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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 325 records · Page 18

High precision monitoring of outgassing species in model EUV photoresists with a cavity ring-down spectrometer

Extreme ultraviolet (EUV) photoresists play a pivotal role in advancing nanopatterning technologies by balancing image quality and sensitivity. The outgassing behavior of photoresist thin films under EUV and deep ultraviolet (DUV) exposure reveals chemical details relevant to their performance. This study focuses on utilizing an analytical technique not previously used in photolithography, the tabletop cavity ring-down spectrometer, to investigate outgassing dynamics in EUV photoresists, enabling precise chemical identification and deeper insights into resist processing. The spectrometer’s enhanced laser path length (~20 km) and broadband absorption capabilities in the CH overtone region allow for sensitive and temporally resolved detection of outgassed species. Using a model resist comprising a polymer matrix with a photoacid generator and quencher, we analyzed the influence of time delays between exposure and Post-Exposure Bake (PEB) as well as storage under varying environmental conditions. Suppression of isobutylene outgassing and thickness loss was observed with extended delays between exposure and PEB, potentially linked to water absorption and acid deactivation. The technique proved highly effective in distinguishing subtle chemical differences between processing stages. Delay times and their environmental conditions, particularly humidity, reduce outgassing and thickness loss of photoresists during PEB, suggesting decreased acid-driven deprotection. This can potentially impact sensitivity, defectivity, and roughness of resist patterns, necessitating precise monitoring and control.

Lüttgenau, Bernhard↗

Time-resolved x-ray absorption spectroscopy probe in ultrafast surface chemistry

To celebrate the scientific achievement of Jo Stöhr, I present here a personal account of the use of x-ray absorption spectroscopy to probe dynamics on surfaces using x-ray lasers. In particular, I will review the investigation of ultrafast processes in adsorbates on surfaces using an optical pump and an x-ray absorption spectroscopy probe. Here, it is shown that it is possible to gain insight into the effects of electronic excitations in metals on adsorbates as well as laser-induced vibrational motions. Furthermore, the ultrafast optical pump allows the detection of the CO precursor state in the desorption channel, species close to the transition state in CO oxidation, and the transient HCO intermediate during CO hydrogenation on Ru(0001).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanoparticle-enabled increase of energy efficiency during laser metal additive manufacturing

The low energy efficiency of the laser metal additive manufacturing (AM) process is a potential sustainability concern for large-scale industrial production. Explicit investigation of the energy efficiency for laser melting requires the direct characterization of melt pool dimension and vapor depression, which is very difficult due to the opaque nature of the molten metal. Here we report the direct observation and quantification of effects of the TiC nanoparticles on the vapor depression and melt pool formation during laser powder bed fusion (LPBF) of Al6061 by in-situ high-speed high-energy x-ray imaging. Based on the quantification results, we calculated the laser melting energy efficiency (defined here as the ratio of the energy needed to melt the material to the energy delivered by the laser beam) with and without TiC nanoparticles during LPBF of Al6061. Here the results show that adding TiC nanoparticles into Al6061 leads to a significant increase of laser melting energy efficiency (114% increase on average, 521% increase under 312 W laser power, 0.4 m/s scan speed). Systematic property measurement, simulation, and x-ray imaging studies enable us, for the first time, to identify that three mechanisms work together to enhance the laser melting energy efficiency: (1) adding TiC nanoparticles increases the absorptivity; (2) adding TiC nanoparticles decreases the thermal conductivity, and (3) adding TiC nanoparticles enables the initiation of vapor depression and multiple reflection at lower laser power (i.e., lowers the laser power threshold for keyholing). The method and mechanisms of using TiC nanoparticles to increase the laser melting energy efficiency during LPBF of Al6061 we reported here may guide the development of feedstock materials for more energy efficient laser metal AM.

36 MATERIALS SCIENCE↗

State-resolved ultrafast charge and spin dynamics in [Co/Pd] multilayers

We use transient absorption spectroscopy with circularly polarized x rays to detect laser-excited hole states below the Fermi level and compare their dynamics with that of unoccupied states above the Fermi level in ferromagnetic [Co/Pd] multilayers. While below the Fermi level, an instantaneous and significantly stronger demagnetization is observed, above the Fermi level, the demagnetization is delayed by 35 ± 10 fs. This provides a direct visualization of how ultrafast demagnetization proceeds via initial spin-flip scattering of laser-excited holes to the subsequent formation of spin waves.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Analysis of hydrogen and lithium isotopes using Laser-Induced Breakdown Spectroscopy

