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Experimental and computational investigation into the hydrodynamics and chemical dynamics of laser ablation aluminum plasmas

Laser ablation plasma chemistry is governed by a complex interplay between hydrodynamic plasma-gas mixing processes, thermodynamics, and rapid high-temperature chemical reactions. Here, in this work, we investigate the gas-phase oxidation chemistry of ns-laser ablation aluminum plasmas in air using optical spectroscopy combined with advanced multi-physics modeling. Experimental measurements demonstrate the formation of AlO in the plasma plume as early as 1 μs while computational results reveal that several Al x O y species are distributed in the periphery of the plume at even earlier times (<20 ns) in the presence of large temperature gradients and strong shockwaves. Interactions with the ablation crater during rapid plume expansion are shown to initiate vortex formation, followed by mixing dynamics that work to pull AlO into the vortices to react with gas-phase Al to form Al 2 O. Oxygen and several aluminum oxides are simultaneously pulled up through the stem of the fireball, encouraging further intermixing between reacting species and enhanced molecular formation. This work concludes that chemical dynamics in laser ablation plasmas is driven by diffusion processes, concentration gradients, and plume hydrodynamics while strong shockwaves generated during laser ablation do not impede chemical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reionization and dark matter decay

Cosmic reionization and dark matter decay can impact observations of the cosmic microwave sky in a similar way. A simultaneous study of both effects is required to constrain unstable dark matter from cosmic microwave background observations. We compare two reionization models with and without dark matter decay. We find that a reionization model that fits also data from quasars and star forming galaxies results in tighter constraints on the reionization optical depth τ{sub reio}, but weaker constraints on the spectral index n {sub s} than the conventional parametrization. We use the Planck 2015 data to constrain the effective decay rate of dark matter to Γ{sub eff} < 2.9 × 10{sup -25}/s at 95% C.L. This limit is robust and model independent. It holds for any type of decaying dark matter and it depends only weakly on the chosen parametrization of astrophysical reionization. For light dark matter particles that decay exclusively into electromagnetic components this implies a limit of Γ < 5.3 × 10{sup -26}/s at 95% C.L. Specifying the decay channels, we apply our result to the case of keV-mass sterile neutrinos as dark matter candidates and obtain constraints on their mixing angle and mass, which are comparable to the ones from the diffuse X-ray background.

79 ASTRONOMY AND ASTROPHYSICS↗

A SYSTEMATIC STUDY OF THE THERMAL AND NONTHERMAL EMISSION IN THE SUPERNOVA REMNANT RCW 86 WITH SUZAKU

Diffusive shock acceleration by the shockwaves in supernova remnants (SNRs) is widely accepted as the dominant source for Galactic cosmic rays. However, it is unknown what determines the maximum energy of accelerated particles. The surrounding environment could be one of the key parameters. The SNR RCW 86 shows both thermal and nonthermal X-ray emission with different spatial morphologies. These emission originate from the shock-heated plasma and accelerated electrons respectively, and their intensities reflect their density distributions. Thus, the remnant provides a suitable laboratory to test possible association between the acceleration efficiency and the environment. In this paper, we present results of spatially resolved spectroscopy of the entire remnant with Suzaku . The spacially resolved spectra are well reproduced with a combination of a power-law for synchrotron emission and a two-component optically thin thermal plasma, corresponding to the shocked interstellar medium (ISM) with kT of 0.3–0.6 keV and Fe-dominated ejecta. It is discovered that the photon index of the nonthermal component becomes smaller when decreasing the emission measure of the shocked ISM, where the shock speed has remained high. This result implies that the maximum energy of accelerated electrons in RCW 86 is higher in the low-density and higher shock speed regions.

