Direct Imaging of Surface Melting on a Single Sn Nanoparticle.

Despite previous studies, understanding the fundamental mechanism of melting metal nanoparticles remains one of the major scientific challenges of nanoscience. Herein, the kinetics of melting of a single Sn nanoparticle was investigated using in situ transmission electron microscopy heating techniques with a temperature step of up to 0.5 °C. We revealed the surface premelting effect and assessed the density of the surface overlayer on a tin particle of 47 nm size using a synergetic combination of high-resolution scanning transmission electron microscopy imaging and low electron energy loss spectral imaging. Few-monolayer-thick disordered phase nucleated at the surface of the Sn particle at a temperature ∼25 °C below the melting point and grew (up to a thickness of ∼4.5 nm) into the solid core with increasing temperature until the whole particle became liquid. We revealed that the disordered overlayer was not liquid but quasi-liquid with a density intermediate between that of solid and liquid Sn.

Effect of Size on the Formation of Solid Solutions in Ag-Cu Nanoparticles.

Modern technologies stimulate the quest for multicomponent nanosized materials with improved properties, which are ultimately defined by the atomic arrangement and interphase interactions in the nanomaterial. Here, we present the results of the experimental study of the formation of solid solutions in Ag-Cu nanoparticles in a wide size and temperature range using in situ TEM techniques. The Ag-Cu nanoparticles with a eutectic ratio of components were formed on an amorphous carbon film by the physical vapor deposition technique. Electron diffraction, HAADF-STEM imaging, energy-dispersive X-ray spectroscopy, chemical element mapping, and electron energy loss spectral imaging were used for the characterization of mixing patterns and composition of phases in AgCu nanoparticles down to the atomic level. As a result, we constructed the solid-state part of the Ag-Cu phase diagram for nanoparticles with a size down to 5 nm. We found a highly asymmetric behavior of the solvus lines. Thus, the content of Cu in Ag gradually increased with a size reduction and reached the ultimate value for our configuration of 27 wt % Cu at a nanoparticle size below ∼8 nm. At the same time, no Cu-rich solid solution was found in two-phase AgCu nanoparticles, irrespective of the size and temperature. Moreover, a quasi-homogeneous solid solution was revealed in AgCu nanoparticles with a size smaller than 8 nm already at room temperature. A size dependence of the terminal temperature T term, which limits the existence of AgCu alloy nanoparticles in a vacuum, was constructed. Evaporation of the AgCu phase with the composition of 86 wt % Ag was observed at temperatures above T term. We show the crucial role of the mutual solubility of components on the type of atomic mixing pattern in AgCu nanoparticles. A gradual transition from a Janus-like to a homogeneous mixing pattern was observed in Ag-Cu nanoparticles (28 wt % Cu) with a decrease in their size.

Synthesis of Nanoparticles and Theoretical Model of Their Retention in Plasma of RF Capacitive Discharge with Vertically Arranged Electrodes in Acetylene.

In the present research, experiments on the formation and retention of nanoparticles (NPs) in the plasma of radio frequency (RF) capacitive discharge in acetylene were carried out with vertically positioned internal electrodes. It has been shown via SEM and TEM techniques that NPs found on the horizontal tube wall after the discharge operation have a spherical shape with a predominant diameter of approximately 400-600 nm. HRTEM analysis reveals their amorphous structure. At the same time, such NPs were not found on vertical electrodes, only a polymer film was deposited. To elucidate the possibility of NPs leaving the plasma in the direction of vertical electrodes, a model of NP retention in the near-electrode sheath of an RF capacitive discharge was elaborated. The model has shown that nanometer- and even micrometer-sized particles formed in the plasma cannot cross the near-electrode sheath and reach the electrode surface. For the plasma consisting of three charged components (positive ions, electrons, and NPs), an analytical model of ambipolar diffusion was developed. Applying this model, it has been shown that the ambipolar electric field can keep the micrometer-sized NPs in the plasma if their concentration is low. However, in the case of a high concentration of NPs, they can be retained with a diameter of no more than a few hundred nanometers due to a significant decrease in the ambipolar electric field. The calculation results are in agreement with our experimental data.