ZnSe:Co—nonlinear optical absorber for giant-pulse eye-safe lasers

ZnSe:Co²⁺ crystals were grown by the Bridgeman technique. Optical absorption measurements showed non-uniform distribution of Co²⁺ ions along the as-grown crystals. Using Pfann formula the distribution coefficient of Co²⁺ ions between crystal and melt was estimated to be 0.5. Transmission dependence on laser power at λ=1535 nm was investigated for different Co²⁺ ions concentration. Maximal final transmission was found for ZnSe samples containing 1.6×10¹⁹ cm⁻³ of Co²⁺ ions. Obtained ZnSe:Co²⁺ samples were used as saturable absorbers to generate giant-pulse eye-safe laser radiation. KIGRE QE-7S rod placed in resonator cavity was used as active element.     

Nonlinear change in refractive index of Co2+:ZnSe at short-pulse single-beam 1.54-μm Z-scan probing

An experimental study and theoretical modeling of the nonlinear change in refractive index of a Co^{2 +}: ZnSe crystal at the short-pulse single-beam probing at the wavelength 1.54 μm is reported. In the experimental conditions of negligible contributions in the index non-linearity stemming from the Kerr-effect and inhomogeneous heating, the nonlinear change in refractive index in Co^{2 +}:ZnSe is shown to be caused by the resonant Co^{2 +} population-perturbation effect (i.e., by the Co^{2 +} ground-state absorption saturation). The Z-scan single-beam technique and novel theoretical approach addressing the resonant nonlinear refraction in a saturable doped medium are used, respectively, for an experimental and theoretical inspection of the phenomenon. For a set of Co^{2 +}:ZnSe samples with different concentrations of Co^{2 +} ions at the short-pulse (200 ns) mJ-range probing, we show that the maximal nonlinear change in refractive index is about of units of 10^{− 4} at the chosen wavelength.     

Magnetic and luminescent properties of manganese-doped ZnSe crystals

Magnetic and photoluminescent properties of manganese-doped ZnSe crystals with different impurity concentrations were investigated. The concentration of Mn²⁺ ions in ZnSe crystals has been varied from 0.01 to 0.3 at%. Magnetic and photoluminescent studies have confirmed the introduction of Mn in ZnSe crystals. It was established that Mn²⁺ ions are responsible for the emission bands with maximum at 616 nm and 633 nm, which correspond to ⁴T₂→⁶A₁ and ⁴T₁→⁶A₁ intracentre transitions of Mn²⁺ ions respectively. It was found that the concentration quenching of the photoluminescent bands is associated with Mn²⁺ ions, which are due to the formation of Mn–Mn clusters. Magnetic properties studies have shown that at high doping levels the manganese atoms form Mn–Mn clusters in ZnSe. From the temperature dependence of magnetic susceptibility of ZnSe:Mn crystals that follows the Curie–Weiss law, it was possible to estimate the Curie–Weiss temperature Θ(x) and the effective Mn–Mn antiferromagnetic exchange constant (J₁).     

Spectral kinetic properties and lasing characteristics of diode-pumped Cr<Superscript>2+</Superscript>:ZnSe single crystals

The temperature and concentration quenching of the luminescence of Cr²⁺ ions in Cr:ZnSe crystals is experimentally investigated and the radiative lifetime of the upper lasing level is determined. The values of the cross sections of absorption from the ground state of Cr²⁺ ions in Cr:ZnSe crystals are refined. It is shown that the absorption from the excited state of Cr²⁺ ions is negligible near 1.5 μm. Lasing in Cr:ZnSe single crystals is implemented with an efficiency of 31% and an output power of 186 mW using laser diode pumping at a wavelength of 1.77 μm.     

Saturable absorbers for passive Q-switching of erbium lasers emitting in the region of 3 μm

The phototropic properties of Fe:ZnSe, Co:ZnSe, and Co:ZnS single crystals have been investigated. It is shown that these crystals can be used to advantage as the saturable absorbers in solid-state erbium lasers emitting in the region of the 3-μm range. The absorption cross sections of the ground states of the Co²⁺ ion in the ZnSe (σ_GSA = 11·10⁻²⁰ cm²) and ZnS (σ_GSA = 5.6·10⁻²⁰ cm²) crystals and of the Fe²⁺ ion in the ZnSe (σ_GSA = 50·10⁻²⁰ cm²) crystal at λ = 2.79 μm were determined experimentally. It has been established that the above-indicated crystals in the excited state absorb light weakly. The use of these crystals as passive Q switches made it possible to realize, for the first time, the regime of Q-switching of a Cr,Er:YSGG laser emitting at a wavelength of 2.79 μm. Single pulses with an energy of 60 mJ and a duration of 170 nsec were obtained in the regime of passive Q-switching. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 6, pp. 747–751, November–December, 2005.     

