Characterization of a 10.3-microm pulsed DFB quantum cascade laser

We have measured the output parameters of a 10.3-microm pulsed distributed-feedback (DFB) quantum cascade (QC) laser manufactured by Alpes Lasers and intended for high-sensitivity detection of ammonia and ethylene. The laser beam was collimated with an AR-coated aspheric ZnSe lens with focal length of 11.6mm and clear aperture of 16.5mm. Near- and far-field distributions of the laser emission were recorded with an infrared imaging camera. The fast-and slow-axis laser beam divergences were measured to be 1.2 and 1.4 mrad (FWHM), respectively. The divergence was found to be increasing with injection current. An air-spaced Fabry-Perot interferometer with free spectral range of 0.05 cm(-1) was used to measure the frequency tuning rates of the laser. The laser was tuned by either heat sink temperature, injection current or pulse repetition rate with rates of approximately -8 x 10(-2)cm(-1)K(-1), -7 x 10(-2)cm(-1)A(-1) and -9 x 10(-4)cm(-1)kHz(-1), respectively. The laser frequency decreased linearly with a rate of 10(-2)cm(-1)ns(-1) ( approximately 300 MHzns(-1)) for laser pulses varied from 10 to 50 ns, and the frequency chirp rate was found to decrease for longer laser pulses.     

The role of the laser pulse duration in infrared matrix-assisted laser desorption/ionization mass spectrometry

The role of the laser pulse duration in matrix-assisted laser desorption/ionization mass spectrometry with infrared lasers (IR-MALDI-MS) emitting in the 3 microm wavelength range has been evaluated. Mass spectrometric performance and characteristics of the IR-MALDI process were examined by comparing a wavelength-tuneable mid-infrared optical parametric oscillator (OPO) laser of 6 ns pulse duration, tuned to wavelengths of 2.79 and 2.94 microm, with an Er:YAG laser (lambda = 2.94 microm) with two pulse durations of 100 and 185 ns, and an Er:YSGG laser (lambda = 2.79 microm) with a pulse duration of 75 ns. Threshold fluences for the desorption of cytochrome C ions were determined as a function of the laser pulse duration for various common IR-MALDI matrices. For the majority of these matrices a reduction in threshold fluence by a factor of 1.2-1.9 was found by going from the 75-100 ns long pulses of the Erbium lasers to the short 6 ns OPO pulse. Within the experimental accuracy threshold fluences were equal for the 100 and the 185 ns pulse duration of the Er:YAG laser. Some pronounced pulse duration effects related to the ion formation from a glycerol matrix were also observed. The effect of the laser pulse length on the duration of ion emission was furthermore investigated.     

Detection efficiencies in nano- and femtosecond laser ablation inductively coupled plasma mass spectrometry

Detection efficiencies of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), defined as the ratio of ions reaching the detector and atoms released by LA were measured. For this purpose, LA of silicate glasses, zircon, and pure silicon was performed using nanosecond (ns) as well as femtosecond (fs) LA. For instance, ns-LA of silicate glass using helium as in-cell carrier gas resulted in detection efficiencies between approximately 1E-7 for low and 3E-5 for high mass range elements which were, in addition, almost independent on the laser wavelength and pulse duration chosen. In contrast, the application of argon as carrier gas was found to suppress the detection efficiencies systematically by a factor of up to 5 mainly due to a less efficient aerosol-to-ion conversion and ion transmission inside the ICP-MS.     

