Laser-related spectroscopy of ion-doped crystals for tunable solid-state lasers

In this work an overview of transition metal (TM) ion- and rare earth (RE) ion-doped crystals for application as tunable solid-state lasers will be given. Spectroscopic and laser results will be presented including recent research and advances in this field. Within this work tunability is defined as the possibility to achieve laser oscillation in the vibronic sideband of a transition. Tunable solid-state lasers are of interest for a wide field of applications, e.g. in scientific research, in medicine, for measurement and testing techniques, ultra short pulse generation, and communication. They can also be used as coherent light sources for second-harmonic generation, for optical parametric oscillators, and for sum- and difference-frequency generation. Tunable laser media based on 3d?3d transitions of transition-metal ions and 4f?5d transitions of rare-earth ions cover nowadays almost the whole spectral range between 270 nm and 4500 nm, see Fig. 1 [1-15]. In comparison to laser systems based on the 4f?4f transitions of trivalent rare-earth ions, tunable lasers based on 3d?3d and 4f?5d transitions are in general affected by a higher probability of excited-state absorption (ESA), a higher probability of non-radiative decay, and a higher saturation intensity leading to higher laser thresholds. Often laser oscillation cannot be obtained at all. These general topics will be considered in Sect. 1, where the basic aspects of tunable solid-state lasers are discussed: these are the preparational, the spectroscopic, and the laser aspect. In Sect. 2, the investigation of transition metal ion-doped crystals with respect to the realization of tunable laser oscillation is presented. The work is focused on transition-metal ions of the 3d row (Fe row) and divided into two subsections according to the octahedral and tetrahedral coordinations of the ion investigated. Each subsection is structured according to the electron configurations: 3d¹, 3d³, 3d⁴, and 3d⁸ for the octahedrally coordinated ions and 3d¹, 3d², and 3d⁴ for the tetrahedrally coordinated ions. Section 3 deals with interconfigurational transitions of divalent and trivalent rare-earth ions. Finally, in Sect. 4 the work is summarized. Received: 22 December 2000 / Published online: 30 March 2001     

Sensitized deep-ultraviolet up-conversion emissions of Gd3+ via Tm3+ and Yb3+ in hexagonal NaYF4 nanorods

Deep-ultraviolet (UV) up-conversion (UC) emissions in the region of 270～330 nm of Gd³⁺ under the excitation of a 980 nm laser diode in hexagonal Yb³⁺-Tm³⁺-Gd³⁺ triply doped NaYF₄ nanorods synthesized using a hydrothermal method are reported. Spectral analyses indicate that the UV UC emissions originate from highly efficient energy transfer from Yb³⁺ to Tm³⁺, then to Gd³⁺ions, and the intensity of the emission as well as the ratios of the emission peaks are strongly dependent on the doping concentrations and pump power. The materials are envisioned to have potential applications in anti-counterfeiting, optical and magnetic dual modal nanoprobes for biomedicine, solution-based scintillator materials and UV compact solid-state lasers.     

Cr,Nd:YAG self-Q-switched laser with high efficiency output

The high efficient laser performance of self-Q-switched laser in the co-doped Cr⁴⁺,Nd³⁺:YAG microchip with 1.8 mm thickness was demonstrated. The slope efficiency is varied with the reflectivity of output coupler at 1064 nm, and the highest slope efficiency of 26% was obtained for 95% reflectivity of output coupler at 1064 nm. The pulse width, the single pulse energy and the pulse repetition rate for different reflectivity of the output couplers were measured, and the experimental results agree with the numerical calculations of the passively Q-switched rate equations. This can lead to develop the diode laser pumped monolithic self-Q-switched solid-state microchip lasers, especially for the intracavity frequency-doubled solid-state microchip lasers.     

Out of the blue: semiconductor laser pumped visible rare‐earth doped lasers

The rise of semiconductor‐based pump sources such as In_xGa_1‐xN‐laser diodes or frequency‐doubled optically pumped semiconductor lasers with emission wavelengths in the blue encourages a revisitation of the rare‐earth ions Pr³⁺, Sm³⁺, Tb³⁺, Dy³⁺, Ho³⁺ and Er³⁺ with respect to their properties as active ions in crystalline solid‐state laser materials with direct emission in the visible spectral range. Nowadays, some of these blue‐pumped visible lasers compete with Nd³⁺‐lasers in terms of efficiency and direct lasing at various colors from the cyan‐blue to the deep red can be addressed in very simple and compact laser setups. This paper highlights the spectroscopic properties of suitable rare‐earth ions for visible lasing and reviews the latest progress in the field of blue‐pumped visible rare‐earth doped solid‐state lasers.

