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Electron transport measurements on 60-nm-thick multilayers containing N = 2–58 individual Ru and Co layers are employed to quantify the specific resistance of Ru/Co interfaces. Sputter deposition on Al2O3(0001) at Ts = 400 °C leads to a 0001 preferred orientation with x-ray diffraction (XRD) Ru and Co 0002 peaks that shift closer to each other with increasing N, suggesting interfacial intermixing. The intermixing is quantified by x-ray reflectivity (XRR) and confirmed by an XRD Ru/Co alloy peak that develops during in situ synchrotron annealing as well as for deposition at a higher Ts = 600 °C. The room-temperature resistivity increases from 15.0 to 47.5 μΩ cm with decreasing superlattice period Λ = 60–2 nm. This is attributed to increasing electron scattering at the intermixed metal interfaces. The transport data are well described by a parallel conductor model that treats metal layers and the intermixed alloy as parallel resistors, where the resistivity of the intermixed alloy of 60.4 μΩ cm is determined from a co-deposited Ru/Co sample. Data fitting provides values for the effective thickness of the intermixed interface of 16.8 nm, in good agreement with the XRR value, yielding a Ru/Co contact resistance of 8.5 × 10−15 Ω m2 for interfaces deposited at 400 °C. The overall results show that the Ru/Co contact resistance is dominated by a high-resistivity interfacial alloy and, therefore, is a strong function of the deposition process, particularly the processing temperature. [ABSTRACT FROM AUTHOR]

The formation of AlN/AlGaN short period superlattices (SPSLs) was investigated though the introduction of a constant Ga overpressure during the metal modulated epitaxy (MME) growth of AlN. A combination of x-ray diffraction (XRD) and scanning transmission electron microscopy (STEM) analyses found that control over the Al composition in the AlGaN layer was achieved through modulating the Ga beam equivalent pressure (BEP), with a minimum partial pressure of 3 × 10−7 Torr needed for Ga to incorporate at a growth temperature of 825 °C. A minimum Al composition in the AlGaN layer of 72% was achieved for a Ga BEP of 1 × 10−6 Torr using this method. An apparent limit of the AlGaN layer thickness of 3–4 ML indicated that the incorporation of Ga was confined to the consumption region of the MME growth process. Determination of this behavior made clear the requirements of having both XRD and STEM in order to be able to fully characterize the SPSL layer structure. Finally, AFM imaging highlighted that the presence of Ga on the surface behaved as a surfactant, with a minimum RMS roughness of 0.46 nm achieved at the maximum Ga BEP of 1 × 10−6 Torr. [ABSTRACT FROM AUTHOR]

NiO/ZnO heterostructures are grown on c-sapphire substrates using the pulsed laser deposition technique. X-ray diffraction (XRD) study shows that the ZnO layer epitaxially grows along the [0001]-direction on the (0001)sapphire surface, as expected, while the epitaxial NiO film is found to be deposited along the [001]-direction on the (0001)ZnO surface. Moreover, the presence of three (001)NiO domains laterally rotated by 30 ° with respect to each other has also been confirmed by XRD and precision electron diffraction techniques in NiO layers. The study reveals the continuous nature of the NiO film, which also possesses a very smooth surface morphology. In a sharp contrast, ZnO films are found to grow along the [0001]-direction when deposited on (111)NiO layers. These films show columnar morphology. (001)NiO/(0001)ZnO layers exhibit the rectifying current–voltage characteristics that suggests the existence of p–n junctions in these devices. However, the behavior could not be observed in (0001)ZnO/(111)NiO heterojunctions. The reason could be the columnar morphology of the ZnO layer. Such a morphology can facilitate the propagation of metal ions from the contact pads to the underlying NiO layer and suppress the p–n junction effect. [ABSTRACT FROM AUTHOR]

The ferroelectric properties evidenced on undoped hafnium oxide, which are similar to those of doped HfO 2 , are rather unexpected since it is believed that doping is a prerequisite for stabilizing HfO 2 ferroelectric behavior. Two different origins were invoked to account for this behavior. The first is related to the thermodynamic conditions of orthorhombic/ferroelectric HfO2 phase formation, favored upon the monoclinic/non-ferroelectric one by its lower surface energy in very small crystallites, i.e., in very thin layers. The second one is related to the existence of mechanical stress within the HfO 2 layer, which allows stabilization of the non-centrosymmetric orthorhombic/ferroelectric phase. The mechanical stress is either due to doping or the top and bottom metal layers in the metal/HfO 2 /metal stack. The origin of undoped HfO 2 ferroelectric behavior is still under debate. In this work, additional evidence of the role of mechanical stress in stabilizing the HfO 2 orthorhombic/tetragonal (o/t) phase is presented. The effect of top and bottom TiN electrodes on the crystallization of Gd-doped and undoped HfO 2 layers was studied as a function of HfO 2 layer thickness. The results show that the HfO 2 o/t phase of undoped HfO 2 disappears when the bottom TiN electrode is absent. In contrast, Gd-doped HfO 2 layers show the presence of a high o/t phase amount, even without the TiN bottom layer. The mechanical stress role is further evidenced by atomic plane interplanar distance measurements, which show large deformation between in-plane and out-of-plane x-ray diffraction geometries, only in the case of Gd-doped HfO 2. [ABSTRACT FROM AUTHOR]

