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Journal of Applied Physics

Enhanced nonradiative relaxation and photoluminescence quenching in random, doped nanocrystalline powders

Xiulin Ruan, Massoud Kaviany

Published May 11, 2005• 27 citations
Publisher

Abstract

Nonradiative relaxation and photoluminescence quenching in nanocrystalline powders doped with rare-earth elements are of interest in optical bistability, random laser, and other optoelectronic applications. Here, the luminescence quenching of a one-dimensional random medium made of multilayer nanoparticles (Y2O3) doped with rare-earth elements (Yb3+) is analyzed by considering the transport, transition, and interaction of the fundamental energy carriers. The nonradiative decay and luminescence quenching in random media are enhanced compared to single crystals, due to multiple scattering, enhanced absorption, and low thermal conductivity. The coherent wave treatment is used to calculate the photon absorption, allowing for field enhancement and photon localization. The luminescent and thermal emission is considered as incoherent. The size-dependent absorption coefficient and penetration depth are observed. The nonradiative decay is identified as a multiphonon relaxation process, and is found to be enhanced compared to bulk materials. The luminescence quenching and nonlinear thermal emission, occurring with increasing irradiation intensity, are predicted.

DOI
10.1063/1.1900937

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Nonradiative relaxation and photoluminescence quenching in nanocrystalline powders doped with rare-earth elements are of interest in optical bistability, random laser, and other optoelectronic applications. Here, the luminescence quenching of a one-dimensional random medium made of multilayer nanoparticles (Y2O3) doped with rare-earth elements (Yb3+) is analyzed by considering the transport, transition, and interaction of the fundamental energy carriers. The nonradiative decay and luminescence quenching in random media are enhanced compared to single crystals, due to multiple scattering, enhanced absorption, and low thermal conductivity. The coherent wave treatment is used to calculate the photon absorption, allowing for field enhancement and photon localization. The luminescent and thermal emission is considered as incoherent. The size-dependent absorption coefficient and penetration depth are observed. The nonradiative decay is identified as a multiphonon relaxation process, and is found to be enhanced compared to bulk materials. The luminescence quenching and nonlinear thermal emission, occurring with increasing irradiation intensity, are predicted.
The enhanced laser cooling performance of rare-earth-ion-doped nanocrystalline powders is predicted, compared to the bulk material, using Yb3+:Y2O3{\mathrm{Yb}}^{3+}:{\mathrm{Y}}_{2}{\mathrm{O}}_{3}Yb3+:Y2​O3​ as the model material. This is achieved by enhancing the off-resonance, phonon-assisted absorption, which is proportional to the three factors considered in this paper: the dopant concentration, the pumping field energy, and the excitation coefficient. Using the energy transfer theory for concentration quenching, the optimum concentration corresponding to the maximum cooling power is found to be considerably larger than the currently used value, suggesting noticeable enhancement effects for laser cooling. The pumping field energy is enhanced in random nanopowders compared with bulk crystals under the same irradiation, due to the multiple scattering of photons. Photons are thus localized in the medium and do not propagate through, increasing the photon absorption of the pumping beam (and it is shown that the reabsorption of the fluorescence is negligible). Using molecular dynamics simulations, the phonon density of states (DOS) of the nanopowder is calculated, and found to have broadened modes, and extended small tails at low and high frequencies. The second-order electronic transition rate for the anti-Stokes luminescence is calculated using the Fermi golden rule, which includes the influence of this phonon DOS, and is shown to have enhancement effects on the laser cooling efficiency using nanopowders. It is finally concluded that these three enhancement mechanisms are essentially to increase the population of the three participating carriers (electron, photon, and phonon) in the interacting volume, and this also points out directions for enhancing laser cooling performance in bulk materials.
This paper reports on the characterization of nanocrystalline powders of ytterbium doped YLiF4 for applications in optical refrigeration. Here we used powders with nanocrystals of Yb 3+ concentrations of (10, 15, 20) mol % and lengths (70, 66, 96) nm. Our preliminary spectroscopic measurements did not show an enhancement in the absorption at the long-wavelength tail of the spectra of the nanocrystalline powder when compared with bulk Yb:YLiF4, indicating that the increase of the phonon-assisted excitation is not large enough to play a significant role in cooling in the present conditions. One advantage of nanocrystalline powders over bulk crystals is the possibility of enhancing the absorption by the realization of cavity-less pump recycling through photon localization [1]. While photon localization also increases the reabsorption of the fluorescence depending on the quantum efficiency of the material and can mitigate cooling, it allows the use of crystals of low enough concentrations to avoid deleterious effects such as ion-ion energy transfer followed by quenching. The pump intensity enhancement favors upconversion luminescence to visible wavelengths, which can be used for optical refrigeration and extends the scope of the application for the material. We observed both green and blue emission from the samples and investigate the processes which lead to it. We present the experimental investigation of the nanocrystals’ absorption and emission spectra and the first excited state lifetime measurements, which are used to estimate the nanocrystal’s photoluminescence quantum efficiency.