New improvements in methane detection using a Helmholtz resonant photoacoustic laser sensor: a comparison between near-IR diode lasers and mid-IR quantum cascade lasers

Atmospheric methane was detected by combining a photoacoustic (PA) sensor with several lasers emitting in both the near- and mid-infrared spectral ranges to check the achievable detection limits. The PA spectrometer is based on differential Helmholtz resonance. Near-infrared telecommunication-type laser diodes of increasing power, from Sensors Unlimited Inc. and Anritsu, were first used to scan the 2 nu(3) band of CH(4) near 1.65 microm. The best achieved detection limit is 0.15 ppm of methane at atmospheric pressure and with a 1s integration time. The PA sensor was then operated in conjunction with a quantum cascade laser from Alpes Lasers emitting near 7.9 microm on the nu(4) band of CH(4). The achieved detection limit is then of 3 ppb. The dramatic improvement in the detection limit obtained with the QC laser is due to the stronger optical power as well as to the capability of reaching the fundamental bands of methane lying in the mid-infrared spectral range.     

High-resolution spectra of bromo methane and methyl bromide obtained by a continuously tunable 10-bar CO2 laser based photoacoustic spectrometer.

High resolution spectral data of 100 ppmV (10(-6) per volume) concentrations of the trace gases bromo methane (BM, CH3Br), and methyl bromide (DME, (CH3)2O), buffered in synthetic air (80% N2, 20% O2) at atmospheric pressure and room temperature are reported. The spectra are recorded with a continuously tunable 10-bar CO2 laser based photoacoustic (PA) spectrometer. The tuning range covers 76 cm(-1) between 9.2 microm (1087 cm(-1)) and 10.7 microm (935 cm(-1)) at a constant narrow line-width of 0.018 cm(-1) (540 MHz). The non-resonant PA measuring cell employs an in-line 10-microphone array. The estimated detection limits for BM and DME are approximately 2 ppmV for a signal-to-noise ratio (SNR) of 3. This corresponds to a calculated detection limit of approximately 76 ppbV for ethylene.     

Influence of the laser fluence in infrared matrix-assisted laser desorption/ionization with a 2.94 microm Er : YAG laser and a flat-top beam profile

The dependence of the signal intensity of analyte and matrix ions on laser fluence was investigated for infrared matrix-assisted laser desorption/ionization (IR-MALDI) mass spectrometry using a flat-top laser beam profile. The beam of an Er : YAG laser (wavelength, 2.94 microm; pulse width, 90 ns) was coupled into a sapphire fiber and the homogeneously illuminated end surface of the fiber imaged on to the sample by a telescope. Three different laser spot sizes of 175, 350 and 700 microm diameter were realized. Threshold fluences of common IR matrices were determined to range from about 1000 to a few thousand J m(-2), depending on the matrix and the size of the irradiated area. In the MALDI-typical fluence range, above the detection threshold ion signals increase strongly with fluence for all matrices, with a dependence similar to that for UV-MALDI. Despite the strongly different absorption coefficients of the tested matrices, varying by more than an order of magnitude at the excitation laser wavelength, threshold fluences for equal spot sizes were found to be comparable within a factor of two. With the additional dependence of fluence on spot size, the deposited energy per volume of matrix at threshold fluence ranged from about 1 kJ mol(-1) for succinic acid to about 100 kJ mol(-1) for glycerol.     

Application of antimonide diode lasers in photoacoustic spectroscopy

First investigations of photoacoustic (PA) spectroscopy (PAS) of methane using an antimonide semiconductor laser are reported. The laser fabrication is made in two steps. The structure is firstly grown by molecular beam epitaxy, then a metallic distributed-feedback (DFB) grating is processed. The laser operates at 2371.6 nm in continuous wave and at room temperature. It demonstrates single-mode emission with typical tuning coefficients of 0.04 nm mA(-1) and 0.2 nm K(-1). PA detection of methane was performed by coupling this laser into a radial PA cell. A detection limit of 20 ppm has been achieved in a preliminary configuration that was not optimised for the laser characteristics.     

