Optical absorption in early stage low temperature laser produced plasma

We describe a new technique to measure the UV/visible absorption spectrum of the ablated material during the laser pulse. The technique utilizes the continuum emission from one laser produced plasma as a light source to measure the absorption properties of a second laser produced plasma which is formed on a semi-transparent target with an array of 40 μm holes. A 6 ns, 1064 nm laser was used to ablate a Ag target and the plasma absorption was measured in the range 450–625 nm for a laser fluence of 1 J cm⁻². The total absorption cross-section is (0.5–1.5)×10⁻¹⁷ cm² in the range 450–540 nm. By comparing the measured absorption with a calculation using the plasma spectroscopy code FLYCHK it can be concluded that, in the wavelength region examined here, the absorption is mainly due to bound-bound transitions.     

High resolution ethylene absorption spectrum between 6035 and 6210 cm-1

A two-channel photo-acoustic spectrometer (PA spectrometer) with a near infrared diode laser was used for taking measurements of a high resolution ethylene absorption spectrum. A semiconductor TEC-100 laser with an outer resonator generates a continuous single-frequency radiation in the range 6030–6300 cm^-1. A newly designed model of photo-acoustic detector (PAD) in the form of a ring type resonator provides for measurement of weak absorption cross-section equal to 4×10^-23 cm²/mol at a laser radiation power of 3 mW. The PAD threshold sensitivity is 2×10^-9 cm^-1 Hz^-1/2 W, when the signal to noise ratio equals to 1. The ethylene absorption spectrum within the range 6035–6210 cm^-1 was measured for the first time with a spectral resolution of 10 MHz. The reported line centre positions have an uncertainty of ± 0.0005 cm^-1. The precise measurements of ethylene absorption cross-sections were carried out using the mixture of high purity ethylene and broadening gas (nitrogen) at the mixture ratio 1:50–1:200. Measurements were carried out at a mixture pressure of about 4.2 kPa. PACS 42.62.Fi; 42.55.Px     

Nonlinear optical absorption and refraction of epitaxial Ba0.6Sr0.4TiO3 thin films on (001) MgO substrates

Highly epitaxial Ba_0.6Sr_0.4TiO₃ (BST) ferroelectric thin films were fabricated on (001) MgOsubstrates by pulsed laser deposition. The nonlinear optical absorption coefficients (β) and refraction indices (γ) of the BST thin films on (001) MgO substrates were investigated using the single beam Z-scan technique with femtosecond laser pulses at the wavelengths of 790 nm and 395 nm, respectively, at room temperature. The nonlinear absorption coefficients of BST thin films were measured to be ∼0.087 cm/GW and ∼0.77 cm/GW at 790 nm and 395 nm, respectively. The nonlinear refraction indices of BST thin films exhibit a strong dispersion from a positive value of 6.1×10^-5 cm²/GW at 790 nm to a negative value of -4.0×10^-5 cm²/GW at 395 nm near band gap. The dispersion of γ is roughly consistent with Sheik-Bahae’s theory for the bound electronic nonlinear refraction resulting from the two-photon resonance. These results show that the BST film is a promising material as a candidate for nonlinear optical applications. PACS 42.70.Mp; 78.20.-e; 81.05.-t     

Reduced absorption of neon-like bromine X-ray laser radiation in helium

We have measured the absorption of the 19.47-nm neon like bromine (J=2–1) X-ray laser line in low-pressure helium. The experiment was motivated by the coincidence of this line with the low-absorption wing of an autoionizing transition in helium. We observe that, with 1 mbar of helium, the continuum background and another bromine X-ray laser line at 19.82 nm are strongly reduced, enhancing the relative strength of the 19.47-nm laser line. Increasing the helium pressure to 1.5 mbar makes the continuum virtually disappear, resulting in an almost monochromatic emission of the X-ray laser line. An estimate of the absorption cross section for the 19.47-nm line is given as ≈3.9×10^-19 cm² and for the nearby continuum as 0.9–1.3×10^-18 cm². Received: 8 March 1999 / Revised version: 26 April 1999 / Published online: 11 August 1999     