Transition metal ions in crystals: A refined treatment and deduction of coulomb and exchange interaction constants

Making use of Racah's irreducible tensor operator technique a refined treatment for the 3d-transition metal ions in crystals has been presented. The refined theory has been applied to analyse the recently observed fine optical spectra of MgF₂:Co²⁺ and MgF₂:Mn²⁺. Important differences have been noticed in the assignments of the optical lines obtained from the present analysis and from the conventional three-parameter theory. First numerical values of the exchange and Coulomb integrals in these systems have also been given.     

Absorption Spectra of Single Crystals of EuGa2S4 and EuGa2S4:Co

The optical properties of EuGa₂S₄ and EuGa₂S₄:Co single crystals in a range of temperatures from 77 to 300 K are investigated. The single crystals are obtained by the Bridgman method and are characterized by tetragonal syngony. The behavior of the optical transitions in the photon energy range 1.70–2.45 eV and the temperature range 77–300 K is determined. It is established that in the energy range 1.77–1.90 eV absorption is associated with transitions of the Co²⁺ ion, while in the range 2.20–2.40 eV, with indirect allowed optical transitions.     

Magnetic and magnetotransport properties of Co-doped manganites with perovskite structure

A systematic study of the doping of the Mn-sites by cobalt in three series of manganites — La_0.76Ba_0.24(Mn_1−xCo_x)O₃ single crystals, La_2/3Ba_1/3(Mn_1−xCo_x)O₃ and La(Mn_1−xCo_x)O₃ ceramics has been performed. It was found that La(Mn_1−xCo_x)O₃ annealed at 800°C in the range 0.4x0.9 is a mixture of ferromagnetic domains with ordered Mn and Co ions and ionically disordered spin-glass domains. In the quenched samples the fraction of spin-glass-type component increases strongly. The La_2/3Ba_1/3(Mn_1−xCo_x)O₃ solid solutions exhibit also an evidence for phase separation in the range 0.5x0.8. All the La(Mn_1−xCo_x)O₃ samples show an insulating behavior, however, magnetoresistance reduces strongly when the cobalt content rises to x=0.5. The La_0.76Ba_0.24(Mn_1−xCo_x)O₃ single crystals show first-order phase transition below their Curie points associated with a change of ground state of the Co²⁺ ions. The magnetic phase diagrams are depicted. The results are discussed in terms of positive Mn³⁺–O–Mn⁴⁺, Mn³⁺–O–Mn³⁺, Mn⁴⁺–O–Co²⁺ and negative Mn⁴⁺–O–Mn⁴⁺, Co²⁺–O–Co²⁺, Co²⁺–O–Mn³⁺ superexchange interactions as well as Co²⁺ and Mn⁴⁺ ionic ordering.     

Charge Exchange of the Centers in Electron–Irradiated Zinc Selenide

The optical absorption induced by the photosensitive centers formed upon electron irradiation (E = 5 MeV, = 1.7·10¹⁸ cm^–2) of polycrystalline ZnSe has been studied. A comparison of the optical properties of the irradiated crystals with the known data for ZnS has allowed the assumption that the 496–, 563–, and 652–nm bands in ZnSe are associated with the anion vacancies being in different charge states. The ratio between the concentrations of the optical absorption centers in the crystals photoexcited at 80 K is determined by the electron traps participating in the processes of charge exchange of the vacancies.     

Design and Synthesis of Highly Photostable Yellow–Green Emitting 1,8-Naphthalimides as Fluorescent Sensors for Metal Cations and Protons

Two highly photostable yellow–green emitting 1,8-naphthalimides 5 and 6, containing both N-linked hindered amine moiety and a secondary or tertiary cation receptor, were synthesized for the first time. Novel compounds were configured as “fluorophore–spacer–receptor” systems based on photoinduced electron transfer. Photophysical characteristics of the dyes were investigated in DMF and water/DMF (4:1, v/v) solution. The ability of the new compounds to detect cations was evaluated by the changes in their fluorescence intensity in the presence of metal ions (Cu²⁺, Pb²⁺, Zn²⁺, Ni²⁺, Co²⁺) and protons. The presence of metal ions and protons was found to disallow a photoinduced electron transfer leading to an enhancement in the dye fluorescence intensity. Compound 5, containing secondary amine receptor, displayed a good sensor activity towards metal ions and protons. However the sensor activity of dye 6, containing a tertiary amine receptor and a shorter hydrocarbon spacer, was substantially higher. The results obtained indicate the potential of the novel compounds as highly photostable and efficient “off–on” pH switchers and fluorescent detectors for metal ions with pronounced selectivity towards Cu²⁺ ions.     