Observation of infrared free-induction decay and optical nutation signals from nitrous oxide using a current modulated quantum cascade laser

Free induction decay (FID), optical nutation, and rapid passage induced signals in nitrous oxide, under both optically thin and optically thick conditions, have been observed using a rapid current pulse modulation, or chirp, applied to the slow current ramp of a quantum cascade (QC) laser. The variation in optical depth was achieved by increasing the pressure of nitrous oxide in a long path length multipass absorption cell. This allows the variation of optical depth to be achieved over a range of low gas pressures. Since, even at the highest gas pressure used in the cell, the chirp rate of the QC laser is faster than the collisional reorientation time of the molecules, there is minimal collisional damping, allowing a large macroscopic polarization of the molecular dipoles to develop. This is referred to as rapid passage induced polarization. The resultant FID signals are enhanced due to the constructive interference between the field within the gas generated by the slow ramp of the laser (pump), and that of the fast chirp of the laser (probe) signal generated by pulse modulation of the continuously operating QC laser. The FID signals obtained at large optical depth have not been observed previously in the mid-infrared regions, and unusual oscillatory signals have been observed at the highest gas pressures used.     

Energy transfer distributed feedback dye laser using Rhodamine B-Acid blue 7 dye mixture

The characteristics of energy transfer distributed feedback dye laser (ETDFDL) are studied both theoretically and experimentally in a mixture of Rhodamine B and Acid blue 7 dyes pumped by 532 nm Nd:YAG laser. The behaviour of donor and acceptor DFDL, the dependence of their pulse width and output power on pump power and donor-acceptor concentrations are studied. Experimentally, the tunability is achieved over the spectral range 565-680 nm using a prism dye cell arrangement. The output energy of DFDL is measured at the emission peaks of donor and acceptor for different pump powers and donor-acceptor concentrations. The output pulse of DFDL is found to be as narrow as 40-ps duration, which is nearly 100-fold shorter than the pump pulse. The pulse linewidth is of the order of 0.1 A.     

Preliminary results of heterodyne detection with quantum-cascade lasers in the 9 microm region

In this paper, we describe recent results in mid-infrared heterodyne detection using quantum-cascade (QC) lasers as local oscillator (LO). In the 9 microm range, the heterodyne detection technique was first developed with CO(2) lasers and then with Pb-salt diode lasers. Quantum-cascade lasers are promising high quality tunable mid-infrared sources. We developed a quantum-cascade laser based heterodyne spectrometer. Atmospheric absorption spectra of ozone are presented.     

Laser flash photolysis of tert-butyl aroylperbenzoates: kinetics of the singlet and triplet states and the aroylphenyl radicals

tert-Butyl aroylperbenzoates (1-4) were studied by laser flash photolysis (LFP). LFP (380 nm, pulse width approximately 350 fs) of 2 and 3 allowed direct observation of their singlet states, which showed broad absorption (lambda(max) approximately 625 nm; tau approximately 20 and approximately 7.9 ps, respectively). The triplet state of each (lambda(max) approximately 530-560 nm) rapidly dissociates by O-O cleavage as indicated by the short triplet lifetimes (e.g., triplet lifetime of 3 approximately 0.74 ns). The approximately 550 nm absorption obtained from the 355 nm LFP (pulse width approximately 7 ns) of 1, 2, and 4 has been assigned to the corresponding aroylphenyl radicals. Two representative radicals (4-benzoylphenyl 5 and 3-(4'-methylbenzoyl)phenyl 6) investigated in detail showed solvent-dependent lifetimes. Absolute bimolecular rate constants of reactions of these radicals with various quenchers including double-bond-containing monomers have been observed to range from 7.56 x 10(7) to 1.68 x 10(9) M(-1) s(-1) in CCl(4) at room temperature. A possible structure of the aroylphenyl radicals and the transition responsible for the 550 nm absorption are discussed.     

