Radiative and non-radiative decays from the excited state of Ti3+ ions in oxide crystals

The fluorescence spectra of Ti³⁺ in Y₃Al₅O₁₂ (YAG), Al₂O₃ (sapphire), YAlO₃ (YAP) observed at 10 K are composed of zero-phonon lines accompanied by the broad vibronic sidebands. The temperature dependence of the fluorescence lifetime and of the total intensity of the broadband measured in YAG and Al₂O₃ indicate that the radiative decay times from the excited states are nearly constant in the range 10–300 K. This demonstrates that the broadband radiative emissions in Ti³⁺:YAG and Ti³⁺:Al₂O₃ are due to magnetic dipole transitions or to electric dipole transitions induced by static odd-parity distortion, respectively. The decrease of the fluorescence lifetime with increasing temperature in Ti³⁺:YAG and Ti³⁺:Al₂O₃ is due to non-radiative decay from the excited state which occurs through phonon-assisted tunnelling between the excited and ground states. The radiative decay of Ti³⁺:YAP is enhanced with increasing temperature, indicating that radiative decay rate contains a term associated with odd-parity phonons. Nevertheless, a non-radiative decay rate of 3.6 × 10⁴ s^–1 observed in the temperature range 10–300 K is due to excited state absorption, which depopulates the excited state and quenches the fluorescence at the laser wavelength.     

Efficient Continuous Wave-laser emission of Pr3+-doped fluorides at room temperature

We report, to our knowledge for the first time, Continuous Wave (CW) laser emission at room temperature of Pr:LiYF₄ (Pr.YLF) at six wavelengths: 522, 545, 607, 639.5, 720 and 907.4 nm. The pump source was an argon-ion laser tuned to a wavelength of = 457.9 nm. The maximum output powers at 522 nm (³P_i ³H₅) and 639.5 nm (³P₀ ³F₂) were 144 and 266 mW, respectively. We also observed CW laser action of Pr:GdLiF₄ (Pr: GLF) at = 639 nm and of Pr:KYF₄ (Pr: KYF) at = 642.5 nm.     

Infrared excited-state absorption and stimulated-emission cross sections of Er3+-doped crystals

Detailed spectra of the excited-state absorption and the stimulated-emission cross-sections of Er³⁺ -doped Y₃Al₅O₁₂, YAlO₃, LiYF₄, and KYF₄ crystals are analyzed in the infrared wavelength regions from 700 to 2100 nm. The spectra were measured with a pump and probe technique employing a double modulation scheme. For Er (2%): Y₃Al₅O₁₂ also the stimulated emission at 3 µm and the reabsorption due to excited-state absorption from the lower laser level are investigated.     

Temperature dependence of the lifetime of Cr3+ luminescence in garnet crystals

The coexistence of sharp R-lines from the ² E state and the broad band from the ⁴ T ₂ state in the photoluminescence spectra of Cr³⁺:Gd₃Sc₂Ga₃O₁₂ (GSGG) and Cr³⁺:Y₃Ga₅O₁₂ (YGG) is observed at low temperature (10K). The decay lifetimes of the broad emission bands of Cr³⁺ in GSGG and YGG are very close to those of the R-lines being, respectively, 0.23 ms and 2.5 ms. These results are explained in terms of the extent of the mixing of the ⁴ T ₂ vibronic wavefunction with that of the ² E lowest excited state by tunnelling.     

Temperature dependence of the lifetime of Cr3+ luminescence in garnet crystals I

The lifetimes of the R-lines from the ² E level and the broad bands from the ⁴ T ₂ level of Cr³⁺ ions in various garnet crystals vary with the energy separation between the ² E and ⁴ T ₂ levels, which change systematically with the composition of host crystal. The trend of the Cr³⁺ lifetimes, as well as their temperature dependences in garnet crystals, is explained by zero-point vibration and phonon-assisted tunnelling between the ² E and ⁴ T ₂ states of Cr³⁺ ion.     

Polarized and time-resolved measurements of excited-state absorption and stimulated emission in Ti:YAlO3 and Ti:Al2O3

Pump-induced excited-state absorption (ESA) in the whole range of pump wavelengths prevents effective laser action of Ti:YAlO₃. The time-resolved measurement of this absorption allows the separation of excited-state absorption and losses due to transient colour centres. The influence of polarization on the ESA of Ti:YAlO₃ is only weak, as it is expected for a charge-transfer transition. No significant stimulated emission (SE) could be measured in the whole fluorescence region. In comparison, Ti:Al₂O₃ shows a broad SE spectrum corresponding to the tuning range of this laser material. The strongest SE was measured for Ec, which is the preferred polarization for laser action of Ti:Al₂O₃. Below 350 nm the long-wavelength edge of an ESA band was found.     

