 /Pt. Similarly, the Co-based catalyst support material displayed an ethanol oxidation activity, which is 2.3 times higher than both Pt/C and Y 2 NiMnO 6 /Pt. This clear enhancement in the activity for Y 2 CoMnO 6 can largely be attributed to strong metal-support interactions, as evidenced by a downshift in the binding energy of the Pt 4f bands, measured by XPS, which is often correlated not only with a downshift in the d-band center but also to a decreased adsorption of poisoning adsorbates. Moreover, when used as catalysts for the oxygen evolution reaction, Y 2 CoMnO 6 displayed a much greater activity as compared with Y 2 NiMnO 6 . This behavior can largely be attributed not only to a preponderance of comparatively more favorable oxidation states and electronic configurations but also to the formation of an active layer on the surface of the Y 2 CoMnO 6 catalyst, which collectively give rise to improved performance metrics and greater stability as compared with both IrO 2 and Y 2 NiMnO 6 . Overall, these results highlight the importance of both the chemical composition and the electronic structure of double perovskites, especially when utilized in multi-functional roles as either supports or catalysts.

30 DIRECT ENERGY CONVERSION↗

Heteroanionic Control of Exemplary Second-Harmonic Generation and Phase Matchability in 1D LiAsS 2– x Se x

The isostructural heteroanionic compounds β-LiAsS 2–x Se x (x = 0, 0.25, 1, 1.75, 2) show a positive correlation between selenium content and second-harmonic response and greatly outperform the industry standard AgGaSe 2 . These materials crystallize in the noncentrosymmetric space group Cc as one-dimensional $\frac{1}{∞}$ [AsQ 2 ] - (Q = S, Se, S/Se) chains consisting of corner-sharing AsQ3 trigonal pyramids with charge-balancing Li + atoms interspersed between the chains. LiAsS 2–x Se x melts congruently for 0 ≤ x ≤ 1.75, but when the Se content exceeds x = 1.75, crystallization is complicated by a phase transition. This behavior is attributed to the β- to α-phase transition present in LiAsSe 2 , which is observed in the Se-rich compositions. The band gap decreases with increasing Se content, starting at 1.63 eV (LiAsS 2 ) and reaching 1.06 eV (β-LiAsSe 2 ). Second-harmonic generation measurements as a function of wavelength on powder samples of β-LiAsS 2–x Se x show that these materials exhibit significantly higher nonlinearity than AgGaSe 2 (d 36 = 33 pm/V), reaching a maximum of 61.2 pm/V for LiAsS 2 . In comparison, single-crystal measurements for LiAsSSe yielded a d eff = 410 pm/V. LiAsSSe, LiAsS 0.25 Se 1.75 , and β-LiAsSe 2 show phase-matching behavior for incident wavelengths exceeding 3 μm. The laser-induced damage thresholds from two-photon absorption processes are on the same order of magnitude as AgGaSe 2 , with S-rich materials slightly outperforming AgGaSe 2 and Se-rich materials slightly underperforming AgGaSe 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of heteroatom incorporation on electronic communication in metal chalcogenide nanoclusters

Metal chalcogenide nanoclusters (NC), specifically of type TM 6 E 8 (L) 6 (TM = transition metal, E = chalcogen, L = ligand) have garnered attention in recent years as promising catalysts and biosensors due to their remarkable electronic and magnetic properties, as well as their ability to undergo supramolecular assembly into 2D materials. Furthermore, the undercoordinated metal chalcogenide NCs have shown distinct surface reactivity, which is strongly dependent on the composition of the TM core. The differences in the reactivity of the undercoordinated species have been attributed to differences in ligand binding energies. Although ligand binding energies in homometallic NCs have been extensively studied, little is known about the effect of heteroatoms in the core on the strength of ligand binding in metal chalcogenide NCs. In this work, we provide new insights into this topic by examining the relative stability of [Co 6−x Fe x S 8 (PEt 3 ) 6 ] + (x = 0–6) NCs towards fragmentation using collision energy-resolved collision-induced dissociation (CID) experiments. We observe that the ligand binding energy gradually decreases until four Fe atoms are incorporated into the cluster core and then gradually increases until all the Co atoms are replaced with Fe. This experimental trend was compared with the results of density functional theory (DFT) calculations, which indicate drastic differences in the electronic communication between Co and Fe atoms in the TM core. By understanding the effect of heteroatom incorporation on ligand binding energy to the NC core, our work provides important insights into the effect of atom-by-atom substitution on the functional properties of tunable nanostructures.

Havenridge, Shana [Argonne National Laboratory (AN↗

Demonstration of thermal limit mean transverse energy from cesium antimonide photocathodes

The mean transverse energy (MTE) of electrons emitted from cathodes is a critical parameter that determines the brightness of electron beams for applications, such as x-ray free electron lasers, particle colliders, and ultrafast electron scattering experiments. Achieving a MTE close to the thermal limit is a key step toward realizing the full potential of electron sources in these applications. Cesium antimonide (Cs 3 Sb) is a technologically important material with a long history of use in photon detection and electron sources. The smallest MTE of electrons photoemitted from Cs 3 Sb has always been appreciably greater than the thermal limit and was attributed to surface non-uniformities. In this work, we present comprehensive measurements of the photoemission electron energy spectra (PEES), quantum efficiency, and MTE from Cs 3 Sb in a wide photoexcitation energy range from 1.5 to 2.3 eV. Our PEES measurements demonstrate a notably low photoemission threshold of around 1.5 eV, which is in contrast with the previously perceived threshold of 1.8–2.0 eV. Moreover, we show that the MTE at this threshold of 1.5 eV nearly converges to the thermal limit at 300 K. At 1.8 eV, the MTE measured is 40 meV, which is comparable to the previously reported value. Here, we conclude that this MTE value at 1.8 eV photon energy is not due to surface roughness effects as previously believed, but is a direct consequence of the excess energy.