79 ASTRONOMY AND ASTROPHYSICS↗

An enhanced rate of tidal disruptions in the centrally overdense E+A galaxy NGC 3156

Time domain optical surveys have discovered roughly a dozen candidate stellar tidal disruption flares in the last five years, and future surveys like the Large Synoptic Survey Telescope will likely find hundreds to thousands more. These tidal disruption events (TDEs) present an interesting puzzle: a majority of the current TDE sample is hosted by rare post-starburst galaxies, and tens of percents of the galaxies are hosted in even rarer E+A galaxies, which make up ∼0.1% of all galaxies in the local universe. E+As are therefore overrepresented among TDE hosts by 1–2 orders of magnitude, a discrepancy unlikely to be accounted for by selection effects. We analyze Hubble Space Telescope photometry of one of the nearest E+A galaxies, NGC 3156, to estimate the rate of stellar tidal disruption produced as two-body relaxation diffuses stars onto orbits in the loss cone of the central supermassive black hole. The rate of TDEs produced by two-body relaxation in NGC 3156 is large when compared to other galaxies with similar black hole mass: N-dot {sub TDE}∼1×10{sup −3} yr{sup −1}. This suggests that the preference of TDEs for E+A hosts may be due to central stellar overdensities produced in recent starbursts.

79 ASTRONOMY AND ASTROPHYSICS↗

The j and k dependencies of the line coupling and line mixing effects: Theoretical studies of the relaxation matrices of N 2 -broadened CH 3 D

Line coupling and line mixing effects in parallel and perpendicular bands of CH 3 D perturbed by N 2 have been studied. The work focuses on exhibiting the j and k dependencies of these two processes. The calculations were based on a previously reported anisotropic intermolecular potential including both the long-range multipole, induction, and dispersion forces and a short-range atom-atom model. Throughout this work, it is shown that components with L 1 = 3 of the atom-atom model are dominant contributions to the diffusion operator. As a consequence, in comparison with other molecular systems such as the CH 3 Cl-N 2 and CH 3 I-N 2 , theoretically predicted line coupling and line mixing effects exhibit completely new j and k dependencies. In general, the theoretically calculated halfwidths and intra-doublets’ off-diagonal elements of the relaxation matrix are in reasonable agreement with measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Plasma-Assisted Pre-Chamber Ignition System for Highly Dilute Stoichiometric Heavy-Duty Natural Gas Engines (Final Technical Report)

This project explored advanced ignition technologies to significantly enhance efficiency and reduce operating costs for heavy-duty natural gas engines operating at stoichiometric conditions, while meeting ultra-low NOx emission standards. The main goal was to develop and validate a plasma-assisted pre-chamber ignition system that could deliver at least a 2% increase in brake thermal efficiency (BTE) and a 4% decrease in total cost of ownership (TCO) compared to a typical multi-cylinder engine with three-way catalyst aftertreatment, ensuring compatibility with the expected 2027 EPA/CARB regulations. In the first half of the project, the research team concentrated on developing and testing plasma-assisted pre-chamber ignition using nanosecond pulsed discharges. Extensive experiments were conducted in an optically accessible rapid-compression and expansion machine, a constant-volume chamber, and an optical single-cylinder engine. Experiments were coupled with CFD simulations. The work produced unique insights into pre-chamber flame formation, jet ignition, dilution effects, and flame quenching at pressures, temperatures, and dilution levels relevant to engines. Although plasma-assisted ignition showed promise in controlled lab settings, the research also identified fundamental and practical challenges when applying this technology to real engine conditions. Midway through the project, a crucial pivot was made, guided by three key findings. First, the power electronics required for nanosecond plasma discharges were found to be too costly for commercial use, undermining the project’s cost-of-ownership goals. Second, nanosecond plasma ignition was highly sensitive to turbulent flow in the pre-chamber, resulting in lower ignition reliability than traditional spark under engine-like conditions. Third, achieving a truly diffuse low-temperature plasma at high pressures near top dead center was not possible, reducing the anticipated chemical enhancement benefits. These results collectively suggested that continuing with plasma-assisted ignition was unlikely to meet both efficiency and cost objectives. In response, the project shifted focus to a more realistic approach: enhancing traditional spark-based pre-chamber ignition with significantly less spark energy. Using insights gained earlier in the project, the team redesigned the pre-chamber to maintain high dilution tolerance and quick combustion, even with lower ignition energy. Testing confirmed that with optimized pre-chamber design and combustion timing, a lower-energy spark could reliably ignite highly diluted stoichiometric mixtures, reduce burn time, and boost thermal efficiency. Final engine testing and techno-economic analysis verified that this revised approach successfully achieved the project goals. The optimized pre-chamber ignition system provided over a 2% increase in calculated brake thermal efficiency compared to the baseline engine. Notably, the lower ignition energy and simplified hardware reduced component stress, extended maintenance intervals, and lowered the total cost of ownership. When used with stoichiometric operation and traditional three-way aftertreatment, the system remained compatible with near-zero NOx emissions targets without increasing cost or complexity in the emissions control system. In summary, although the project deviated from its initial plasma-assisted ignition idea, the work produced a more practical and commercially viable solution. The results show that precisely optimized, low-energy pre-chamber spark ignition can significantly improve efficiency and reduce overall ownership costs for heavy-duty natural gas engines. This directly aligns with DOE goals for cleaner, more efficient, and cost-effective transportation technologies.

