Dirac semimetals have attracted a great deal of current interests due to their potential applications in topological quantum computing, low-energy electronic devices, and single photon detection in the microwave frequency range. Herein are results from analyzing the low magnetic (B) field weak-antilocalization behaviors in a Dirac semimetal Cd3As2 thin flake device. At high temperatures, the phase coherence length lφ first increases with decreasing temperature (T) and follows a power law dependence of lφ ∝ T-0.4. Below ~3 K, lφ tends to saturate to a value of~180 nm. Another fitting parameter α, which is associated with independent transport channels, displays a logarithmic temperature dependence for T>3 K, but also tends to saturate below~3 K. The saturation value,~1.45, is very close to 1.5, indicating three independent electron transport channels, which we interpret as due to decoupling of both the top and bottom surfaces as well as the bulk. This result, to our knowledge, provides first evidence that the surfaces and bulk states can become decoupled in electronic transport in Dirac semimetal Cd3As2.
This report is the final documentation for the one-year LDRD project 226360: Simulated X-ray Diffraction and Machine Learning for Optimizing Dynamic Experiment Analysis. As Sandia has successfully developed in-house X-ray diffraction tools for study of atomic structure in experiments, it has become increasingly important to develop computational analysis methods to support these experiments. When dynamically compressed lattices and orientations are not known a priori, the identification requires a cumbersome and sometimes intractable search of possible final states. These final states can include phase transition, deformation and mixed/evolving states. Our work consists of three parts: (1) development of an XRD simulation tool and use of traditional data science methods to match XRD patterns to experiments; (2) development of ML-based models capable of decomposing and identifying the lattice and orientation components of multicomponent experimental diffraction patterns; and (3) conducting experiments which showcase these new analysis tools in the study of phase transition mechanisms. Our target material has been cadmium sulfide, which exhibits complex orientation-dependent phase transformation mechanisms. In our current one-year LDRD, we have begun the analysis of high-quality c-axis CdS diffraction data from DCS and Thor experiments, which had until recently eluded orientation identification.
Niobium doped lead-tin-zirconate-titanate ceramics near the PZT 95/5 orthorhombic AFE – rhombohedral FE morphotropic phase boundary Pb1-0.5y(Zr0.865-xTixSn0.135)1-yNbyO3 were prepared according to a 22+1 factorial design with x = 0.05, 0.07 and y = 0.0155, 0.0195. The ceramics were prepared by a traditional solid-state synthesis route and sintered to near full density at 1250°C for 6 hours. All compositions were ~98% dense with no detectable secondary phases by XRD. The ceramics exhibited equiaxed grains with intergranular porosity and grain size was ~5 μm, decreasing with niobium substitution. Compositions exhibited remnant polarization values of ~32 μC/cm2, increasing with Ti substitution. Depolarization by the hydrostatic pressure induced FE-AFE phase transition was drastically affected by variation of the Ti and Nb substitution, increasing at a rate of 113 MPa / 1% Ti and 21 MPa / 1% Nb. Total depolarization output was insensitive to the change in Ti and Nb substitution, ~32.8 μC/cm2 for the PSZT ceramics. The R3c-R3m and R3m-Pm3m phase transition temperatures on heating ranged from 90 to 105°C and 183 to 191°C, respectively. Ti substitution stabilized the R3c and R3m phases to higher temperatures, while Nb substitution stabilized the Pm3m phase to lower temperatures. Thermal hysteresis of the phase transitions was also observed in the ceramics, with transition temperature on cooling being as much as 10°C lower.
Negative and zero coefficient of thermal expansion (CTE) materials are of interest for developing polymer composites in electronic circuits that match the expansion of Si and in zero CTE supports for optical components, e.g., mirrors. In this work, the processing challenges and stability of ZrW2O8, HfW2O8, HfMgW3O12, Al(HfMg)0.5W3O12, and Al0.5Sc1.5W3O12 negative and zero thermal expansion coefficient ceramics are discussed. Al0.5Sc1.5W3O12 is demonstrated to be a relatively simple oxide to fabricate in large quantity and is shown to exhibit single phase up to 1300 °C in air and inert N2 environments. The negative and zero CTE behavior was confirmed with dilatometry. Thermal conductivity and heat capacity were reported for the first time for HfMgW3O12 and Al0.5Sc1.5W3O12 and thermal conductivity was found to be very low (~0.5 W/mK). Grüneisen parameter is also estimated. Methods for integration of Al0.5Sc1.5W3O12 with other materials was examined and embedding 50 vol% of the ceramic powder in flexible epoxy was demonstrated with a commercial vendor.