Application of a continuous-wave tunable erbium-doped fiber laser to molecular spectroscopy in the near infrared

Development of a continuous-wave tunable fiber laser-based spectrometer for applied spectroscopy is reported. Wide wavelength tunability of an erbium-doped fiber laser (EDFL) was investigated in the near-infrared region of 1543–1601 nm. Continuous mode-hop free fine frequency tuning has been accomplished by temperature tuning in conjunction with mechanical tuning. The overall spectroscopic performance of the EDFL was evaluated in terms of frequency tunability along with its suitability for molecular spectroscopy. High-resolution absorption spectra of acetylene (C₂H₂) were recorded near 1544 nm with a minimum measurable absorption coefficient of about 3.5×10^-7 cm^-1/Hz^1/2 for direct absorption spectroscopy associated with a 100-m long multipass cell. Detections of C₂H₂ at different concentration levels were performed as well with high dynamic detection range varying from 100% purity to sub ppmv using cavity ring down spectroscopy. A 3σ-detection-limited minimum detectable concentration (MDC) of 400 ppbv has been obtained by using the transition line P_e(22) of the ν₁+ν₃+ν₅ ¹(Π_g)-ν₅ ¹(Π_u) hot band near 1543.92 nm with a detection bandwidth of 2.3 Hz. This corresponds to a minimum detectable absorption coefficient of 6.6×10^-11 cm^-1/Hz^1/2. The sensitivity limit could be further improved by almost one order of magnitude (down to ∼60 ppbv) by use of the P_e(27) line of the ν₁+ν₃(Σ_u ⁺)-0(Σ_g ⁺)combination band near 1543.68 nm. PACS 42.55.Wd; 42.62.Fi; 07.57.Ty; 07.88.+y     

Multipass optical cell based upon two cylindrical mirrors for tunable diode laser absorption spectroscopy

A compact multipass optical cell based upon a front cylindrical mirror with a central input/output hole and a rear cylindrical mirror is described for application to tunable diode laser absorption spectroscopy. Rotation of the rear cylindrical mirror and small variations of the cell base length (∼110 mm) have been used to achieve different spot patterns and path lengths. CO₂ and CH₄ direct absorption measurements using the developed cell with a fibre-coupled distributed-feedback laser at 1605.5 nm have been performed. A noise-equivalent absorption sensitivity of 2.5×10^-8 cm^-1 Hz^-1/2 has been determined for 138 passes in the cell and averaging of 2000 consecutive scans within 1.93 s. PACS 42.55.Px; 39.30.+w; 42.62.Fi; 42.60.-v     

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.     

Wavelength stabilization of an Ar+ laser with an external129I2 absorption cell

Wavelength stabilization of the green Ar⁺ laser line at 514.5 nm by¹²⁹I₂ absorption was found to be more favourable than by¹²⁷I₂ absorption because the maximum of¹²⁹I₂ absorption is closer to the center of the 514.5 nm gain curve. A simple method for stabilizing a short air cooled laser with only one servo loop is given, yielding a stability of 10⁻⁸ λ.     

Telecom-grade fiber laser-based difference-frequency generation and ppb-level detection of benzene vapor in air around 3 μm

We report on the development of a field deployable compact laser instrument tunable over ∼232 cm⁻¹ from 3.16 to 3.41 μm (2932.5–3164.5 cm⁻¹) for chemical species monitoring at the ppb-level. The laser instrument is based on widely tunable continuous-wave difference-frequency generation (DFG), pumped by two telecom-grade fiber lasers. DFG power of ∼0.3 mW near 3.3 μm with a spectral purity of ∼3.3 MHz was achieved by using moderate pumping powers: 408 mW at 1062 nm and 636 mW at 1570 nm. Spectroscopic performance of the developed DFG-based instrument was evaluated with direct absorption spectra of ethylene at 3.23 μm (∼3094.31 cm⁻¹). Absorption spectra of vapor-phase benzene near 3.28 μm (∼3043.82 cm⁻¹) were recorded with Doppler-limited resolution. Line intensities of the most intense absorption lines of the ν ₁₂ band near 3043.8 cm⁻¹ were determined to support development of sensitive mid-infrared trace gas detection of benzene vapor in the atmosphere. Detection of benzene vapor in air at different concentration levels has been performed for the first time using multi-pass cell enhanced direct absorption spectroscopy at ∼3.28 μm with a minimum detectable concentration of 50 ppb (1σ).     

