Influence of MgO codoping on the optical properties of Er3+-doped near-stoichiometric LiNbO3

Four near-stoichiometric lithium niobate (NSLN) crystals codoped with Er³⁺ (1 mol%) and MgO (0, 0.5, 1.0, and 2.0 mol%) were grown from K₂O-based flux in air using top seeded solution growth technique. The [Li]/[Nb] ratio, estimated from the blueshift of ultraviolet absorption edge, is 97.2% in NSLN:Er. MgO; codoping can increase the segregation coefficient of Er³⁺ in NSLN:Er:MgO crystal. The photorefractive damage threshold is enhanced by three orders of magnitude for NSLN:Er codoped with 1 mol% MgO, it coincides with the peak shift of OH⁻ absorption spectrum from 3481 to 3535 cm⁻¹. Judd–Ofelt theory based on absorption spectra is used to analyze the influence of MgO concentration on the Judd–Ofelt intensity parameter, transition strength, fluorescence branching ratio, and stimulated emission cross section. From the time-resolved emission spectra and the comparison among emission spectra, two Er³⁺ crystal-field sites are ascertained in NSLN:Er codoped with 2 mol% MgO, this coincides with the bimodal structure in X-ray photoelectron spectrometry spectra. The upconversion processes under pulse excitation is proposed based on the pump energy dependence and decay kinetics. The distribution of Er³⁺-clustered sites in NSLN:Er:MgO series is discussed based on the nonexponential decay curves monitored at 550 nm under two-photon excitation.     

Generation of nanosecond terahertz pulses by the optical rectification method

The possibility of the generation of quasi-cw terahertz radiation by the optical rectification method for broad-band Fourier unlimited nanosecond laser pulses has been experimentally demonstrated. The broadband radiation of a LiF dye-center laser is used as a pump source of a nonlinear optical oscillator. The energy efficiency of terahertz optical frequency conversion in a periodically polarized lithium niobate crystal is 4 × 10⁻⁹ at a pump power density of 7 MW/cm².     

Analysis of trace impurities in semiconductor gas via cavity-enhanced direct frequency comb spectroscopy

Cavity-enhanced direct frequency comb spectroscopy (CE-DFCS) has demonstrated powerful potential for trace-gas detection based on its unique combination of high bandwidth, rapid data acquisition, high sensitivity, and high resolution, which is unavailable with conventional systems. However, previous demonstrations have been limited to proof-of-principle experiments or studies of fundamental laboratory science. Here, we present the development of CE-DFCS towards an industrial application—measuring impurities in arsine, an important process gas used in III–V semiconductor compound manufacturing. A strongly absorbing background gas with an extremely complex, congested, and broadband spectrum renders trace detection exceptionally difficult, but the capabilities of CE-DFCS overcome this challenge and make it possible to identify and quantify multiple spectral lines associated with water impurities. Further, frequency combs allow easy access to new spectral regions via efficient nonlinear optical processes. Here, we demonstrate detection of multiple potential impurities across 1.75–1.95 μm (5710–5130 cm⁻¹), with a single-channel detection sensitivity (simultaneously over 2000 channels) of ∼4×10⁻⁸ cm⁻¹ Hz^−1/2 in nitrogen and, specifically, an absorption sensitivity of ∼4×10⁻⁷ cm⁻¹ Hz^−1/2 for trace water doped in arsine.     

Influence of post-grown Li-rich and Li-poor vapor transport equilibration on composition, OH− absorption and optical-damage threshold of Mg (5 mol%) : LiNbO3 crystals

Li-rich (Li-poor) vapor transport equilibration (VTE) treatments on a number of Z-cut 0.47 mm thick congruent MgO (5 mol% in melt) : LiNbO₃ crystals were carried out at 1100°C over different durations ranging in 1–172 (40–395) h. Neutron activation analysis shows that neither Li-rich nor Li-poor VTE-induced Mg and Nb loss from the crystal occurred. The Li₂O content in the crystal was measured as a function of VTE duration by the gravimetric method. The Li-rich/Li-poor VTE effects on OH⁻ absorption were studied in comparison with the as-grown crystal. The study shows that the Li-rich VTE results in OH⁻ absorption band annihilation. After further oxidation treatment the band reemerges and peaks at the same wavenumber as that of the as-grown crystal (∼3535.6 cm⁻¹), showing that the MgO concentration in the Li-rich VTE crystal is still above the optical-damage threshold. The Li-poor VTE causes OH⁻ band shift to 3486.3–3491.6 cm⁻¹, indicating that the MgO concentration in all Li-poor VTE crystals is all below the optical-damage threshold. Further successive Li-rich VTE and oxidation treatments on the Li-poor VTE-treated crystal lead the band to shift back to 3535.6 cm⁻¹, showing that the post Li-rich VTE brought the Li-poor VTE-treated crystal above the optical-damage threshold again. It is found that the peaking position, band width, peaking absorption and band area of the absorption at ∼3486 cm⁻¹ all increase monotonously with the decrease of the Li₂O content arising from prolonged Li-poor VTE, and quantitative relationships to the Li₂O content are established for the latter two parameters. The VTE effects on the OH⁻ absorption are conducted with the VTE-induced OH⁻ content alteration and charge redistribution.     

