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At least 739 records · Page 41
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

3D Lead-Organoselenide-Halide Perovskites and their Mixed-Chalcogenide and Mixed-Halide Alloys

Here, we incorporate Se into the 3D halide perovskite framework using the zwitterionic ligand: SeCYS ( + NH 3 (CH 2 ) 2 Se - ), which occupies both the X - and A + sites in the prototypical ABX 3 perovskite. The new organoselenide-halide perovskites: (SeCYS)PbX 2 (X=Cl, Br) expand upon the recently discovered organosulfide-halide perovskites. Single-crystal X-ray diffraction and pair distribution function analysis reveal the average structures of the organoselenide-halide perovskites, whereas the local lead coordination environments and their distributions were probed through solid-state 77 Se and 207 Pb NMR, complemented by theoretical simulations. Density functional theory calculations illustrate that the band structures of (SeCYS)PbX 2 largely resemble those of their S analogs, with similar band dispersion patterns, yet with a considerable band gap decrease. Optical absorbance measurements indeed show band gaps of 2.07 and 1.86 eV for (SeCYS)PbX 2 with X=Cl and Br, respectively. We further demonstrate routes to alloying the halides (Cl, Br) and chalcogenides (S, Se) continuously tuning the band gap from 1.86 to 2.31 eV–straddling the ideal range for tandem solar cells or visible-light photocatalysis. The comprehensive description of the average and local structures, and how they can fine-tune the band gap and potential trap states, respectively, establishes the foundation for understanding this new perovskite family, which combines solid-state and organo-main-group chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

The high intensity diffractometer for residual stress analysis (HIDRA), a third generation residual stress mapping neutron diffractometer at the high flux isotope reactor

This paper describes the hardware and software upgrades, operation, and performance of the high intensity diffractometer for residual stress analysis (HIDRA) instrument, a residual stress mapping neutron diffractometer located at the High Flux Isotope Reactor at Oak Ridge National Laboratory in Oak Ridge Tennessee, USA. Following a major upgrade in 2018, the new instrument has a single 3 He multiwire 2D 30 × 30 cm 2 position sensitive detector, yielding a field of view of 17° 2θ. Further, the increase in the field of view (from 4° 2θ) from the previous model instrument has contributed to the tremendous improvement in the out of plane solid angle such that the 3D count rate could be obtained easily. Accordingly, the hardware, software, Data Acquisition System (DAS), and so on have also been updated. Finally, all these enhanced features of HIDRA have been ably demonstrated by conducting multi directional diffraction measurements in the quenched 750-T74 aluminum, and the evolved and improved strain/stress mappings are presented.

3D printing↗
DOE OSTI2022

Accurate quantification of lattice temperature dynamics from ultrafast electron diffraction of single-crystal films using dynamical scattering simulations

In ultrafast electron diffraction (UED) experiments, accurate retrieval of time-resolved structural parameters, such as atomic coordinates and thermal displacement parameters, requires an accurate scattering model. Unfortunately, kinematical models are often inaccurate even for relativistic electron probes, especially for dense, oriented single crystals where strong channeling and multiple scattering effects are present. This article introduces and demonstrates dynamical scattering models tailored for quantitative analysis of UED experiments performed on single-crystal films. As a case study, we examine ultrafast laser heating of single-crystal gold films. Comparison of kinematical and dynamical models reveals the strong effects of dynamical scattering within nm-scale films and their dependence on sample topography and probe kinetic energy. Applying to UED experiments on an 11 nm thick film using 750 keV electron probe pulses, the dynamical models provide a tenfold improvement over a comparable kinematical model in matching the measured UED patterns. Also, the retrieved lattice temperature rise is in very good agreement with predictions based on previously measured optical constants of gold, whereas fitting the Debye–Waller factor retrieves values that are more than three times lower. Altogether, these results show the importance of a dynamical scattering theory for quantitative analysis of UED and demonstrate models that can be practically applied to single-crystal materials and heterostructures.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Intercalation-Induced Reversible Electrochromic Behavior of Two-Dimensional Ti 3 C 2 T x MXene in Organic Electrolytes

