S. A. Ambrozevich

Spectroscopic investigation of colloidal CdS quantum dots–methylene blue hybrid associates

Spectral properties of hydrophilic associates of colloidal CdS quantum dots (QDs) with methylene blue molecules (MB) prepared by sol–gel method have been studied. The two basic types of hybrid associates were found using FTIR spectra technique. The first-type associates are characterized by planar location of MB heterocycle on QDs spherical interface. In this case MB dimerization is not observed. Both nitrogen and sulfur heteroatoms and double =N+–(CH3)2 bonds of MB are participants of association which causes to conformation of MB heterocycle and π-conjugation length decrease. In UV–Vis absorption and luminescence spectra blue shift of MB peaks for QD-MB associates in comparison with MB spectra in solutions and gelatin was found. The second type of association mostly involves MB nitrogen heteroatoms and CdS QDs interface atoms. At the same time, peaks of UV–Vis and luminescence spectra are red shifted. In this case, dimerization manifestation of MB in QD-MB associates was found. Using the time correlated single photon counting technique resonance electronic excitation energy transfer from recombination luminescence center of CdS QDs to MB molecules was found. Its efficiency is in the range of 0.36–0.51.

Surface states effect on photoluminescence of CdS colloidal nanocrystals

CdS colloidal nanocrystals with an average size of 4.5 nm and oleic acid as surfactant were studied using photoluminescence spectroscopy and time-correlated single photon counting technique at different temperatures. Observed spectra revealed three thermally activated luminescence bands at 2.15, 1.76, and 1.37 eV in addition to conventional band edge recombination of the nanocrystals. We present a kinetic model based on concept of single emitters which quantitatively describes the luminescence of the ensemble of the nanocrystals in the temperature range 10–300 K. We determined activation energies (18.2 and 8.6 meV) for transitions responsible for the luminescence. The 1.76 eV band most probably emerges from the intrinsic defects on the surface of CdS, whereas bands at 2.15 and 1.37 eV result from the influence of oleic acid bonded to the surface of the nanocrystals.

Optimization of carrier mobility in luminescence layers based on europium β-diketonates in hybrid light-emitting structures

The hole conductivity in films of three compounds, complexes based on europium β-diketonates, deposited by vacuum evaporation is studied by the time-of-flight technique. It is shown that no carrier photogeneration is observed in films under pulsed excitation with 337 nm light. The introduction of pentacene-based photogeneration layers into the samples made it possible to observe transient-current curves. It was found that a dispersive component of the transient current, associated with hole transport, is observed in a complex of europium with an auxiliary ligand based on bathophenanthroline. These data were used to determine the hole mobility. No dispersive component of the transient current was observed in complexes with an auxiliary ligand based on phenanthroline. A conclusion is made that the latter is due to the low mobility in compounds of this kind. This is attributed to a decrease in the degree of conjugation of the aromatic system, which occurs on passing from bathophenanthroline to phenanthroline.

Characterization of defects in colloidal CdSe nanocrystals by the modified thermostimulated luminescence technique

The temperature dependencies of the luminescence spectra of 5-nm-diameter CdSe semiconductor nanocrystals synthesized by colloidal-chemistry methods are investigated. The two bands observed in these spectra around 2.01 and 1.37 eV correspond to band-to-band transitions and luminescence of defect states, respectively. A model explaining the temperature behavior of the luminescence band intensities both upon cooling and heating is put forward. A new modification of spectrally resolved thermostimulated luminescence technique making it possible to determine the activation energies and the character of traps responsible for the temperature dependence of the luminescence intensities is suggested. This technique is used to obtain the activation energies of the emission and capture of electrons at traps (190 and 205 meV, respectively) and to determine the depth of the electron level (57 meV) responsible for luminescence in the 1.37-eV region.

Density of surface states in colloidal CdSe nanoplatelets

With the use of a novel thermoluminescence technique, a new type of surface traps is observed in colloidal CdSe nanocrystals of planar geometry (nanoplatelets). The emptying of these traps, which cannot be detected by means of the conventional thermally stimulated luminescence scheme, proceeds via a cascade process involving their own excited states. An energy-level diagram of nanoplatelets taking into account the specific characteristics of these traps is proposed and the density of surface states, featuring two peaks at energies of 100 and 280 meV, is determined.

Experimental determination of energy transfer in Eu(III) complexes, based on pyrazole substituted 1, 3-diketones

We succeeded in synthesis of the novel Eu-based luminophore with almost 100% efficiency of energy transfer from ligands to the lanthanide ion. The luminophores with β- diketonate ligands were characterized by means of optical spectroscopy. Impact of different types of β-diketonates on the quantum yield of luminescence was revealed. A β-diketonate complex exhibiting the highest luminescence quantum yield and prospective for OLED applications was determined. The reasons for decreasing quantum efficiencies for other types of investigated ligands are discussed.

Correlation between photon-emission intervals in blinking luminescence of single CdSe/CdS nanocrystals

The statistics of luminescence from single CdSe/CdS core/shell semiconductor nanocrystals under CW laser excitation at room temperature is experimentally investigated by recording sequences of absolute arrival times of the emitted photons. It is shown that the correlation coefficient for consecutive intervals between the photon-arrival times differs from zero. The correlation persists for photon-arrival intervals separated by two or more photon-detection events, until the time between the two intervals becomes, on average, as long as 180 ms, which corresponds to about 103 detected photons. A simulation of the luminescence process supports the conclusion that this correlation is linked to the blinking character of the quantum-dot luminescence.

Energy transfer from TPD to CdSe/CdS/ZnS colloidal nanocrystals

The efficiency of electronic-excitation energy transfer from organic semiconductor TPD to CdSe/CdS/ZnS nanocrystals passivated with different organic ligands is investigated. It is shown that the rate of energy transfer from TPD to nanocrystals decreases with increasing thickness of the passivation coating. It is suggested that the Förster mechanism is responsible for the excitation transfer.

Study of photophysical properties of composite materials based on polystyrene, polymethyl methacrylate, and Eu(III) complex with 1-(1,5-dimethyl-1h-pyrazole-4-yl)-4,4,4-trifluorobutane-1,3-dion and 1,10-phenanthroline

The effect of the polymer matrix on luminescence properties of the europium complex we synthesized is studied. It is shown that the interaction of complex molecules with the matrix has practically no effect on the photoluminescence spectrum shape. The excited state lifetime decreases no more than twice.

Experimental setup for determining the carrier mobility using a transit time technique

A new scheme of the experimental setup for measuring the carrier mobility in thin films of organic semiconductor materials was proposed. Major factors controlling the time of exponential relaxation of the measuring system were analyzed. On this basis, conclusions were made on operating parameters of the measuring equipment required to reduce as much as possible the relaxation time. According to this, a new setup was developed. A qualitative improvement of current kinetic curves for a control sample was experimentally shown using the new setup. This allowed determination of transit times and carrier mobilities with high reliability.