43 PARTICLE ACCELERATORS↗

Monolithically Integrated $\varepsilon$-Ge/In x Ga 1-x As Quantum Well Laser Design: Experimental and Theoretical Investigation

Here, we have analyzed the electrical and optical phenomenon occurring in a $\varepsilon$-Ge/In x Ga 1-x -Ge/In x Ga 1-x As quantum well (QW) laser through self-consistent physical solvers calibrated using in-house experimental results. A separate confinement heterostructure QW design is proposed to enable lasing from tensile strained germanium ($\varepsilon$-Ge/In x Ga 1-x -Ge) in the range of 1.55 um to 4 um wavelengths as a function of QW thickness and indium (In) composition. Different recombination mechanisms were analyzed as a function of tensile strain in $\varepsilon$-Ge/In x Ga 1-x -Ge QW. Minority carrier lifetime and band alignment are key attributes of a QW laser, which were measured using microwave photoconductive decay and x-ray photoelectron spectroscopy (as a function of In composition), respectively. The transition point of Ge to a direct bandgap material is re-affirmed to be at $\varepsilon$-Ge/In x Ga 1-x = 1.6% (In ~24%) and the transition from type I to type II for $\varepsilon$-Ge/In x Ga 1-x -Ge/In x Ga 1-x As QW is found to be at In ~55%. Also, the transition to a TM mode dominant laser is identified at In ~15%. Using a tunable waveguide design to optimize confinement as a function of In composition, strain, wavelength, QW thickness, refractive index, and geometry, the $\varepsilon$-Ge/In x Ga 1-x -Ge QW laser design provided a net material gain of ~2000 cm -1 and a threshold current density of ~5 kA/cm 2 , which is an improvement over existing Ge based lasers. In conclusion, the impact of In composition and QW thickness on the band structure, polarized gain spectra, and various lasing metrics were analyzed to show $\varepsilon$-Ge/In x Ga 1-x -Ge/InGaAs QW lasers as promising for integrated photonics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Thermodynamic Origin of Reaction Non-Uniformity in Battery Porous Electrodes and Its Mitigation

The development of non-uniform reaction current distribution within porous electrodes is a ubiquitous phenomenon during battery charging/discharging and frequently controls the rate performance of battery cells. Reaction inhomogeneity in porous electrodes is usually attributed to the kinetic limitation of mass transport within the electrolyte and/or solid electrode phase. In this work, however, we reveal that it is also strongly influenced by the intrinsic thermodynamic behavior of electrode materials, specifically the dependence of the equilibrium potential on the state of charge: the electrode reaction becomes increasingly non-uniform when the slope of the equilibrium potential curve is reduced. We employ numerical simulations and equivalent circuit model to elucidate such a correlation and show that the degree of reaction inhomogeneity and the resultant discharge capacity can be predicted by a dimensionless reaction uniformity number. For electrode materials that have equilibrium potentials insensitive to the state of charge and exhibit significant reaction non-uniformity, we demonstrate several approaches to spatially homogenizing the reaction current inside porous electrodes, including matching the electronic and ionic resistances, introducing graded electronic conductivity and reducing the surface reaction kinetics.

25 ENERGY STORAGE↗

The effect of changes in the USF/NASA toxicity screening test method on data from some cellular polymers

Rankings of relative toxicity can be markedly affected by changes in test variables. Revision of the USF/NASA toxicity screening test procedure to eliminate the connecting tube and supporting floor and incorporate a 1.0 g sample weight, 200 C starting temperature, and 800 C upper limit temperature for pyrolysis, reversed the rankings of flexible polyurethane and polychloroprene foams, not only in relation to each other, but also in relation to cotton and red oak. Much of the change is attributed to reduction of the distance between the sample and the test animals, and reduction of the sample weight charged. Elimination of the connecting tube increased the relative toxicity of the polyurethane foams. The materials tested were flexible polyurethane foam, without and with fire retardant; rigid polyurethane foam with fire retardant; flexible polychloroprene foam; cotton, Douglas fir, red oak, hemlock, hardboard, particle board, polystyrene, and polymethyl methacrylate.

Hilado, C. J.↗

CNO abundances and hydrodynamic studies of the Nova outburst. V - 1.00-solar-mass models with small mass envelopes

The paper reports on an investigation into the consequences of thermonuclear runaways in accreted hydrogen envelopes of 100 millionths of a solar mass on 1-solar-mass white dwarfs. These evolutionary sequences predict that from 10 to 50 millionths of a solar mass will be ejected with speeds from 300 to 3800 km/s (kinetic energies of 10 to the 44th-45th power ergs). Absolute visual magnitudes as high as -8.1 are attained, well within the observed range for fast novae. In addition, the shapes of the theoretical light curves are more reminiscent of an observed fast-nova light curve than those in earlier studies. The ejected material is strongly enhanced in the products of incomplete CNO burning; the most abundant of the ejected nuclei is C-13, followed by N-14 and C-12. The differences from previous studies are attributable to the lower peak temperatures reached in these sequences. These models also produce a large overabundance of Li-7, suggesting that novae may represent significant contributors to the galactic enrichment of this nucleus.

Starrfield, S.↗