Tm and Tm-Tb-doped germanate glasses for S-band amplifiers

The mechanism involved in the Tm³⁺(³F₄)→Tb³⁺(⁷F_0,1,2) energy transfer as a function of the Tb concentration was investigated in Tm:Tb-doped germanate (GLKZ) glass. The experimental transfer rate was determined from the best fit of the ³F₄ luminescence decay due to the Tm→Tb energy transfer using the Burshtein model. The result showed that the 1700 nm emission from ³F₄ can be completely quenched by 0.8 mol% of Tb³⁺. As a consequence, the ⁷F₃ state of Tb³⁺ interacts with the ³H₄ upper excited state of Tm³⁺ slighting decreasing its population. The effective amplification coefficient β(cm⁻¹) that depends on the population density difference Δn=n(³H₄)-n(³F₄) involved in the optical transition of Tm³⁺ (S-band) was calculated by solving the rate equations of the system for continuous pumping with laser at 792 nm, using the Runge-Kutta numerical method including terms of fourth order. The population density inversion Δn as a function of Tb³⁺ concentration was calculated by computational simulation for three pumping intensities, 0.2, 2.2 and 4.4 kWcm⁻². These calculations were performed using the experimental Tm→Tb transfer rates and the optical constants of the Tm (0.1 mol%) system. It was demonstrated that 0.2 mol% of Tb³⁺ propitiates best population density inversion of Tm³⁺ maximizing the amplification coefficient of Tm-doped (0.1 mol%) GLKZ glass when operating as laser intensity amplification at 1.47 μm.     

Multiphoton ultraviolet and visible upconversion luminescence of TmYb co-doped oxyfluoride glass

The ultraviolet upconversion luminescence of Tm³⁺ ions sensitized by Yb³⁺ ions in oxyfluoride glass when excited by a 975 nm diode laser was studied in this paper. One typical ultraviolet upconversion luminescence lines positioned at 362.3 nm was found. It can be attributed to the five-photon upconversion luminescence transition of ¹D₂ → ³H₆. Several visible upconversion luminescence lines at 451.1 nm, (477.9 nm, 462.5 nm), 648.7 nm, (680.5 nm, 699.5 nm) and (777.5 nm, 800.7 nm) were found also, which results from the fluorescence transitions of five-photon ¹D₂ → ³F₄, three-photon ¹G₄ → ³H₆, three-photon ¹G₄ → ³F₄, two-photon ³F₃ → ³H₆ and two-photon ³H₄ → ³H₆ of Tm³⁺ ion, respectively. The theoretical analysis suggests that the upconversion mechanism of the 362.3 nm ¹D₂ → ³H₆ upconversion luminescence is the cross energy transfer of {³H₄(Tm³⁺) → ³F₄(Tm³⁺), ¹G₄(Tm³⁺) → ¹D₂(Tm³⁺)} and {¹G₄(Tm³⁺) → ³F₄(Tm³⁺), ³H₄(Tm³⁺) → ¹D₂(Tm³⁺)} between Tm³⁺ ions. In addition, the upconversion luminescence of ¹G₄ and ³H₄ state results from the sequential energy transfer {²F_5/2(Yb³⁺) → ²F_7/2(Yb³⁺), ³H₄(Tm³⁺) → ¹G₄(Tm³⁺)} and {²F_5/2(Yb³⁺) → ²F_7/2(Yb³⁺), ³F₄(Tm³⁺) → ³F₂(Tm³⁺)} from Yb³⁺ ions to Tm³⁺ions, respectively.     

Bulk and surface properties of spinel Co3O4 by density functional calculations

DFT calculations are employed to bulk and surface properties of spinel oxide Co₃O₄. The bulk magnetic structure is calculated to be antiferromagnetic, with a Co²⁺ moment of 2.631 μ_B in the antiferromagnetic state. There are three predicted electron transitions O(2p) → Co²⁺(t_2g) of 2.2 eV, O(2p) → Co³⁺(e_g) of 2.9 eV and Co³⁺(t_2g) → Co²⁺(t_2g) of 3.3 eV, and the former two transitions are close to the corresponding experimental values 2.8 and 2.4 eV. The naturally occurring Co₃O₄ (1 1 0) and (1 1 1) surfaces were considered for surface calculations. For ideal Co₃O₄ (1 1 0) surfaces, the surface relaxations are not significant, while for ideal Co₃O₄ (1 1 1) surfaces the relaxation of Co²⁺ cations in the tetrahedral sites is drastic, which agrees with the experiment observation. The stability over different oxygen environments for possible ideal and defect surface terminations were explored.     