In situ high-pressure Raman spectroscopy and synchrotron angular dispersive x-ray diffraction techniques, combined with first-principles calculations, have been performed to investigate the 1-methylhydantoin (C4H6N2O2, 1-MH) molecular crystal. High-pressure experiments have shown that phase I (monoclinic system) begins to transform into phase II (orthorhombic system) at pressures above 4.0 GPa, and the transformation range is from 4.0 to 14.2 GPa. It is proposed that the mechanism of phase transition is the interlayer contraction and rearrangement of the hydrogen-bonding network due to the enhanced strong hydrogen-bonded interactions at high pressures. This study provides some theoretical basis for this rare pressure-induced phase transition from low symmetry to high symmetry in organic supramolecular polymorphism. [ABSTRACT FROM AUTHOR]

The mechanisms contributing to the electromechanical response of piezoelectric ceramics in the shear mode have been investigated using high-energy synchrotron x-ray diffraction. Soft lead zirconate titanate ceramic specimens were subjected to an electric field in the range 0.2–3.0 MV m−1, perpendicular to that of the initial poling direction, while XRD patterns were recorded in transmission. At low electric field levels, the axial strains remained close to zero, but a significant shear strain occurred due to the reversible shear-mode piezoelectric coefficient. Both the axial and shear strains increased substantially at higher field levels due to irreversible ferroelectric domain switching. Eventually, the shear strain decreased again as the average remanent polarization became oriented toward the electric field direction. The lattice strain and domain orientation distributions follow the form of the total strain tensor, enabling the domain switching processes to be monitored by the rotation of the principal strain axis. Reorientation of this axis toward the electric field direction occurred progressively above 0.6 MV m−1, while the angle of rotation increased from 0° to approximately 80° at the maximum field of 3.0 MV m−1. A strong correlation was established between the effective strains associated with different crystallographic directions, which was attributed to the effects of elastic coupling between grains in the polycrystal. [ABSTRACT FROM AUTHOR]

The exploration of the photophysical properties of push–pull molecules incorporating pyrimidine rings as electron-attracting moieties in their structure continues to be a fascinating area of investigation. A thorough examination of these properties not only contributes to fundamental knowledge but also provides crucial insights for the rational design of emissive materials in prospective applications. In this context, this work conducts an in-depth analysis of four families of 4,6-bis(arylvinyl)pyrimidines, evaluating the influence of substituents on both the aryl groups and position 2 of the pyrimidine ring. While previous research has primarily focused on solution studies, this work emphasizes the importance of examining solid-state photophysics. Through a multidisciplinary approach encompassing optical techniques, x-ray diffraction, and quantum chemical calculations, a comprehensive understanding of the structure-property relationships is achieved. This study underscores the intricate interplay between molecular structure, aggregation, and fluorescence behavior in pyrimidines, offering valuable insights with broader implications beyond academic realms. [ABSTRACT FROM AUTHOR]

High energy x-ray pair distribution function measurements show the average coordination number of the first shell in liquid sulfur is 1.86 ± 0.04 across the λ-transition, not precisely 2.0 as widely accepted. This indicates that upon melting, liquid sulfur does not comprise solely of S8 rings but also possesses a significant number of short chains. Intensities of the pre-peak and first diffraction peak of the x-ray structure factor and third peak height of the pair distribution function all show deviations at the λ-transition temperature Tλ, associated with the break-up of S8 rings and the start of oligomer polymerization. A significant number of non-bonded or loosely bonded "interstitial atoms," with an average coordination number of 0.20 ± 0.005, are also observed in the so-called "forbidden zone" between the first and second shells upon melting. The number of interstitial atoms is found to decrease to a minimum at the λ-transition, but the majority persist into the high temperature polymerized liquid. The existence of short chains and nearby interstitial atoms represent the two main factors required to initiate the S8-ring to chain transition, as proposed by recent molecular dynamics simulations. [ABSTRACT FROM AUTHOR]

