In this report, we describe a general methodology to determine the extent of alloying or atomic distribution quantitatively in bimetallic nanoparticles (NPs) by X-ray absorption spectroscopy (XAS). The structural parameters determined in these studies serve as a quantitative index and provide a general route to determine the structural aspects of the bimetallic NPs. We have derived various types of possible structural models based on the extent of alloying and coordination number parameters of bimetallic NPs. We also discussed the nature of homo- and heterometallic interactions in bimetallic NPs based on the extent of alloying. Herein, we use carbon-supported platinum-ruthenium bimetallic nanoparticles to demonstrate the proposed methodology, and this can be extended further to get more insights into the alloying extent or atomic distribution of other bimetallic systems. The results demonstrated in this paper open up methods to determine the atomic distribution of bimetallic NPs, which is an extremely important parameter that strongly influences the physicochemical properties of NPs and their applications.

Lithium dendrite growth dynamics on Cu surface is first visualized through a versatile and facile experimental cell by in operando transmission X-ray microscopy (TXM). Galvanostatic plating and stripping cycle(s) are applied on each cell. Upon plating/stripping at ∼1 mA cm −2 , mossy lithium is clearly found growing and shrinking on the Cu surface as the application time increases. It is interesting to note that the aspect ratio (height/width) of deposited lithium has increased with charge passed during plating, indicating a faster growing from the base. In addition, the dendritic or mossy lithium has also been observed when various high current densities (25, 12.5, and 6.3 mA cm −2 ) are applied in different cycles, showing a severe dendritic lithium formation that could be induced by inhomogeneous current distribution. The clear structure of dead lithium is found after the cycling, which also shows a lower efficiency and higher hazard when a higher current density is applied. This work explores TXM as a useful tool for in operando dynamic visualization and quantitative measurement of lithium dendrite, which is difficult to achieve with ex situ measurements and other microscopy techniques. The understanding of the growth mechanism from TXM can be beneficial for the development of safe lithium ion and lithium metal batteries.

An energy-tunable transmission hard x-ray microscope with close to 60 nm spatial resolution in three dimensions ͑3D͒ has been developed. With a cone beam illumination, a zone plate of 50 nm outmost zone width, a stable mechanical design, and software feedback, we obtained tomographic data sets that are close to 60 nm spatial resolution. Meanwhile, the element specific imaging was also obtained by a differential absorption contrast technique used below and above the absorption of the element. Examples of advanced intergraded circuit devices are used to demonstrate the element selectivity and spatial resolution in 3D of the microscope.

Although bimetallic core@shell structured nanoparticles (NPs) are achieving prominence due to their multifunctionalities and exceptional catalytic, magnetic, thermal, and optical properties, the rationale underlying their design remains unclear. Here we report a kinetically controlled autocatalytic chemical process, adaptable for use as a general protocol for the fabrication of bimetallic core@shell structured NPs, in which a sacrificial Cu ultrathin layer is autocatalytically deposited on a dimensionally stable noble-metal core under kinetically controlled conditions, which is then displaced to form an active ultrathin metal-layered shell by redox-transmetalation. Unlike thermodynamically controlled under-potential deposition processes, this general strategy allows for the scaling-up of production of high-quality core-shell structured NPs, without the need for any additional reducing agents and/or electrochemical treatments, some examples being Pd@Pt, Pt@Pd, Ir@Pt, and Ir@Pd. Having immediate and obvious commercial potential, Pd@Pt NPs have been systematically characterized by in situ X-ray absorption, electrochemical-FTIR, transmission electron microscopy, and electrochemical techniques, both during synthesis and subsequently during testing in one particularly important catalytic reaction, namely, the oxygen reduction reaction, which is pivotal in fuel cell operation. It was found that the bimetallic Pd@Pt NPs exhibited a significantly enhanced electrocatalytic activity, with respect to this reaction, in comparison with their monometallic counterparts.

A hard x-ray transmission microscope with 30 nm spatial resolution has been developed employing the third diffraction order of a zone plate objective. The microscope utilizes a capillary type condenser with suitable surface figure to generate a hollow cone illumination which is matched in illumination range to the numerical aperture of the third order diffraction of a zone plate with an outmost zone width of 50 nm. Using a test sample of a 150 nm thick gold spoke pattern with finest half-pitch of 30 nm, the authors obtained x-ray images with 30 nm resolution at 8 keV x-ray energy.

