Power dependence of upconversion luminescence

Spectroscopic data are of essential value for understanding the excitation mechanisms in luminescent and laser materials. Special attention has been devoted to the investigation of upconversion-induced luminescence, partly because of the availability of near-infrared pump sources for the excitation of visible luminescence and laser emission and partly because these mechanisms can introduce a loss channel for devices emitting in the infrared region. Typical upconversion processes are pump excited-state absorption (ESA) and energy-transfer upconversion (ETU). For the interpretation of short-wavelength luminescence, it is often assumed that the order n of the upconversion process, i.e. the number n of pump photons required to excite the emitting state, is indicated by the slope of the luminescence intensity versus pump power in double-logarithmic representation. However, a saturation of upconversion luminescence with rising pump power was already observed 30 years ago. We show theoretically by assuming the simplest possible rate-equation model that the experimentally observed decrease in power dependence of an upconversion luminescence with rising pump power is purely determined by the competition between linear decay and upconversion processes for the depletion of the intermediate excited states. An upconversion luminescence which is excited by the subsequent absorption of n photons has a dependence on absorbed pump power P which may range from Pn in the limes of infinitely short lifetimes of the intermediate excited states down to P1 for the upper state and less than P1 for the intermediate states in the limes of infinitely strong upconversion rates. Whereas the upper limes is valid universally, the lower limes for the intermediate states depends on whether the excitation is achieved via ETU or ESA and whether the states decay predominantly via ground-state luminescence or multiphonon relaxation into the next lower-lying state. These results allow for the interpretation of a measured power dependence of multiphoton-excited luminescence with respect to the order of the process and its physical origin and strength. We have verified experimentally the convergence into both limes by upconversion luminescence in Cs3Lu2Cl9:1% Er3+ and Cs3Er2Cl9

Heisenberg Dimer Single Molecule Magnets in a Strong Magnetic Field

We calculate the static and dynamic properties of single crystal, single molecule magnets consisting of equal spin $S=1/2$ or 5/2 dimers. The spins in each dimer interact with each other via the Heisenberg exchange interaction and with the magnetic induction ${\bf B}$ via the Zeeman interaction, and interdimer interactions are negligible. For antiferromagnetic couplings, the static magnetization and specific heat exhibit interesting low temperature $T$ and strong ${\bf B}$ quantum effects. We calculate the frequency spectrum of the Fourier transform of the real part of the time autocorrelation function ${\cal C}_{11}(t)$ for arbitrary $T, {\bf B}$, and compare our results with those obtained for classical spins. We also calculate the inelastic neutron magnetic dynamical structure factor $S({\bf q},\omega)$ at arbitrary $T, {\bf B}$.Comment: 11 pages, 14 figures, submitted to Phys. Rev.

Liquid phase epitaxy and optical investigation of KYb(WO4)2 thin layers

In recent years, Yb3+ has attracted much attention as an activating ion because of its small quantum defect for laser emission from 2F5/2 to 2F7/2 at ~1.03 µm [1], which provides high efficiency and reduced heat generation. Of high practical interest is the thin-disk laser concept [2], which possesses a tremendous advantage over rod lasers because of its axial-cooling approach and consequent weak thermal lensing and good beam quality.\ud A promising material for Yb3+ thin-disk lasers is KYb(WO4)2 (KYbW) [3]. It can be grown from high-temperature solutions [4]. Nevertheless, the growth of high-quality, single-crystalline layers with thickness in the range of the absorption length of ~13 µm at 981 nm has as yet not been reported. A suitable substrate material is KY(WO4)2 (KYW), but the relatively large differences in the thermal expansion coefficients between KYW and KYbW along the [100], [001], and especially [010] directions [5] favor low temperatures for the hetero-epitaxial growth.\ud For the first time, we demonstrate liquid phase epitaxy (LPE) of KYbW layers. The layers were grown at start temperatures as low as 520°C, which is favorable in order to decrease the thermal stresses due to the differences in the thermal expansion coefficients of substrate and layer. Moreover, the choice of [010]-oriented substrates bypasses the large difference in the thermal expansion coefficient along the [010] direction. KY1-xYbx(WO4)2 layers with varying x = 0.03-1.00 were grown by LPE. The chloride solvent consisted of the eutectic composition [6] 24.4 mol.% KCl, 30.4 mol.% NaCl, and 42.2 mol.% CsCl. The growth temperature spanned the range from 580 to 500°C and the cooling rate was 0.67-1.00 Kh-1. Crack-free, transparent KYbW layers were grown on (010) substrates.\ud Spectroscopic investigations have shown that the lifetime of ~250 µs measured in our LPE-grown KYbW layers is dominated by radiative decay and is very similar to that measured in top-seeded-solution-grown bulk samples [4]. Fast energy migration among the Yb3+ ions and energy transfer to small amounts of Tm3+ and Er3+ ions present in the YbCl3 reagent lead to visible upconversion luminescence in the layers under 981-nm excitation.\ud \ud [1] T.Y. Fan, IEEE J. Quantum Electron. 29, 1457 (1993).\ud [2] A. Giesen, H. Hügel, A. Voss, K. Wittig, U. Brauch, H. Opower, Appl. Phys. B 58, 365 (1994).\ud [3] P. Klopp, U. Griebner, V. Petrov, X. Mateos, M.A. Bursukova, M.C. Pujol, R. Solé, J. Gavaldà, M. Aguiló, F. Güell, J. Massons, T. Kirilov, F. Díaz, Appl. Phys. B 74, 185 (2002).\ud [4] M.C. Pujol, M.A. Bursukova, F. Güell, X. Mateos, R. Solé, J. Gavaldà, M. Aguiló, J. Massons, F. Díaz, P. Klopp, U. Griebner, V. Petrov, Phys. Rev. B 65, 165121 (2002).\ud [5] M.C. Pujol, X. Mateos, R. Solé, J. Massons, J. Gavaldà, F. Díaz, M. Aguiló, Mater. Sci. Forum 378-381, 710 (2001).\ud [6] D. Ehrentraut, M. Pollnau, S. Kück, Appl. Phys. B 75, 59 (2002)

