ABSTRACT
Atomic motions and morphological evolution of growing Co-Ag nanoparticles are followed in situ and in real time, by wide and small angle X-ray scattering obtained simultaneously in grazing incidence geometry (GISAXS and GIWAXS), in single or multi-wavelength anomalous modes. The structural analysis of the experimental data is performed with the aid of equilibrium Monte Carlo simulations and of molecular-dynamics simulations of nanoparticle growth. Growth is performed by depositing Co atoms above preformed Ag nanoparticles. This growth procedure is strongly out of equilibrium, because Ag tends to surface segregation, and generates complex growth sequences. The real time analysis of the growth allows to follow the nanoparticle evolution pathways almost atom-by-atom, determining the key mechanisms during Co deposition: starting with the incorporation of Co atoms in sub-surface positions, to the off-center Co domain formation, then by which the nanoparticles finally approach their equilibrium quasi-Janus then core-shell structures.
ABSTRACT
Localized Surface Plasmon Resonance (LSPR) of noble metal nanoparticles has attracted a lot of attention in recent years as enhancer of the photocatalytic activity in the visible light domain. Rare are the experimental in situ studies, coupling structural and optical responses, but they are mandatory for a deep understanding of the mechanisms underlying LSPR. Herein we present an in situ investigation during the growth of gold nanoparticles (NPs) on TiO2(110) in the 2-6 nm size range. We probed the structural and morphological properties of the supported nanoparticles by performing GIXRD and GISAXS simultaneously with their optical response in p and s polarizations recorded by SDRS. The rutile surface state turns out to have a major effect on the Au NPs growth and on their plasmonic response, both in frequency and vibration modes. The roughening of the TiO2(110) surface weakens the interaction strength between the NPs and the substrate, favoring the growth of textured in-plane randomly orientated NPs. Compared to the epitaxial clusters growing on the flat TiO2 surface, these textured NPs are characterized by a LSPR blue shift and by the presence of LSPR vibration modes perpendicular to the surface for sizes smaller than about 4 nm.
ABSTRACT
The growth by pulsed laser deposition of fully epitaxial nanocomposites made of Co x Ni1-x nanowires (NW) vertically self-assembled in Sr0.5Ba0.5TiO3/SrTiO3(001) layers is reported. The diameter of the wires can be tuned in the 1.8-6 nm range. The composition of the wires can be controlled, with the growth sequence and the fcc crystallographic structure of the wires preserved for Co content up to 78%. The nanocomposite systems obtained display a uniaxial magnetic anisotropy with out-of-plane easy axis as shown through analysis of ferromagnetic resonance measurements. It is shown that the magnitude of the magnetic anisotropy depends sensitively on the structural quality of the nanocomposites.The energy barrier for magnetization reversal scales as the square of the diameter of the NW and reaches 60 [Formula: see text] for 6 nm diameter, with T amb = 300 K.
ABSTRACT
Controlling aging of catalysts is of crucial importance to preserve their properties, in particular for bimetallic nanoparticles (NPs) where reaction can modify the composition. Herein, we have studied the stability upon oxygen exposure of gold-copper NPs supported on rutile. We have used in situ scanning tunneling microscopy to follow the evolution of individual Au, Cu and Au-Cu NPs with various compositions grown on the TiO2(110) surface, during each step from their nucleation to their modification with oxygen. We demonstrated a direct relation between the stability of the nanoparticles and their Au concentration. Whereas pure Cu nanoparticles dissociate under O2, Au-Cu NPs containing at least 20% Au are stable. This is explained by a modification of the local density of states of Cu atoms upon alloying.
ABSTRACT
The step period (Lambda) of vicinal surfaces can be used as a new parameter for the control of metallic heteroepitaxial growth. This is evidenced here in the case of Ag/Cu(211). The deposition of 1 monolayer (ML) exhibits a c(2 x 10) superstructure leading to the formation of [111] steps in the Ag adlayer in contrast with the original [100] steps for the Cu substrate. This wetting layer can be viewed as a (133) Ag plane and it will be the starting point for the epitaxial growth. The deposition of 4 ML shows that the thin Ag film results homogeneous and no twins or stacking faults are detected. Moreover, the film grows along the [133] axis which is the orientation that minimizes the misfit between Cu(211) and the Ag film. Thus, the use of a regular stepped substrate allows one to select the crystallographic orientation of the growth and seems to be a way to avoid the creation of stacking faults.