MXenes, a large family of two-dimensional materials, have attracted tremendous attention due to their unique physical and chemical properties. Reversible ion intercalation between MXene layers allows modification of the optical, thermal, magnetic, and chemical properties. The electrochemical charge/discharge of MXenes in aqueous electrolytes was reported to lead to reversible electrochromic behavior. In this work, the electrochromic effect of semitransparent Ti 3 C 2 T x MXene film was probed by electrochemical intercalation of Li ions. Correspondingly, a peak shift of 100 nm was observed in the UV-vis spectrum. By combining in-situ Raman spectroscopy, in-situ X-ray diffraction, and density functional theory calculations, we show that the electrochromic shift is primarily due to the formation of robust O-Li bonds and the emerging bands induced changes of inter-band excitations. Finally, understanding the mechanism of electrochromic behavior in Ti 3 C 2 T x lays the foundations of designating 2D materials with durable, controllable, and efficient intercalation-induced electrochromic behaviors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Structural features of early fuel cycle taggant incorporation for intentional nuclear forensics

To develop strategies for incorporating transition metal taggants (Fe, Cr, and Ni) into oxide fuels and to understand how these taggant candidates persist through early fuel cycle processes, synthetic procedures are modified from established production routes to yield intentionally tagged early fuel cycle intermediates including uranyl nitrate hexahydrate (UNH, UO 2 (NO 3 ) 2 ·6H 2 O), uranyl peroxide tetrahydrate (studtite, UO 2 O 2 ·4H 2 O), and uranyl peroxide dihydrate (metastudtite, UO 2 O 2 ·2H 2 O). First, Fe, Cr, and Ni nitrate solutions are introduced to an aqueous solution of UNH followed by precipitation to produce tagged UNH. Then, studtite is precipitated from UNH followed by dehydration to metastudtite. Structural influences of taggant incorporation within all synthesized phases are investigated using powder X-ray diffraction (PXRD) and Raman spectroscopy to provide insight into crystallographic modifications resulting from the addition of tags to these early fuel cycle materials and elucidate the chemical form of taggants introduced at these stages. The possibility of segregation of taggant species into discrete phases within U matrices was examined using scanning electron microscopy with energy dispersive X-ray spectroscopy. Taggant concentrations in solid-phase materials were determined using inductively coupled plasma-optical emission spectroscopy. Observations from Raman spectroscopy and PXRD indicate that introducing transition metal tags during uranyl nitrate precipitation results in potential impurity phase segregation in UNH, but transition metal incorporation is suggested by results for tagged uranyl peroxide materials. Further, results from this study will inform strategies for optimizing taggant incorporation in UO 2 .

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Epitaxial PbGeSe thin films and their photoluminescence in the mid-wave infrared

PbSe is a narrow bandgap IV–VI compound semiconductor with application in mid-wave infrared optoelectronics, thermoelectrics, and quantum devices. Alkaline-earth or rare-earth elements such as Sr and Eu can substitute Pb to widen the bandgap of PbSe in heterostructure devices, but they come with challenges such as deteriorating optical and electronic properties, even in dilute concentrations due to their dissimilar atomic nature. We substitute Pb instead with column IV Ge and assess the potential of rocksalt phase PbGeSe as a wider bandgap semiconductor in thin films grown by molecular beam epitaxy on GaAs substrates. Low sticking of GeSe adatoms requires synthesis temperatures below 260 °C to incorporate Ge, but this yields poor structural and compositional uniformity as determined by x-ray diffraction. Consequently, as-grown films in the range Pb0.94Ge0.06Se–Pb0.83Ge0.17Se (6%–17% Ge) show much less bandgap widening in photoluminescence than prior work on bulk crystals using absorption. We observe that post-growth rapid thermal annealing at temperatures of 375–450 °C improves the crystal quality and recovers bandgap widening. Rapid interdiffusion of Ge during annealing, however, remains a challenge in harnessing such PbGeSe materials for compositionally sharp heterostructures. Annealed 17% Ge films emit light at 3–3.1 μm with a minimal shift in wavelength vs temperature. These samples are wider in bandgap than PbSe films by 55 meV at room temperature, and the widening increases to 160 meV at 80 K, thanks to sharply different dependence of bandgap on temperature in PbSe vs PbGeSe.