03 NATURAL GAS↗

Hubble Space Telescope Imaging of the Ultra-compact High Velocity Cloud AGC 226067: A Stripped Remnant in the Virgo Cluster

We analyze the optical counterpart to the ultra-compact high velocity cloud AGC 226067, utilizing imaging taken with the Advanced Camera for Surveys (ACS) on the Hubble Space Telescope . The color–magnitude diagram of the main body of AGC 226067 reveals an exclusively young stellar population, with an age of ∼7–50 Myr, and is consistent with a metallicity of [Fe/H] ∼ −0.3 as previous work has measured via H ii region spectroscopy. Additionally, the color–magnitude diagram is consistent with a distance of D ≈ 17 Mpc, suggesting an association with the Virgo cluster. A secondary stellar system located ∼1.′6 (∼8 kpc) away in projection has a similar stellar population. The lack of an old red giant branch (≳5 Gyr) is contrasted with a serendipitously discovered Virgo dwarf in the ACS field of view (Dw J122147+132853), and the total diffuse light from AGC 226067 is consistent with the luminosity function of the resolved ∼7–50 Myr stellar population. The main body of AGC 226067 has a M {sub V} = −11.3 ± 0.3, or M {sub stars} = 5.4 ± 1.3 × 10{sup 4} M {sub ⊙} given the stellar population. We searched 20 deg{sup 2} of imaging data adjacent to AGC 226067 in the Virgo Cluster, and found two similar stellar systems dominated by a blue stellar population, far from any massive galaxy counterpart—if this population has star-formation properties that are similar to those of AGC 226067, it implies ∼0.1 M {sub ⊙} yr{sup −1} in Virgo intracluster star formation. Given its unusual stellar population, AGC 226067 is likely a stripped remnant and is plausibly the result of compressed gas from the ram pressure stripped M86 subgroup (∼350 kpc away in projection) as it falls into the Virgo Cluster.

79 ASTRONOMY AND ASTROPHYSICS↗

Energy Coupling Mechanisms and Scaling Behavior Associated with Laser Powder Bed Fusion Additive Manufacturing

In situ optical absorptivity measurements are carried out to clarify the physics of the laser-material interactions involved and to validate both finite element and analytical models describing laser powder bed fusion processing. Absorption of laser energy is evaluated directly using precise calorimetry measurements and compared to melt pool depths for common structural metal alloys (Ti-6Al-4V, Inconel 625, and stainless steel 316L) as a function of incident laser power, scan velocity and laser beam diameter. Changes in both absorptivity and melt pool depths for all materials are found to vary strongly across the conduction-keyhole mode threshold. A hydrodynamic finite element model is coupled to a ray-tracing-based absorptivity model, yielding excellent agreement with the experimental results and elucidating additional physics. The experimental results are further analyzed using normalized enthalpy ( β ) and normalized thermal diffusion length ( L* th ) relations and demonstrate that the normalized melt pool depth ( d* = d/a , where d is melt pool depth and a is beam radius) is proportional to βL* th , while absorptivity follows an asymptotic exponential function against βL* th . Expressions for melt pool depth and laser absorptivity across different materials and laser scan systems are derived and thus provide useful tools to accelerate the optimization of laser processing parameters for metal 3D printing processes.