The understanding of the formation mechanism of nanoparticles is essential for the successful particle design and scaling-up process. This paper reports findings of an X-ray absorption spectroscopy (XAS) investigation, comprised of X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) regions, to understand the mechanism of the carbon-supported Pt-Ru nanoparticles (NPs) formation process. We have utilized Watanabe's colloidal reduction method to synthesize Pt-Ru/C NPs. We slightly modified the Watanabe method by introducing a mixing and heat treatment step of Pt and Ru oxidic species at 100 degrees C for 8 h with a view to enhance the mixing efficiency of the precursor species, thereby one can achieve improved homogeneity and atomic distribution in the resultant Pt-Ru/C NPs. During the reduction process, in situ XAS measurements allowed us to follow the evolution of Pt and Ru environments and their chemical states. The Pt LIII-edge XAS indicates that when H2PtCl6 is treated with NaHSO3, the platinum compound is found to be reduced to a Pt(II) form corresponding to the anionic complex [Pt(SO3)4]6-. Further oxidation of this anionic complex with hydrogen peroxide forms dispersed [Pt(OH)6]2- species. Analysis of Ru K-edge XAS results confirms the reduction of RuIIICl3 to [RuII(OH)4]2- species upon addition of NaHSO3. Addition of hydrogen peroxide to [RuII(OH)4]2- causes dehydrogenation and forms RuOx species. Mixing of [Pt(OH)6]2- and RuOx species and heat treatment at 100 degrees C for 8 h produced a colloidal sol containing both Pt and Ru metallic as well as ionic contributions. The reduction of this colloidal mixture at 300 degrees C in hydrogen atmosphere for 2 h forms Pt-Ru nanoparticles as indicated by the presence of Pt and Ru atoms in the first coordination shell. Determination of the alloying extent or atomic distribution of Pt and Ru atoms in the resulting Pt-Ru/C NPs reveals that the alloying extent of Ru (JRu) is greater than that of the alloying extent of Pt (JPt). The XAS results support the Pt-rich core and Ru-rich shell structure with a considerable amount of segregation in the Pt region and with less segregation in the Ru region for the obtained Pt-Ru/C NPs.

Oxynitrides can suppress the diffusion of boron from the polycrystalline silicon gate electrode to the channel region of an ultralarge scale integrated device, and are therefore important potential substrates for thin SiO2 gates. Direct oxynitridation of Si in N2O is a simple and manufacturable N incorporation scheme. We have used rapid thermal oxidation to grow O2- and N2O-oxides of technological importance (∼10 nm thick) in the temperature range 800–1200 °C. Accurate measurements of the N content of the N2O-oxides were made using nuclear reaction analysis. N content increases linearly with oxidation temperature, but is in general small. A 1000 °C N2O-oxide contains about 7×1014 N/cm2, or the equivalent of about one monolayer of N on Si (100). Nonetheless, this small amount of N can retard boron penetration through the dielectric by two orders of magnitude as compared to O2-oxides. The N is contained in a Si-O-N phase within about 1.5 nm of the Si/SiO2 interface, and can be pushed away from the interface by O2-reoxidation. We have measured Si/SiO2 interfacial roughness by x-ray reflectometry, and found that it decreases with increasing oxidation temperature for both O2- and N2O-oxides, although the N2O-oxides are smoother. The enhanced smoothness of N2O-oxides is greater the greater the N content. N2O-oxides are promising candidates for thin ultralarge scale integrated circuit gate dielectrics.

The chemical state and formation mechanism of Pt-Ru nanoparticles (NPs) synthesized by using ethylene glycol (EG) as a reducing agent and their stability have been examined by in situ X-ray absorption spectroscopy (XAS) at the Pt L III and Ru K edges. It appears that the reduction of Pt(IV) and Ru(III) precursor salts by EG is not a straightforward reaction but involves different intermediate steps. The pH control of the reaction mixture containing Pt(IV) and Ru(III) precursor salts in EG to 11 led to the reduction of Pt(IV) to Pt(II) corresponding to [PtCl 4 ] 2-whereas Ru III Cl 3 is changed to the [Ru(OH) 6 ] 3-species. Refluxing the mixture containing [PtCl 4 ] 2-and [Ru(OH) 6 ] 3-species at 160°C for 0.5 h produces Pt-Ru NPs as indicated by the presence of Pt and Ru in the first coordination shell of the respective metals. No change in XAS structural parameters is found when the reaction time is further increased, indicating that the Pt-Ru NPs formed are extremely stable and less prone to aggregation. XAS structural parameters suggest a Pt-rich core and a Ru-rich shell structure for the final Pt-Ru NPs. Due to the inherent advantages of the EG reduction method, the atomic distribution and alloying extent of Pt and Ru in the Pt-Ru NPs synthesized by the EG method are higher than those of the Pt-Ru/C NPs synthesized by a modified Watanabe method.