The detection and quantification of hydrogen (1,2,3H) and lithium (6,7Li) isotopes are critical to several energy and defense application areas, including hydrogen storage, nuclear forensics, and safeguards/non-proliferation. In this context, laser-induced breakdown spectroscopy (LIBS) is very promising and it comes with certain advantages such as rapid detection, and standoff capability. Although LIBS provides experimental simplicity and is capable of detecting all elements in the periodic table in any phase (solid, liquid, or gas), there exist certain challenges for isotopic analyses of H and Li due to spectral broadening, the presence of closely spaced fine and hyperfine structures, and line distortion effects (e.g., self-absorption and self-reversal) present in laser-produced plasmas. This article reports recent developments in H and Li isotopic analysis using LIBS, and existing challenges.

(020.3260) Isotope shifts, (140.3440) Laser-induce↗

Measurement and control of optical nonlinearities in dispersive dielectric multilayers

Dispersive dielectric multilayer mirrors, high-dispersion chirped mirrors in particular, are widely used in modern ultrafast optics to manipulate spectral chirps of ultrashort laser pulses. Dispersive mirrors are routinely designed for dispersion compensation in ultrafast lasers and are assumed to be linear optical components. In this work, we report the experimental characterization of an unexpectedly strong nonlinear response in these chirped mirrors. At modest peak intensities <2 TW/cm 2 —well below the known laser-induced damage threshold of these dielectric structures—we observed a strong reflectivity decrease, local heating, transient spectral modifications, and time-dependent absorption of the incident pulse. Through computational analysis, we found that the incident laser field can be enhanced by an order of magnitude in the dielectric layers of the structure. The field enhancement leads to a wavelength-dependent nonlinear absorption, that shows no signs of cumulative damage before catastrophic failure. The nonlinear absorption is not a simply two-photon process but instead is likely mediated by defects that facilitate two-photon absorption. To mitigate this issue, we designed and fabricated a dispersive multilayer design that strategically suppresses the field enhancement in the high-index layers, shifting the high-field regions to the larger-bandgap, low-index layers. This strategy significantly increases the maximum peak intensity that the mirror can sustain. However, our finding of an onset of nonlinear absorption even at ‘modest’ fluence and peak intensity has significant implications for numerous past published experimental works employing dispersive mirrors. Additionally, our results will guide future ultrafast experimental work and ultrafast laser design.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

MicroPulse DIAL (MPD) – a diode-laser-based lidar architecture for quantitative atmospheric profiling

Abstract. Continuous water vapor and temperature profiles are critically needed for improved understanding of the lower atmosphere and potential advances in weather forecasting skill. Ground-based, national-scale profiling networks are part of a suite of instruments to provide such observations; however, the technological method must be cost-effective and quantitative. We have been developing an active remote sensing technology based on a diode-laser-based lidar technology to address this observational need. Narrowband, high-spectral-fidelity diode lasers enable accurate and calibration-free measurements requiring a minimal set of assumptions based on direct absorption (Beer–Lambert law) and a ratio of two signals. These well-proven quantitative methods are known as differential absorption lidar (DIAL) and high-spectral-resolution lidar (HSRL). This diode-laser-based architecture, characterized by less powerful laser transmitters than those historically used for atmospheric studies, can be made eye-safe and robust. Nevertheless, it also requires solar background suppression techniques such as narrow-field-of-view receivers with an ultra-narrow bandpass to observe individual photons backscattered from the atmosphere. We discuss this diode-laser-based lidar architecture's latest generation and analyze how it addresses a national-scale profiling network's need to provide continuous thermodynamic observations. The work presented focuses on general architecture changes that pertain to both the water vapor and the temperature profiling capabilities of the MicroPulse DIAL (MPD). However, the specific subcomponent testing and instrument validation presented are for the water vapor measurements only. A fiber-coupled seed laser transmitter optimization is performed and shown to meet all of the requirements for the DIAL technique. Further improvements – such as a fiber-coupled near-range receiver, the ability to perform quality control via automatic receiver scanning, advanced multi-channel scalar capabilities, and advanced processing techniques – are discussed. These new developments increase narrowband DIAL technology readiness and are shown to allow higher-quality water vapor measurements closer to the surface via preliminary intercomparisons within the MPD network itself and with radiosondes.