We attain N-polar and Al-polar AlN thin films on Si(111) substrates by plasma-assisted molecular beam epitaxy. The polarity of AlN epilayers has been validated by wet chemical etching using tetramethylammonium hydroxide and by the direct cross-sectional observation of atomic stacking under high-angle annular dark-field scanning transmission electron microscopy. For the 290 nm-thick as-grown N-polar AlN epilayer, x-ray diffraction (XRD) (002) and (102) ω rocking curve peak full width half maximums (FWHMs) are 475 and 1177 arcsec, and the surface mean square roughness (RMS) is 0.30 nm. We flipped the polarity using the metal-flux-modulation-epitaxy (MME) strategy. The MME strategy promotes anti-phase boundaries (APBs) on the { 2 2 ¯ 01 } crystalline planes instead of commonly observed lateral planar APBs in AlN epilayers. Merging of the tilted APBs at ∼50 nm leads to a complete Al-polar surface. For the 180 nm-thick Al-polar AlN epilayer, XRD (002) and (102) peak FWHMs are 1505 and 2380 arcsec, and the surface RMS is 1.41 nm. Strain analysis by XRD and Raman spectroscopy indicates a uniform tensile strain of 0.160% across the N-polar AlN epilayer surface and a strain distribution of 0.113%–1.16% through the epilayer. In contrast, the Al-polar AlN epilayer exhibits a much broader tensile strain distribution of 0.482%–2.406% along the growth direction, potentially due to the interaction of polarity inversion and strain relaxation. [ABSTRACT FROM AUTHOR]

Using hydrophobic aerogel (AGL) as the carrier, the catalyst supported p-toluene sulfonic acid (p-TSA) is synthesized, and the impact of the hydrophobicity of the catalyst on the formaldehyde–ethylene condensation reaction is investigated. Water contact angle, XRD, N2 adsorption/desorption, IR, and thermogravimetric analysis are used to characterize the catalyst. The outcomes demonstrate the ability of p-TSA to be loaded onto the carrier and the strong hydrophobicity of the catalyst when using AGL as the carrier. The elemental analysis results indicate that when AGL is employed as the carrier, the catalyst not only has more active sites than the SiO2-supported catalyst, but can also effectively limit the loss of active sites, reducing the loss rate from 25.82% to 15.03%. The findings demonstrate that 1,3-dioxane (1,3-DX) had a higher selectivity, rising from 16.2% to 33.3% when using AGL as the carrier. It is discovered that 1,3-propanediol (1,3-PDO) can be directly synthesized with a selectivity of up to 80.5% by employing acetic acid as a solvent in place of water. [ABSTRACT FROM AUTHOR]

The effect of cadmium ions introduced into fluorophosphate glass on the growth and photoluminescence (PL) of the CsPb1–xCdxBr3 perovskite nanocrystals (NCs) is systematically studied. The x-ray diffraction patterns have shown that cadmium ions are really incorporated into the NCs that results in a decrease in the lattice constant from 5.85 (x = 0) to 5.75 Å (x = 0.45). At the large cadmium content in the glass (x > 0.38), simultaneous formation of the perovskite CsPb1–xCdxBr3 NCs and the non-luminescent CsCdBr3 NCs in the hexagonal phase is found. It is also found that the lattice contraction leads to an increase in the bandgap energy and a noticeable shift of the PL band to the blue region of the spectrum (from 2.42 to 2.68 eV) with a drop in quantum yield from 85% for CsPbBr3 NCs down to 4% for CsPb0.55Cd0.45Br3 NCs. It is shown that the PL quantum yield decreases due to the formation of deep trap states, which manifest themselves as a PL band in the energy range of 1.6–2.5 eV at cryogenic temperatures. A simple model explaining the behavior of the PL band as a function of temperature in the range from 30 to 300 K is proposed. [ABSTRACT FROM AUTHOR]

X-ray self-heating is a common by-product of X-ray Free Electron Laser (XFEL) techniques that can affect targets, optics, and other irradiated materials. Diagnosis of heating and induced changes in samples may be performed using the x-ray beam itself as a probe. However, the relationship between conditions created by and inferred from x-ray irradiation is unclear and may be highly dependent on the material system under consideration. Here, we report on a simple case study of a titanium foil irradiated, heated, and probed by a MHz XFEL pulse train at 18.1 keV delivered by the European XFEL using measured x-ray diffraction to determine temperature and finite element analysis to interpret the experimental data. We find a complex relationship between apparent temperatures and sample temperature distributions that must be accounted for to adequately interpret the data, including beam averaging effects, multivalued temperatures due to sample phase transitions, and jumps and gaps in the observable temperature near phase transformations. The results have implications for studies employing x-ray probing of systems with large temperature gradients, particularly where these gradients are produced by the beam itself. Finally, this study shows the potential complexity of studying nonlinear sample behavior, such as phase transformations, where biasing effects of temperature gradients can become paramount, precluding clear observation of true transformation conditions. [ABSTRACT FROM AUTHOR]

