Before the 1960s, all anti-Stokes emissions, which were known to exist, involved emission energies in excess of excitation energies by only a few kT. They were linked to thermal population of energy states above excitation states by such an energy amount. It was the well-known case of anti-Stokes emission for the so-called thermal bands or in the Raman effect for the well-known anti-Stokes sidebands. Thermoluminescence, where traps are emptied by excitation energies of the order of kT, also constituted a field of anti-Stokes emission of its own. Superexcitation, i.e., raising an already excited electron to an even higher level by excited-state absorption (ESA), was also known but with very weak emissions. These types of well-known anti-Stokes processes have been reviewed in classical textbooks on luminescence.1 All fluorescence light emitters usually follow the well-known principle of the Stokes law which simply states that excitation photons are at a higher energy than emitted ones or, in other words, that output photon energy is weaker than input photon energy. This, in a sense, is an indirect statement that efficiency cannot be larger than 1. This principle is

Upconversion and Anti-Stokes Processes with f and d Ions in Solids

The free‐ion energy‐level schemes of the Pr3+, Nd3+, Pm3+, Sm3+, Dy3+, Ho3+, Er3+, and Tm3+ aquo ions have been determined from their absorption spectra in dilute acid solution at 25°. Energy‐level assignments were made by comparison with crystal spectra, and on the basis of correlations between calculated and observed band intensities. For most of the ions, it was possible to identify several transitions giving rise to bands at energies as high as 45 000–50 000 cm−1. Sufficient numbers of assignments were made to justify inclusion of the effects of configuration interaction in the calculation of the energy‐level parameters. Variation of the electrostatic, spin–orbit coupling, and configuration‐interaction parameters across the lanthanide series is examined.

Electronic Energy Levels in the Trivalent Lanthanide Aquo Ions. I. Pr3+, Nd3+, Pm3+, Sm3+, Dy3+, Ho3+, Er3+, and Tm3+

Uniform, spherical-shaped TiO2:Eu nanoparticles with different doping concentrations have been synthesized through controlled hydrolysis of titanium tetrabutoxide under appropriate pH and temperature in the presence of EuCl3·6H2O. Through air annealing at 500°C for 2 h, the amorphous, as-grown nanoparticles could be converted to a pure anatase phase. The morphology, structural, and optical properties of the annealed nanostructures were studied using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy [EDS], and UV-Visible diffuse reflectance spectroscopy techniques. Optoelectronic behaviors of the nanostructures were studied using micro-Raman and photoluminescence [PL] spectroscopies at room temperature. EDS results confirmed a systematic increase of Eu content in the as-prepared samples with the increase of nominal europium content in the reaction solution. With the increasing dopant concentration, crystallinity and crystallite size of the titania particles decreased gradually. Incorporation of europium in the titania particles induced a structural deformation and a blueshift of their absorption edge. While the room-temperature PL emission of the as-grown samples is dominated by the 5D0 - 7Fj transition of Eu+3 ions, the emission intensity reduced drastically after thermal annealing due to outwards segregation of dopant ions.

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Effects of crystallization and dopant concentration on the emission behavior of TiO2:Eu nanophosphors

Intracavity semiconductor saturable absorber mirrors (SESAM's) offer unique and exciting possibilities for passively pulsed solid-state laser systems, extending from Q-switched pulses in the nanosecond and picosecond regime to mode-locked pulses from 10's of picoseconds to sub-10 fs. This paper reviews the design requirements of SESAM's for stable pulse generation in both the mode-locked and Q-switched regime. The combination of device structure and material parameters for SESAM's provide sufficient design freedom to choose key parameters such as recovery time, saturation intensity, and saturation fluence, in a compact structure with low insertion loss. We have been able to demonstrate, for example, passive modelocking (with no Q-switching) using an intracavity saturable absorber in solid-state lasers with long upper state lifetimes (e.g., 1-/spl mu/m neodymium transitions), Kerr lens modelocking assisted with pulsewidths as short as 6.5 fs from a Ti:sapphire laser-the shortest pulses ever produced directly out of a laser without any external pulse compression, and passive Q-switching with pulses as short as 56 ps-the shortest pulses ever produced directly from a Q-switched solid-state laser. Diode-pumping of such lasers is leading to practical, real-world ultrafast sources, and we will review results on diode-pumped Cr:LiSAF, Nd:glass, Yb:YAG, Nd:YAG, Nd:YLF, Nd:LSB, and Nd:YVO/sub 4/.

