The photoinduced formation of thin film structures from a Ti-alkoxide precursor (OPy)2Ti(TAP)2, where OPy = OC6H6N, TAP = OC6H2[CH2N(CH3)2]3-2,4,6, was demonstrated via direct deposition from a pyridine-based solution and by optical illumination of a solid-state spin-coated thin film of the compound. Photopatterned physical relief structures were produced using both of these deposition methods and feature sizes as small as ∼1 μm were readily achieved. Surface investigations of the material’s nanostructure revealed that films photo-deposited from solution exhibited nanometer-scale surface roughness with evenly distributed surface porosity (∼10 nm sized pores) while films produced through the illumination of spin-coated thin films exhibited, in comparison, a reduction in surface roughness. Vibrational spectra were compared with the results of quantum chemical computations (density-functional theory) of potential photoproducts in an attempt to identify and distinguish the dominant structural groups resulting from the optical processing of each precursor form (i.e., solution versus solid-state). It was determined that ultraviolet irradiation for both thin-film formation techniques resulted in a disruption of the ligand groups, facilitating the initiation of hydrolysis and condensation reactions in the films.

The decomposition mechanism of block copolymer templates inside as-synthesized mesostructured solids has been systematically studied using solid-state 1H magic angle spinning nuclear magnetic resonance spectroscopy, thermogravimetric analysis, and high-vacuum Fourier transform infrared spectrometry. It is shown that there exists hydrogen-bonding interaction between silanols and block copolymers at the inorganic–organic interface in the self-assembled as-synthesized mesostructured solids, which plays an important role in protecting the surfactants against decomposition during the high-temperature hydrothermal treatment process. Increasing silanol concentration can enhance the hydrogen-bonding interaction and thus shows better “protection” effect. Moreover, the thermal decomposition of the block copolymer in as-synthesized mesostructured solids in air commences at higher temperatures compared with that in acidic solution or in air, providing further evidence in support of the silanol protection mechanism.

The possibility and suitability of micro-Raman spectroscopy as a noncontact, in-line measurement technique for boron (B) concentration in ultrathin (20~35 nm thick) Si1–xGex layers epitaxially grown on 300 mm diameter p−-Si(100) wafers, by ultrahigh vacuum chemical vapor deposition, was investigated. Raman spectra from Si1–xGex/Si(100) wafers were measured under 363.8, 457.9, 488.0, and 514.5 nm excitation. Strong correlation was found between B content and characteristics of the Si–Si Raman peak from the Si1–xGex films. As B concentration increased from undoped to 9.1 × 1020 atoms/cm3, the Si–Si Raman peak broadened and the peak height became smaller for a given Ge content. The B concentration in Si1–xGex film estimated from Raman measurement was in good agreement with secondary ion mass spectroscopy analysis results. Boron concentration as low as 8.7 × 1017 atoms/cm3 can be detected by Raman spectroscopy, which is ~30 times more sensitive than the detection limit (2.7 × 1019 atoms/cm3) of high-resolution x-ray diffraction.

Electropulsing-induced evolution of texture during recrystallization of Fe–3%Si alloy strip was studied using electron backscattered diffraction and x-ray diffraction techniques. Under electropulsing, various textures occurred during several seconds of recrystallization in the alloy. The Goss texture (G-texture) with high energy storage developed with increasing misorientation distribution of the low-angle grain boundaries. The mechanism of the electropulsing-induced G-texture evolution was discussed from the point of view of electropulsing dynamics.

Line width and line thickness thermal strain components in passivated Al and Cu lines were observed to relax much more than the line length strain component. Although the width-to-thickness ratios were large, 3.5 and 4.4 for Al and Cu lines, respectively, the behaviors of the thermal stresses were far from the equibiaxial. Observed changes in deviatoric strains between room temperature and 190 °C for Al and 300 °C for Cu were consistent with a model in which the changes in line width and line thickness strains were simply related to changes in line length strains by the uniaxial Poisson’s ratio. Changes in line length strains were determined by the differences in metal and substrate thermal expansion coefficients and the magnitudes of temperature changes through retained elastic strain coefficients for Al of 30% for heating and for Cu of 60% for heating and 80% for cooling, with the balance accommodated by relaxation.

Cadmium selenide (CdSe) belongs to a class of important II–VI semiconductors widely used in optical, sensor, and laser materials and quantum-dot light-emitting diodes. Here we present the first direct calorimetric measurement of the surface energy of wurtzite CdSe. CdSe nanoparticles with particle size between 20 and 60 nm were prepared by a hydrothermal method without additives to control morphology, and the surface energy was derived from the drop solution enthalpies in molten sodium molybdate and from water adsorption calorimetry. The surface energy of the hydrated surface is 1.31 ± 0.26 J/m2, whereas that of the anhydrous surface is 1.65 ± 0.27 J/m2. These values are significantly lower than those for ZnO and many other oxides.