Xiao, Kelly (ORCID:0000000321000838)↗
DOE OSTI2024

Isotropic negative thermal expansion in ZrW 2 O 8 and HfW 2 O 8 from 1100 to 1275°C

Abstract ZrW 2 O 8 (ZrO 2 •2WO 3 ) and HfW 2 O 8 (HfO 2 •2WO 3 ) have been the focus of thermal expansion studies due to their isotropic negative thermal expansion (NTE) measured previously at temperatures below 775°C. This work presents measurements of these materials at their thermodynamically stable temperature ranges of 1105 and 1257°C for ZrW 2 O 8 and 1105–1276°C for HfW 2 O 8 , where they were characterized with in situ, powder X‐ray diffraction. The linear coefficients of thermal expansion were measured to be −5.52 × 10 −6 and −4.87 × 10 −6 °C −1 for ZrW 2 O 8 and HfW 2 O 8 , respectively. The mechanism leading to this NTE is discussed. Powder samples were synthesized by a solution‐based process called the organic–inorganic steric entrapment method. In situ characterization in air was carried out at the National Synchrotron Light Source II using a hexapole lamp, optical furnace and the Advanced Photon Source using a quadrupole lamp, optical furnace to achieve elevated temperatures.

Materials Science↗
DOE OSTI2020

Polyhydrido Copper Nanoclusters with a Hollow Icosahedral Core: [Cu 30 H 18 {E 2 P(OR) 2 } 12 ] (E=S or Se; R= n Pr, i Pr or i Bu)

Although atomically precise polyhydrido copper nanoclusters are of prime interest for a variety of applications, they have so far remained scarce. Here, we describe the synthesis of a dithiophosphate-protected copper(I) hydride-rich nanocluster (NC), [Cu 30 H 18 {S 2 P(O n Pr) 2 } 12 ] ( 1 H ), fully characterized by various spectroscopic methods and single-crystal X-ray diffraction. The X-ray structure of 1 H reveals an unprecedented central Cu 12 hollow icosahedron. Six faces of this icosahedron are capped by Cu 3 triangles, the whole Cu 30 core being wrapped by twelve dithiophosphate ligands and the whole cluster has ideal S 6 symmetry. The locations of the 18 hydrides in 1 H were ascertained by a single-crystal neutron diffraction study. They are composed of three types: capping μ 3 -H, interstitial μ 4 -H (seesaw) and μ 5 -H ligands (square pyramidal), in good agreement with the DFT simulations. The numbers of hydrides and ligand resonances in the 1 H NMR spectrum of 1 H are in line with their coordination environment in the solid state, retaining the S 6 symmetry in solution. Furthermore, two new Se-protected polyhydrido copper nanoclusters, [Cu 30 H 18 {Se 2 P(OR) 2 } 12 ] ( 2 H : R= i Pr 3 H : R= i Bu) were synthesized from their sulfur relative 1 H via ligand displacement reaction and their X-ray structures feature the exceptional case where both the NC shape and size are fully conserved during the course of ligand exchange. DFT and TD-DFT calculations allow understanding the bonding and optical properties of clusters 1 H – 3 H . In addition, the reaction of 1 H with [Pd(PPh 3 ) 2 Cl 2 ] in the presence of terminal alkynes led to the formation of new bimetallic Cu–Pd alloy clusters [PdCu 14 H 2 {S 2 P(O n Pr) 2 } 6 (C≡CR) 6 ] ( 4 : R=Ph; 5 : R = C 6 H 4 F).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Direct observation of strain-enhanced hydrogen segregation and failure at high-angle grain boundaries in nickel