Spectroscopic and lasing properties of Er3+:Yb3+-doped fluoride phosphate glasses

Er³⁺ emission and lasing properties at 1.5 μm were studied in fluoride phosphate glasses (FP20) with different doping concentrations as well as in a commercial phosphate glass (Kigre QX). Emission decay behaviour at 1 μm and 1.5 μm was examined with respect to energy transfer between ytterbium and erbium. Emission cross-sections were determined using the reciprocity and Füchtbauer–Ladenburg methods. Gain spectra were calculated for the glasses and related to differences in the tuning curves and lasing properties. The temperature rise due to the quantum defect was determined via the ratios of green upconversion luminescence for different pump powers. The results from the laser and tuning experiments indicate that the FP20 glass offers good possibilities in broadband amplification and the generation of ultrashort pulses. Received: 24 August 2000 / Revised version: 27 October 2000 / Published online: 7 February 2001     

Crystalline structure and optical spectroscopy of Er3+-doped KGd(WO4)2 single crystals

4 )₂ single crystals doped with Er³⁺ have been grown by the flux top-seeded-solution growth method. The crystallographic structure of the lattice has been refined, being the lattice constants a=10.652(4), b=10.374(6), c=7.582(2) Å, β=130.80(2)°. The refractive index dispersion of the host has been measured in the 350–1500 nm range. The optical absorption and photoluminescence properties of Er³⁺ have been characterised in the 5–300 K temperature range. At 5 K, the absorption and emission bands show the (2J+1)/2 multiplet splittings expected for the C₂ symmetry site of Er in the Gd site. The energy positions and halfwidths of the 72 sublevels observed have been tabulated as well as the cross sections of the different multiplets. Six emission band sets have been observed under excitation of the ⁴F_7/2 multiplet. The Judd–Ofelt (JO) parameters of Er³⁺ in KGW have been calculated: Ω₂=8.90×10^-20 cm², Ω₄=0.96×10^-20 cm², Ω₆=0.82×10^-20 cm². Lifetimes of the ⁴S_3/2, ⁴F_9/2, and ⁴I_11/2 multiplets have been measured in the 5–300 K range of temperature and compared with those calculated from the JO theory. A reduction of the ⁴S_3/2 and ⁴I_11/2 measured lifetimes with increasing erbium concentration has been observed, moreover the presence of multiphonon non-radiative processes is inferred from the temperature dependence of the lifetimes. Received: 15 December 1997/Revised version: 10 July 1998     

Excited state absorption and stimulated emission of Nd3+ in crystals III: LaSc3(BO3)4, CaWO4, and YLiF4

3+ ions in CaWO₄, LaSc₃(BO₃)₄, and YLiF₄ crystals are presented. The spectra were measured by a continuous-wave pump and probe technique. It is shown that ESA is a negligible loss mechanism in cw lasers emitting at 1.06 μm. In contrast, the effective emission cross sections in Nd:CaWO₄ and Nd:LaSc₃(BO₃)₄ around 1.35 μm are considerably diminished. Received: 8 May 1998/Revised version: 7 September 1998     

Excited state absorption and stimulated emission of Nd3+ in crystals. Part 2: YVO4, GdVO4, and Sr5(PO4)3F

3+ ion in the crystals YVO₄, GdVO₄, and Sr₅(PO₄)₃F. The measurements were performed in the spectral region of the main laser transitions ⁴F_3/2→⁴I_9/2, ⁴F_3/2→⁴I_11/2, and ⁴F_3/2→⁴I_13/2by a continuous wave pump and probe technique. The calibrated gain and ESA spectra are presented and possible implications of ESA on the laser performance are estimated. It is shown that ESA can be a small loss factor to the laser emission near 1060 nm but does considerably diminish the effective emission cross sections near 1340 nm especially in Nd:YVO₄ and Nd:GdVO₄. Received: 29 January 1998/Revised version: 8 May 1998     

Stimulated emission and laser action of Pr3+-doped YA1O3

Groundstate absorption, fluorescence, excited-state absorption, and stimulated emission of Pr:YA1O₃ were measured in dependence on the polarization. The results reflect the anisotropy of the host lattice. Especially the polarized spectra of the stimulated emission fit very well with the laser data of this material. Seven cw laser transitions in the visible spectral range obtained so far in Pr:YA1O₃ with argon-ion laser pumping were identified in the spectra of the stimulated emission. In addition, two infrared cw laser transitions were realized. The best results were achieved for the³ P ₀³ F ₄ laser transition at 746.9 nm with a maximum slope efficiency of 24.6%, a maximum output power of 49.6 mW, and a laser threshold of 25 mW.     

Luminescence from Ti2+ ions in LiF crystals

Luminescence of Ti²⁺: LiF crystals in the wavelength range 650–900 nm excited using laser radiation is reported. The values of 10Dq and the Racah B parameter obtained from the present results indicate that in LiF the ¹ E, ¹ T ₂, and ³ T ₂ energy levels are almost at the cross-over point in the Tanabe-Sugano diagram. In consequence photoluminescence from all three energy levels to the ground state is observed. At low temperature (T 14 K) the emission is mainly due to sharp emission lines with weak vibronic structure due to the ¹ E, ¹ T ₂³ T ₁ transitions of Ti²⁺ ions. The ³ T ₂³ T ₁ broad-band emission is weak at low temperature, becoming stronger at 300 K due to a phonon-assisted tunnelling process, similar to that observed in Cr³⁺: garnets [1]. The excitation spectrum of these lines is a broad peak at 590 nm due to absorption in the ³ T ₁³ T ₂ transition.     