36 MATERIALS SCIENCE↗

Classifying the full SDSS-IV MaNGA Survey using optical diagnostic diagrams: Presentation of AGN catalogs in flexible apertures

Accurate active galactic nucleus (AGN) identifications in large galaxy samples are crucial for the assessment of the role of AGN and AGN feedback in the co-evolution of galaxies and their central supermassive black holes. Emission-line flux-ratio diagnostics are commonly used to identify AGN in optical spectra. New large samples of integral field unit observations allow exploration of the role of aperture size in the classification process. In this paper, we present galaxy classifications for all 10010 galaxies observed within the Mapping Nearby Galaxies at Apache Point Observatory (MaNGA) survey. We use Baldwin-Philips-Terlevich line flux-ratio diagnostics combined with an Hα equivalent threshold in 60 apertures of varying size for the classification, and provide the corresponding catalogs. MaNGA-selected AGN primarily lie below the main sequence of star-forming galaxies, and reside in massive galaxies with stellar masses of ~10 11 M ⊙ and a median Hα-derived star formation rate of ~1.44M ⊙ yr -1 . We find that the number of “fake” AGN increases significantly beyond selection apertures of >1.0 R eff because of increased contamination from diffuse ionized gas (DIG). A comparison with previous works shows that the treatment of the underlying stellar continuum and flux measurements can significantly impact galaxy classification. Our work provides the community with AGN catalogs and galaxy classifications for the full MaNGA survey.

79 ASTRONOMY AND ASTROPHYSICS↗

SDSS-IV MaNGA: the physical origin of off-galaxy H α blobs in the local Universe

ABSTRACT H α blobs are off-galaxy emission-line regions with weak or no optical counterparts. They are mostly visible in H α line, appearing as concentrated blobs. Such unusual objects have been rarely observed and studied, and their physical origin is still unclear. We have identified 13 H α blobs in the public data of MaNGA survey, by visually inspecting both the optical images and the spatially resolved maps of H α line for ∼4600 galaxy systems. Among the 13 H α blobs, 2 were reported in previously MaNGA-based studies and 11 are newly discovered. This sample, though still small in size, is by far the largest sample with both deep imaging and integral field spectroscopy. Therefore, for the first time we are able to perform statistical studies to investigate the physical origin of H α blobs. We examine the physical properties of these H α blobs and their associated galaxies, including their morphology, environments, gas-phase metallicities, kinematics of ionized gas, and ionizing sources. We find that the H α blobs in our sample can be broadly divided into two groups. One is associated with interacting/merging galaxy systems, of which the ionization is dominated by shocks or diffuse ionized gas. It is likely that these H α blobs used to be part of their nearby galaxies, but were stripped away at some point due to tidal interactions. The other group is found in gas-rich systems, appearing as low-metallicity star-forming regions that are visually detached from the main galaxy. These H α blobs could be associated with faint discs, spiral arms, or dwarf galaxies.

79 ASTRONOMY AND ASTROPHYSICS↗

DED Additively Manufactured HEAs Optimized via Parametric Study of Functionally Graded Materials