Impedance spectroscopy studies were conducted on amorphous tantalum oxide thin films prepared using pulsed-DC reactive sputtering, which were post-annealed to crystallize the films. X-ray diffraction results showed that crystallization to Ta2O5 β phase occurs for samples annealed above 650 °C, with a crystallite size of ∼40 nm. The film microstructure was studied by electron microscopy, and remnants of the columnar amorphous microstructure were found in the polycrystalline films. Complex impedance analyses revealed significant differences in dielectric behavior between the amorphous and crystalline films. Lumped circuit models were conducted on the films using resistors, capacitors, and constant phase elements. Amorphous films exhibited a single relaxation with Arrhenius activation energy of 1.1–1.3 eV. Crystallized films exhibited two relaxations with activation energies equal to 1.1 ± 0.08 and 0.6 ± 0.03 eV. The relative permittivity of the bulk crystalline grain in tantalum oxide films is close to the established permittivity of the β phase (εr = 40) of Ta2O5.

Microstructural and electrical properties of Gd-doped CeO2 (GDC; Ce0.9Gd0.1O1.95) thin films prepared by pulsed laser deposition as an electrolyte in solid-oxide fuel cells (SOFCs) were investigated. The GDC thin films were prepared on various substrates including single-crystal yttria-stabilized zirconia (YSZ) and magnesium oxide (MgO) substrates. The GDC thin-film electrolytes with different grain sizes and grain morphologies were prepared by varying the deposition parameters, such as substrate temperature, oxygen partial pressure, target repetition rate, and laser ablation energy. The microstructural properties of these films were examined using X-ray diffraction (XRD), transmission electron microscopy (TEM), and atomic force microscopy (AFM). Alternating-current (AC) and direct-current (DC) electrical measurements through in-plane method show that the electrical property of the GDC thin film strongly depends on grain size, e.g., the total conductivity of the films deposited at 700 °C (7.3 × 10−3 S/cm) is about 20 times higher than the ones deposited at room temperature (3.6 × 10−4 S/cm) at the measurement temperature of 600 °C.

High-concentration niobium (V)-doped titanium dioxide (TiO2) nanoparticles of the nonequilibrium chemical composition have been synthesized via Ar/O2 radio-frequency thermal plasma oxidation of mist precursor solutions with various Nb5+ concentrations (Nb/(Ti + Nb) = 0–25.0 at.%). The solubility as high as ∼25.0 at.% has not been achieved before by wet-chemical techniques. The preferable anatase formation was attained in the plasma-synthesized powders and was enhanced by the niobium doping. All the powders were heated at high temperatures (600–800 °C) to investigate their phase transformation, band gap variation, inter-particulate binding behavior, and photocatalytic stability. The transformation from anatase to rutile was effectively inhibited by increasing the Nb5+ content. The Nb5+ doping prevented the band gap of TiO2 from narrowing after the heating. At high temperatures, Nb5+ doping could not only preserve particle size but also prevent inter-particulate binding. High concentration (25.0 at.%) Nb5+ doping retained the photocatalytic performance almost invariably irrespective of being thermally treated.

Broadband spectral conversion from visible light to near-infrared radiation in Ce3+–Nd3+/Yb3+ codoped yttrium aluminum garnet is reported. Excitation, emission spectra, and decay curves have been measured to prove the energy transfer from Ce3+ to Nd3+ or Yb3+. The energy transfer efficiencies have been estimated, and the mechanisms of the energy transfer between Ce3+ and Nd3+/Yb3+ have been proposed. Ce3+–Nd3+ codoped YAG can obtain more effective emission in the desired near-infrared region (around 1100 nm) through broadband conversion, showing potential application to improve the conversion efficiency of Si solar cells.

Flake-like Fe particles with controllable size and structures were achieved by modulating only the grinding speed; evidence provided by x-ray diffraction, scanning electron microscopy, resistivity measurement system, and vector network analyzer disclosed the conductivity; and microwave electromagnetic (EM) and absorbing characteristics of the resultant products strongly depended on their morphology and structure. As grinding speed (V) increases from 0 to 250 revolutions per minute (rpm), the crystalline size decreases; meanwhile, both internal strain and diameter/thickness ratio increase and the conductivity reaches the maximal value at V = 140 rpm because of the improvement of the surface conductivity. Thin flake-like Fe particles facilely obtained at high grinding speed present higher values of the permittivity and permeability than spherical particles, which are ascribed to the multiple polarizations and the natural resonance. Thus, the aforementioned products with high permeability and low cost may be promising candidates for EM compatibility materials.