Anomalous behavior of optogalvanic signal in a miniature neon discharge lamp

A strong optogalvanic effect has been observed in a negative glow of a miniature neon discharge lamp using tunable pulse dye laser pumped by a copper vapor laser. A comparative study on temporal evolution of optogalvanic signal in a positive and negative dynamic resistance region of the discharge is described. Dye laser beam was tuned to various neon transitions 1s_i → 2p_j (Paschen notations) within 570-617 nm wavelength range. Anomalous behavior of optogalvanic signal was observed at 588.2 nm for (1s₅ → 2p₂) neon transition at low discharge current (<220 μA). This anomalous behavior is the attributes of damped oscillations of optogalvanic signal that correlate with negative dynamic resistance (dV/di < 0) of the discharge. Penning ionization at low discharge current and small energy mismatch is assumed to be the main cause of the negative dynamic resistance. Penning ionization process has been explained by resonantly ionizing energy transfer via collisions between neon buffer gas atoms in the lowest metastable state (1s₅) and electrode sputtered atoms in ground state using their partial energy level diagram.     

Spectral performance and intensive green upconversion luminescence in Er/Yb-codoped NaY(WO4)2 crystal

Using Czochralski (CZ) pulling method, an Er³⁺/Yb³⁺-codoped NaY(WO₄)₂ crystal was prepared. Absorption spectra, emission spectra and excitation spectra of this crystal were measured at room temperature. Some optical parameters, such as intensity parameters, spontaneous emission probabilities and lifetimes, were calculated from absorption spectra with Judd-Ofelt (J-O) theory. Upconversion luminescence excited by a 970 nm diode laser was studied. In this crystal, green upconversion luminescence is particularly intensive. Energy transfer mechanisms that play an important role in upconversion processes were analyzed. Two cross-relaxation processes: ⁴G_11/2 + ⁴I_9/2 → ²H_11/2 (or ⁴S_3/2) + ²H_11/2 (or ⁴S_3/2), and ⁴G_11/2 + ⁴I_15/2 → ²H_11/2 (or ⁴S_3/2) + ²I_13/2, which contribute to the intensive green luminescence under 378 nm excitation, were put forward. Background energy transfer ⁴G_11/2(Er³⁺) + ²F_7/2(Yb³⁺) → ⁴F_9/2(Er³⁺) + ²F_5/2(Yb³⁺) was also demonstrated.     

An alternative interpretation of the optical spectra for Fe-doped KTaO3 crystals

In this paper, the excitation spectrum and luminescence at 14 569, 17 225, 18 829 and 14 659 cm^-1 for Fe³⁺ ion at the K⁺ site of KTaO₃ crystals are assigned, respectively, to the ⁶A₁(S)→⁴T₁(G), ⁴T₂(G), ⁴E₁(G)[⁴A₁(G)] and ⁴T₁(G)→⁶A₁(S) transitions rather than to the ⁶A₁(S)→⁴T₁(G), ²T₂(I), ⁴T₂(G) and ⁴T₁(G)→⁶A₁(S) transitions given in a previous paper [Bryknar et al., Radiat. Eff. Def. Solids 149(1999)51]. On the basis of this assignment, the reasonable optical spectrum parameters (in particular, the cubic field parameter Dq≈−640 cm⁻¹) are obtained. The validity of this assignment is discussed.     