Development of a tunable mid-IR difference frequency laser source for highly sensitive airborne trace gas detection

The development of a compact tunable mid-IR laser system at 3.5 μm for quantitative airborne spectroscopic trace gas absorption measurements is reported. The mid-IR laser system is based on difference frequency generation (DFG) in periodically poled LiNbO₃ and utilizes optical fiber amplified near-IR diode and fiber lasers as pump sources operating at 1083 nm and 1562 nm, respectively. This paper describes the optical sensor architecture, performance characteristics of individual pump lasers and DFG, as well as its application to wavelength modulation spectroscopy employing an astigmatic Herriott multi-pass gas absorption cell. This compact system permits detection of formaldehyde with a minimal detectable concentration (1σ replicate precision) of 74 parts-per-trillion by volume (pptv) for 1 min of averaging time and was achieved using calibrated gas standards, zero air background and rapid dual-beam subtraction. This corresponds to a pathlength-normalized replicate fractional absorption sensitivity of 2.5×10^-10 cm^-1. Received: 29 April 2002 / Published online: 21 August 2002 RID="*" ID="*"Corresponding author. Fax: +1-303/497-1492, E-mail: dr@ucar.edu     

Nonlinear optical properties of sol-gel-type glasses containing oxidized Cu2Se nanoparticles

Nonlinear absorption of sol-gel-type glasses containing oxidized Cu₂Se nanoparticles (25 nm in radius) is investigated with the aid of the picosecond excitation-probing technique. The oxidation of Cu₂Se nanoparticles leads to the appearance of a wide absorption band, which has a maximum roughly at 1 μm and which is bleached on exposure to laser pulses. The time of relaxation of the bleached state approaches 300 psec, and the cross section for absorption at 1.06 μm is equal to about 1.3·10⁻¹⁶ cm², as evaluated from the measured absorption saturation curve. The regime of Q-switching is obtained for a number of solid-state lasers with generation wavelengths 1.06, 1.34, and 1.54 μm, when sol-gel-type glasses containing oxidized Cu₂Se nanoparticles were used as passive shutters. Translated from Zhurnal Prikladnoi Spektroskopii, Vol, 67, No. 2, pp. 203–207, March–April, 2000.     

An off-axis cavity-enhanced absorption spectrometer at 1605 nm for the 12CO2/13CO2 measurement

A distributed feedback diode laser sensor based upon off-axis cavity-enhanced absorption spectroscopy at 1605.5 nm has been developed for ¹³C¹⁶O₂/¹²C¹⁶O₂ isotope ratio measurements in synthetic air and human breath. A noise-equivalent absorption sensitivity of 3.9×10^-10 cm^-1 Hz^-1/2 has been determined for a cavity base length of 28.2 cm and averaging 4000 scans within 8.688 s. For 5% CO₂ concentration measurements, δ¹³C standard deviations of 1.8 ‰ and 3.7 ‰ have been estimated for five successive measurements based on peak height and integrated area estimations at 107.9 Torr, respectively. The contributions of amplified spontaneous emission of the laser and a radiation that is spatially uncoupled into the cavity mode have been described for cavity transmittance measurements. The limitations of the developed sensor and further steps towards precision and accuracy improvements are discussed. PACS 42.55.Px; 39.30.+w; 42.62.Fi; 42.60.-v     

Optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS) in a ring cavity

Optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS) has been demonstrated by coupling a distributed feedback diode laser to a ring cavity. Frequency-selected light decaying from the ring cavity is retro-reflected, inducing a counter-propagating intra-cavity beam, and providing optical feedback to the laser. At specific laser-to-cavity distances, all cavity mode frequencies return to the diode laser with the same phase, allowing spectra to be accumulated across the range of frequencies of the current-tuned laser. OF-CEAS has been used to measure very weak oxygen isotopologue (¹⁶O¹⁸O and ¹⁶O¹⁷O) absorptions in ambient air at wavelengths near 762 nm using the electric-dipole forbidden O₂ A-band. A bandwidth reduced minimum detectable absorption coefficient of 2.2×10⁻⁹ cm⁻¹ Hz^−1/2 is demonstrated.     

Growth and laser properties of Nd<Superscript>3+</Superscript>:Sr<Subscript>6</Subscript>YSc(BO<Subscript>3</Subscript>)<Subscript>6</Subscript> crystal

The crystal of Nd³⁺:Sr₆YSc(BO₃)₆ with dimensions of O 19×42 mm³ was grown by the Czochralski method. It’s spectral and laser properties have been investigated. The absorption cross section is 1.47×10^-20 cm² with a FWHM 12.0 nm at 807 nm, the emission cross section is 1.57×10^-19 cm² at 1060 nm, and the fluorescence lifetime is 76 μs at room temperature. The maximum laser output is 25.7 mJ at 1.06 μm pumped by a single Xenon flash lamp and the overall and average slope efficiencies are 0.12% and 0.09%, respectively. The laser energy threshold value is 1.28 J. PACS 42.55.Rz; 42.70.Hj; 78.20.-e     

Nonlinear optical characterization of LaEr(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript> thin films using the <Emphasis Type="BoldItalic">Z</Emphasis> -scan technique

The nonlinear optical properties of thin films of LaEr(MoO₄)₃ were studied using a ∼30 ps Nd:YAG laser at 532 nm with a repetition rate of 250 Hz. Closed aperture Z-scan measurement revealed a negative nonlinearity in the LaEr(MoO₄)₃. The nonlinear refractive index γ=1.38×10^-10 cm²/W and nonlinear absorption coefficient β=16.8×10^-6 cm/W were calculated from the Z-scan data. The fluorescent upconversion spectra were recorded with 980 nm excitation. An optical switching mechanism based on nonlinear absorption is also presented experimentally. PACS 81.15.Fg; 77.84.Bw; 33.50.Dq; 42.70.Mp     

Growth,spectroscopic and laser properties of Yb<Superscript>3<Emphasis Type="Bold">+</Emphasis></Superscript>-doped GdAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> crystal: a candidate for infrared laser crystal

Yb³⁺:GdAl₃(BO₃)₄ (hereafter Yb³⁺:GAB) crystals with large sizes and good optical quality have been grown by the top-seed solution growth (TSSG) method. The polarized absorption and emission spectra have been investigated at room temperature. For the σ-polarization, the intensities of both absorption and emission spectra are stronger than those for the π-polarization, the σ-absorption cross section of Yb³⁺ in GAB being 3.43×10^-20 cm² at 977 nm, and the σ-emission cross section being 0.98×10^-20 cm² at 1045 nm. The fluorescence lifetime of the ² F _5/2→² F _7/2 transition was measured to be 800 μs in the 5% doped sample used for our laser experiments, 993 μs in a 10% doped sample and 569 μs in a 0.5% doped sample. The laser parameters were estimated as: β_min=0.022, I_sat=10.4 kW/cm² and I_min=0.23 kW/cm². About 0.4 W laseroutput at the wavelength of 1043 nm was achieved when the Yb³⁺:GAB crystal was pumped by a 974 nm laser diode, with 27.4% slope efficiency. PACS 42.55.-f; 42.70.Hj; 78.20.-e; 81.10.Dn     

Comparison of the influence of the fictive and the annealing temperature on the UV-transmission properties of synthetic fused silica