Time-resolved spectra of excited-state absorption in Er3+ doped YAlO3

A pump- and probe-beam technique is used for measuring time-resolved excited-state absorption (ESA) and stimulated-emission (SE) spectra of Er³⁺ doped YAlO₃. The Er^{3+ 4} I _15/2 ⁴ F _7/2 transition of the sample is excited at 488 nm by an excimer laser pumped dye laser. The ESA and SE of broadband xenon flashlamp light is monitored between 300 and 860 nm by an optical multichannel analyzer (OMA). The analysis of the experimental results provides information on the effective cross sections _ESA and _SE originating from several levels and on the populations of these levels. To our knowledge this represents the first detailed investigation of time-resolved ESA and SE over a broad spectral range in rare-earth doped materials.     

Excited state absorption and stimulated emission of Nd3+ in crystals. Part I: Y3Al5O12, YAlO3, and Y2O3

4 F_3/2 excited state of the Nd³⁺ ion in Y₃Al₅O₁₂, YAlO₃, and Y₂O₃ were measured in a continuous wave pump- and probe experiment in a wide spectral range from 850 nm (780 nm for Y₃Al₅O₁₂) to 1500 nm. The cross sections were determined from a comparison with the emission spectra and the simultaneously measured ground state absorption bleaching. The strongest excited state absorption transitions were found in the 1220–1400 nm spectral region due to transitions to the ²G_9/2 and ⁴G_7/2 levels. The spectral positions of the measured transitions are in good agreement with the theoretically expected transitions calculated from the known Stark-level splittings. Received: 4 December 1997/Revised version: 8 May 1998     

Origin of athermal refractive index changes observed in Yb doped YAG and KGW

Time-resolved excited-state absorption and fluorescence measurements were performed in the Yb³⁺ doped YAG and KGW laser crystals. The results indicate that the athermal refractive index changes observed in previous transient interferometric and diffraction grating experiments can be related to polarisability changes caused by the existence of strong UV charge transfer absorption bands.     

Optical spectra and luminescence dynamics of Pr3+ and Nd3+ in SrLaAlO4 single crystals

Single crystals of SrLaAlO₄: Pr³⁺ and SrLaAlO₄: Nd³⁺ have been grown by the Czochralski method and their optical properties have been studied for different activator concentrations. The absorption and emission spectra of the activators are inhomogeneously broadened because the Sr²⁺ and La³⁺ ions are distributed randomly on the sites ofC ₄ symmetry, however, the symmetry selection rules are still obeyed. Strong self-quenching of the praseodymium luminescence occurs by cross relaxation which is supposed to be assisted by phonon emission in the case of the³ P ₀ level. Self-quenching of Nd³⁺ luminescence disappears at low temperature indicating that the condition of resonance in the cross-relaxation process is fulfilled only for higher components of the ground state.Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Wroclaw, Poland     

Laser emission from mixtures of dipyrromethene dyes in liquid solution and in solid polymeric matrices

Laser emission from binary mixtures of different dyes both in liquid solution and incorporated into solid polymeric matrices, covering the spectral region from green to red, is investigated. Mixtures of two synthesized dyes, analogs of the commercial dye Pyrromethene 567 (PM567), allowed covering the spectral range from green to orange. Tuning ranges in solid state of up to 42 nm with good photostabilities were demonstrated. To extend the tuning range to the red, binary mixtures of the dyes Pyrromethene 597 (PM597)/Pyrromethene 650 (PM650), PM567/DCM, and PM597/DCM were also studied. In liquid solution, a mixture of dyes PM567 and DCM allowed for narrow-linewidth laser emission continuously tunable over a range of 85 nm. In solid-state, mixtures of dyes PM597 and PM650 allowed laser emission tunable over two separate spectral regions up to a wavelength of 619 nm.     

Relaxation-oscillations in the C → A laser emission of XeF in Ar crystals

Transversely pumped 1 cm long crystals are operated in a plan-parallel cavity with dielectric mirrors of 100% and 30% reflectivity. Relaxation-oscillations in the laser emission at 540 nm with frequencies in the range of (1 to 1.8)·10⁹ s^–1 are observed. A square root dependence on pump rate is shown and an internal loss coefficient of 5.4 cm^–1 is derived.On leave from the Polish Academy of Sciences IF-FM, Fiszera 14, PL-80-952 Gdansk, Poland     

Orthorhombic NaREGeO4 crystals with Nd3+ ions; structure and formation,luminescence properties and stimulated emission

The papers of scientific workers at A. V. Shubnikov Institute of Crystallography published in the last decade and dealing with the olivine-like rare-earth germanates NaREGeO₄ (RE=Gd, Y, and Lu) are reviewed. In particular, the physicochemical perculiarities of the formation and some data on growing these compounds in hydrothermal conditions and from the flux are surveyed. The results of the X-ray structural analysis — the basic atomic coordinates and all interatomic distances are presented. Special attention is given to luminescence properties and stimulated emission of Nd³⁺ ions in octahedral positions of the NaREGeO₄ crystal structure.