Rotational and vibrational temperatures of electronically excited BiN radicals in a chemiluminescent flame

Rotational and vibrational temperatures of electronically excited BiN radicals in a low-pressure Bi_x+N/N₂*/N₂+Ar chemiluminescent flame have been deduced from high-resolution Fourier-transform emission spectra. Bands of three electronic transitions, a³Σ⁺(a₁1)→X¹Σ⁺(X0⁺), b⁵Σ⁺(b₁0⁺)→X¹Σ⁺(X0⁺), and b⁵Σ⁺(b₁0⁺)→a ³Σ⁺(a₁1), were analysed to determine the optical temperatures in the a³Σ⁺(a₁1) and b⁵Σ⁺(b₁0⁺) states. The rotational temperatures characterising the rotational populations in the a₁1, v=0 and 1 states were determined from the a₁→X, 0-2, 0-3, 0-4, 1-1, and 1-2 bands. The b₁→X, 0-8 and 0-11 bands, and the b₁→a₁, 0-0 bands served to determine the rotational temperature of the radicals in the b₁0⁺, v=0 state. The temperatures derived from the various bands and transitions were well consistent and the mean rotational temperature was determined to be 353±18 K, which is close to the translational temperature of the gas.Vibrational temperatures of the radicals in the a₁1 and b₁0⁺ states were derived from band intensities of the a₁→X and from the b₁→X as well as b₁→a₁ systems, respectively. The Franck-Condon factors needed were calculated with RKR potentials deduced from literature values of the rotational and vibrational constants in the three states involved. The a₁1 vibrational temperature (336±21 K) was close to the rotational temperature, while the b₁0⁺ vibrational temperature (438±36 K) differed, likely due to the previously observed perturbation of the b₁0⁺ state.     

Simultaneous dual-wavelength oscillation at 1357 nm and 1444 nm in a Kr-flashlamp pumped Nd:YAG laser

A Nd:YAG laser pumped by a Kr-flashlamp with simultaneous dual-wavelength operation at 1357 nm (⁴F_3/2 → ⁴I_13/2(R₁ → X₄)) and 1444 nm (⁴F_3/2 → ⁴I_13/2(R₁ → X₇)) is demonstrated and its characteristics was analyzed. The output energy of 82 mJ at 1357 nm and 138 mJ at 1444 nm were achieved simultaneously with the maximum electrical input energy of 44 J. Stability of the output energy in the dual-wavelength operation was 1.41% at the maximum input energy of 44 J. However, the stabilities at each wavelength in the dual-wavelength operation showed much lower stability.     

Configuration dependence of photon stimulated ion desorption from methyl ester compounds induced by core excitation

Photon stimulated ion desorption (PSID) from methyl ester terminated self-assembled monolayer (MHDA-SAM, HS(CH₂)₁₅COOCH₃) and methyl mercaptoacetate (MA, HSCH₂COOCH₃) on Ag has been investigated using soft X-ray in the C and O K-edge regions. In MHDA-SAM on Ag, site-selective ion desorption has been clearly observed at resonant core excitations of C_1s, O_1s(OCH₃) → σ^∗(OCH₃) and O_1s(OCH₃) → σ^∗(COCH₃). Ion intensity in MA on Ag is obviously reduced for (n = 1-3) at C_1s, O_1s(OCH₃) → σ^∗(OCH₃) excitations, and no site-selective reaction at O_1s(OCH₃) → σ^∗(COCH₃) excitations has been observed. These reactions may be influenced by configurational difference of reactive sites. It is suggested that surface effects on the selective reaction due to positioning methyl ester group near the surface plays an important role.     

Inhomogeneous broadening of the dynamically split Kramers spectral line and up-conversion in the pair and quartet centers in CaF2:Nd

The site-selective and time-resolved fluorescence laser spectroscopy and kinetic measurements with high spectral and nanosecond temporal resolution was applied to analyze the high-energy wing of the M and N absorption bands of the ⁴I_9/2(1)→⁴G_5/2(1) crystal-field (CF) transition in a CaF₂:Nd³⁺ (0.6 wt%) crystal at 4.2 K. It was found that at helium temperatures the dynamically split spectral line assigned as the ⁴I_9/2(1)→⁴G_5/2(1) (CF) transition of coherently coupled Nd³⁺ ions in the pair M- and quartet N-centers of CaF₂:Nd³⁺ (0.6 wt%) is inhomogeneously broadened. It consists of the pair M- and quartet N-centers with at least 0.1 A variation of the positions of the fluorescence-excitation spectral lines registered at the ⁴F_3/2(1)→⁴I_9/2(1) CF transition. Small fluorescence-lifetimes variation of the ⁴F_3/2 and ⁴D_3/2 levels from the small variation of the distances R between Nd³⁺ ions in the pair is found. At least 2.7% variation of the value of the Nd-Nd distance R in the pair M-center was determined from the lifetime variation of the ⁴F_3/2 manifold with the assumption of a dipole-dipole interaction between the ions in the pair.The energy transfer up-conversion process responsible for the UV fluorescence observed when pumping the ⁴I_9/2(1)→⁴G_5/2(1) transition has been determined.     