Understanding the mechanisms underlying hydrogen embrittlement remains difficult, even in single-element metals. Both microstructure and stress state influence hydrogen distribution in metals and alloys, which impacts deformation and failure. Here, in this work, we use in-situ Kelvin probe force microscopy (KPFM) to monitor the hydrogen distribution in pure nickel over time at 1.1 % and 3.5 % strain. The sample strained to 3.5 % results in preferential hydrogen segregation to high-angle grain boundaries whereas the sample strained to 1.1 % does not exhibit preferential hydrogen segregation. Optical digital image correlation (DIC) shows that hydrogen charging results in both localized and reduced strains during tensile testing of a notched sample. Later stages of deformation and failure (e.g. microcracking) are studied by using in-situ transmission X-ray microscopy (TXM). TXM reveals nanoscale structural changes to a propagating crack in a hydrogen environment. Localized void growth and secondary cracking occur at grain boundaries near the primary crack front. Correlative electron backscattering diffraction (EBSD) is used to relate the cracking at grain boundaries to the hydrogen segregation observed in KPFM. These findings are unified in a proposed hydrogen embrittlement mechanism that describes the interaction of hydrogen with grain boundaries, and the role of grain boundaries in hydrogen embrittlement.

Grain boundary fracture↗
DOE OSTI2025

3D strain field reconstruction by inversion of dynamical scattering

Strain governs not only the mechanical response of materials but also their electronic, optical, and catalytic properties. For this reason, the measurement of the 3D strain field is crucial for a detailed understanding and for further development of material properties through strain engineering. However, measuring strain variations along the electron beam direction has remained a major challenge for (scanning-) transmission electron microscopy (S/TEM). In this article, we present a method for 3D strain field determination using 4D-STEM. The method is based on the inversion of dynamical diffraction effects, which occur at strain field variations along the beam direction. We test the method against simulated data with a known ground truth and demonstrate its application to an experimental 4D-STEM dataset from an inclined pseudomorphically grown Al0.47Ga0.53N layer.

Niermann, Laura↗
DOE OSTI2024

Disorder and diffuse scattering in single-chirality (TaSe 4 ) 2 ⁢I crystals

The quasi-one-dimensional chiral compound (TaSe 4 ) 2 I has been extensively studied as a prime example of a topological Weyl semimetal. Upon crossing its phase transition temperature $T$ CDW ≈263K, (TaSe 4 ) 2 I exhibits incommensurate charge density wave (CDW) modulations described by the well-defined propagation vector ∼(0.05,0.05,0.11), oblique to the TaSe 4 chains. Although optical and transport properties greatly depend on chirality, there is no systematic report about chiral domain size for (TaSe 4 ) 2 I. In this study, our single-crystal scattering refinements reveal a bulk iodine deficiency, and Flack parameter measurements on multiple crystals demonstrate that separate (TaSe 4 ) 2 I crystals have uniform handedness, supported by direct imaging and helicity-dependent terahertz emission spectroscopy. Our single-crystal x-ray scattering and calculated diffraction patterns identify multiple diffuse features and create a real-space picture of the temperature-dependent (TaSe 4 ) 2 I crystal structure. Further, the short-range diffuse features are present at room temperature and decrease in intensity as the CDW modulation develops. These transverse displacements, along with electron pinning from the iodine deficiency, help explain why (TaSe 4 ) 2 I behaves as an electronic semiconductor at temperatures above and below $T$ CDW , despite a metallic band structure calculated from density functional theory of the ideal structure.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Synthesis of inter‐lanthanide sesquioxides LnLn'O 3 by polymeric steric entrapment