Nanothermite NiO–Al is a promising material system for low gas emission heat sources; yet, its reactive properties are highly dependent on material processing conditions. In the current study, sputter deposition is used to fabricate highly controlled nanolaminates comprised of alternating NiO and Al layers. Films having an overall stoichiometry of 2Al to 3NiO were produced with different bilayer thicknesses to investigate how ignition and self-sustained, high temperature reactions vary with changes to nanometer-scale periodicity and preheat conditions. Ignition studies were carried out with both hot plate and laser irradiation and compared to slow heating studies in hot-stage x-ray diffraction. Ignition behavior has bilayer thickness and heating rate dependencies. The 2Al/3NiO with λ ≤ 300 nm ignited via solid/solid diffusion mixing (activation energy, E a = 49 ± 3 kJ/mole). Multilayers having λ ≥ 500 nm required a more favorable mixing kinetics of solid/liquid dissolution into molten Al ( E a = 30 ± 4 kJ/mole). This solid/liquid dissolution E a is a factor of 5 lower than that of the previously reported powder compacts due to the elimination of a passivating Al oxide layer present on the powder. The reactant mixing mechanism between 300 and 500 nm bilayer thicknesses was dependent on the ignition source's heating rate. The self-propagating reaction velocities of 2Al/3NiO multilayers varied from 0.4 to 2.5 m/s. Pre-heating nanolaminates to temperatures below the onset reaction temperatures associated with forming intermediate nickel aluminides at multilayer interfaces led to increased propagation velocities, whereas pre-heating samples above the onset temperatures inhibited subsequent attempts at laser ignition.
Tungsten (W) films have many applications in the semiconducting industry for sensor technology. Deposition conditions can significantly impact the resulting W films in terms of the phases present (α-BCC or β-A12), microstructural grain orientation (texture), and residual strain. Tilt-A-Whirl methodology has been employed for the evaluation of a W film showing both texture and residual strain. Sin2(ψ) analysis of the film was performed to quantify the strongly tensile in-plane strain (+0.476%) with an estimated in-plane tensile stress of ~1.9 GPa. The 3D dataset was also evaluated qualitatively via 3D visualization. Visualization of 3D texture/strain data poses challenges due to peak broadening resulting from defocusing of the beam at high ψ tilt angles. To address this issue, principal component analysis (PCA) was employed to diagnose, model, and remove the broadening component from the diffraction data. Evaluation of the raw data and subsequent corrected data (after removal of defocusing effects) has been performed through projection of the data into a virtual 3D environment (via CAD2VR software) to qualitatively detect the impact of residual strain on the observed pole figure.
The formation of Al3Sc, in 100 nm Al0.8Sc0.2 films, is found to be driven by exposure to high temperature through higher deposition temperature or annealing. High film resistivity was observed in films with lower deposition temperature that exhibited a lack of crystallinity, which is anticipated to cause more electron scattering. An increase in deposition temperature allows for the nucleation and growth of crystalline Al3Sc regions that were verified by electron diffraction. The increase in crystallinity reduces electron scattering, which results in lower film resistivity. Annealing Al0.8Sc0.2 films at 600 °C in an Ar vacuum environment also allows for the formation and recrystallization of Al3Sc and Al and yields saturated resistivity values between 9.58 and 10.5 μΩ-cm regardless of sputter conditions. Al3Sc was found to nucleate and grow in a random orientation when deposited on SiO2, and highly {111} textured when deposited on 100 nm Ti and AlN films that were used as template layers. The rocking curve of the Al3Sc 111 reflection for the as-deposited films on Ti and AlN at 450 °C was 1.79° and 1.68°, respectively. Annealing the film deposited on the AlN template reduced the rocking curve substantially to 1.01° due to recrystallization of Al3Sc and Al within the film.