The bΣ(b0) → XΣ(X10,X21) and aΔ(a2) → X21 transitions of AsBr

Emission spectra of the b¹Σ⁺(b0⁺) → X³Σ⁻(X₁0⁺,X₂1) and a¹Δ(a2) → X₂1 transitions of AsBr have been measured in the near-infrared spectral region with a Fourier-transform spectrometer. The arsenic bromide radicals were generated in fast-flow systems by reaction of arsenic vapor (As_x) with bromine and were excited by microwave-discharged oxygen. The most prominent features in the spectrum are the Δv = +1,0,−1, and −2 band sequences of the b¹Σ⁺(b0⁺) → X³Σ⁻(X₁0⁺) transition in the range 11 700-12 700 cm⁻¹. With lower intensities, the Δv = 0 and −1 sequences of the b¹Σ⁺(b0⁺) → X³Σ⁻(X₂1) sub-system show up in the same range. Further to the red, between 6000 and 6700 cm⁻¹, the Δv = 0, +1, and −1 sequences of the hitherto unknown a¹Δ(a2) → X₂1 transition are observed. Analyses of medium- and high-resolution spectra have yielded improved molecular constants for the X₁0⁺, X₂1, and b0⁺ states and first values of the electronic energy and the vibrational constants of the a2 state.     

Influence of ligand coordination of cobalt ions on structural properties of ZnO-ZnF2-B2O3 glass system by means of spectroscopic studies

The glasses of the composition 10ZnO-30ZnF₂-60B₂O₃ doped with different concentrations of CoO were prepared. Differential scanning calorimetric (DSC) studies, optical absorption, photoluminescence and infrared spectra of these glasses have been carried out. DSC studies have indicated that the resistance of the glass against devitrification increases with the increase in the concentration of CoO. Optical absorption spectra have exhibited one octahedral band due to ⁴T_1g(F)→²T_1g(H) and two tetrahedral bands due to ⁴A₂(⁴F)→⁴T₁(⁴P) ⁴A₂(⁴F)→⁴T₁(⁴F) transitions of Co²⁺ ions at about 525, 570 and 1400 nm, respectively. As the concentration of CoO is increased the tetrahedral bands are observed to grow at the expense of octahedral band. The luminescence spectra have exhibited two emission bands in the spectral regions of 600-700 nm and 800-900 nm due to ⁴T₁(⁴P)→⁴A₂(⁴F) and ⁴T₁(⁴P)→⁴T₂(⁴F) tetrahedral transitions of Co²⁺ ions, respectively. With the increasing content of cobalt ions in the glass matrix, the half width and intensity of these bands are observed to increase. The analysis of the results of these two spectra coupled with IR spectra has indicated that as the concentration of CoO is increased in the glass matrix, the tetrahedral occupancy of cobalt ions dominates over the octahedral occupancy and increase the rigidity of the glass network.     

The study of the 1s4-2pj optogalvanic transients in a neon discharge plasma

Time dependent optogalvanic signals induced by the 1s₄ → 2p_j laser excitations have been studied in neon DC plasma. The decay rates related to all the four 1s_i levels have been derived by fitting the waveforms with a mathematical rate equation model. The temporal signatures of three transitions namely 638.3, 650.7 and 724.5 nm related to the 2p₇, 2p₈ and 2p₁₀ upper levels, respectively, have been found to be different from the rest of the transitions. We relate these effects to the population redistribution of decaying channels and to the processes responsible for the optogalvanic effect.     