The detailed study of the effect of the initial microstructure on its evolution under hydrostatic compression before, during, and after the irreversible α → ω phase transformation and during pressure release in Zr using in situ x-ray diffraction is presented. Two samples were studied: one is plastically pre-deformed Zr with saturated hardness and the other is annealed. Phase transformation α → ω initiates at lower pressure for a pre-deformed sample but for a volume fraction of ω Zr, c > --> 0.7 , a larger volume fraction is observed for the annealed sample. This implies that the proportionality between the athermal resistance to the transformation and the yield strength in the continuum phase transformation theory is invalid; an advanced version of the theory is outlined. Phenomenological plasticity theory under hydrostatic loading is outlined in terms of microstructural parameters, and plastic strain is estimated. During transformation, the first rule is suggested, i.e., the average domain size, microstrain, and dislocation density in ω Zr for c < 0.8 are functions of the volume fraction, c of ω Zr only, which are independent of the plastic strain tensor prior to transformation and pressure. The microstructure is not inherited during phase transformation. Surprisingly, for the annealed sample, the final dislocation density and the average microstrain after pressure release in the ω phase are larger than for the severely pre-deformed sample. The results suggest that an extended experimental basis is required for the predictive models for the combined pressure-induced phase transformations and microstructure evolutions. [ABSTRACT FROM AUTHOR]

In the present work, we have investigated the structural response of transition metal double perovskite oxide Nd 2 CoFeO 6 under pressure by XRD and Raman spectroscopic measurements. From XRD data, we have observed a pressure-induced structural transition from the orthorhombic phase to the monoclinic phase at about 14.8 GPa. An anomalous increase in compressibility at a much lower pressure (∼ 1.1 GPa) is seen where no structural transition occurs. At about the same pressure, a sudden drop in the slope of the Raman shift is observed. Further investigation at low temperatures reveals that the B 1 g Raman mode is strongly affected by magnetic interactions. Additional high-pressure Raman experiments with the application of a magnetic field have indicated that the mentioned anomaly around 1.1 GPa can be explained by a high-spin to low-spin transition of Co 3 + . [ABSTRACT FROM AUTHOR]

We have conducted a detailed high-pressure (HP) investigation on Eu-doped BaTiO3 using angle-resolved x-ray diffraction, Raman spectroscopy, and dielectric permittivity measurements. The x-ray diffraction data analysis shows a pressure-induced structural phase transition from the ambient tetragonal to the mixed cubic and tetragonal phases above 1.4 GPa. The tetragonality of the sample due to the internal deformation of the TiO6 octahedra caused by the charge difference from Eu doping cannot be lifted by pressure. Softening, weakening, and disappearance of low-frequency Raman modes indicate ferroelectric tetragonal to the paraelectric cubic phase transition. However, the pressure-induced increase in the intensity of [E(LO), A1(LO)] and the octahedral breathing modes indicate that the local structural inhomogeneity remains in the crystal and is responsible for spontaneous polarization in the sample. The low-frequency electronic scattering response suggests pressure-induced carrier delocalization, leading to a semi-metallic state in the system. Our HP dielectric constant data can be explained by the presence of pressure-induced localized clusters of microscopic ferroelectric ordering. Our results suggest that the HP phase coexistence leads to a ferroelectric-like semi-metallic state in Eu-doped BaTiO3 under extreme quantum limits. [ABSTRACT FROM AUTHOR]

We have conducted a detailed high-pressure (HP) investigation on Eu-doped BaTiO3 using angle-resolved x-ray diffraction, Raman spectroscopy, and dielectric permittivity measurements. The x-ray diffraction data analysis shows a pressure-induced structural phase transition from the ambient tetragonal to the mixed cubic and tetragonal phases above 1.4 GPa. The tetragonality of the sample due to the internal deformation of the TiO6 octahedra caused by the charge difference from Eu doping cannot be lifted by pressure. Softening, weakening, and disappearance of low-frequency Raman modes indicate ferroelectric tetragonal to the paraelectric cubic phase transition. However, the pressure-induced increase in the intensity of [E(LO), A1(LO)] and the octahedral breathing modes indicate that the local structural inhomogeneity remains in the crystal and is responsible for spontaneous polarization in the sample. The low-frequency electronic scattering response suggests pressure-induced carrier delocalization, leading to a semi-metallic state in the system. Our HP dielectric constant data can be explained by the presence of pressure-induced localized clusters of microscopic ferroelectric ordering. Our results suggest that the HP phase coexistence leads to a ferroelectric-like semi-metallic state in Eu-doped BaTiO3 under extreme quantum limits. [ABSTRACT FROM AUTHOR]