In this work, elastic properties of Mg-based bulk metallic glasses (BMGs) with different chemical compositions were investigated. By compositional tuning in the quaternary Mg–Cu–Ag–Y alloys, the Poisson’s ratio ν of 0.332 is achieved at Mg56Cu21Ag14Y9 BMG, in excess of the previously suggested critical value (ν = 0.31–0.32) for the brittle-to-tough transition in metallic glasses. With the properties of the constituent elements, the predicted values of the bulk modulus B and shear modulus μ of Mg-based BMGs are 8% and 10% greater than the measured value, respectively. Notch toughness KQ of the ten investigated Mg-based BMGs varies between 3.6 and 8.2 MPa√m. Intrinsic brittleness of Mg glass is associated with its tiny plastic zone size (in micrometer scale) and weak resistance to crack propagation. The toughness variations are lack of significant correlation with the ν or μ. Among the investigated alloys, the Mg59.5Cu22.9Ag6.6Gd11 BMG manifests a good combination of improved toughness and high glass-forming ability.

Substrate influence is a common problem when using instrumented indentation (also known as nano-indentation) to evaluate the elastic modulus of thin films. Many have proposed models to be able to extract the film modulus (Ef) from the measured substrate-affected modulus, assuming that the film thickness (t) and substrate modulus (Es) are known. Existing analytic models work well if the film is more compliant than the substrate. However, no analytic model accurately predicts response when the modulus of the film is more than double the modulus of the substrate. In this work, a new analytic model is proposed. This new model is shown by finite-element analysis to be able to accurately predict composite response over the domain 0.1 < Ef /Es < 10. Finally, the new model is used to analyze experimental data for compliant films on stiff substrates and stiff films on compliant substrates.

Controlling the grain size and morphology of cast cobalt-based components is important for optimizing a component’s in-service properties. This work investigates the role of boron on the grain size of binary cobalt–boron alloys by application of contemporary grain refinement theory. Boron solute is found to refine the width of the columnar grains but fails to promote the columnar to equiaxed transition. The lack of equiaxed grains is attributed to the thermal solidification conditions and a lack of potent nucleant particles. The refinement of the columnar grains with boron solute may be due to a growth restriction mechanism.

Microstructural investigation and thermodynamic simulation were carried out to study precipitation during the solidification of AZ31 Mg alloy containing up to 1wt% Sr. Increasing Sr content from 0.01 to 1 wt% led to the formation of an Al–Sr line compound (Al4Sr) and to the suppression of Al–Mg precipitate (β-Mg17Al12). Transmission electron microscopic (TEM) investigation and energy dispersive spectroscopic analysis on extracted precipitates revealed Mg and Zn solubility in the Al4Sr particles. It is shown that Sr content also affects the precipitation of Al–Mn precipitates. Thermodynamic calculations predict that the increase in Sr content limits the Al–Mn reaction and the precipitation of Al–Mn precipitates with low Al/Mn ratio. Microstructural investigations determined the presence of two Al–Mn precipitates (Al8Mn5 and AlMn), either in the form of large dendritic plates or small nano-scale particles in the Mg matrix. It has been calculated by the thermodynamic model and confirmed by TEM that by increasing the Sr content, solubility of Al solid decreases whereas the level of Mn increases slightly.

Hydrogen is considered by some to be a promising non-CO2-emitting energy carrier for the future. However, to realize a hydrogen economy, there are several technological barriers to overcome. Currently, safe and efficient storage of hydrogen is a bottleneck in the practical usage of hydrogen for fuels. In this article, we present a review on the first-principles computational approach in designing hydrogen storage materials with an emphasis on molecular hydrogen storage in nanostructured materials. Given the limitation of pristine nanostructures for room-temperature hydrogen storage, the strategy of decorating the backbone structure of the nanostructure with transition metal atoms in order to enhance the hydrogen adsorption energy is addressed, and the interplay between the Coulomb interactions and the so-called Kubas interaction (nondissociative weak chemisorption via electron donation and back-donation channels) has been studied. The influence of electron spin on the hydrogen binding energy, problems of metal clustering and oxidation, and the structural instability that may arise during hydrogen sorption are also discussed. We address the limitations and challenges in the development of high-capacity hydrogen storage materials and provide perspectives for how computational materials design can help cope with those problems.

The behavior of nuclear fuel in a reactor is a complex phenomenon that is influenced by a large number of materials properties, which include thermomechanical strength, chemical stability, microstructure, and defects. As a consequence, a comprehensive understanding of the fuel material behavior presents a significant modeling challenge, which must be mastered to improve the efficiency and reliability of current nuclear reactors. It is also essential to the development of advanced fuel materials for next-generation reactors. Over the last two decades, the use of density functional theory (DFT) has greatly contributed to our understanding by providing profound information on nuclear fuel materials, ranging from fundamental properties of f-electron systems to thermomechanical materials properties. This article briefly summarizes the main achievements of this first-principles computational methodology as it applies to nuclear fuel materials. Also, the current status of first-principles modeling is discussed, considering existing limitations and drawbacks such as size limitation and the added complexity associated with high temperature analysis. Finally, the future role of DFT modeling in the nuclear fuels industry is put into perspective.