     

Middle-infrared luminescence of Nd ions in silver halide crystals

The optical absorption and the luminescence emission in the middle infrared (mid-IR) were investigated in AgCl_xBr_1−x crystals doped with Nd³⁺ ions. Strong luminescence emission, in the spectral range 4.5-5.8 μm, in mid-IR was observed for the first time in Nd³⁺-doped silver halide crystals. Various optical parameters were calculated for the Nd³⁺-doped crystals, using the Judd-Ofelt approximation. The measured results and the calculated parameters indicate that these doped crystals could be used for the development of mid-IR solid-state lasers or mid-IR fiber lasers.     

Concentration quenched luminescence and energy transfer analysis of Nd3+ ion doped Ba-Al-metaphosphate laser glasses

This paper reports the dopant ion (Nd³⁺) concentration effects on its luminescence properties in a new glass system based on barium-alumino-metaphosphates. Amongst the studied concentrations range of 0.276–13.31×10²⁰ ions/cm³, the glass with 2.879×10²⁰ ions/cm³ (1 mol%) Nd³⁺ concentration shows intense NIR emission from ⁴F_3/2 excited state, followed by a decrease in emission intensity for further increase in Nd³⁺ ion concentration. The observed luminescence quenching is ascribed to Nd³⁺ self-quenching through the donor-donor migration assisted cross-relaxation mechanism. The microscopic energy transfer parameters for donor-acceptor energy transfer, C _DA, and donor-donor energy migration, C _DD, have been obtained from the theoretical fittings to experimental decay curves and the spectral overlap model respectively. The C _DD parameters (×10^?39 cm⁶/sec) are found to be about three orders greater than that of C _DA (×10^?42 cm⁶/sec) for Nd³⁺ self-quenching in this host, demonstrating that the excitation energy migration among donors is due to the hopping mechanism. The energy transfer micoparameters obtained in the present study are comparable to the values reported for commercially available laser glasses LHG-8 and Q-98.     

Study of the Structures of the Tetragonal Paramagnetic Centers in the Mixed Fluorite Crystals with Rare-Earth Ions by EPR

Electron paramagnetic resonance (EPR) of the mixed fluorite crystals with the general formula (MeF₂)_1?x?y (REF₃) _x (RF₃) _y (Me = Ca, Sr, Ba; R = Y, La, Lu; RE—paramagnetic trivalent rare-earth ions) were studied comprehensively by different authors and several structural models of paramagnetic centers were considered. However, a lot of details of EPR spectra still remain unexplained. In this work some modifications of the simplest models are proposed which allow explaining adequately the variety of the tetragonal centers in crystals grown under the different conditions. The calculated from the proposed models components of g-factors for Ce³⁺, Nd³⁺, Sm^3+, Er³⁺ ions are in a good agreement with the experimental values.     

Comparative investigation of spectroscopic and laser emission characteristics under direct 885-nm pump of concentrated Nd:YAG ceramics and crystals

A high-resolution spectroscopic and emission-decay investigation of highly concentrated Nd:YAG single crystals and ceramics shows that the state of the Nd³⁺ ions and their interaction in these materials are similar and can be used for construction of efficient solid-state lasers directly pumped in the emitting level. This possibility is demonstrated by continuous-wave emission of concentrated Nd:YAG crystals with up to 3.5 at. % Nd and ceramics with up to 6.8 at. % Nd under resonant 885-nm end pump. Received: 28 May 2001 / Final version: 17 August 2001 / Published online: 10 October 2001     

Photothermally Induced Bistability of Emission of Yb-doped Ca4NdO(BO3)3 Single Crystals

We report on studies of changes in the emission spectra (excited at 808 nm) of the Yb-doped Ca₄NdO(BO₃)₃ single crystals due to the photothermal effects caused by the pulsed Nd:YAG laser. Increase of the sample's surface temperature after laser treatment leads to significant enhancement of the 1040 to 1060 nm emission (ascribed to the Nd^{3+ 4}F_3/2 → ⁴I_9/2, ⁴I_11/2 transitions) and simultaneous decrease of the 975 to 1050 nm emission (corresponding to the Yb^{3+ 2}F_5/2 → ²F_7/2 transition). We explain such an increase of the Nd³⁺ luminescence by thermally activated Yb³⁺ → Nd³⁺ energy transfer.     

Efficient diode-pumped Nd:YVO4 continuous-wave laser at 1.34 μm

We report a high-power continuous-wave(cw) diode-pumped efficient 1.34 μm Nd:YVO₄ laser. The laser properties of a low Nd³⁺-doped concentration of the Nd:YVO₄ crystal operating at 1.34 μm formed with a simple plane-concave cavity have been demonstrated. With the incident pump power of 22 W, an output power of 8.24 W was obtained, giving an optical conversion efficiency of 37.5% and slope efficiency of 40%. The thermal effects of cw end-pumped solid-state lasers were studied.     