Lanthanide oxides are well known in the fields of optical, electronic, and magnetic materials. Even so, there are many application spaces yet to be explored. Previous modeling of inter-lanthanide sesquioxides, in which the compound contains two lanthanide cations, predicts the lowest level energy structure as a function of chemistry, which this work seeks to verify. Three materials of interest, ErLuO 3 , LaLuO 3 , and SmLuO 3 , were synthesized for the first time by the polymeric steric entrapment (PSE) method. X-ray diffraction confirms the stable state predictions of ErLuO 3 and SmLuO 3 forming a bixbyite type structure and LaLuO 3 forming a perovskite type structure. This work demonstrates PSE as a viable and reliable route toward the synthesis of these unique materials.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Computing virtual dark-field X-ray microscopy images of complex discrete dislocation structures from large-scale molecular dynamics simulations

Dark-field X-ray microscopy (DFXM) is a novel diffraction-based imaging technique that non-destructively maps the local deformation from crystalline defects in bulk materials. While studies have demonstrated that DFXM can spatially map 3D defect geometries, it is still challenging to interpret DFXM images of the high-dislocation-density systems relevant to macroscopic crystal plasticity. This work develops a scalable forward model to calculate virtual DFXM images for complex discrete dislocation structure(s) (DDS) obtained from atomistic simulations. Our new DDS-DFXM model integrates a non-singular formulation for calculating the local strain from the DDS and an efficient geometrical optics algorithm for computing the DFXM image from the strain field. We apply the model to complex DDS obtained from a large-scale mol­ecular dynamics simulation of compressive loading on single-crystal silicon. Simulated DFXM images exhibit prominent contrast for dislocation features between the multiple slip systems, demonstrating the potential of DFXM to resolve features from dislocation multiplication. In conclusion, the integrated DDS-DFXM model provides a toolbox for DFXM experimental design and image interpretation in the context of bulk crystal plasticity for a range of measurements across shock plasticity and the broader materials science community.

X-ray imaging↗
DOE OSTI2024

Incorporation of rare earth elements $\text{Sc}$, $\text{Y}$ and $\text{La}$ into gibbsite

Rare earth elements (REE) are increasingly critical resources in technological applications, but the current understanding of their separation by uptake into minerals remains limited. We examined the adsorption and solubilization of scandium (Sc), yttrium (Y), and lanthanum (La) into aluminum hydroxide (gibbsite, Al(OH) 3 ). Based on spectroscopic investigations such as inductively coupled plasma-optical emission spectroscopy (ICP-OES) and time of flight-secondary ion mass spectrometry (ToF-SIMS), only Sc exhibited favorable incorporation and adsorption (0.66 and 0.06 atom%, respectively). Analysis of solid state 45 Sc magic angle spinning-nuclear magnetic resonance spectroscopy (MAS-NMR) indicated that Sc exhibits an octahedral coordination consistent with isolated substitutions for Al in the gibbsite structure, leading to a increase in lattice constants detectable by X-ray diffraction. Density functional theory (DFT) calculations reinforced this interpretation by reproducing the detected structural distortion as well as demonstrating the relatively favorable energetic basis for Sc incorporation into gibbsite by substitution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Semi-transparent p-type barium copper sulfide as a back contact interface layer for cadmium telluride solar cells