Influence of Yb concentration on upconversion luminescence of Ho

Upconversion (UC) emissions at 360 ((⁵F, ³F, ⁵G)₂ → ⁵I₈), 392 (³K₇/⁵G₄ → ⁵I₈), 428 (⁵G₅ → ⁵I₈), 554 (⁵S₂/⁵F₄ → ⁵I₈), 667 (⁵F₅ → ⁵I₈) and 754 (⁵S₂/⁵F₄ → ⁵I₇) nm were obtained in 0.1 mol% Ho³⁺/x mol% Yb³⁺:Y₂O₃ (x = 2, 5, 8, 11, 15) bulk ceramics under infrared (IR) excitation at 976 nm. The intensity of the UC luminescence centered at 554 and 754 nm increased with Yb³⁺ concentration from 2 to 5 mol% and decreased from 5 to 15 mol%, while the UC luminescence centered at 392, 428 and 667 nm increased with Yb³⁺ concentration from 2 to 11 mol%, then started to reduce with Yb³⁺ concentration until 15 mol%. This comes from the competition between the energy back transfer (EBT) process [⁵S₂/⁵F₄(Ho) + ²F_7/2(Yb) → ⁵I₆(Ho) + ²F_5/2(Yb) as well as ⁵F₅(Ho) + ²F_7/2(Yb) → ⁵I₇(Ho) + ²F_5/2(Yb)] and spontaneous radiation process. The intensity of the UC luminescence centered at 360 nm always increases with Yb³⁺ concentration from 2 to 15 mol%. We believe that it may come from the cooperation of energy transfer process from Yb³⁺ ions in the ²F_5/2 state and the cross energy transfer process ⁵S₂/⁵F₄ + ⁵I₆ → (⁵F, ³F, ⁵G)₂ + ⁵I₈.     

Continuous-wave dual-wavelength operation at 1062 and 1338 nm in Nd:YAl3(BO3)4 and observation of yellow laser light generation at 592 nm by their self-sum-frequency-mixing

We report simultaneous oscillation in continuous wave at 1062 and 1337 nm in a Nd³⁺:YAl₃(BO₃)₄ nonlinear crystal associated to the infrared laser channels ⁴F_3/2 → ⁴I_11/2 and ⁴F_3/2 → ⁴I_13/2 of Nd³⁺. Generation of yellow laser light at 592 nm produced by Type I self-sum-frequency-mixing of both fundamental infrared laser waves is observed under non-optimal phase matching conditions.     

Optical investigation of charge-transfer transitions in spinel Co3O4

Optical transitions in normal-spinel Co₃O₄ have been identified by investigating the variation of its optical absorption spectrum with the replacement of Co by Zn. Three optical-transition structures were located at about 1.65, 2.4, and 2.8 eV from the measured dielectric function of Co₃O₄ by spectroscopic ellipsometry. The variation of the absorption structures with the Zn substitution (Zn_xCo_3−xO₄) can be explained in terms of charge-transfer transitions involving d states of Co ions. The 1.65 eV structure is assigned to a d-d charge-transfer transition between the t_2g states of octahedral Co³⁺ ion and t₂ states of tetrahedral Co²⁺ ion, t_2g(Co³⁺)→t₂(Co²⁺). The 2.4 and 2.8 eV structures are interpreted as due to charge-transfer transitions involving the p states of O²⁻ ion: p(O²⁻)→t₂(Co²⁺) for the 2.4 eV absorption and p(O²⁻)→e_g(Co³⁺) for the 2.8 eV absorption. The observed gradual reduction of the 1.65 and 2.4 eV absorption strength with the increase of the Zn composition for Zn_xCo_3−xO₄ can be explained in terms of the substitution of the tetrahedral Co²⁺ sites by Zn²⁺ ions. The crystal-field splitting Δ_Oh between the e_g and the t_2g states of the octahedral Co³⁺ ion is estimated to be 2 eV.     

Structure and luminescence studies of tris(nitrato-O,O′)bis(2,2′-bipyridyl-N,N′)dysprosium(III) complex

The title compound, [Dy(NO₃)₃(bipy)₂], is isostructural with the La, Pr, Nd, Eu and Lu analogues where bipy=2, 2′-bipyridyl. The Dy complex was crystallized in orthorhombic with space group Pbcn. The Dy(III) ion was coordinated with the two bipy ligands and three nitrate anions giving a ten coordination number. Measurements of the molar conductance in ethanol and water solutions indicate that the complex is non-electrolyte. A comparative study of the emission of [Dy(NO₃)₃(bipy)₂] complex with those of the adduct mixture of bipy and Dy at a 1:1 ratio, has been investigated. In the solid state, photoluminescence (PL) spectrum of the complex had sharp emission bands corresponding to the ⁴F_9/2→⁶H_15/2 (476.5 and 482 nm), ⁴F_9/2→⁶H_13/2(572.6 and 573.8 nm), ⁴F_9/2→⁶H_11/2 (661.6 nm) and ⁴H_3/2→⁶H_15/2 (961.0 nm) transitions. The hypersensitive peak of the complex has the yellow emission stronger than the blue emission in the solid state as well as in the solution. The complex has a good thermal stability due to the role of π-π interactions stacking.     