Pulsed-power generators can produce well-controlled continuous ramp compression of condensed matter for high-pressure equation-of-state studies using the magnetic loading technique. X-ray diffraction (XRD) data from dynamically compressed samples provide direct measurements of the elastic compression of the crystal lattice, onset of plastic flow, strength-strain rate dependence, structural phase transitions, and density of crystal defects, such as dislocations. Here, we present a cost-effective, compact, pulsed x-ray source for XRD measurements on pulsed-power-driven ramp-loaded samples. This combination of magnetically driven ramp compression of materials with a single, short-pulse XRD diagnostic will be a powerful capability for the dynamic materials' community to investigate in situ dynamic phase transitions critical to equation of states. We present results using this new diagnostic to evaluate lattice compression in Zr and Al and to capture signatures of phase transitions in CdS.
Niobium (Nb)-doped lead-tin-zirconate-titanate (PSZT) ceramics near the lead-zirconate-titanate 95/5 orthorhombic AFE-rhombohedral FE morphotropic phase boundary (PSZT 13.5/81/5.5 -1.6Nb) were prepared with up to 10 mol.% of hafnium (Hf) substituted for zirconium. The ceramics were prepared by a traditional solid-state synthesis route and sintered to near full density at 1150°C for 6 h in sealed alumina crucibles with self-same material as the lead vapor source. All compositions were ~98% dense with no detectable secondary phases by X-ray diffraction. The grain size was ~3 μm for all compositions, consisting of equiaxed grains with intergranular porosity. The compositions exhibited remnant polarization values of ~32 μC/cm2. Depolarization by the hydrostatic pressure-induced FE-AFE phase transition occurred at 310 MPa for all compositions, resulting in a total depolarization output of 32.4 μC/cm2 for the PSZT ceramics. Evaluation of the R3c-R3m and R3m-Pm $\bar{3}$ m phase transition temperatures by impedance spectroscopy showed temperatures on heating ranging from 86 to 92°C and 186 to 182°C, respectively, for increasing nominal Hf content. Thermal hysteresis of the phase transitions was also observed in the ceramics, with the transition temperature on cooling being 1–4°C lower. The study demonstrated that the PSZT ceramics are relatively insensitive to variations in Hf content in the range of 0 to 10 mol.%.
A rapid and facile design strategy to create a highly complex optical tag with programmable, multimodal photoluminescent properties is described. This was achieved via intrinsic and DNA-fluorophore hidden signatures. As a first covert feature of the tag, an intricate novel heterometallic near-infrared (NIR)-emitting mesoporous metal-organic framework (MOF) was designed and synthesized. The material is constructed from two chemically distinct, homometallic hexanuclear clusters based on Nd and Yb. Uniquely, the Nd-based cluster is observed here for the first time in a MOF and consists of two staggered Nd μ3-oxo trimers. To generate controlled, multimodal, and tailorable emission with difficult to counterfeit features, the NIR-emissive MOF was post-synthetically modified via a fluorescent DNA oligo labeling design strategy. The surface attachment of several distinct fluorophores, including the simultaneous attachment of up to three distinct fluorescently labeled oligos was achieved, with excitation and emission properties across the visible spectrum (480-800 nm). The DNA inclusion as a secondary covert element in the tag was demonstrated via the detection of SYBR Gold dye association. Importantly, the approach implemented here serves as a rapid and tailorable way to encrypt distinct information in a facile and modular fashion and provides an innovative technology in the quest toward complex optical tags.
