RESUMO
An original method was proposed to reduce the quenching of the NIR fluorescence of colloidal solutions of 0.1 at. % Nd3+: LaF3 nanoparticles (NPs) synthesized by aqueous co-precipitation method followed by hydrothermal microwave treatment. For this, an aqueous colloidal solution of NPs was precipitated by centrifugation and dissolved in the same volume of DMSO. The kinetics of static fluorescence quenching of Nd3+ donors of doped NPs dispersed in two solvents was analyzed to determine and to compare the concentrations of OH- quenching acceptors uniformly distributed throughout the volume of the NPs. The dependences of the relative fluorescence quantum yield φ of colloidal solutions on the concentration of OH- groups in the NPs were calculated and were also used to determine concentration of acceptors in the volume of NPs in different solvents. It was found that the concentration of OH- groups in NPs dispersed in DMSO is almost two times lower than in NPs dispersed in water. This gives an almost two-fold increase in the relative fluorescence quantum yield φ for the former. The sizes of synthesized NPs were monitored by common TEM and by applying a rapid procedure based on optical visualization of the trajectories of the Brownian motion of NPs in solution using a laser ultramicroscope. The use of two different methods made it possible to obtain more detailed information about the studied NPs.
RESUMO
Two series of stable aqueous colloidal solutions of Nd3+: LaF3 single-phase well-crystallized nanoparticles (NPs), possessing a fluorcerite structure with different activator concentrations in each series, were synthesized. A hydrothermal method involving microwave-assisted heating (HTMW) in two Berghof speedwave devices equipped with one magnetron (type I) or two magnetrons (type II) was used. The average sizes of NPs are 15.4 ± 6 nm (type I) and 21 ± 7 nm (type II). Both types of NPs have a size distribution that is well described by a double Gaussian function. The fluorescence kinetics of the 4F3/2 level of the Nd3+ ion for NPs of both types, in contrast to a similar bulk crystal, demonstrates a luminescence quenching associated not only with Nd-Nd self-quenching, but also with an additional Nd-OH quenching. A method has been developed for determining the spontaneous radiative lifetime of the excited state of a dopant ion, with the significant contribution of the luminescence quenching caused by the presence of the impurity OH- acceptors located in the bulk of NPs. The relative quantum yield of fluorescence and the fluorescence brightness of an aqueous colloidal solution of type II NPs with an optimal concentration of Nd3+ are only 2.5 times lower than those of analogous Nd3+: LaF3 single crystals.
RESUMO
The competence of the reversible exciplex formation and parallel quenching of excitation (by electron or energy transfer) was considered using a non-Markovian pi-forms approach, identical to integral encounter theory (IET). General equations accounting for the reversible quenching and exciplex formation are derived in the contact approximation. Their general solution was obtained and adopted to the most common case when the ground state particles are in great excess. Particular cases of only photoionization or just exciplex formation separately studied earlier by means of IET are reproduced. In the case of the irreversible excitation quenching, the theory allows specifying the yields of the fluorescence and exciplex luminescence, as well as the long time kinetics of excitation and exciplex decays, in the absence of quenching. The theory distinguishes between the alternative regimes of (a) fast equilibration between excitations and exciplexes followed by their decay with a common average rate and (b) the fastest and deep excitation decay followed by the weaker and slower delayed fluorescence, backed by exciplex dissociation.