Liquid phase epitaxy and spectroscopic investigation of optically active KYb(WO4)2 thin layers

In recent years, Yb3+ has attracted much attention as an activating ion because of its small quantum defect for laser emission from 2F5/2 to 2F7/2 at ~1.03 µm, which provides high efficiency and reduced heat generation. A promising material for Yb3+ lasers is KYb(WO4)2 (KYbW) [1]. It can be grown from high-temperature solutions [2]. A suitable substrate material for the growth of single-crystalline layers with thicknesses in the range of the absorption length of ~13 µm at 981 nm is KY(WO4)2 (KYW).\ud We demonstrate the liquid phase epitaxy (LPE) of KYbW layers at start temperatures as low as 520°C from the chloride solvent KCl-NaCl-CsCl. This temperature is favorable in order to decrease the thermal stresses due to the differences in the thermal expansion coefficients of substrate and layer. Moreover, the choice of [010]-oriented KYW substrates bypasses the large difference in the thermal expansion coefficient along the [010] direction. Our spectroscopic investigations show that the fluorescence lifetime of ~250 µs measured in our LPE-grown KYbW layers is dominated by radiative decay and is very similar to that measured in top-seeded-solution-grown bulk samples [2]. Fast energy migration among the Yb3+ ions and energy transfer to small amounts of Tm3+ and Er3+ ions present in the YbCl3 reagent lead to visible upconversion luminescence in the layers under 981-nm excitation.\ud \ud [1] P. Klopp, U. Griebner, V. Petrov, X. Mateos, M.A. Bursukova, M.C. Pujol, R. Solé, J. Gavaldà, M. Aguiló, F. Güell, J. Massons, T. Kirilov, F. Díaz, Appl. Phys. B 2002, 74, 185\ud [2] M.C. Pujol, M.A. Bursukova, F. Güell, X. Mateos, R. Solé, J. Gavaldà, M. Aguiló, J. Massons, F. Díaz, P. Klopp, U. Griebner, V. Petrov, Phys. Rev. B 2002, 65, 16512

Excited-state absorption in Er:BaY2F8 and Cs3Er2Br9 and comparison with Er:LiYF4

The influence of Excited-State Absorption (ESA) on the green laser transition and the overlap of Ground-State Absorption (GSA) and ESA for 970 nm upconversion pumping in erbium is investigated in Er3+:BaY2F8 and Cs3Er2Br9. Results are compared to Er3+:LiYF4. In Er3+:BaY2F8, a good overlap between GSA and ESA is found at 969 nm in one polarization direction. The emission cross section at 550 nm is a factor of two smaller than in LiYF4. In Cs3Er2Br9, the smaller Stark splitting of the levels shifts the wavelengths of the green emission and ESA from 4I13/2 off resonance. It enhances, however, ground-state reabsorption. The emission cross section at 550 nm is comparable to LiYF4. Upconversion leads to significant green fluorescence from 2H9/2. A significant population of the 4111/2 level and ESA at 970 nm are not present under 800 nm pumping

Q-dependence of the inelastic neutron scattering cross section for molecular spin clusters with high molecular symmetry

For powder samples of polynuclear metal complexes the dependence of the inelastic neutron scattering intensity on the momentum transfer Q is known to be described by a combination of so called interference terms. They reflect the interplay between the geometrical structure of the compound and the spatial properties of the wave functions involved in the transition. In this work, it is shown that the Q-dependence is strongly interrelated with the molecular symmetry of molecular nanomagnets, and, if the molecular symmetry is high enough, is actually completely determined by it. A general formalism connecting spatial symmetry and interference terms is developed. The arguments are detailed for cyclic spin clusters, as experimentally realized by e.g. the octanuclear molecular wheel Cr8, and the star like tetranuclear cluster Fe4.Comment: 8 pages, 1 figures, REVTEX