This research is an outgrowth of earlier experiments that demonstrated bistable luminescence in heavy metal halide crystals doped with trivalent ytterbium ions. This type of instability has importance as a fundamentally new physical phenomenon with a potential application for fast all-optical switching as well as a limitation on compact solid state laser performance. In this thesis, the investigation of luminescent instabilities is extended to bistable energy transfer processes in crystals and to the observation of bistable blackbody emission in rare earth nanopowders. High resolution laser spectroscopy was used to study bistable luminescence and energy transfer in Yb,Er:CsCdBr3 crystals at cryogenic temperatures. For the first time, it was found that bistable behavior associated with Yb 3+ ions was transferred to Er 3+ through resonant energy transfer. Bistability of the resulting sensitized luminescence caused sufficiently dramatic changes in the crystal dynamics so as to change the color of emission from yellow to green. This color changing phenomenon is fully explained in the present work and is referred to as chromatic switching. Temperature is a critical variable that is known to govern luminescent instabilities in all current theories. Therefore, in a search for new systems with luminescent instabilities at high temperatures, materials with extreme thermal properties were investigated as part of this research. Yb,Er:Y 2O3 nanopowders were selected for this purpose. Nanopowders exhibit greatly reduced thermal conductivity and were verified during the course of this work to cause enhanced absorption as the result of multiple scattering. Significant spectral differences between Yb,Er:Y2O 3 nanopowders and single crystals also emerged. Measurements of erbium upconversion luminescence versus pump intensity in resonance with the ytterbium absorption transition revealed striking new optical phenomena: strong luminescent quenching, intense bistable blackbody emission, and the formation of single crystal micro-tubes directly from powder samples. A simple theoretical model was successfully developed to explain all these optical effects by a detailed balance approach to thermal transport that explicitly included erbium and ytterbium atomic level occupation probabilities, blackbody radiation and radiation trapping. Calculations of nanopowder sample luminescence accurately reproduced experimentally observed quenching, the onset of blackbody emission, bistability and details of hysteresis loops. The model also predicted that absorbed powers of less than 15 mW could melt yttria nanopowders (melting point = 2410°C), again in agreement with experiments. This work is expected to enable new approaches to laser processing of ceramics and laser machining of reflective metals, notably aluminum, using low power lasers.
Intrinsic bistability in active optical compounds doped with rare-earth ions has attracted widespread interest because of its relevance for optical signal switching and routing. In this paper, room temperature strong bistability effect of Ybsensitized Tm upconversion emission is reported in zirconium dioxide nanocrystal host matrix under infrared diode laser irradiation. The distinct optical bistability behavior is simultaneously observed in three emission bands of Tm ion around 480, 650/680 and 800 nm which are assigned to the radiative transitions of 1G4→3H6, 1G4→3F4/3F2,3→3H6, and 3H4→3H6, respectively. The bistability loops exhibit uniformly clockwise cycle characterized by a relatively lower trace of emission intensity at decreasing pump power than the trace at increasing pump power. Multiphoton upconversion processes are analyzed to determine the Yb→Tm energy transfer mechanism. Such strong bistability effect is associated with thermally enhanced nonradiative decay and reduced luminescence quantum yield due to the strong pump-induced local thermal loading.
Nanostructured rare-earth-ion-doped materials are increasingly being investigated for on-chip implementations of quantum information processing protocols as well as commercial applications such as fluorescent lighting. However, achieving high-quality and optimized materials at the nanoscale is still challenging. Here we present a detailed study into the restriction of phonon processes in the transition from bulk crystals to small ($\ensuremath{\le}40$-nm) nanocrystals by observing the relaxation dynamics between crystal-field levels of Tb3+:Y3Al5O12{\mathrm{Tb}}^{3+}:{\mathrm{Y}}_{3}{\mathrm{Al}}_{5}{\mathrm{O}}_{12}Tb3+:Y3​Al5​O12​. We find that the population relaxation dynamics are modified as the particle size is reduced, consistent with our simulations of inhibited relaxation through a modified vibrational density of states and hence modified phonon emission. However, our experiments also indicate that nonradiative processes not driven by phonons are also present in the smaller particles, causing transitions and rapid thermalization between the levels on a time scale of <100ns<100\phantom{\rule{0.16em}{0ex}}\mathrm{ns}<100ns.