Spuler, Scott M.↗

Insight into the Chemistry of PETN Under Shock Compression Through Ultrafast Broadband Mid-Infrared Absorption Spectroscopy

In this study, thin films of pentaerythritol tetranitrate (PETN) were shock compressed using the laser driven shock apparatus at Los Alamos National Laboratory (LANL). Two spectroscopic probes were available to this apparatus: visible white light transient absorption spectroscopy (VIS) from 400 to 700 nm and mid-infrared transient absorption spectroscopy (MIR) from 1150 to 3800 cm –1 . Important PETN vibrational modes are the symmetric and antisymmetric NO 2 stretches at 1280 and 1650 cm –1 , respectively, as well as CH stretches at ~2900 cm –1 . Shock strength was varied from approximately 3 to 55 GPa to span from the chemically unreactive regime to the regime in which fast chemical reaction took place on the 250 ps time scale of the measurements. VIS and MIR results suggest irreversible chemistry was induced in PETN at pressures above 30 GPa. At lower shock pressures, the spectroscopy showed minimal changes attributable to pressure induced effects. Under the higher-pressure reactive conditions, the frequency region at the antisymmetric NO 2 stretch mode had a significantly increased absorption while the region around the symmetric NO 2 stretch did not. No observable increased absorption occurred in the higher frequency regions where CH-, NH-, and OH- bond absorptions would be observed. A broad absorption appeared on the shoulder at the red-edge of the CO 2 vibrational band around 2200 cm –1 . In addition to the experiments, reactive molecular dynamics were carried out under equivalent shock conditions to correlate the evolution of the infrared spectrum to molecular processes. The simulations show results consistent to experiments up to 30 GPa but suggest that NO and NO 2 related features provided the strongest contributions to the shocked infrared changes. Proposed mechanisms for shocked PETN chemistry are analyzed as consistent or inconsistent with the data presented here. Our experimental data suggests C≡O or N 2 O bond formation, nitrite formation, and absence of significant hydroxyl or amine concentrations in the initial chemistry steps in PETN shocked above 30 GPa.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Calibration of hydrogen atoms measurement using femtosecond two-photon laser-induced fluorescence

What we believe to be a new calibration method for H-fs-TALIF is proposed, and the ratio of two-photon absorption cross-sections, σ (2) , for atomic hydrogen (H) and krypton (Kr) is determined using the broadband emission of a femtosecond laser system. The estimated ratio of the two-photon absorption cross-sections for H and Kr is σ (2) (Kr)/σ (2) (H) = 0.027 ± 20%, which is nearly twenty times lower than values previously obtained with narrowband nanosecond lasers. This discrepancy highlights the need for independent calibration of TALIF measurements for a specific laser pulsewidth range.

Starikovskiy, Andrey [Princeton Univ., NJ (United ↗

High-resolution x-ray spectrometer for x-ray absorption fine structure spectroscopy

Two extended x-ray absorption fine structure flat crystal x-ray spectrometers (EFX’s) were designed and built for high-resolution x-ray spectroscopy over a large energy range with flexible, on-shot energy dispersion calibration capabilities. The EFX uses a flat silicon [111] crystal in the reflection geometry as the energy dispersive optic covering the energy range of 6.3–11.4 keV and achieving a spectral resolution of 4.5 eV with a source size of 50 μm at 7.2 keV. A shot-to-shot configurable calibration filter pack and Bayesian inference routine were used to constrain the energy dispersion relation to within ±3 eV. The EFX was primarily designed for x-ray absorption fine structure (XAFS) spectroscopy and provides significant improvement to the Laboratory for Laser Energetics’ OMEGA-60 XAFS experimental platform. The EFX is capable of performing extended XAFS measurements of multiple absorption edges simultaneously on metal alloys and x-ray absorption near-edge spectroscopy to measure the electron structure of compressed 3d transition metals.

47 OTHER INSTRUMENTATION↗

Measurements of K-edge and L-edge extended x-ray absorption fine structure at the national ignition facility (invited)

High-energy-density laser facilities and advances in dynamic compression techniques have expanded access to material states in the Terapascal regime relevant to inertial confinement fusion, planetary science, and geophysics. However, experimentally determining the material temperature in these extreme conditions has remained a difficult challenge. Extended X-ray Absorption Fine Structure (EXAFS), referring to the modulations in x-ray absorption above an absorption edge from photoelectrons’ interactions with neighboring atoms, has proven to be a versatile and robust technique for probing material temperature and density for mid-to-high Z elements under dynamic compression. The current platform at the National Ignition Facility has developed six configurations for EXAFS measurements between 7 and 18 keV for different absorption edges (Fe K, Co K, Cu K, Ta L3, Pb L3, and Zr K) using a curved-crystal spectrometer and a bright, continuum foil x-ray source. Here, in this work, we describe the platform geometry, x-ray source performance, spectrometer resolution and throughput, design considerations, and data in ambient and dynamic-compression conditions.