High precision measurements of atmospheric nitrous oxide and methane using thermoelectrically cooled mid-infrared quantum cascade lasers and detectors

A compact, fast response, mid-infrared absorption spectrometer using thermoelectrically (TE) cooled pulsed quantum cascade (QC) lasers and TE detectors has been developed to demonstrate the applicability of QC lasers for high precision measurements of nitrous oxide and methane in the earth's atmosphere. Reduced pressure extractive sampling with a 56 m path length, 0.5 l volume, multiple pass absorption cell allows a time response of <0.1s which is suitable for eddy correlation flux measurements for these gases. Precision of 0.3 ppb (rms, 1s averaging time) or 0.1% of the ambient concentration for N(2)O (4 ppb or 0.2% of ambient for CH(4)), has been demonstrated using QC lasers at 4.5 microm (7.9 microm for CH(4)), corresponding to an absorbance precision of 4 x 10(-5) Hz(-1/2) (8 x 10(-5) Hz(-1/2) for CH(4)). Stabilization of the temperature of the optical bench and the pulse electronics results in a minimum Allan variance corresponding to 0.06 ppb for N(2)O with an averaging time of 100 s (0.7 ppb with an averaging time of 200 s for CH(4)). The instrument is capable of long-term, unattended, continuous operation without cryogenic cooling of either laser or detector.     

Preliminary results of heterodyne detection with quantum-cascade lasers in the 9 μm region

In this paper, we describe recent results in mid-infrared heterodyne detection using quantum-cascade (QC) lasers as local oscillator (LO). In the 9 μm range, the heterodyne detection technique was first developed with CO₂ lasers and then with Pb-salt diode lasers. Quantum-cascade lasers are promising high quality tunable mid-infrared sources. We developed a quantum-cascade laser based heterodyne spectrometer. Atmospheric absorption spectra of ozone are presented.     

Pulsed Laser Photoacoustic Instrument Operating under Visible and Ultraviolet Range

A pulsed laser photoacoustic (PA) instrument operating under visible and ultraviolet range was reported, which used a YAG pumped dye laser (width 8 ns, repetition rate 10 Hz) as the light source. Photoacoustic spectra of C2H2 overtone excitation and A1Au←X1Σ+g electronic transition were obtained using the instrument and the dependence of PA signal intensity on the sample pressure and the laser energy was measured. The application of pulsed PA to electronic transition was less reported before. Because of the simplification of its theoretical treatment and experimental operation, the pulsed PA instrument can replace resonant (or non-resonant) moderate cw PA instrument in almost all the cases except the ultra high-resolution spectroscopy. The difference between pulsed and cw moderate PA was also discussed in the text.     

A tunable picosecond dye laser for use in dioxin analysis.

A distributed-feedback dye laser with a quenching cavity was designed and constructed for generating a tunable picosecond pulse with a narrow spectral linewidth. This nearly transform-limited pulse was succeedingly amplified by a triple-pass off-axis amplifier. The pulse duration and the spectral linewidth were 60 ps and 9.4 pm, respectively. The amplified pulse was frequency-doubled by second-harmonic generation, producing a 0.5-mJ pulse with no background emission. The potential advantage of this laser in the analysis of dioxin based on supersonic jet/resonance-enhanced multiphoton ionization/mass spectrometry is discussed.     

Investigation of Nonlinear Optical Modulation Characteristics of MXene VCrC for Pulsed Lasers

We report the surface morphology and the nonlinear absorption characteristics of MXene VCrC nanosheets prepared by the liquid-phase exfoliation method. The self-made MXene VCrC was applied as a saturable absorber in the Tm:YAP laser experiments, performing excellent Q-switching optical modulation characteristics in infrared range. With this absorber, a stable passively Q-switched 2 μm laser was achieved. Under an incident pump power of 3.52 W, a maximum output power of 280 mW was obtained with a T = 3% output coupler at a repetition frequency of 49 kHz. The corresponding pulse energy and peak power were 5.7 μJ and 6.6 W, respectively. The shortest pulse duration was 658 ns at the repetition rate of 63 kHz with a T = 1% output coupler.     

