Project description:Yb3+-doped phosphate glasses containing different amounts of SiO₂ were successfully synthesized by the conventional melt-quenching method. The influence mechanism of SiO₂ on the structural and spectroscopic properties was investigated systematically using the micro-Raman technique. It was worth noting that the glass with 26.7 mol % SiO₂ possessed the longest fluorescence lifetime (1.51 ms), the highest gain coefficient (1.10 ms·pm²), the maximum Stark splitting manifold of ²F7/2 level (781 cm-1), and the largest scalar crystal-field NJ and Yb3+ asymmetry degree. Micro-Raman spectra revealed that introducing SiO₂ promoted the formation of P=O linkages, but broke the P=O linkages when the SiO₂ content was greater than 26.7 mol %. Based on the previous 29Si MAS NMR experimental results, these findings further demonstrated that the formation of [SiO₆] may significantly affect the formation of P=O linkages, and thus influences the spectroscopic properties of the glass. These results indicate that phosphosilicate glasses may have potential applications as a Yb3+-doped gain medium for solid-state lasers and optical fiber amplifiers.
Project description:Atomic layer deposition (ALD) can provide nanometer-thin films with excellent conformality on demanding three-dimensional (3D) substrates. This also holds for plasma-assisted ALD, provided that the loss of reactive radicals through surface recombination is sufficiently low. In this work, we determine the surface recombination probability r of oxygen radicals during plasma ALD of SiO2 and TiO2 for substrate temperatures from 100 to ∼240 °C and plasma pressures from 12 to 130 mTorr (for SiO2). For both processes, the determined values of r are very low, i.e., ∼10-4 or lower, and decrease with temperature and pressure down to ∼10-5 within the studied ranges. Accordingly, deposition on trench structures with aspect ratios (ARs) of <200 is typically not significantly limited by recombination and obtaining excellent film conformality is relatively facile. For higher AR values, e.g., approaching 1000, the plasma time needed to reach saturation increases exponentially and becomes increasingly dependent on the process conditions and the corresponding value of r. Similar dependence on process conditions can be present for plasma ALD of other materials as well, where, in certain cases, film growth is already recombination-limited for AR values of ∼10. Radical recombination data and trends as provided by this work are valuable for optimizing plasma ALD throughput and feasibility for high-AR applications and can also serve as input for modeling of radical recombination mechanisms.
Project description:Nitrogen activation, especially dissociation (production of atomic nitrogen), is a key step for efficient nitrogen fixation, such as nitrogen reduction to produce ammonia. Nitrogen reduction reactions using water as a direct hydrogen source have been studied by many researchers as a green ammonia process. We studied the reaction mechanism and found that the nitrogen reduction could be significantly improved via efficient production of atomic nitrogen through electric discharge. In the present study, we focused on packed-bed dielectric barrier discharge (PbDBD) using dielectric beads as the packing material. The experimental results showed that more atomic nitrogen was produced in the nitrogen activation by the discharge in which the discharge space was filled with the dielectric beads than in the nitrogen activation by the discharge without using the dielectric beads. Then, it was clarified that the amount of atomic nitrogen increased as the dielectric constant of the beads to be filled increased, and the amount of atomic nitrogen produced increased up to 13.48 times. Based on the results, we attempted ammonia synthesis using water as a direct hydrogen source with the efficiently generated atomic nitrogen. When the atomic nitrogen gas generated by the PbDBD was sprayed onto the surface of the water phase and subsequently reacted as a plasma/liquid interfacial reaction, the nitrogen fixation rate increased by 7.26-fold compared to that when using the discharge without dielectric beads, and the ammonia production selectivity increased to 83.7%.
Project description:Understanding the response of ceramics operating in extreme environments is of interest for a variety of applications. Ab initio molecular dynamic simulations have been used to investigate the effect of structure and B-site (=Ti, Zr) cation composition of lanthanum-based oxides (La2B2O7) on electronic-excitation-induced amorphization. We find that the amorphous transition in monoclinic layered perovskite La2Ti2O7 occurs for a lower degree of electronic excitation than for cubic pyrochlore La2Zr2O7. While in each case the formation of O2-like molecules drives the structure to an amorphous state, an analysis of the polyhedral connection network reveals that the rotation of TiO6 octahedra in the monoclinic phase can promote such molecule formation, while such octahedral rotation is not possible in the cubic phase. However, once the symmetry of the cubic structure is broken by substituting Ti for Zr, it becomes less resistant to amorphization. A compound made of 50% Ti and 50% Zr (La2TiZrO7) is found to be more resistant in the monoclinic than in the cubic phase, which may be related to the lower bandgap of the cubic phase. These results illustrate the complex interplay of structure and composition that give rise to the radiation resistance of these important functional materials.
Project description:The varying degrees of configurational disorder in metallic glasses are investigated quantitatively by molecular dynamics studies. A parameter, the quasi-nearest atom, is used to characterize the configurational disorder in metallic glasses. Our observations suggest configurational disorder play a role in structural heterogeneity, plasticity and dynamic relaxations in metallic glasses. The broad configurational disorder regions distribution is the indicator of abundant potential deformation units and relaxations. Plastic flow, as well as relaxation, is believed to start at configurational disorder regions. The width of the shear bands and dynamic relaxations can then be regulated by the degree of configurational disorder regions in metallic glasses.