Design,synthesis and sensor activity of a highly photostable blue emitting 1,8-naphthalimide

This work reports on the design, synthesis and photophysical properties of a highly photostable blue emitting 1,8-naphthalimide, containing hindered amine radical scavenger moiety and a tertiary amine cation receptor. The novel compound was configured as “fluorophore-spacer-receptor” system based on photoinduced electron transfer. Photophysical characteristics of the examined compound were investigated in DMF and water/DMF (4:1, v/v) solution. The ability of the new compound to detect cations was evaluated by the changes in its fluorescence intensity in the presence of metal ions (Cu²⁺, Pb²⁺, Cd²⁺, Ni²⁺, Co²⁺, Fe³⁺ and Zn²⁺) and protons. The presence of metal ions and protons was found to disallow a photoinduced electron transfer resulting in enhancement of the 1,8-naphthalimide fluorescence intensity. Among the tested metal ions only Cu²⁺ was efficiently detected. Also, it is clearly shown that the 2,2,6,6-tetramethylpiperidine fragment, incorporated in the structure of the novel 1,8-naphthalimide, considerably improves the sensor's photostability, sensitivity and selectivity.     

Nonlinear transmittance of ZnSe:Fe<Superscript>2+</Superscript> crystal at a wavelength of 2.92 μm

ZnSe crystals doped with Fe²⁺ ions are produced with the diffusion method under the conditions for thermodynamic equilibrium of solid ZnSe, solid Fe, and vapors (S_ZnSe-S_Fe-V). The transmittance of the samples is varied from 7 to 50% (in the absence of the antireflection coating) for a wavelength of about 3 μm. It is demonstrated that the transmittance of the ZnSe:Fe²⁺ crystals increases with an increase in the energy density of the high-power laser radiation with a wavelength of 2.92 μm. An equation that describes the propagation of the resonant radiation in a medium with saturable absorption at an arbitrary ratio of the radiation pulse duration to the relaxation time of the medium is introduced for the analysis of the experimental dependence of the transmittance on the energy density.     

EPR diagnostics of laser materials based on ZnSe crystals doped with transition elements

The electron paramagnetic resonance (EPR) spectra observed in laser materials based on zinc selenide (ZnSe) crystals doped with transition elements have been analyzed and identified. It has been shown that, in addition to working impurities (Cr²⁺, Co²⁺, or Fe²⁺), the diffusion layer exhibits EPR spectra of accompanying impurities due to the diffusion of transition elements (chromium, cobalt, or iron) used in the preparation of active materials for quantum electronics (lasers, switches) operating in the mid-infrared range. EPR diagnostics of these impurities can be used in the development of appropriate regimes for minimizing concentrations of accompanying impurities that adversely affect the performance characteristics of laser materials. It has been found that, during the diffusion of transition metals, ions of the accompanying impurity Mn²⁺, which is characterized by extremely informative EPR spectra, are embedded in the crystal lattice. It has been proposed to use these ions as ideal markers to control, on the electronic level, the crystal structure of the active diffusion layer.     

EPR spectroscopy of weak exchange interactions between Co2+ ions in ZnO

Electron paramagnetic resonance (EPR) is used to identify the next nearest neighbour Co²⁺ pairs coupled by spin–spin interaction in Co‐doped ZnO single crystals grown by the hydrothermal technique. These dimer centers are described by a spin Hamiltonian with exchange coupling terms written as interaction between identical effective spins S^eff = 1/2 of the lowest ground state Kramers doublets of the two Co²⁺ ions. The exchange parameters of weakly ferromagnetically coupled next nearest neighbor Co²⁺ pairs are estimated. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Raman spectroscopy of very small Cd1−xCoxS quantum dots grown by a novel protocol: direct observation of acoustic‐optical phonon coupling

Glass‐embedded Cd_1−xCo_xS quantum dots (QDs) with mean radius of R ≈ 1.70 nm were successfully synthesized by a novel protocol on the basis of the melting‐nucleation synthesis route and herein investigated by several experimental techniques. Incorporation of Co²⁺ ions into the QD lattice was evidenced by X‐ray diffraction and magnetic force microscopy results. Optical absorption features with irregular spacing in the ligand field region confirmed that the majority of the incorporated Co²⁺ ions are under influence of a low‐symmetry crystal field located near to the Cd_1−xCo_xS QD surface. Electron paramagnetic resonance data confirmed the presence of Co²⁺ ions in a highly inhomogeneous crystal field environment identified at the interface between the hosting glass matrix (amorphous) and the crystalline QD. The acoustic‐optical phonon coupling in the Cd_1−xCo_xS QDs (x ≠ 0.000) was directly observed by Raman measurements, which have shown a high‐frequency shoulder of the longitudinal optical phonon peak. This effect is tuned by the size‐dependent sp‐d exchange interaction due to the magnetic doping, causing variations in the coupling between electrons and longitudinal optical phonon. Copyright © 2013 John Wiley & Sons, Ltd.     

