Sergey V. Adichtchev

Surface enhanced Raman scattering of light by ZnO nanostructures

Raman scattering (including nonresonant, resonant, and surface enhanced scattering) of light by optical and surface phonons of ZnO nanocrystals and nanorods has been investigated. It has been found that the nonresonant and resonant Raman scattering spectra of the nanostructures exhibit typical vibrational modes, E2(high) and A1(LO), respectively, which are allowed by the selection rules. The deposition of silver nanoclusters on the surface of nanostructures leads either to an abrupt increase in the intensity (by a factor of 103) of Raman scattering of light by surface optical phonons or to the appearance of new surface modes, which indicates the observation of the phenomenon of surface enhanced Raman light scattering. It has been demonstrated that the frequencies of surface optical phonon modes of the studied nanostructures are in good agreement with the theoretical values obtained from calculations performed within the effective dielectric function model.

Surface enhanced Raman scattering by CdS quantum dots

Surface enhanced Raman scattering is studied in nanostructures with CdS quantum dots formed using the Langmuir-Blodgett technology. Features due to quantum dot longitudinal optical phonons are observed in the Raman spectra of both free CdS quantum dots and such dots distributed in an organic matrix. The surface enhanced Raman scattering by nanostructures with CdS quantum dots covered by an Ag cluster film is observed experimentally. Applying Ag clusters onto the nanostructure surfaces results in a sharp (40-fold) increase in the intensity of Raman scattering by optical phonons in the quantum dots. It is shown that the dependence of surface enhanced Raman scattering on the excitation energy is resonant with a maximum at the energy corresponding to the maximum absorption coefficient of Ag clusters.

Vibrational spectra of quantum dots formed by Langmuir–Blodgett technique

Phonon spectra of CdS, ZnS, PbS, CuS, Ag2S, and ZnO quantum dots formed by using the Langmuir–Blodgett technology are investigated by Raman and infrared spectroscopies. The Raman spectra of structures show peaks corresponding to the scattering by longitudinal and transverse optical (LO and TO) phonons localized in quantum dots that confirm the formation of nanocrystals. In addition to TO and LO phonon modes, the modes observed in the IR spectra between the frequency positions of LO and TO phonons are attributed to the surface optical phonons in quantum dots.

CdZnS quantum dots formed by the Langmuir–Blodgett technique

CdZnS quantum dots (QDs) with systematically varied Zn content (from 0 to 100%) are formed in an organic matrix using the Langmuir–Blodgett technique. Annealing of the QD structures leads to a removal of the organic matrix and an increase in the Zn content for free-standing CdZnS QDs. After annealing, the size of QDs as determined from UV–vis absorption experiments is in good agreement with electron microscopy measurements. Analysis of UV–vis absorption and Raman scattering data demonstrates strong changes in the content of the CdZnS QDs upon annealing. A model of the process of QD formation is developed using the precipitation model and is found to adequately describe the experimental results.

Low-frequency Raman scattering of light by silver nanoparticles

Silver nanoparticles sprayed onto a crystalline quartz substrate are characterized by means of the low-frequency Raman scattering. Contributions of silver nanoparticles of different sizes to the Raman scattering spectrum are estimated. Data of scanning electron microscopy are used to verify the validity of the results obtained.

Surface-enhanced Raman scattering by semiconductor nanostructures

Surface-enhanced Raman scattering by optical and surface phonons in CdS, GaN, and CuS nanocrystals, and AlN nanowires is detected and studied. It is found that the presence of metal (Ag, Au, and Pt) nanoclusters noticeably modifies the Raman spectra of the nanostructures and results in a resonant increase in the intensity of optical phonon modes in CdS and CuS nanocrystals or in the emergence of surface modes in GaN nanocrystals and AlN nanowires. It is shown that the frequencies of the surface optical phonon modes of the examined nanostructures are in good agreement with the theoretical values calculated within the framework of the dielectric continuum model.

Structural Anomalies in Ionic Liquids near the Glass Transition Revealed by Pulse EPR

Unusual physical and chemical properties of ionic liquids (ILs) open up prospects for various applications. We report the first observation of density/rigidity heterogeneities in a series of ILs near the glass transition temperature ( Tg) by means of pulse electron paramagnetic resonance (EPR). Unprecedented suppression of molecular mobility is evidenced near the glass transition, which is assigned to unusual structural rearrangements of ILs on the nanometer scale. Indeed, pulse and continuous wave EPR clearly indicate the occurrence of heterogeneities near Tg, which exist in a rather broad temperature range of ∼50 K. The two types of local environments are evidenced, being drastically different by their stiffness. The more rigid one suppresses molecular mobility, whereas the softer one instead promotes diffusive molecular rotation. Such properties of ILs near Tg are of general importance; moreover, the observed density/rigidity heterogeneities controlled by temperature might be considered as a new type of tunable reaction nanoenvironment.

Surface-enhanced Raman scattering by GaN and ZnO nanostructures

Surface enhanced Raman scattering is studied in nanostructures with GaN and ZnO nanocolumns. Features related to optical phonons of nanocolumns are observed in the Raman spectra of both free-standing GaN and ZnO nanostructures. Strong enhancement of the Raman scattering intensity by surface optical phonons in GaN and ZnO nanocolumns is observed by deposition of silver clusters onto the nanostructure surfaces.