Investigation of the optical anisotropy of PET and PEN films by VIS-FUV to IR spectroscopic ellipsometry

In the last years, a significant amount of research is being performed in the field of polymer research for novel applications, such as flexible electronic devices, photovoltaic cells, high performance optics, data storage, etc. Toward this direction, in this work, the optical anisotropy of biaxially stretched poly(ethylene terephthalate) (PET) and poly(ethylene naphthalate) (PEN) films has been extensively investigated. The optical properties of the films have been studied in terms of their optical, electronic and vibrational response, by Fourier transform IR spectroscopic ellipsometry (FTIRSE) (900-3500 cm⁻¹) and Vis-fUV variable angle SE (1.5-6.5 eV) techniques. The films optical anisotropy is the result of the stretching procedure during their fabrication, which results to the structural rearrangement of the macromolecular chains parallel to the stretching direction and to a higher structural symmetry. During the SE spectra analysis, the films have been approximated as uniaxial materials with their optic axis parallel to the sample/ambient interface leading to the accurate determination of the principal components ?_||(ω) and ?_⊥(ω) of the dielectric function ?(ω). The detailed study of the electronic transitions has been performed in the Vis-fUV region, where the characteristic features corresponding to the n → π* electronic transitions of the carbonyl -CO group and the ¹A_1g → ¹B_1u transition due to the π → π* excitation of the π-electron structures have been identified and analysed. Furthermore, the FTIRSE spectra allowed the accurate identification and assignment of the features of ?(ω) to the vibrational modes of the various bonding structures characteristic of the PET and PEN macromolecular chains.     

Thermal decomposition of toluene: Overall rate and branching ratio

The two-channel thermal decomposition of toluene, C₆H₅CH₃ → C₆H₅CH₂ + H (1) and C₆H₅CH₃ → C₆H₅ + CH₃ (2), was investigated in shock tube experiments over the temperature range of 1400-1780 K at a pressure of 1.5 (±0.1) bar. Rate coefficients for reactions (1) and (2) were determined by monitoring benzyl radical (C₆H₅CH₂) absorption at 266 nm during the decomposition of toluene diluted in argon and modeling the temporal behavior of the benzyl concentration with a kinetic model. The first-order rate coefficients determined at a pressure of 1.5 bar are expressed by k₁(T) = 2.09 × 10¹⁵ exp (−87510 [cal/mol]/RT) [s⁻¹] and k₂(T) = 2.66 × 10¹⁶ exp (−97880 [cal/mol]/RT) [s⁻¹]. The resulting branching ratio, k₁/(k₁ + k₂), ranges from 0.8 at 1350 K to 0.6 at 1800 K.     

Silicon donor and Stokes terahertz lasers

Two types of lasers based on hydrogen-like impurity-related transitions in bulk silicon operate at frequencies between 1 and 7 THz (wavelength range of 50-230 μm). These lasers operate under mid-infrared optical pumping of n-doped silicon crystals at low temperatures (<30 K). Dipole-allowed optical transitions between particular excited states of group-V substitutional donors are utilized in the first type of terahertz silicon lasers. These lasers have a gain ∼1-3 cm⁻¹ above the laser thresholds (>1 kW cm⁻²) and provide 10 ps-1 μs pulses with a few mW output power on discrete lines. Raman-type Stokes stimulated emission in the range 4.6-5.8 THz has been observed from silicon crystals doped by antimony and phosphorus donors when optically excited by radiation from a tunable infrared free electron laser. The scattering occurs on the 1s(E)→1s(A₁) donor electronic transition accompanied by an emission of the intervalley transverse acoustic g-phonon. The Stokes lasing has a peak power of a few tenths of a mW and a pulse width of a few ns. The Raman optical gain is about 7.4 cm GW⁻¹ and the optical threshold intensity is ∼100 kW cm⁻².