Optical anticounterfeiting tags utilize the photoluminescent properties of materials to encode unique patterns, enabling identification and validation of important items and assets. These tags must combine optical complexity with ease of production and authentication to both prevent counterfeiting and to remain practical for widespread use. Metal-organic frameworks (MOFs) based on polynuclear, rare earth clusters are ideal materials platforms for this purpose, combining fine control over structure and composition, with tunable, complex energy transfer mechanisms via both linker and metal components. Here we report the design and synthesis of a set of heterometallic MOFs based on combinations of Eu, Nd, and Yb with the tetratopic linker 1,3,6,8-tetrakis(4-carboxyphenyl)pyrene. The energetics of this linker facilitate the intentional concealment of the visible emissions from Eu while retaining the infrared emissions of Nd and Yb, creating an optical tag with multiple covert elements. Unique to the materials system reported herein, we document the occurrence of a previously not observed 11-metal cluster correlated with the presence of Yb in the MOFs, coexisting with a commonly encountered 9-metal cluster. We demonstrate the utility of these materials as intricate optical tags with both rapid and in-depth screening techniques, utilizing orthogonal identifiers across composition, emission spectra, and emission decay dynamics. This work highlights the important effect of linker selection in controlling the resulting photoluminescent properties in MOFs and opens an avenue for the targeted design of highly complex, multifunctional optical tags.
Novel materials based on the aluminum oxyhydroxide boehmite phase were prepared using a glycothermal reaction in 1,4-butanediol. Under the synthesis conditions, the atomic structure of the boehmite phase is altered by the glycol solvent in place of the interlayer hydroxyl groups, creating glycoboehmite. The structure of glycoboehmite was examined in detail to determine that glycol molecules are intercalated in a bilayer structure, which would suggest that there is twice the expansion identified previously in the literature. This precursor phase enables synthesis of two new phases that incorporate either polyvinylpyrrolidone or hydroxylpropyl cellulose nonionic polymers. These new materials exhibit changes in morphology, thermal properties, and surface chemistry. All the intercalated phases were investigated using PXRD, HRSTEM, SEM, FT-IR, TGA/DSC, zeta potential titrations, and specific surface area measurement. These intercalation polymers are non-ionic and interact through wetting interactions and hydrogen bonding, rather than by chemisorption or chelation with the aluminum ions in the structure.
Solar thermochemical hydrogen (STCH) production is a promising method to generate carbon neutral fuels by splitting water utilizing metal oxide materials and concentrated solar energy. The discovery of materials with enhanced water-splitting performance is critical for STCH to play a major role in the emerging renewable energy portfolio. While perovskite materials have been the focus of many recent efforts, materials screening can be time consuming due to the myriad chemical compositions possible. This can be greatly accelerated through computationally screening materials parameters including oxygen vacancy formation energy, phase stability, and electron effective mass. In this work, the perovskite Gd0.5La0.5Co0.5Fe0.5O3 (GLCF), was computationally determined to be a potential water splitter, and its activity was experimentally demonstrated. During water splitting tests with a thermal reduction temperature of 1,350°C, hydrogen yields of 101 μmol/g and 141 μmol/g were obtained at re-oxidation temperatures of 850 and 1,000°C, respectively, with increasing production observed during subsequent cycles. This is a significant improvement from similar compounds studied before (La0.6Sr0.4Co0.2Fe0.8O3 and LaFe0.75Co0.25O3) that suffer from performance degradation with subsequent cycles. Confirmed with high temperature x-ray diffraction (HT-XRD) patterns under inert and oxidizing atmosphere, the GLCF mainly maintained its phase while some decomposition to Gd2-xLaxO3 was observed.
We present progress on the synthesis of semimetal Cd3As2 by metal–organic chemical-vapor deposition (MOCVD). Specifically, we have optimized the growth conditions needed to obtain technologically useful growth rates and acceptable thin-film microstructures, with our studies evaluating the effects of varying the temperature, pressure, and carrier-gas type for MOCVD of Cd3As2 when performed using dimethylcadmium and tertiarybutylarsine precursors. In the course of the optimization studies, exploratory Cd3As2 growths are attempted on GaSb substrates, strain-relaxed InAs buffer layers grown on GaSb substrates, and InAs substrates. Notably, only the InAs-terminated substrate surfaces yield desirable results. Extensive microstructural studies of Cd3As2 thin films on InAs are performed by using multiple advanced imaging microscopies and x-ray diffraction modalities. The studied films are 5–75 nm in thickness and consist of oriented, coalesced polycrystals with lateral domain widths of 30–80 nm. The most optimized films are smooth and specular, exhibiting a surface roughness as low as 1.0 nm rms. Under cross-sectional imaging, the Cd3As2-InAs heterointerface appears smooth and abrupt at a lower film thickness, ~30 nm, but becomes quite irregular as the average thickness increases to ~55 nm. The films are strain-relaxed with a residual biaxial tensile strain (εxx = +0.0010) that opposes the initially compressive lattice-mismatch strain of Cd3As2 coherent on InAs (εxx = −0.042). Importantly, phase-identification studies find a thin-film crystal structure consistent with the P42/nbc space group, placing MOCVD-grown Cd3As2 among the Dirac semimetals of substantial interest for topological quantum materials studies.