Complex concentrated alloys (CCAs) are a system of alloys composition of nearly equiatomic elements, creating a state of high configurational entropy in the material. These alloys are of interest for various industrial applications due to their high strength and hardness, wide operational temperature range, creep and diffusion resistance, and radiation resistance. In the current work CoCrFeNi-base CCAs are synthesize by combining three commonly industrial alloys: IN718, SS316L, and 70Co30Cr (commercially known as Stellite 21), in-situ utilizing directed energy deposition (DED) additive manufacturing (AM). One bulk specimen is fabricated with a 1:1:1 ratio of IN718, SS316L, and 70Co30Cr where IN718 is a source of nickel and chrome, SS316 is a source of iron and chrome, and 70Co30Cr is a source of cobalt and supplemental chrome. Additionally, a functionally graded material (FGM) of the identified CCA system from SS316 was fabricated with 10 layers, where the initial five layers are the base material of SS316L and graded by steps of 20% to transition to the CCA system. Overall build quality, microstructure, compositional distribution, phases analysis, and microhardness were studied by laser optical microscopy, scanning election microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray diffraction analysis (XRD), and Vickers microhardness techniques. Overall build quality showed a successful bulk build with acceptable density, however unmelted particles are observed in the as-built alloy. Compositional results show that the system meets the Boltzmann’s hypothesis definition of an HEA, and that an FCC CCA was produced with increased hardness, small grain size, and superior hardness properties to the SS316L substrate. While initial XRD results show predominately FCC structure, EDS analysis of interdendritic regions show the existence of Laves phases in the material. The fabrication of an FGM CCA allowed for potential screening of additional alloy mixes which may be of interest to explore in future research, and the resulting composition is compared to predicted values. This novel method of CCA fabrication results in substantial cost savings of these CCA systems over traditional methods.

36 MATERIALS SCIENCE↗

X-ray ptychographic and fluorescence microscopy of frozen-hydrated cells using continuous scanning

X-ray microscopy can be used to image whole, unsectioned cells in their native hydrated state. It complements the higher resolution of electron microscopy for submicrometer thick specimens, and the molecule-specific imaging capabilites of fluorescence light microscopy. We describe here the first use of fast, continuous x-ray scanning of frozen hydrated cells for simultaneous sub-20 nm resolution ptychographic transmission imaging with high contrast, and sub-100 nm resolution deconvolved x-ray fluorescence imaging of diffusible and bound ions at native concentrations, without the need to add specific labels. Here, by working with cells that have been rapidly frozen without the use of chemical fixatives, and imaging them under cryogenic conditions, we are able to obtain images with well preserved structural and chemical composition, and sufficient stability against radiation damage to allow for multiple images to be obtained with no observable change.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Extending the range of validity of Fourier's law into the kinetic transport regime via asymptotic solution of the phonon Boltzmann transport equation

We derive the continuum equations and boundary conditions governing phonon-mediated heat transfer in the limit of a small but finite mean-free path from the asymptotic solution of the linearized Boltzmann equation in the relaxation time approximation. Our method uses the ratio of the mean-free path to the characteristic system length scale, also known as the Knudsen number, as the expansion parameter to study the effects of boundaries on the breakdown of the Fourier description. We show that, in the bulk, the traditional heat conduction equation using Fourier's law as a constitutive relation is valid at least up to second order in the Knudsen number for steady problems and first order for time-dependent problems. Yet, this description does not hold within distances on the order of a few mean-free paths from the boundary; this breakdown is a result of kinetic effects that are always present in the boundary vicinity and require solution of a Boltzmann boundary layer problem to be determined. Matching the inner, boundary layer solution to the outer, bulk solution yields boundary conditions for the Fourier description as well as additive corrections in the form of universal kinetic boundary layers; both are found to be proportional to the bulk-solution gradients at the boundary and parametrized by the material model and the phonon-boundary interaction model (Boltzmann boundary condition). Our derivation shows that the traditional no-jump boundary condition for prescribed temperature boundaries and the no-flux boundary condition for diffusely reflecting boundaries are appropriate only to zeroth order in the Knudsen number; at higher order, boundary conditions are of the jump type. We illustrate the utility of the asymptotic solution procedure by demonstrating that it can be used to predict the Kapitza resistance (and temperature jump) associated with an interface between two materials. All results are validated via comparisons with low-variance deviational Monte Carlo simulations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

HST emission line galaxies at z ∼ 2: Comparing physical properties of Lyman alpha and optical emission line selected galaxies

