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Proceedings of SPIE, the International Society for Optical Engineering/Proceedings of SPIE

Characterization of fluoride nanocrystals for optical refrigeration

Elton Soares de Lima Filho, Marta Quintanilla, Fiorenzo Vetrone, Galina A. Nemova, Venkata Krishnaiah Kummara, Raman Kashyap

Published Mar 10, 2015• 7 citations

Abstract

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.

DOI: 10.1117/12.2079856

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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.

The enhanced laser cooling performance of rare-earth-ion-doped nanocrystalline powders is predicted, compared to the bulk material, using

{\mathrm{Yb}}^{3+}:{\mathrm{Y}}_{2}{\mathrm{O}}_{3}

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.

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.

Optical refrigeration of solids with anti-Stokes fluorescence has been widely explored as a vibration-free cryogenic cooling technology. A minimum temperature of 87 K has been demonstrated with rare-earth-ion-doped crystals using optical refrigeration. However, the depletion of the upper-lying energy levels in the ground-state manifold hinders further cooling to below the liquid nitrogen ( LN 2 ) temperatures, restricting its applications. In this work, we introduce a Purcell-enhanced optical refrigeration method to circumvent this limitation. This approach enhances the emission of high-energy photons by coupling the emitters to an optical cavity, blueshifting the mean emission wavelength. Such Purcell-enhanced emission facilitates cooling starting from a lower-energy level in the ground-state manifold, which exhibits a higher occupation below the LN 2 temperatures. Using experimentally measured optical coefficients, our theoretical analysis predicts a minimum achievable internal temperature of about 38 K for a Yb 3 + : YLiF 4 nanocrystal near a cavity under realistic conditions. The proposed method is applicable to other rare-earth-ion-doped materials and semiconductors and will have applications in creating superconducting and other quantum devices through solid-state cooling.

We report the first demonstration of solid-state optical refrigeration of a Ho-doped material. A 1 mol% Ho-doped Yttrium Lithium Fluoride (YLF) crystal is cooled by mid-IR laser radiation, and its external quantum efficiency and parasitic background absorption are evaluated. Using detailed temperature-dependent spectroscopic analysis the minimum achievable temperature of a 1% Ho:YLF sample is estimated. Owing to its narrower ground- and excited-state manifolds, larger absorption cross-section, and coincidence of optimum cooling wavelength of 2070 nm with commercially available high-power and highly efficient Tm-fiber lasers, Ho^3+-doped crystals are superior to Tm^3+-doped systems for mid-IR optical refrigeration. With further improvement in material purity and increased doping concentration, they offer great potential towards enhancing the cooling efficiency nearly two-fold over the best current Yb:YLF systems, achieving lower temperatures as well as for realization of eye-safe mid-IR high-power radiation balanced lasers.

In the perspective of building a solid state cryocooler based on optical refrigeration, it is strategic to develop high purity crystals and to have a full understanding of the mechanisms that can reduce cooling efficiency. In this paper we highlight two loss mechanisms that can hinder the optical refrigeration performance of a Yb:YLF monocrystal: the presence of impurities and fluorescence reabsorption. We show how the presence of impurities can be inferred by measuring the mean lifetime of the Yb optical transition. We measure how a few ppms of other rare earth ions can be detrimental for optical refrigeration by exciting a cooling Yb:YLF sample with two laser sources. We also report the first practical demonstration of the negative effect of fluorescence reabsorption on the cooling performance.