Fabrication and optical characterization of stable suspensions of iron- or copper-doped lithium niobate nanocrystals in heptane

Stable suspensions of iron- or copper-doped lithium niobate nanocrystals in heptane are prepared by high-energy ball milling of iron- and copper-doped bulk crystals for 25 h. The distribution of particle sizes is determined by means of dynamic light scattering with more than 90% of the crystals in the range of 10–25 nm. The optical absorption of the suspensions suggests a changed environment of the dopants. PACS 77.84.Nh; 78.67.Bf; 81.07.-b     

Infrared absorption spectra of pure and doped YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> single crystals

Several weak absorption bands have been observed in the optical absorption spectra of pure and rare-earth-doped YAl₃(BO₃)₄ single crystals in the 3350– 3650 cm⁻¹ wave number region. Two of them, peaking at about 3377 cm⁻¹ and 3580 cm⁻¹ in the 8 K spectra, appear in most of the samples. They are tentatively attributed to the stretching mode of OH⁻ ions incorporated in the crystal during the growth. An additional absorption band at about 5250 cm⁻¹ at 8 K has also been detected in almost all samples. The temperature and polarization dependences of these bands, and their possible origin, are discussed.     

3.5-μm high-resolution gas sensing employing a LiNbO3 QPM-DFG waveguide module

Diode laser technology coupled with a wavelength-conversion unit to produce mid-infrared narrow bandwidth laser light applicable to trace-gas detection and with the potential for high-resolution spectroscopy is described. Quasi-phase-matched difference-frequency generation (QPM-DFG) in a compact and fibre-coupled periodically poled lithium niobate (PPLN) waveguide module mixing 1063 and 1525-nm radiations has been adopted for generating 34 μW of 3.5-μm wavelength laser light. Optical detection methods, including sensitive wavelength modulation spectroscopy and a rapid wavelength chirp technique, have been employed with a single-pass cell to investigate methane and formaldehyde absorption profiles around 2855 cm⁻¹, as proof of principle experiments for high sensitivity and resolution spectroscopy on atmospherically important molecules.     

Generation of small bound polarons in lithium niobate crystals on the subpicosecond time scale

Light pulses of 240 fs duration and 388-nm wavelength generate in lithium niobate crystals transient absorption. The absorption changes are observed with delayed ultra-short pulses (wavelength 776 nm) and with continuous-wave light (wavelength 785 nm) over 10 decades from 400 fs up to 10 s after the pump pulse. The decay is well described by one stretched-exponential function over the entire temporal range. We attribute the absorption changes to small bound polarons because of the temporal, spectral, and polarization fingerprints. The polarons are formed in less than 400 fs after the pump illumination, ruling out that phonons with wavenumbers below 100 cm^-1 are the main cause for polaron generation and indicating that the breathing mode of the oxygen octahedra is of relevance. An upper limit of the generated polaron concentration is estimated as ≈4.4×10¹⁸ cm^-3 with an intensity of ≈220 GW/cm². PACS 71.38.Ht; 78.47.+p; 77.84.Dy; 42.50.Gy; 42.70.Mp; 72.20.Jv     

LiNbO<Subscript>3</Subscript>:Yb<Superscript>3+</Superscript> crystals for optical temperature sensors

Possibilities of using lithium niobate crystals, doped with ytterbium (LN:Yb³⁺) as materials for optical temperature sensor (OTS), are discussed. We consider both the radiative and absorptive characteristics of the crystals, assuming that their temperature dependences are caused by the Boltzmann factor of the initial population of Stark sublevels of the ion. It is shown that the crystals can be used as materials for OTS in the temperature range 150–400 K.     

Application of 940 nm high-power DFB lasers for line-broadening measurements at normal pressure using a robust and compact setup

High-power distributed-feedback (DFB) lasers for the wavelength range near 940 nm (i.e. about 10,600 cm⁻¹) were used for line-broadening measurements of individual rotational-vibrational absorption lines of water vapour at atmospheric pressure using a minimalist set-up. The laser has a maximum output power larger than 500 mW. Over the whole power range from threshold to maximum power, it operates in single mode operation with a tuning range of 4.7 nm, i.e. 50 cm⁻¹, at 20°C. With an emission line-width ≤2 MHz (0.66×10⁻⁴ cm⁻¹), the device is well suited for high-resolution spectroscopy.     