We compare the physical and morphological properties of z ∼ 2 Lyα emitting galaxies (LAEs) identified in the HETDEX Pilot Survey and narrow band studies with those of z ∼ 2 optical emission line selected galaxies (oELGs) identified via HST WFC3 infrared grism spectroscopy. Both sets of galaxies extend over the same range in stellar mass (7.5<logM/M{sub ⊙}<10.5), size (0.5 < R < 3.0 kpc), and star formation rate (∼1<SFR<100 M{sub ⊙} yr{sup −1}). Remarkably, a comparison of the most commonly used physical and morphological parameters—stellar mass, half-light radius, UV slope, SFR, ellipticity, nearest neighbor distance, star formation surface density, specific SFR, [O iii] luminosity, and [O iii] equivalent width—reveals no statistically significant differences between the populations. This suggests that the processes and conditions which regulate the escape of Lyα from a z ∼ 2 star-forming galaxy do not depend on these quantities. In particular, the lack of dependence on the UV slope suggests that Lyα emission is not being significantly modulated by diffuse dust in the interstellar medium. We develop a simple model of Lyα emission that connects LAEs to all high-redshift star-forming galaxies where the escape of Lyα depends on the sightline through the galaxy. Using this model, we find that mean solid angle for Lyα escape is Ω{sub Lyα}=2.4±0.8 steradians; this value is consistent with those calculated from other studies.

79 ASTRONOMY AND ASTROPHYSICS↗

Hard X-ray emission from Sh 2-104: a NuSTAR search for gamma-ray counterparts

We present NuSTAR hard X-ray observations of Sh 2–104, a compact H ii region containing several young massive stellar clusters (YMSCs). We have detected distinct hard X-ray sources coincident with localized VERITAS TeV emission recently resolved from the giant gamma-ray complex MGRO J2019+37 in the Cygnus region. Fainter, diffuse X-rays coincident with the eastern YMSC in Sh2-104 likely result from the colliding winds of a component star. Just outside the radio shell of Sh 2–104 lies 3XMM J201744.7+365045 and a nearby nebula, NuSTAR J201744.3+364812, whose properties are most consistent with extragalactic objects. The combined XMM-Newton and NuSTAR spectrum of 3XMM J201744.7+365045 is well-fit to an absorbed power-law model with N{sub H}=(3.1±1.0)×10{sup 22} cm{sup −2} and a photon index Γ=2.1±0.1. Based on possible long-term flux variation and the lack of detected pulsations (≤43% modulation), this object is likely a background active galactic nucleus rather than a Galactic pulsar. The spectrum of the NuSTAR nebula shows evidence of an emission line at E = 5.6 keV, suggesting an optically obscured galaxy cluster at z = 0.19 ± 0.02 (d = 800 Mpc) and L {sub X} = 1.2 × 10{sup 44} erg s{sup −1}. Follow-up Chandra observations of Sh 2–104 will help identify the nature of the X-ray sources and their relation to MGRO J2019+37. We also show that the putative VERITAS excess south of Sh 2–104, is most likely associated with the newly discovered Fermi pulsar PSR J2017+3625 and not the H ii region.

79 ASTRONOMY AND ASTROPHYSICS↗

Charge transport mechanism analysis of Al/CdS:Sr{sup 2+}/ITO device under dark and light

In this study, we have synthesized CdS:Sr{sup 2+} by hydrothermal technique. Material property has been studied by X-ray diffraction (XRD), Scanning electron microscope (SEM) and UV-vis absorption spectroscopy. XRD data revealed that there are mixed phases of CdS and SrS in the synthesized sample. The optical band gap of the material was estimated as 3.15 eV from UV-vis data. The synthesized material has been applied in metal-semiconductor device and transport properties have been analyzed by measuring current–voltage characteristics under dark and light conditions at room temperature. Variation in different device parameters like ideality factor, barrier height and series resistance of Al/CdS:Sr{sup 2+}/ITO device were analyzed by using Cheung’s function.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

