Igor Dmitruk

Size-Selective Growth and Stabilization of Small CdSe Nanoparticles in Aqueous Solution

Using cysteine and its derivatives as capping molecules, we investigated the influence of the physical structure and chemical nature of capping molecules on the selective growth and stabilization of small CdSe nanoparticles (NPs) in aqueous solution at room temperature. Our investigations revealed specific roles for each functional group of cysteine, and we could correlate this structure and nature of the capping molecules with the size, size restriction, size distribution, and stability of the NPs. For selective growth and stabilization of the NPs in aqueous solution, their capping molecules should have at least one functional group with strong nucleophilicity as well as another free, charged functional group. Capping molecules acting as a monodentate ligand were more effective than those acting as a bidentate ligand for restricting the NPs to a smaller size, whereas the former was less effective than the latter for getting a narrower NP size distribution. Capping molecules with relatively bulky spatial geometry near the ligand-NP interface resulted in the formation of NPs with poor short- and long-term stabilities, whereas those having relatively compact spatial geometry near the interface led to NPs with at least moderate short-term stability. We saw that capping molecules having relatively compact outermost spatial geometry led to NPs with excellent long-term stability, whereas those having relatively bulky outermost spatial geometry produced NPs with at most only moderate long-term stability. Our results clearly showed general trends for the possibility of selective growth of stable semiconductor NPs with particular sizes in aqueous solution.

Lipid nanocapsules for intracellular drug delivery of anticancer drugs.

Very stable and small CdSe nanoparticles (NPs) were synthesized from the aqueous solutions containing L-cysteine (Cys) at room temperature. The Cys-capped CdSe NPs showed a very sharp excitonic peak at 420 nm. Its very small full width at half maximum (18 nm) indicates very high quality of the CdSe NPs. Their absorption features experienced little change over a month, implying an excellent stability of the CdSe NPs. The synthesis conditions were very critical to the optical property and stability of the CdSe NPs: only those prepared at specific conditions (n(Se-precursor)/n(Cd-precursor) = 0.25-0.5, n(Cys)/n(Cd-precursor) = approximately 9, pH = approximately 12) showed very sharp absorption peaks and maintained an excellent stability against time. Under these conditions, the peaks always appear at nearly the same wavelength, indicating that these NPs are selectively stable and grow at a particular size and structure.

Surface plasmon as a probe for melting of silver nanoparticles

The temperature dependence of the surface plasmon energy and bandwidth for silver nanoparticles in the size range 8-30 nm embedded in a silica matrix has been studied using diffuse reflection spectroscopy. The dependence shows a non-monotonic jump-like behaviour indicating a low-temperature size-dependent melting of silver nanoparticles. The melting point decreases with the decrease of the nanoparticle size. The hysteresis in the temperature dependence of the surface plasmon bandwidth has been observed, indicating the first-order phase transition.

Influence of interparticle interaction on melting of gold nanoparticles in Au/polytetrafluoroethylene nanocomposites

The temperature dependence of the surface plasmon resonance energy and width in 5 nm spherical gold nanoparticles embedded in a polymer polytetrafluoroethylene matrix has been studied using absorption spectroscopy. The jumplike features have been observed in these dependences indicating the melting of gold nanoparticles at temperatures considerably lower than the bulk melting point. The interaction between gold nanoparticles sufficiently affects the melting of nanoparticles. The increase in the filling factor of the particles leads to a decrease in the melting temperature of gold nanoparticles.

Properties of Nanostructure Formed on SiO2/Si Interface by Laser Radiation

The aim of this work is to study optical properties of Si nanohills formed on the SiO2/Si interface by the pulsed Nd:YAG laser radiation. Nanohills which are self-organized on the surface of Si, are characterized by strong photoluminescence in the visible range of spectra with long wing in the red part of spectra. This peculiarity is explained by Quantum confinement effect in nanohillsnanowires with graded diameter. We have found a new method for graded band gap semiconductor formation using an elementary semiconductor. Graded change of band gap arises due to Quantum confinement effect.