Green-emissive transparent BaSi2O5:Eu film phosphor on quartz glass created by a sputtering thermal diffusion process

Eu²⁺-doped BaSi₂O₅ film phosphors on quartz substrates are fabricated by radio-frequency magnetron sputtering thermal diffusion. The BaSi₂O₅: Eu²⁺ phosphor crystals have some preferred orientations that are lattice-spacing matched with the crystallized β- SiO₂ crystals, and they show pore and grain boundary-free morphology with a rod-like shape fused into the crystallized β- SiO₂ crystals. The BaSi₂O₅: Eu²⁺ film phosphor has a high transparency, with a transmittance of about 30% in visible light. The BaSi₂O₅: Eu²⁺ film phosphor shows 510 nm green emission from the f–d transition of the Eu²⁺ ions, and in particular the best sample shows a green photoluminescence brightness of about 5% of a BaSi₂O₅: Eu²⁺ powder phosphor screen. These excellences in optical properties can be explained by less optical scattering at pores or grain boundaries, and less reflection at the continuously index-changed interface.     

Effect of hydroxyl and oxygen ions on optical stability of F-centers in KBr crystals

The effect of the anionic impurities OH^–, O ₂ ^§- , and O^2– on the optical stability of F-centers in KBr crystals was investigated. It is shown that the stability of F-centers is independent of the presence of hydroxyl ions (OH^–) and molecular oxygen ions (O ₂ ^– ) in the crystal lattice. It is suggested that the low stability of F-centers in KBr-KOH crystals is due to doubly charged oxygen ions.Translated from Izvestiya Vysshikh Uchebnykh Zavendenii, Fizika, No. 10, pp. 107–112, October, 1972.     

Evidence for exciton binding at Ni impurity sites in ZnSe

A broad charge transfer band is observed in the photoluminescence excitation (PLE) spectrum of the 2.5 μ Ni²⁺ luminescence in ZnSe : Ni. This band lies above the highest energy d-d excitation bands and exhibits a ZPL at 1.8163 eV and LO(#38;0lambda;) phonon replicas at higher energy. In contrast, PLE spectra of Co²⁺ luminescence in ZnSe:Co contain only d-d excitation bands. The charge transfer band in ZnSe:Ni is interpreted as evidence for bound exciton formation at the Ni site. The recombination energy of this exciton is transferred efficiently to the excited d-band states of the Ni ion, leading to characteristic Ni²⁺d-d luminescence.     

Absorption background and laser properties of YAP:Nd

YAP:Nd laser crystals suffer to a greater extent than YAG:Nd from colour centres formation. Stable brownish-yellow or green colourations are evoked by non-oxidizing treatment at high (>1500 °C) temperature. The former colouration may be attributed to holes in the oxygen neighbourhood of Y³⁺ at Al sites, the latter to the F⁺ centres. Brownish-red colouration of less stability is induced by optical pumping of Nd³⁺ containing crystals. It may be attributed to holes in oxygen neighbourhood of Nd³⁺.Dependences of the colourations on the preparation methods are described. YAP:Nd,Zr laser rods, oxygen annealing of which was followed by medium (1100–1400 °C) temperature treatment in vacuum or hydrogen showed no anomalous colouration and extremely low losses at Nd³⁺ emission wavelength independent of pumping power. Using such rods, an overall efficiency of 2·5% and a slope efficiency of 3·0% in CW lasers were reached.     

Electronic structure and ferromagnetism of polycrystalline Zn1−xCoxO (0≤x≤0.15)

The electronic structure of polycrystalline ferromagnetic Zn_1−xCo_xO (0.05≤x≤0.15) and the oxidation state of Co in it, have been investigated. The Co-doped polycrystalline samples are synthesized by a combustion method and are ferromagnetic at room temperature. XPS and optical absorption studies show evidence for Co²⁺ ions in the tetrahedral symmetry, indicating substitution of Co²⁺ in the ZnO lattice. However, powder XRD and electron diffraction data show the presence of Co metal in the samples. This give evidence to the fact that some Co²⁺ ion are incorporated in the ZnO lattice which gives changes in the electronic structure whereas ferromagnetism comes from the Co metal impurities present in the samples.