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Semiconductor saturable absorber mirrors (SESAM's) for femtosecond to nanosecond pulse generation in solid-state lasers

CRYSTALLINE MATERIALS Introduction Physical Properties Optical Properties Mechanical Properties Thermal Properties Magnetooptic Properties Electrooptic Properties Elastooptic Properties Nonlinear Optical Properties GLASSES Introduction Commercial Optical Glasses Specialty Optical Glasses Fused Silica Fluoride Glasses Chalcogenide Glasses Magnetooptic Properties Electrooptic Properties Elastooptic Properties Nonlinear Optical Properties Special Glasses POLYMERIC MATERIALS Optical Plastics Index of Refraction Nonlinear Optical Properties Thermal Properties Engineering Data METALS Physical Properties of Selected Metals Optical Properties Mechanical Properties Thermal Properties Mirror Substrate Materials LIQUIDS Introduction Water Physical Properties of Selected Liquids Index of Refraction Nonlinear Optical Properties Magnetooptic Properties Commercial Optical Liquids GASES Introduction Physical Properties of Selected Gases Index of Refraction Nonlinear Optical Properties Magnetooptic Properties Atomic Resonance Filters APPENDICES Safe Handling of Optical Materials Abbreviations, Acronyms, and Mineralogical or Common Names for Optical Materials Abbreviations for Methods of Preparing Optical Materials and Thin Films Fundamental Physical Constants Units and Conversion Factors

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Handbook of Optical Materials

The absorption and emission cross sections of the transition between the ground spin-orbit multiplet and the lowest excited multiplet were measured for Er/sup 3+/, Tm/sup 3+/, and Ho/sup 3+/ ions in a variety of crystalline hosts. The materials that were investigated include LiYF/sub 4/, BaY/sub 2/F/sub 8/, Y/sub 3/Al/sub 5/O/sub 12/, LaF/sub 3/, KCaF/sub 3/, YAlO/sub 3/, and La/sub 2/Be/sub 2/O/sub 5/. The absolute magnitudes of the emission cross sections were determined from the absorption spectra, with the aid of the principle of reciprocity. The calculated radiative emission lifetimes derived from these measured cross sections agree well with the measured emission decay times for most materials. The potential use of these rare-earth-doped materials in pulsed laser applications requires that the ground state exhibit adequate splitting to minimize the detrimental effects of the ground state thermal population, and also that the emission cross section be sufficiently large to permit efficient extraction energy. The systems based on Ho/sup 3+/ in the eightfold coordinated sites of LiYF/sub 4/, BaY/sub 2/F/sub 8/, and Y/sub 3/Al/sub 5/O/sub 12/ appear to be the most promising. >

Infrared cross-section measurements for crystals doped with Er/sup 3+/, Tm/sup 3+/, and Ho/sup 3+/

The emission and absorption properties of numerous host crystals doped with Yb/sup 3+/ ions have been studied. The hosts which have been selected include LiYF/sub 4/, LaF/sub 3/, SrF/sub 2/, BaF/sub 2/, KCaF/sub 3/, KY/sub 3/F/sub 10/, Rb/sub 2/NaYF/sub 6/, BaY/sub 2/F/sub 8/, Y/sub 2/SiO/sub 5/, Y/sub 3/Al/sub 5/O/sub 12/, YAlO/sub 3/, LuPO/sub 4/, Ca/sub 5/(PO/sub 4/)/sub 3/F, LiYO/sub 2/, and ScBO/sub 3/. Spectral determinations have been made of the resonant absorption and emission cross sections between 850 and 1100 nm, and the emission decay times of the upper laser level have been measured. The emission cross sections have been evaluated using the absorption cross section and principle of reciprocity, and again using the Fuchtbauer-Ladenberg formula. Agreement between the two methods is within 20% for most materials. The results are discussed in the framework of requirements for an effective diode-pumped Yb/sup 3+/ laser system. Ca/sub 5/(PO/sub 4/)/sub 3/F:Yb is predicted to exhibit the most useful laser properties and is expected to be far superior to Y/sub 3/Al/sub 5/O/sub 12/:Yb in many key microscopic parameter values. >