Optical study of ZnP2 nanoparticles in zeolite Na–X

We report that for the first time the nanoparticles of II-V semiconductor (ZnP2) were prepared and studied. ZnP2 nanoparticles were prepared by incorporation into zeolite Na-X matrix. Absorption, diffuse reflection (DR) and photoluminescence (PL) spectra of the ZnP2 nanoclusters incorporated into the supercages of zeolite Na-X were measured at the temperature 77 K. Five bands B1-B5 are observed in both the DR and PL spectra demonstrating the blue shift from the line of free exciton in bulk crystal. We attribute the B1-B5 bands to some stable nanoclusters with size less than the size of zeolite Na-X supercage. We observed Stokes shift of the PL bands from the respective absorption bands. The nonmonotonic character of its dependence on the cluster size can be explained as the result of competition of the Frank-Condon shift and the shift due to electronic relaxation.

Monodispersity and ordering of semiconductor quantum dots synthesised in ionic liquid crystalline phase of cadmium alkanoates

Structural and optical properties of cadmium alkanoates nanocomposites with cadmium sulfide (CdS) quantum dots (QDs) have been studied by using various techniques: small angle X-ray scattering, transmission electron microscopy, optical absorption spectroscopy and photoluminescence. QDs are chemically synthesised in thermotropic ionic liquid crystalline (ILC) phase of cadmium alkanoates that have smectic-type ordering and are used as nanoreactors. Anisotropic glassy nanocomposites are obtained by rapid cooling the thermotropic ILC nanocomposites to the room temperature. For synthesis of CdS QDs are used cadmium capronate matrix or cadmium octanoate matrix and their binary mixture. Our results show that in the new cadmium alkanoates matrices, the CdS QDs have a small dispersion of their sizes, their shape is nearly spherical, they are stable over time and they are ordered in a layered smectic A matrix. QDs in cadmium octanoate and in cadmium capronate matrices have the dominant characteristic sizes of 2.7 and 2.8 nm, respectively. In the binary mixture, the QDs have two dominant characteristic sizes of 2.7 and 3.6 nm. The glassy nanocomposites show spectra both of absorption and of photoluminescence in near-ultraviolet and blue visible spectral range.

Multiserial Structure of Excitonic Energy Spectrum in Monoclinic ZnP2 Crystal

One-photon excitonic absorption spectra of the monoclinic ZnP 2 (β-ZnP 2 ) crystals are analysed. There exist four series characterized by the serial law E n = E g - Ry/n 2 + Δ/n 3 with the same value of energy gap Eg = 1.6026 meV. By variational calculations of the exciton energy dependence on the anisotropy parameter, we conclude an appearance of several hydrogen-like series caused by the splitting of excitonic states with different quantum numbers l and |m| due to the low symmetry of the crystal. Conclusions are made that two series with Δ = 0 can be attributed to the P-states of an exciton, and two others with Δ ¬= 0 to the S-states of an exciton. Calculations of e-h exchange interaction in an S-exciton are performed. Splitting of the series with Δ ¬= 0 is interpreted to have exchange origin (ortho-para-splitting). Its value is obtained to be 12.7 meV.

Radiative transitions in an excitonic molecule

Abstract The ratio of intensities of inverse hydrogenlike series (IHS) luminescence bands which are due to two-electron transitions in an excitonic molecule (EM) have been calculated. The rates of two-photon and two-electron spontaneous transitions in the excitonic molecule have been estimated. Their ratio has been obtained as 0.13. The correlation between theoretical estimations and experimental results obtained from the luminescence spectra of β - ZnP2 crystals has been analyzed.

BIEXCITONIC LIQUID IN MONOCLINIC ZINC DIPHOSPHIDE CRYSTALS

Abstract The dielectric gas-dielectric liquid phase transition in the system of excitonic molecules in β - ZnP2 crystals is considered. The influence of crystal anisotropy is under discussion. The features of β - ZnP2 photoluminescence (PL) spectra under intermediate excitation intensities (Iexc ∼ 103 - - 105 W/cm2) at liquid helium temperatures are considered. In previous works optical manifestations of the dielectric biexcitonic liquid have been observed. An experimental study of the phase diagram of this liquid is performed. Biexcitonic liquid critical parameters are estimated.