Equilibrium studies of mercury(II) complexes with penicillamine

A solid-phase microextraction method coupled with a flame photometric detector was developed for the analysis of organophosphorus pesticides in water. Two kinds of fiber (100 mum polydimethyl siloxane (PDMS) and 85 mum polyacrylate (PA) fibers) were used and compared. Parameters that may affect the extraction, such as the duration of absorption and desorption, temperature of absorption, ionic strength, elutropic strength, and concentration of humic acid were investigated. Higher sensitivity and lower detection limits were achieved using a PA fiber than using a PDMS fiber. The detection limit is less than 0.3 mug l(-1) for most of the analytes, except for mevinphos (420 mug l(-1)). The precision is better than 9%.     

1-(芘-1-基)-3-(4-甲氧基苯基)丙烯酮的合成及三阶非线性光学性质

合成了一种新的有机非线性光学(NLO)材料1-(芘-1-基)-3-(4-甲氧基苯基)丙烯酮(PMPAK),通过¹H NMR、IR、HR-MS和元素分析表征其结构。 以Nd:YAG-Laser System作为光源,激光波长450 nm,脉冲宽度4 ns(FWHM),采用4f相位相干成像技术测定了PMPAK的三阶NLO性质并确定了相关参数:非线性折射率n₂=-1.84×10^-16 m²/W,非线性吸收系数β=2.53×10^-9 m/W,非线性极化率χ⁽³⁾=1.137×10^-10 esu。     

Mie lidar observations of lower tropospheric aerosols and clouds

Mie lidar system is developed at Laser Science and Technology Centre, Delhi (28.38°N, 77.12°E) by using minimal number of commercially available off-the-shelf components. Neodymium Yttrium Aluminum Garnet (Nd:YAG) laser operating at 1064nm with variable pulse energies between 25 and 400 mJ with 10 Hz repetition rate and 7ns pulse duration is used as a transmitter and off-axis CASSEGRAIN telescope with 100mm diameter as a receiver. Silicon avalanche photodiode (Si-APD) module with built-in preamplifier and front-end optics is used as detector. This system has been developed for the studies of lower tropospheric aerosols and clouds. Some experiments have been conducted using this set up and preliminary results are discussed. The characteristics of backscattered signals for various transmitter pulse energies are also studied. Atmospheric aerosol extinction coefficient values are calculated using Klett lidar inversion algorithm. The extinction coefficient, in general, falls with range in the lower troposphere and the values lie typically in the range 7.5×10(-5) m(-1) to 1.12×10(-4) m(-1) in the absence of any cloud whereas this value shoots maximum up to 1.267×10(-3) m(-1) (peak extinction) in the presence of clouds.     

Dihydrophenanthrene-type intermediates during photoreaction of trans-4'-benzyl-5-styrylfuran

[structure: see text] Photoreaction of trans-4'-benzyl-5-styrylfuran (trans-BSF) has been studied by the 355-nm laser flash photolysis (LFP) in CH2Cl2 using a Nd3+:YAG laser (30 ps, 5 mJ pulse(-1) or 5 ns, 30 mJ pulse(-1)). Transient fluorescence and absorption spectra assigned to the singlet excited trans-BSF were observed during the 30-ps LFP, whereas a transient absorption spectrum with two peaks at 400 and 510 nm, assigned to the trans-fused dihydrophenanthrene (DHP)-type intermediate (DP1), was observed during the 5-ns LFP. It is clearly suggested that a two-photon absorption process is involved in the formation of DP1. The first photoreaction is the photoisomerization of trans-BSF, which occurs to give cis-BSF. The second photoreaction process is photocyclization of cis-BSF, which occurs to give DP1 decaying with the half lifetime (tau1/2) of 2.8-4.0 micros to produce another DHP-type intermediate (DP2) with an absorption peak at 400 nm in the absence of O2, through [1,9]-hydrogen shift. DP2 decayed with tau1/2 > 500 micros to give the product through aromatization. In O2-saturated CH2Cl2, DP1 decayed with tau1/2 = 250 ns to give a radical intermediate (X) with two peaks at 410 and 510 nm, through hydrogen abstraction of DP1 by O2. X decayed with tau1/2 = 150 micros to give the product through successive hydrogen abstraction.