′ and NBOH). Samples with high OH content exhibit gradual recovery from the absorption band within several minutes after exposure to the KrF laser radiation. The formation of the KrF laser-induced 210 nm absorption band depends on the fictive temperature and on the OH content. Low fictive temperature, as a measure for the number of intrinsic defects, retards E^′ generation at the beginning of intense KrF excimer laser irradiation when the majority of defects are generated from precursor defects. However, for longer irradiation periods with pulse numbers of the order of 10⁵ pulses, a high OH content is the beneficial parameter. The accompanying atomic hydrogen is essential for the suppression of the 210 nm absorption band. This happens by transformation of the E^′ centers into Si-H defects. In contrast to a generally held view, annealing (decreasing of the fictive temperature) of fused silica does not always reduce UV induced defect generation. For example, annealing of the samples in an argon atmosphere causes a significantly higher 210 nm absorption increase during KrF excimer laser irradiation (240000 pulses) compared to nonannealed samples. Two spectroscopic methods to determine the OH content of fused silica were applied: Raman and infrared spectroscopy, which in this work lead to differing results. The energetics of the 210 nm absorption band generation and bleaching is summarized by a diagram explaining the interaction of the 248 nm laser radiation with fused silica. Received: 2 June 1997/Accepted: 13 June 1997     

Tunable diode laser spectroscopy of ethylene oxide near 1693 nm

We describe the application of the vertical-cavity surface-emitting laser (VCSEL) to absorption spectroscopy of the ethylene oxide (EO) Q-branch near 1693 nm. The VCSEL was electrically scanned over spectral intervals of up to ∼13 cm⁻¹ at a 1 kHz repetition rate. A methane absorption line at 5903.3 cm⁻¹ and Fabry–Pérot etalon with a free spectral range of 0.4 cm⁻¹ were used to calibrate frequency scale. The EO was mixed with ambient air, and total gas pressure and mixing ratios were varied from a few mbar to 1 bar and from ∼10² to 10⁵ parts per million, respectively. A rapid roll off of EO absorbance at 5903.7 cm⁻¹ was observed at gas pressures below ∼0.5 bar. A linear dependence of EO peak absorbance on mixing ratio was found at a total gas pressure of 1 bar. We conclude that monolithic VCSELs operating near 1693 nm could be used in EO sensors with a detection limit in the ppb range.     

High-sensitivity detection of NO2 using a 740 nm semiconductor diode laser

 An AlGaAs diode laser was used to detect NO₂ absorption lines belonging to the (0 0 0)–(2 13 1) vibrational band, within the X˜² A ₁ electronic ground state, at 739 nm. A simple absorption spectrometer based on wavelength-modulation spectroscopy with second-harmonic detection was developed. The minimum detectable pressure of pure NO₂ was 0.1 μbar with 2 m absorption path-length, corresponding to an absorbance of 10^-6. High-sensitivity detection of NO₂ was also performed in the presence of N₂ and air at different total pressures: The effects on the detection limit of our apparatus were accurately investigated. The minimum NO₂ concentration at 500 mbar of air was measured to be 2 ppm. Received: 11 June 1996 / Revised version: 11 October 1996     

Cavity-enhanced absorption spectroscopy with a rapidly swept diode laser

Cavity-enhanced absorption spectroscopy is explained in terms of the transmission function of a rapidly swept interferometer, and the integrated transmission is shown to be proportional to the cavity ringdown time. The technique is demonstrated on the b¹Σ_g ⁺-X³Σ_g ^-  (1,0) band in molecular oxygen at 687 nm using a tunable diode laser and a relative-ly high-Q optical cavity (finesse ≈4000). A detection limit of 3×10^-8 cm^-1 s^1/2 is achieved for a 0.8 cm^-1 scanning range. Received: 24 June 2002 / Revised version: 5 August 2002 / Published online: 15 November 2002 RID="*" ID="*"Corresponding author. Fax: +44-1865/275410, E-mail: peverall@physchem.ox.ac.uk