Laser beam directed energy deposition has become an increasingly popular advanced manufacturing technique for materials discovery as a result of the in situ alloying capability. In this study, we leverage an additive manufacturing enabled high throughput materials discovery approach to explore the composition space of a graded Wx(CoCrFeMnNi)100−x sample spanning 0 ≤ x ≤ 21 at%. In addition to microstructural and mechanical characterization, synchrotron high speed x-ray computer aided tomography was conducted on a W20(CoCrFeMnNi)80 composition to visualize melting dynamics, powder-laser interactions, and remelting effects of previously consolidated material. Results reveal the formation of the Fe7W6 intermetallic phase at W concentrations> 6 at%, despite the high configurational entropy. Unincorporated W particles also occurred at W concentrations> 10 at% accompanied by a dissolution band of Fe7W6 at the W/matrix interface and hardness values greater than 400 HV. The primary strengthening mechanism is attributed to the reinforcement of the Fe7W6 and W phases as a metal matrix composite. The in situ high speed x-ray imaging during remelting showed that an additional laser pass did not promote further mixing of the Fe7W6 or W phases suggesting that, despite the dissolution of the W into the Fe7W6 phase being thermodynamically favored, it is kinetically limited by the thickness/diffusivity of the intermetallic phase, and the rapid solidification of the laser-based process.
Zirconium-based metal-organic frameworks, including UiO-66 and related frameworks, have become the focus of considerable research in the area of chemical warfare agent (CWA) decontamination. However, little work has been reported exploring these metal-organic frameworks (MOFs) for CWA sensing applications. For many sensing approaches, the growth of high-quality thin films of the active material is required, and thin film growth methods must be compatible with complex device architectures. Several approaches to synthesize thin films of UiO-66 have been described but many of these existing methods are complex or time consuming. We describe the development of a simple and rapid microwave assisted synthesis of oriented UiO-66 thin films on unmodified silicon (Si) and gold (Au) substrates. Thin films of UiO-66 and UiO-66-NH2 can be grown in as little as 2 min on gold substrates and 30 min on Si substrates. The film morphology and orientation are characterized and the effects of reaction time and temperature on thin film growth on Au are investigated. Both reaction time and temperature impact the overgrowth of protruding discrete crystallites in the thin film layer but, surprisingly, no strong correlation is observed between film thickness and reaction time or temperature. We also briefly describe the synthesis of Zr/Ce solid solution thin films of UiO-66 on Au and report the first synthesis of a solid solution thin film MOF. Finally, we demonstrate the utility of the microwave method for the facile functionalization of two sensor architectures, plasmonic nanohole arrays and microresonators, with UiO-66 thin films.
This study relates structure, properties and thermodynamics, through synthesis, characterization and heat of formation measurements of rare earth iridate pyrochlore (RE2Ir2O7; RE = Y, Eu, Pr) crystalline powders. The RE2Ir2O7 phases are synthesized by high temperature solid-state synthesis methods. X-ray diffraction and elemental analysis techniques are utilized to validate the synthesis and enable structural comparisons. Trends in the bond angles indicate deviations from the Y and Eu analogs for the Pr2Ir2O7 phase. High temperature oxide melt solution calorimetry is used to determine the heats of formation of each phase. Breaking the trend expected across the rare earth series, the enthalpy of formation for Pr2Ir2O7 is more exothermic than the anticipated from the Y and Eu analogs.