36 MATERIALS SCIENCE↗

Elastic wave suppression through additively manufactured petal lattice metamaterials

Lattice-core sandwich structure metamaterials are lightweight alternatives to monolithic materials that can present better mechanical, thermal, and energy dampening performance. Manufacturing lattice metamaterials to follow curved surfaces can pose a challenge, as the lattices rely on their geometric orientation to the substrate for their mechanical properties. This work rationally designed a lattice structure where the surface is broken up into “petals” connected to the underlying lattice, which localizes the petals’ impact response. This design opens a pathway for implementation of lattice-core sandwich structures onto complex surface geometries. These petal structures were evaluated for their energy absorption efficiency experimentally by utilizing pressure waves generated with nanosecond lasers and computationally via finite element modeling. The lattice structures exhibited a two-orders-of-magnitude decrease in transmitted pressure compared to their constituent steel at equivalent mass. Furthermore, localizing energy absorption into petal structures provided a 44% reduction in peak load compared to a continuous “single-petal” design.

Sarracino, Alex↗

Standoff Detection of Chemical Plumes Using Swept-ECQCL Remote Detection Technology: Results from EMRTC Complex Terrain Dual Tracer Experiment

As part of the Complex Terrain Dual Tracer Experiments performed in support of the LYNM program, a swept-wavelength external cavity quantum cascade laser (swept-ECQCL) remote detection system was deployed to measure chemical plume propagation with high temporal resolution. The swept-ECQCL remote detection technology was initially developed at PNNL, and is now under further development at Opticslah, LLC under SBIR funding from DOE (DOE SBIR Phase I Project DE-SC0019855, Remote Detection Technologies, Program Manager Chris Ramos). The swept-ECQCL technology provides a single-frequency infrared laser source which is rapidly scanned over a large wavelength range to measure the infrared absorption of gases, liquids, or solids. Analysis of the measured infrared absorption spectrum is used to detect, identify, and quantify the chemical species which are present. While most previous laser-based techniques used small wavelength tuning ranges to measure only a few isolated spectral lines of a few species, the swept-ECQCL provides the large tuning range needed to measure multiple species simultaneously, and to detect broad absorption features from large molecules or condensed phase materials. In addition, the swept-ECQCL systems have high enough spectral resolution and sensitivity to measure narrow lines of small molecules and determine isotope ratios. The remote detection system for gas plumes is based on the swept-ECQCL technology, and consists of a swept-ECQCL source, infrared detector, control electronics, and beam transmitting and alignment optics. The remote detection system directs the infrared output of the swept-ECQCL to a target retro reflector typically located at ~10-10,000 m distance. The swept-ECQCL wavelength is varied continuously over a large wavelength range (>1000 nm) at rates up to 1000 Hz. The swept ECQCL light reflected from the remote target is collected and focused onto an infrared photodetector. By measuring the detector signal continuously as the swept-ECQCL wavelength is varied, a time-series of absorption spectra are measured for the gases along the beam line of-sight. Based on analysis and fitting of the measured absorption spectra, the time-dependent chemical concentrations of species are determined. Multiple species and mixtures can be detected simultaneously, for all species with absorption features above the sensor noise floor. The sensor output is thus a continuous, high-speed record of identified chemicals along with their concentrations and isotope ratios of interest. The high-speed operation enables low-noise operation in conditions of atmospheric turbulence and allows tracking of fluctuating concentrations in transient chemical plumes as needed for reliable remote detection applications. All components operate with minimal cooling requirements and no cryogens are needed. In addition, the output infrared light is invisible with an intensity below the maximum permissible exposure (MPE) threshold of 100 mW/cm2 for these infrared wavelengths and thus eye safe. The measurement concept for plume detection using the swept-ECQCL remote detection system is as follows. The ECQCL beam is directed toward a remote retro-reflector, which reflects the beam back to the ECQCL system where it is focused onto an infrared photodetector. The line-of-sight from the ECQCL system to the retro-reflector defines the measurement path. The detected infrared signal is recorded continuously and detects the absorption of molecular species along the measurement path. Before a plume release, the system measures absorption from atmospheric constituents, which in this LWIR band consist primarily of lines from H 2 O and CO 2 , with additional weaker absorption from N 2 O, NH 3 , and O 3 possibly contributing. The system then measures any changes in absorption due to the tracer compounds when they enter the measurement path. The shape of absorption features is used to distinguish and identify the different tracer compounds, and the strength of the absorption is used to determine the path-integrated concentration – also called the column density.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hot electron preheat in hydrodynamically scaled direct-drive inertial confinement fusion implosions on the NIF and OMEGA