HAMscope: a snapshot Hyperspectral Autofluorescence Miniscope for real-time molecular imaging

We introduce HAMscope, a compact, snapshot hyperspectral autofluorescence miniscope that enables real-time, label-free molecular imaging in a wide range of biological systems. By integrating a thin polymer diffuser into a widefield miniscope, HAMscope spectrally encodes each frame and employs a probabilistic deep learning framework to reconstruct 30-channel hyperspectral stacks (452-703 nm) or directly infer molecular composition maps from single images. A scalable multi-pass U-Net architecture with transformer-based attention and per pixel uncertainty estimation enables high spatio-spectral fidelity (mean absolute error ∼0.0048) at video rates. While initially demonstrated in plant systems, including lignin, chlorophyll, and suberin imaging in intact poplar and cork tissues, the platform is readily adaptable to other applications such as neural activity mapping, metabolic profiling, and histopathology. We show that the system generalizes to out-of-distribution tissue types and supports direct molecular mapping without the need for spectral unmixing. HAMscope establishes a general framework for compact, uncertainty-aware spectral imaging that combines minimal optics with advanced deep learning, offering broad utility for real-time biochemical imaging across neuroscience, environmental monitoring, and biomedicine.

59 BASIC BIOLOGICAL SCIENCES↗

Evaluating the oxidative, photothermal and electrical stability of colloidal nanocrystal solids

IV-VI quantum dot (QD) solids are a novel class of granular electronic materials with great technological potential (e.g., in photodetectors, field-effect transistors (FETs), and solar cells), but their oxidative and thermal instability present a barrier to practical applications [1]. Poor stability is a fundamental issue facing many nanoscale materials due to high surface area and surface energy. Basic studies are needed to elucidate the most important mechanisms of degradation and develop robust countermeasures if QD materials are to become technologically important. This project determined the degradation mechanisms of IV-VI QD solids (primarily PbSe and PbS) and introduced new chemical strategies to drastically improve their performance, stability, and operating lifetimes [2-5]. Our approach was based on (1) detailed testing of QD thin film materials (principally FETs and solar cells) as a function of oxidative and thermal stress, and (2) the use of organic and inorganic approaches to link the QDs into strongly electronically coupled, high-mobility films, prevent their oxidation, and eliminate internal degrees of freedom that lead to film instability and degradation in response to electrical and thermal stress. Stability against oxidation and thermal degradation was the major focus of this project. We have evaluated the stability of QD thin films and interfaces at temperatures less than 100°C (the regime most relevant to solar and transistor applications). Low-temperature oxidation and sintering of QD films have been investigated using optical absorption spectroscopy, Fourier transform infrared spectroscopy (FTIR), current-voltage scanning of transistors and solar cells, X-ray photoelectron spectroscopy, and scanning Kelvin probe microscopy (SKPM). SKPM was used to map the potential profiles of operating QD FETs and solar cells as a function of bias and illumination, which provides detailed information on how the work functions, potential drops and electric field within these devices determine device operation, and set the stage for future studies targeted at understanding and preventing device failure. We pursued two strategies to fabricate QD films with stable electrical characteristics: (1) the use of robust molecular surface ligands [2], and (2) “matrix engineering,” i.e., infilling the QD solid with metal oxide or metal sulfide matrices by low-temperature atomic layer deposition (ALD) to passivate surface states, prevent oxidation, lock the QDs into position, inhibit diffusion, and tune the height and width of the inter-QD potential barriers that govern charge transport [5,6]. Poor stability is a common feature of nanoscale electronic materials, yet stability is all too rarely the focus of basic research. Fundamental studies are therefore needed to elucidate the most important mechanisms of degradation and develop simple yet effective countermeasures. By revealing both how QD solids degrade in response to environmental stresses (oxidative, photothermal, and electric) and how to prevent this degradation, the project has greatly improved our ability to develop stable, high-performance QD materials for real-world applications.

36 MATERIALS SCIENCE↗