Tunable diode laser spectroscopy of benzene near 1684 nm with a low-temperature VCSEL

We describe the application of a long-wavelength vertical-cavity surface-emitting laser (VCSEL) with extended tuning range to the detection of benzene vapor at atmospheric pressure. A benzene absorption feature centered at 1684.24 nm was accessed by reducing the heat sink temperature of a VCSEL designed for room-temperature operation to −55°C. This allowed us to increase the injection current and thus to extend a single-scan tuning interval up to 46.4 cm⁻¹ or 13.2 nm around a central wavelength of 1687.4 nm. Five absorption lines of methane in the 5903–5950 cm⁻¹ range could be acquired within single laser scans at a repetition rate of 500 Hz. A benzene absorption feature between 5926 and 5948 cm⁻¹ was recorded for concentration measurements at atmospheric pressure using a single-pass 1.2 m absorption cell. A 50 ppmv mixture of CH₄ in N₂ was introduced into the cell along with benzene vapor to calibrate benzene concentration measurements. Benzene mixing ratios down to ∼90 ppmv were measured using a direct absorption technique. The minimum detectable absorbance and detection limit of benzene were estimated to be ∼10⁻⁴ and 30 ppmv, respectively. Using the wavelength modulation technique, we measured a second harmonic sensor response to benzene vapor absorption in air at atmospheric pressure as a function of modulation index. We conclude that a low-temperature monolithic VCSEL operating near 1684 nm can be employed in compact benzene sensors with a detection limit in the sub-ppm range.     

Ultraviolet quasi-phase-matched second harmonic generation in surface periodically poled lithium niobate optical waveguides

The compatibility of low concentration (α-phase) proton exchange channel waveguides with electric field surface periodic poling of congruent lithium niobate (SPPLN) crystals has been experimentally demonstrated. With such waveguides, we obtained ultraviolet second harmonic generation (SHG) by first order quasi-phase-matching (QPM), a result made possible by the fabrication, on Z-cut LN crystals, of periodic structures with a pitch down to 750 nm. Nonlinear copropagating QPM-SHG measurements have been carried out on such structures. The pump source was a Ti:sapphire laser with a tunability range of 700–980 nm and a 40 GHz linewidth. We have measured UV continuous wave light at 390 nm by means of a lock-in amplifier and a photodiode with an enhanced response in the UV. The measured conversion efficiency was about 1% W^?1 cm^?2.     

Optical spectra and excited state relaxation dynamics of Sm<Superscript>3+</Superscript> in Gd<Subscript>2</Subscript>SiO<Subscript>5</Subscript> single crystal

Single crystals of gadolinium orthosilicate Gd₂SiO₅ containing 0.5 at% and 5 at% of Sm³⁺ were grown by the Czochralski method. Optical absorption spectra, luminescence spectra and luminescence decay curves were recorded for these systems at 10 K and at room temperature. Comparison of optical spectra recorded in polarized light revealed that the anisotropy of this optically biaxial host affects the intensity distribution within absorption and emission bands related to transitions between multiplets rather than the overall band intensity. It has been found that among four bands of luminescence related to the ⁴G_5/2→⁶H_J (J=5/2–11/2) transitions of Sm³⁺ in the visible and near infrared region the ⁴G_5/2 →⁶H_7/2 one has the highest intensity with a peak emission cross section of 3.54×10⁻²¹ cm² at 601 nm for light polarized parallel to the crystallographic axis c of the crystal. The luminescence decay curve recorded for Gd₂SiO₅:0.5 at% Sm³⁺ follows a single exponential time dependence with a lifetime 1.74 ms, in good agreement with the ⁴G_5/2 radiative lifetime τ _rad=1.78 ms calculated in the framework of Judd-Ofelt theory. Considerably faster and non-exponential luminescence decay recorded for Gd₂SiO₅:5 at% Sm³⁺ sample was fitted to that predicted by the Inokuti-Hirayama theory yielding the microparameter of Sm³⁺–Sm³⁺ energy transfer C _da=1.264×10⁻⁵² cm⁶×s⁻¹.     

Optical absorption in layered MnGaInS<Subscript>4</Subscript> single crystals

Optical absorption in MnGaInS₄ single crystals has been studied. Direct and indirect optical transitions are found to occur in the range of photon energies of 2.37–2.74 eV and in the temperature range of 83–270 K. The temperature dependence of the band gap has been determined; its temperature coefficients E _gd and E _gi are −5.06 × 10⁻⁴ and −5.35 × 10⁻⁴ eV/K, respectively. MnGaInS4 single crystals exhibit anisotropy in polarized light at the absorption edge; the nature of this anisotropy is explained.     