Hot electron preheat has been quantified in warm, directly driven inertial confinement fusion implosions on OMEGA and the National Ignition Facility (NIF), to support hydrodynamic scaling studies. These CH-shell experiments were designed to be hydrodynamically equivalent, spanning a factor of 40 in laser energy and a factor of 3.4 in spatial and temporal scales, while preserving the incident laser intensity of 10 15 W/cm 2 . Experiments with similarly low levels of beam smoothing on OMEGA and NIF show a similar fraction (~0.2%) of laser energy deposited as hot electron preheat in the unablated shell on both OMEGA and NIF and similar preheat per mass (~2 kJ/mg), despite the NIF experiments generating a factor of three more hot electrons (~1.5% of laser energy) than on OMEGA (~0.5% of laser energy). This is plausibly explained by more absorption of hot electron energy in the ablated CH plasma on NIF due to larger areal density, as well as a smaller solid angle of the imploding shell as viewed from the hot electron generating region due to the hot electrons being produced at a larger standoff distance in lower-density regions by stimulated Raman scattering, in contrast to in higher-density regions by two-plasmon decay on OMEGA. Finally, the results indicate that for warm implosions at intensities of around 10 15 W/cm 2 , hydrodynamic equivalence is not violated by hot electron preheat, though for cryogenic implosions, the reduced attenuation of hot electrons in deuterium–tritium plasma will have to be considered.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Adaptive four-level modeling of laser cooling of solids

Laser cooling of rare-earth doped solids has been demonstrated across a wide range of material platforms, inspiring the development of simple phenomenological models such as the four-level model to elucidate the universal properties of laser cooling under various operating conditions. However, these models usually require the input of full absorption spectra that must be provided experimentally or by additional complicated atomic modeling. In this Letter, we propose that a four-level model, when extended to admit effective energy levels adaptive to the pumping photon energy, can accurately predict the cooling efficiency as a function of temperature and pumping frequency using only few inputs such as the absorption coefficient measured at a single frequency and temperature. Our model exploits the quasi-equilibrium properties of the excitation of rare-earth ions for the determination of the effective four energy levels. The model is validated against published experimental results for a span of materials including ytterbium/thulium-doped glass and crystals. With the verified model, we derive explicit expressions for the optimal frequency and the operating bandwidth of pumping lasers. Our model significantly simplifies the modeling process of laser cooling and is expected to stimulate further development of optical refrigeration.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Aggregation of One–Dimensional Wires: The Case of Long Oligoynes

We show an unexpected aggregation phenomenon of a long oligoyne (Py[16]) with 16 contiguous triple bonds and endcapped with bulky 3,5-bi(3,5-bis-tert-butylphenyl)pyridine groups. Aggregation of 1D π-conjugated oligoyne chains is rare given the minimal π–π intermolecular interactions as well as its flexibility that works against self-assembly. In dilute solutions, the reversible aggregation of Py[16] initiates at low temperature in the range of 140–180 K, and is not observed for shorter oligoynes in this series. Cryogenic UV/Vis electronic absorption spectra and vibrational Raman spectra with different laser wavelength lines tuning from in-resonance to off-resonance conditions have been used to extract the vibrational features characterizing the monomer and aggregate species. Theoretical calculations complement the spectroscopic findings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

O 2 -Oxidation of Individual Graphite and Graphene Nanoparticles in the 1200 – 2200 K Range: Particle-to-Particle Variations and the Evolution of the Reaction Rates and Optical Properties

The kinetics for O 2 oxidation of individual graphite and graphene platelet nanoparticles (NPs) were studied as a function of temperature (1200 to 2200 K) at varying oxygen partial pressures, using a single nanoparticle mass spectrometry method. NP temperature (TNP) was measured by measuring the NP thermal emission spectra during the kinetics studies. The initial oxidation efficiency is found to peak in the 1200 to 1500 K range, dropping by an order of magnitude as TNP was increased above 2000 K. There were large NP-to-NP variations in the oxidation rates, attributed to variations in the NP surface structure. In addition, the oxidation efficiencies evolved, non-monotonically, as the NPs reacted, decreasing by factors of between 10 and 300. This evolution of reactivity is attributed to changes in the NP surface structure due to the combination of oxidation and annealing. In conclusion, the optical properties, including wavelength dependence of the emissivity and the absorption cross section for the 532 nm heating laser, also tended to evolve as the NPs oxidized, but differently for each individual NP, presumably reflecting differences in the initial structures and their evolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