Low‐dose ion implanted active waveguides in Nd3+ doped near‐stoichiometric lithium niobate: promising candidates for near infrared integrated laser

By applying low‐dose oxygen ion implantation, active planar waveguides in Nd³⁺ doped near‐stoichiometric lithium niobate laser crystals have been, for the first time to our knowledge, successfully produced. The waveguide exhibits good transmission properties with relatively low propagation loss of ～2 dB/cm. The confocal micro‐luminescence investigations indicate that the emission properties of Nd³⁺ ions in the waveguide are well preserved with respect to the bulk, thus showing promising potentials for efficient waveguide laser action operating at the Nd³⁺ near‐infrared bands. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spectroscopic Study of Neodymium-Doped Sodium–Yttrium Double Fluoride Nd<Superscript>3+</Superscript>:Na<Subscript>0.4</Subscript>Y<Subscript>0.6</Subscript>F<Subscript>2.2</Subscript> crystals

Nd³⁺:Na_0.4Y_0.6F_2.2 (Nd³⁺:NYF) crystals are grown by the Stockbarger–Bridgman method for a stoichiometric mixture prepared by the solid-phase method and containing neodymium up to 20 at. %. The absorption spectrum of Nd³⁺:NYF crystals exhibits bands located in the emission region of laser diodes. The peak absorption cross section of the 796.8-nm band is σ _a = 0.96 × 10^–20 cm² and the bandwidth is Δλ = 17.5 nm. The most intense luminescence band is located at 1.05 μ m and the radiative time of the ⁴F_3/2 level is τ₀ = τ_exp ~ 960 μ s. It is shown that the ²P_3/2 and ⁴D_3/2 levels of Nd³⁺:NYF crystals are also radiative with lifetimes τ exp equal to ~110 and 9.5 μ s, respectively. However, these radiative transitions are partially quenched due to nonradiative relaxation. The intensity parameters Ω t are determined by the Judd–Ofelt method to be Ω₂ = 1.18 × 10^–20, Ω₄ = 1.55 × 10^–20, and Ω 6 = 2.85 × 10–20 cm 2. Using these parameters, the probabilities of radiative transitions and branching ratios are calculated, and the probabilities of nonradiative transitions are estimated. A conclusion is made that Nd³⁺:NYF crystals are promising as active media for diode-pumped tunable lasers, in particular, up-conversion-pumped lasers.     

Modeling the cw lasing regime for diode-pumped solid state lasers

In terms of a system of balance equations, we propose a model for describing the operation of lasers based on solid-state quasi-three-level active media in the cw lasing regime with longitudinal pumping by emission from diode lasers, taking into account the spatial distribution of the pump and lasing light beams. We model the operation of lasers based on the active crystals Yb³⁺:NaLa(MoO₄)₂ and Yb³⁺:YVO₄, taking into account the proposed spatial distribution function of the intensity and the emission spectrum of the pump. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 55–60, January–February, 2007.     

Efficient laser operation of diode-pumped Pr3+,Mg2+:SrAl12O19

We report on diode-pumped laser operation of Pr³⁺,Mg²⁺:SrAl₁₂O₁₉ at lasing wavelengths of λ _L = 724.4 nm, λ _L = 643.5 nm, and λ _L = 622.8 nm. Furthermore, the laser threshold could be reached in the green spectral range. By pumping the crystal longitudinally from each side with two polarization beam combined InGaN laser diodes, a total pump power of ≈4 W was available. In the deep red spectral range, a maximum output power of 564 mW was achieved with a maximum slope efficiency of 50 % with respect to the absorbed pump power. The maximum possible internal losses were estimated to ≈1 %. Beam quality factors M ² were in the range of 1.2–1.5.     

Simultaneous generation of violet,blue, and green lasers using Nd:YAl3(BO3)4 channel waveguides under pumping at 815 nm

Violet, blue, and green lasers were simultaneously generated by nonlinear processes using ultrafast laser inscribed neodymium‐doped yttrium aluminum borate (Nd:YAl₃(BO₃)₄ or Nd:YAB) channel waveguides under pumping at 815 nm. These visible lasers were generated by the frequency doubling, self‐frequency summing, and self‐frequency doubling processes based on a 1062 nm laser radiation that corresponded to the ⁴F_3/2 → ⁴I_11/2 transition of Nd³⁺ ions. Further, the wavelength tunability for the violet and blue lasers was achieved by simply tuning the pump wavelength within the ⁴I_9/2 → ⁴F_5/2 transition. The results obtained indicate that Nd:YAB waveguides are promising candidates for efficient compact visible laser sources. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

A Novel Quinazolinone Derivative as Fluorescence Quenching Off-On Sensor for High Selectivity of Fe3+

A novel quinazolinone compound containing quinazoline-fused moiety has been synthesized as fluorescence Off-On sensor QQ. The probe exhibited highly selective and sensitive recognition toward trivalent ferric ion (Fe³⁺) over other metal ions in HEPES buffer solution (10 mM, pH?=?7.0, DMF-H₂O, 9:1, v/v). The significant quenching in the fluorescence spectral could be served as a selective fluorescence Off-On sensor. The titration study indicated the formation of 1:1 complex between QQ and Fe³⁺.     

