Surface chemistry and density distribution influence on visible luminescence of silicon quantum dots: an experimental and theoretical approach.

The impact of the surface reconstruction of the density distribution and photoluminescence of silicon quantum dots (QDs) embedded in a silicon oxide matrix (SiOx) has been studied. Annealing treatments carried out on the as-deposited samples provoked the effusion of hydrogen species. Moreover, depending on the surrounding density and coalescence of QDs, they resulted in a change in the average size of the particles depending on the initial local environment. The shift in the luminescence spectra all over the visible region (blue, green and red) shows a strong dependence on the resultant change in the size and/or the passivation environment of QDs. Density functional theoretical (DFT) calculations support this fact and explain the possible electronic transitions (HOMO-LUMO gap) involved. Passivation in the presence of oxygen species lowers the band gap of Si29 and Si35 nanoclusters up to 1.7 eV, whereas, surface passivation in the environment of hydrogen species increases the band gap up to 4.4 eV. These results show a good agreement with the quantum confinement model described in this work and explain the shift in the luminescence all over the visible region. The results reported here offer vital insight into the mechanism of emission from silicon quantum dots which has been one of the most debated topics in the last two decades. QDs with multiple size distribution in different local environments (band gap) observed in this work could be used for the fabrication of light emission diodes (LEDs) or shift-conversion thin films in third generation efficient tandem solar cells for the maximum absorption of the solar spectrum in different wavelength regions.

Spontaneous, Solvent-Free, Polymer-Templated, Solid-Solid Transformation of Thin Metal Films into Nanoparticles.

Metal nanoparticles have unusual optical, electronic, sensing, recognition, catalytic, and therapeutic properties. They are expected to form the basis of many of the technological and biological innovations of this century. A prerequisite for future applications using nanoparticles as functional entities is control of the shape, size, and homogeneity of these nanoparticles and of their interparticle spacing and arrangement on surfaces, between electrodes, or in devices. Here, we demonstrate that thin films of gold, silver, and copper sputter-deposited onto the surface of an organic polymer poly[[1,1':4',1″-terphenyl]-4,4″-diyl(2-bromo-1-carboxyethylidene)] (PTBC) undergo spontaneous solid-solid transformation into nanoparticles. Furthermore, we show that, by varying the thickness of the films, the volume-to-surface ratio of the polymer substrate, and the amount of plasticizer, it is possible to control the rate of transformation and the morphology of the nanoparticles formed. PTBC containing Au nanoparticles was found to enhance the cell adhesion and proliferation. To the best of our knowledge, our findings constitute the first experimental evidence of spontaneous, room-temperature, solid-solid transformation of metal films sputtered onto the surface of an organic polymeric substrate into nanoparticles (crystals).

Experimental and theoretical rationalization of the growth mechanism of silicon quantum dots in non-stoichiometric SiN x : role of chlorine in plasma enhanced chemical vapour deposition.

Silicon quantum dots (Si-QDs) embedded in an insulator matrix are important from a technological and application point of view. Thus, being able to synthesize them in situ during the matrix growth process is technologically advantageous. The use of SiH2Cl2 as the silicon precursor in the plasma enhanced chemical vapour deposition (PECVD) process allows us to obtain Si-QDs without post-thermal annealing. Foremost in this work, is a theoretical rationalization of the mechanism responsible for Si-QD generation in a film including an analysis of the energy released by the extraction of HCl and the insertion of silylene species into the terminal surface bonds. From the results obtained using density functional theory (DFT), we propose an explanation of the mechanism responsible for the formation of Si-QDs in non-stoichiometric SiN x starting from chlorinated precursors in a PECVD system. Micrograph images obtained through transmission electron microscopy confirmed the presence of Si-QDs, even in nitrogen-rich (N-rich) samples. The film stoichiometry was controlled by varying the growth parameters, in particular the NH3/SiH2Cl2 ratio and hydrogen dilution. Experimental and theoretical results together show that using a PECVD system, along with chlorinated precursors it is possible to obtain Si-QDs at a low substrate temperature without annealing treatment. The optical property studies carried out in the present work highlight the prospects of these thin films for down shifting and as an antireflection coating in silicon solar cells.

Gold as an intruder in ZnO nanowires.

Several techniques for obtaining ZnO nanowires (ZnO NWs) have been reported in the literature. In particular, vapour-liquid-solid (VLS) with Au as a catalyst is widely used. During this process, Au impurities in the ZnO NWs can be incorporated accidentally, and for this reason we named these impurities as intruders. It is thought that these intruders may produce interesting alterations in the electronic characteristics of nanowires. In the experiment, it is not easy to detect either Au atoms in these nanowires, or the modification that intruders produce in different electrical, optical and other properties. For this reason, in this density functional theory investigation, the effect of Au intruders on ZnO NWs is analysed. Au extended (thread) and point defects (atoms replacing Zn or O, or Au interstitials) are used to simulate the presence of gold atoms. Optimised geometries, band-gaps and density of states indicate that the presence of small amounts of Au drastically modifies the electronic states of ZnO NWs. The results reported here clearly indicate that small amounts of Au have a strong impact on the electronic properties of ZnO NWs, introducing states in the band edges that may promote transitions in the visible spectral region. The presence of Au as an intruder in ZnO NWs enhances the potential use of this system for photonic and photovoltaic applications.

Photoluminescence Study of Gallium Nitride Thin Films Obtained by Infrared Close Space Vapor Transport.

Photoluminescence (PL) studies in GaN thin films grown by infrared close space vapor transport (CSVT-IR) in vacuum are presented in this work. The growth of GaN thin films was done on a variety of substrates like silicon, sapphire and fused silica. Room temperature PL spectra of all the GaN films show near band-edge emission (NBE) and a broad blue and green luminescence (BL, GL), which can be seen with the naked eye in a bright room. The sample grown by infrared CSVT on the silicon substrate shows several emission peaks from 2.4 to 3.22 eV with a pronounced red shift with respect to the band gap energy. The sample grown on sapphire shows strong and broad ultraviolet emission peaks (UVL) centered at 3.19 eV and it exhibits a red shift of NBE. The PL spectrum of GaN films deposited on fused silica exhibited a unique and strong blue-green emission peak centered at 2.38 eV. The presence of yellow and green luminescence in all samples is related to native defects in the structure such as dislocations in GaN and/or the presence of amorphous phases. We analyze the material quality that can be obtained by CSVT-IR in vacuum, which is a high yield technique with simple equipment set-up, in terms of the PL results obtained in each case.