Evaluation of absorption and emission properties of Yb/sup 3+/ doped crystals for laser applications

The absorption and emission properties of transition metal (TM)-doped zinc chalcogenides have been investigated to understand their potential application as room-temperature, mid-infrared tunable laser media. Crystals of ZnS, ZnSe, and ZnTe, individually doped with Cr/sup 2+/, Co/sup 2+/, Ni/sup 2+/, or Fe/sup 2+/ have been evaluated. The absorption and emission properties are presented and discussed in terms of the energy levels from which they arise. The absorption spectra of the crystals studied exhibit strong bands between 1.4 and 2.0 /spl mu/m which overlap with the output of strained-layer InGaAs diodes. The room-temperature emission spectra reveal wide-band emissions from 2-3 /spl mu/m for Cr and from 2.8-4.0 /spl mu/m for Co, Cr luminesces strongly at room temperature; Co exhibits significant losses from nonradiative decay at temperatures above 200 K, and Ni and Fe only luminesce at low temperatures, Cr/sup 2+/ is estimated to have the highest quantum yield at room temperature among the media investigated with values of /spl sim/75-100%. Laser demonstrations of Cr:ZnS and Cr:ZnSe have been performed in a laser-pumped laser cavity with a Co:MgF/sub 2/ pump laser. The output of both lasers were determined to peak at wavelengths near 2.35 /spl mu/m, and both lasers demonstrated a maximum slope efficiency of approximately 20%. Based on these initial results, the Cr/sup 2+/ ion is predicted to be a highly favorable laser ion for the mid-IR when doped into the zinc chalcogenides; Co/sup 2+/ may also serve usefully, but laser demonstrations yet remain to be performed.

Transition metal-doped zinc chalcogenides: Spectroscopy and laser demonstration of a new class of gain media

Transition metal-doped zinc chalcogenides: spectroscopy and laser demonstration of a new class of gain media

A method for calculating induced-emission cross sections in neodymium laser glasses, based on simple absorbance measurements, has been demonstrated. Absorption and emission transition probabilities of four silicate-base neodymium laser glasses have been characterized in terms of the Judd-Ofelt (JO) model of crystal-field-induced electric-dipole transitions. Absolute absorption intensities in 3669A, ED-2, LSG-91H, and S33 glasses were measured and used to determine three phenomenological intensity parameters for each glass which accounted for the measured intensities to within 5 percent (rms). Emission intensities between the metastable4 F_{3/2} and terminal4 I J levels were then calculated for each glass, together with the4 F_{3/2} radiative lifetime, fluorescence branching ratios, and radiative quantum efficiency. Calculated values of these quantities for 3669A and S33 glasses are compared with measured values appearing in the literature. Using experimental line shapes for the4 F_{3/2} \rightarrow 4 I_{11/2} transitions at 1.06μ, induced-emission cross sections for these glasses were calculated.

William F. Krupke

Papers

Infrared cross-section measurements for crystals doped with Er/sup 3+/, Tm/sup 3+/, and Ho/sup 3+/

Evaluation of absorption and emission properties of Yb/sup 3+/ doped crystals for laser applications

Transition metal-doped zinc chalcogenides: Spectroscopy and laser demonstration of a new class of gain media

Transition metal-doped zinc chalcogenides: spectroscopy and laser demonstration of a new class of gain media

Induced-emission cross sections in neodymium laser glasses