Observation of ultra-long lifetime UV-induced infrared absorption in undoped and magnesium-doped congruent lithium niobate crystals

We report experimental observation of ultra-long lifetime UV-induced absorption in undoped and 5 mol.% Mg-doped congruent lithium niobate crystals between 400 nm and 2500 nm wavelength range. The saturated absorption coefficient change in undoped congruent lithium niobate was about 3 to 7 times that in Mg-doped congruent lithium niobate in the mid-infrared spectrum. The UV-illuminated LiNbO₃:Mg was fully recovered in the dark after 2 days, whereas the undoped congruent LiNbO₃ still exhibited nontrivial infrared absorption. We attribute the cause of the UV-induced absorption to the creation of hole-trapped intermediate states O⁻ near lithium vacancies.     

The temperature and light intensity dependence of photorefraction in LiNbO3

In the paper the dependence of the photorefraction (PhR) in LiNbO₃ and LiNbO₃−Fe (0.1 wt%, 0.3wt%) crystals on light intensity (within 10¹⁶–10²³ quanta·cm⁻²·s⁻¹ at wavelengths 496.5 nm and 600 nm) and temperature (in the region 100–500 K) is studied. For all the crystals the limiting values of PhR are similar and atT=293 K Δn _sat ^lim ≈3·10⁻³. In LiNbO₃ the temperature dependence of PhR in the range 100–500 K requires to take into account at least two trapping centres.     

Luminescence of short-lived color centers induced in LiF crystals by a pulsed microwave discharge

A new phenomenon — intense luminescence of noncolored lithium fluoride (LiF) crystals excited by an electrodeless pulsed microwave discharge at the prebreakdown stage of development — is observed. This luminescence consists of the luminescence of short-lived aggregate F₂ and F ₃ ⁺ color centers at room temperature. It is shown that the density of short-lived color centers induced in the surface layer of LiF crystals by a microsecond microwave discharge reaches values of ∼10¹⁹−10²⁰ cm⁻³. Pis’ma Zh. éksp. Teor. Fiz. 66, No. 3, 163–167 (10 August 1997)     

Analysis and optimization of propagation losses in LiNbO3 optical waveguides produced by swift heavy-ion irradiation

The propagation losses (PL) of lithium niobate optical planar waveguides fabricated by swift heavy-ion irradiation (SHI), an alternative to conventional ion implantation, have been investigated and optimized. For waveguide fabrication, congruently melting LiNbO₃ substrates were irradiated with F ions at 20 MeV or 30 MeV and fluences in the range 10¹³–10¹⁴ cm⁻². The influence of the temperature and time of post-irradiation annealing treatments has been systematically studied. Optimum propagation losses lower than 0.5 dB/cm have been obtained for both TE and TM modes, after a two-stage annealing treatment at 350 and 375^∘C. Possible loss mechanisms are discussed.     

Micro-Raman analysis on LiNbO3 substrates and surfaces: Compositional homogeneity and effects of etching and polishing processes on structural properties

In this work we report on micro-Raman analysis on lithium niobate (LN) substrates in order to study the compositional homogeneity of the crystals and to clear up the effects of etching and polishing processes on the surface of wafers and crystals.The fact that the linewidth of some Raman modes scale with the composition of LN crystals, together with the use of a confocal microscope, allowed a three-dimensional determination of the sample stoichiometry and of the crystalline quality. This local tool can supply additional information, which can be complementary to the electro-optic coefficients, carefully measured as well in order to check functional parameters.Raman spectra from buried regions were obtained on as-grown, etched and polished crystals and wafers. The depth profile of the peak energy and the linewidth of the Raman mode at 872 cm⁻¹ indicate that mechanical processing of surfaces causes, in some cases, structural modifications till a depth of 15 μm.     

Femtosecond OPO based on LBO pumped by a frequency-doubled Yb-fiber laser-amplifier system for CARS spectroscopy

We present detailed investigations of a femtosecond green-pumped optical parametric oscillator (OPO) based on lithium triborate. As pump source, a frequency-doubled Yb-fiber laser-amplifier system is used. The OPO generates signal pulses tunable over a spectral range from 780 to 940 nm and idler pulses tunable from 1630 to 1190 nm. More than 250 mW are generated in the signal beam and more than 300 mW in the idler beam. Without dispersion compensation chirped signal pulses with a pulse duration between 100 and 250 fs are measured. Using this system for coherent anti-Stokes Raman scattering spectroscopy, vibrational resonances between 1110 and 6760 cm⁻¹ can be excited. Due to the chirped pulses, a spectral resolution of 100 cm⁻¹ is achieved, which is 2.5 times higher compared to an excitation with time-bandwidth limited pulses.