Project description:The mechanical properties of crystalline materials can be quantitatively described by crystal defects of solute atoms, dislocations, twins, and grain boundaries with the models of solid solution strengthening, Taylor strain hardening and Hall-Petch grain boundary strengthening. However, for metallic glasses, a well-defined structure feature which dominates the mechanical properties of the disordered materials is still missing. Here, we report that nanoscale spatial heterogeneity is the inherent structural feature of metallic glasses. It has an intrinsic correlation with the strength and deformation behavior. The strength and Young's modulus of metallic glasses can be defined by the function of the square root reciprocal of the characteristic length of the spatial heterogeneity. Moreover, the stretching exponent of time-dependent strain relaxation can be quantitatively described by the characteristic length. Our study provides compelling evidence that the spatial heterogeneity is a feasible structural indicator for portraying mechanical properties of metallic glasses.
Project description:The size effect on atomic structure of a Cu64Zr36 amorphous system, including zero-dimensional small-size amorphous particles (SSAPs) and two-dimensional small-size amorphous films (SSAFs) together with bulk sample was investigated by molecular dynamics simulations. We revealed that sample size strongly affects local atomic structure in both Cu64Zr36 SSAPs and SSAFs, which are composed of core and shell (surface) components. Compared with core component, the shell component of SSAPs has lower average coordination number and average bond length, higher degree of ordering, and lower packing density due to the segregation of Cu atoms on the shell of Cu64Zr36 SSAPs. These atomic structure differences in SSAPs with various sizes result in different glass transition temperatures, in which the glass transition temperature for the shell component is found to be 577 K, which is much lower than 910 K for the core component. We further extended the size effect on the structure and glasses transition temperature to Cu64Zr36 SSAFs, and revealed that the T g decreases when SSAFs becomes thinner due to the following factors: different dynamic motion (mean square displacement), different density of core and surface and Cu segregation on the surface of SSAFs. The obtained results here are different from the results for the size effect on atomic structure of nanometer-sized crystalline metallic alloys.
Project description:Two novel core-shell structured SiO2@AIPA-S-Si-Eu and SiO2@AIPA-S-Si-Eu-phen nanocomposites have been synthesized by a bifunctional organic ligands ((HOOC)2C6H3NHCONH(CH2)3Si(OCH2CH3)3) (defined as AIPA-S-Si) connected with Eu3+ ions and silica via covalent bond. And the corresponding core-shell-shell structured SiO2@AIPA-S-Si-Eu@SiO2 and SiO2@AIPA-S-Si-Eu-phen@SiO2 nanocomposites with enhanced luminescence have been synthesized by tetraethyl orthosilicate (TEOS) hydrolysis co-deposition method. The composition and micromorphology of the nanocomposites were characterized by means of Fourier-transform infrared spectroscopy (FT-IR), thermal gravimetric analysis (TG), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectrometry (EDX) and X-ray photoelectron spectroscopy (XPS). The as-synthesized core-shell and core-shell-shell structured nanocomposites have excellent luminescence intensity and long lifetime. The nanocomposites show bright red light under ultraviolet lamp. However, the core-shell-shell structured nanocomposites have stronger luminescence intensity than the corresponding core-shell structured nanocomposites. Meanwhile, the core-shell-shell structured nanocomposites still exhibit good luminescence stability in aqueous solution. In addition, a large number of Si-OH on the surface of the core-shell-shell structured nanocomposites can be attached to many biomacromolecules. Therefore, they have potential applications in the fields of biology and luminescence.
Project description:Molecular dynamics simulations were employed to investigate the plastic deformation within the shear bands in three different metallic glasses (MGs). To mimic shear bands, MG specimens were first deformed until flow localization occurs, and then the volume of the material within the localized regions was extracted and replicated. Homogeneous deformation that is independent of the size of the specimen was observed in specimens with shear band like structure, even at a temperature that is far below the glass transition temperature. Structural relaxation and rapid cooling were employed to examine the effect of free volume content on the deformation behavior. This was followed by detailed atomic structure analyses, employing the concepts of Voronoi polyhedra and "liquid-like" regions that contain high fraction of sub-atomic size open volumes. Results suggest that the total fraction of atoms in liquid-like regions is a key parameter that controls the plastic deformation in MGs. These are discussed in the context of reported experimental results and possible strategies for synthesizing monolithic amorphous materials that can accommodate large tensile plasticity are suggested.
Project description:Area-selective atomic layer deposition (ALD) is rapidly gaining interest because of its potential application in self-aligned fabrication schemes for next-generation nanoelectronics. Here, we introduce an approach for area-selective ALD that relies on the use of chemoselective inhibitor molecules in a three-step (ABC-type) ALD cycle. A process for area-selective ALD of SiO2 was developed comprising acetylacetone inhibitor (step A), bis(diethylamino)silane precursor (step B), and O2 plasma reactant (step C) pulses. Our results show that this process allows for selective deposition of SiO2 on GeO2, SiNx, SiO2, and WO3, in the presence of Al2O3, TiO2, and HfO2 surfaces. In situ Fourier transform infrared spectroscopy experiments and density functional theory calculations underline that the selectivity of the approach stems from the chemoselective adsorption of the inhibitor. The selectivity between different oxide starting surfaces and the compatibility with plasma-assisted or ozone-based ALD are distinct features of this approach. Furthermore, the approach offers the opportunity of tuning the substrate-selectivity by proper selection of inhibitor molecules.