A global design of high power Nd-Yb co-doped fiber lasers

A global optimization method - niche hybrid genetic algorithm (NHGA) based on fitness sharing and elite replacement is applied to optimize Nd³⁺-Yb³⁺ co-doped fiber lasers (NYDFLs) for obtaining maximum signal output power. With a objective function and different pumping powers, five critical parameters (the fiber length, L; the proportion of pump power for pumping Nd³⁺, η; Nd³⁺ and Yb³⁺ concentrations, N_Nd and N_Yb and output mirror reflectivity, R_out) of the given NYDFLs are optimized by solving the rate and power propagation equations. Results show that dividing equally the input pump power among 808 nm (Nd³⁺) and 940 nm (Yb³⁺) is not an optimal choice and the pump power of Nd³⁺ ions should be kept around 10-13.78% of the total pump power. Three optimal schemes are obtained by NHGA and the highest slope efficiency of the laser is able to reach 80.1%.     

Efficient room-temperature operation of Cr3+-sensitized,flashlamp-pumped, 2µm lasers

Utilizing the results of Cr³⁺ → Tm³⁺ transfer efficiency studies, we have demonstrated that yttrium aluminium garnet (YAG) is the preferred host for room-temperature, flashlamp-pumped solid-state lasers operating in the 2.0 µm spectral range. We report data on two different sensitizer-activator combinations in YAG and yttrium scandium gallium garnet (YSGG) laser materials: one is doped with Cr:Tm:Ho and operates on the Ho³⁺⁵I₇ →⁵I₈ transition at 2.097 µm; the other is doped only with Cr:Tm, which lases on the Tm³⁺³F₄ →³H₆ transition at 2.014 µm. We have achieved a slope efficiency of 5.1% with the Cr:Tm:Ho:YAG laser, which is the highest slope efficiency yet reported for a room-temperature, flashlamp-pumped, 2 µm solid-state laser. We have measured thresholds as low as 38 J and output energies >1.5 J for that system. We also report the first room-temperature operation of an efficient flashlamp-pumped Cr:Tm:YAG laser at 2.014 µm. Thresholds as low as 43 J, output energies exceeding 2 J, and slope efficiencies as high as 4.5% have been achieved. This is an order of magnitude higher than the efficiency previously reported for a 2.01 µm Cr:Tm:YAG laser operated at cryogenic temperatures. These two efficient 2 µm laser systems (Cr:Tm:Ho:YAG and Cr:Tm:YAG) are discussed in terms of their potential for Q-switched operation.     

Eu3+-site occupation in CaTiO3 perovskite material at low temperature

In order to clarify the site occupancy of rare-earth ions in rare-earth doped perovskite materials, the un-doped pure CaTiO₃ and Eu³⁺-doped CaTiO₃ samples with a series of Ca/Ti ratio were synthesized via high-temperature solid-state reaction method. X-ray diffraction (XRD) powder patterns confirm that the crystal structure keeps invariant at various Ca/Ti ratios. Measurement results of unit-cell parameters and X-ray photoelectron spectroscopy (XPS) indicate that Eu³⁺ ions enter into the Ca²⁺ site. The high-resolution photoluminescence spectra of Eu³⁺ ions at 20 K in all samples did not witness a significant change under the excitation at different wavelength, implying that Eu³⁺ ions occupy only one type of site. Considering the small spectral splitting range of ⁵D₀ → ⁷F₂ transition and the large intensity ratio of ⁵D₀ → ⁷F₂/⁵D₀ → ⁷F₁, it can be concluded that Eu³⁺ occupies Ca²⁺ site with larger coordinate numbers rather than Ti⁴⁺ site.     

Optimization of the laser performance in Nd3+:YAG ceramic microchip lasers

Based on the four-level system, a theoretical model of diode-laser end-pumped fundamental continuous-wave Nd³⁺:YAG ceramic microchip lasers is proposed. The fluorescence concentration quenching effect and the absorption efficiency of the host have been taken into account in the model. The theoretical results of the numerical calculations are in good agreement with those of experiments. The effects of the concentration of the Nd³⁺:YAG ceramic, the thickness of the Nd³⁺:YAG ceramic, and the transmission of the output coupler on the laser performance (threshold and output power) are addressed. The optimization of the concentration and the thickness for the Nd³⁺:YAG ceramic microchip laser is presented. This modeling is not only applicable to the Nd³⁺:YAG ceramic microchip laser but also to other four-level microchip lasers. PACS 42.55.-f; 42.55.Xi; 42.70.Hj; 02.60.Cb