Optically transparent p-type materials play a critical role in transparent electronics including photovoltaic (PV) devices. P-type sulfide materials offer an alternative to oxides for PV application due to improved hole transport properties. Here, we report the solution-based synthesis of earth-abundant p-type transparent conducting barium copper sulfide (α-BaCu 4 S 3 , BCS) thin films. These films were characterized using scanning electron microscopy, X-ray diffraction, UV–Vis–NIR spectrophotometry, Raman spectroscopy, and spectroscopic ellipsometry. BCS films of ~100 nm thickness transmit >70% of visible light. We report on tests of the hole transport properties of these BCS films for cadmium telluride (CdTe) photovoltaics, finding that the BCS deposition process forms a beneficial tellurium (Te) rich surface on CdTe by selectively removing Cd from the surface. Based on our study, the BCS interface layer plays dual functions for CdTe PV devices as a hole transport material and as an etchant, enhancing the resulting device performance. We observed a significant increase in open-circuit voltage of CdTe solar cells with the BCS buffer layer. Furthermore, we discuss semitransparent CdTe solar cells with BCS as a hole transport layer and indium tin oxide as a finishing electrode. Semitransparent CdTe solar cells shows 13.3% conversion efficiency for the front side illumination and 1.2% efficiency for back side illumination, indicating high recombination of charge carriers generated close to the rear CdTe/BCS/ITO contact.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Effect of rare earth size on network structure and glass forming ability in binary aluminum garnets

Rare earth aluminate glasses are potentially useful for optical, luminescence, and laser applications. As reluctant glass formers, these materials exhibit unconventional atomic structures. To better understand how their structures correlate with glass formation, we investigate two rare earth aluminum garnet melts, La 3 Al 5 O 12 (LAG) and Yb 3 Al 5 O 12 (YbAG), which represent the relative extremes of good and poor glass forming ability in rare earth aluminates. Structural models have been refined to high-energy X-ray diffraction data over 1340–2740 K. Both melts contain mixtures of AlO 4 , AlO 5 , and AlO 6 polyhedra, with larger fractions of [5] Al and [6] Al in YbAG. Extrapolation of the Al–O coordination distributions to the glass transition match closely with 27 Al nuclear magnetic resonance measurements of (La 1−z Y z ) 3 Al 5 O 12 glasses, z = 0 to 1. During cooling, the mean coordination numbers increase for La–O in LAG from 6.45(8) to 6.98(8) and for Yb–O in YbAG from 6.02(8) to 6.21(8). Linkedness among Al–O polyhedra at ∼2450 K is mostly corner-sharing, with 9% edge-sharing in LAG and 19% in YbAG. Among [4] Al units, both melts have 6% edge-sharing that convert to all corner-sharing upon cooling. Network connectivity is compared using a newly defined metric, K n , that is similar to the Q n distribution but that accounts for the edge-sharing and triply bonded oxygen present in these melts. The lower glass forming ability in YbAG as compared to LAG correlates with more edge-sharing, associated with the larger fractions of [5] Al and [6] Al, and lower connectivity among [4] Al units.

Wilke, Stephen K. [Materials Development, Inc., Ar↗
DOE OSTI2023

Deciphering phase evolution in complex metal oxide thin films via high-throughput materials synthesis and characterization

Discovery of structure-property relationships in thin film alloys of complex metal oxides enabled by high-throughput materials synthesis and characterization facilities is demonstrated here with a case-study. In this study, thin films of binary transition metal oxides (Ti–Zn) are prepared by pulsed laser deposition with continuously varying Ti:Zn ratio, creating combinatorial samples for exploration of the properties of this material family. The atomic structure and electronic properties are probed by spatially resolved techniques including x-ray absorption near edge structures (XANES) and x-ray fluorescence (XRF) at the Ti and Zn K-edge, x-ray diffraction, and spectroscopic ellipsometry. The observed properties as a function of Ti:Zn ratio are resolved into mixtures of five distinguishable phases by deploying multivariate curve resolution analysis on the XANES spectral series, under constraints set by results from the other characterization techniques. First-principles computations based on density function theory connect the observed properties of each distinct phase with structural and spectral characteristics of crystalline polymorphs of Ti–Zn oxide. Continuous tuning of the optical absorption edge as a function of Ti:Zn ratio, including the unusual observation of negative optical bowing, exemplifies a functional property of the film correlated to the phase evolution.

36 MATERIALS SCIENCE↗