Frequency- and wavelength-modulation spectroscopies: Comparison of experimental methods using an AlGaAs diode laser

Low-wavelength modulation (1 kHz), high-wavelength modulation (100 MHz) and two-tone frequency modulation (390±5 MHz) spectroscopies are systematically compared by measuring the minimum detectable absorption achieved using an AlGaAs diode laser tuned on a third-overtone methane transition at 886 nm. From the S/N behavior has been extrapolated a minimum relative absorption (1 Hz of bandwidth) of 4.5(1)×10^–7 for the LMW, 9.7(3)×10^–8 for the HWM and 6.4(2)×10^–8 for the TTFM. In the LWM case the detection-limit value is represented by the laser amplitude 1/f excess noise, while for the high-frequency detection techniques this contribution is negligible with respect to other noise sources. These detection limits well agree with the calculated quantum limited values based on measured laser power, modulation index, noise figure of the electronic components, and other parameters of the apparatus.     

Optically stabilized tunable diode-laser system for saturation spectroscopy

We present an optically stabilized lead-salt diode-laser system which is the nucleus of a very-high-resolution instrument for sub-Doppler molecular spectroscopy in the mid-infrared. By application of external optical feedback, we have narrowed the diode-laser linewidth by two orders of magnitude, yielding a spectral width of less than 200 kHz. The diode- laser frequency is stabilized and controlled via the external reflector by variable-frequency offset-locking the diode-laser to a CO laser frequency. This substantial improvement in the spectral properties enabled us to perform a Lamb-dip experiment on a carbonyl sulfide (OCS) absorption line near 1985 cm^–1. We were able to detect a saturated dispersion signal at low pressure (5 Pa) with a signal-to-noise ratio of several thousand. The present paper describes the unique features of the optically stabilized tunable diode-laser system and its use as a spectroscopic tool for sub-Doppler applications.     

Optoacoustic cross-section measurements for ir pulses: CO2 laser absorption by CF3I

The pulsed optoacoustic method is studied to measure absolute infrared multiphoton absorption cross sections. The influence of the thermalisation by the walls of the cell is shown to be very important at low pressure. This influence is analysed both experimentally and theoretically by solving the coupled diffusion and relaxation equations for vibrational and translational energies. The sensitivity of the method is limited by a spurious pressure signal present even with non-absorbing gases. This parasitic signal is attributed to an absorption located on the inner surface of the windows of the cell. For instance, using KCl windows, the observed spurious signal corresponds to about 10⁻⁴ of the total laser energy, transmitted from the windows to the gas. This proportion is independent on the energy fluence. Taking care of these limitations, we have measured the absorption cross section of CF₃I at the different wavelengths of the (001–020) transitions of the CO₂ laser. The typical energy fluences in these experiments were varied from 10⁻³ to 1J/cm². To be in collision free conditions, the CF₃I pressure was made equal to 0.2 Torr.     

The limits of signal averaging in atmospheric trace-gas monitoring by tunable diode-laser absorption spectroscopy (TDLAS)

Modern research in atmospheric chemistry requires highly sensitive techniques for the measurement of concentrations of free radicals which determine the rate of photochemical destruction of most atmospheric pollutants. Tunable diode-laser absorption spectroscopy (TDLAS) has already been successfully used for measurements of very low concentrations of stable gases, but further improvement in its sensitivity by signal averaging has been limited by the stability of the instrument. In this paper the concept of the Allan variance is utilized to analyze the stability of an existing frequency-modulated (FM) TDLAS instrument leading to a detection limit for NO₂ of 34 pptv at 6 Hz detection bandwidth. The stability of the instrument allows averaging over 60 s. Taking into account the measuring cycle consisting of the determination of the sample spectra and zero air spectra as well as gas exchange in the absorption cell, the detection limit achievable with this particular instrument was 10 pptv within 25 s under laboratory conditions. Possibilities of further improvement of the detection limit are discussed.     

Tunnel barrier and noncollinear magnetization effects on shot noise in ferromagnetic/semiconductor/ferromagnetic heterojunctions

Based on the scattering approach, we investigate transport properties of electrons in a one-dimensional waveguide that contains a ferromagnetic/semiconductor/ferromagnetic heterojunction and tunnel barriers in the presence of Rashba and Dresselhaus spin-orbit interactions. We simultaneously consider significant quantum size effects, quantum coherence, Rashba and Dresselhaus spin-orbit interactions and noncollinear magnetizations. It is found that the tunnel barrier plays a decisive role in the transmission coefficient and shot noise of the ballistic spin electron transport through the heterojunction. When the small tunnel barriers are considered, the transport properties of electrons are quite different from those without tunnel barriers.     

Degenerate four-wave mixing in nitrogen dioxide: Application to combustion diagnostics

Single shot degenerate four wave mixing (DFWM) images of the distribution of nitrogen dioxide (NO₂) doped into a propane/air flame at concentrations of the order of 7000 ppm have been obtained. These images indicate the relative concentration of NO₂ in different parts of the flame with an estimated spatial resolution of 150 m.Initial experiments were performed using NO₂ in a glass cell with nitrogen buffer gas. DFWM signals were generated using both the frequency doubled output of a pulsed ND:YAG laser and the tunable blue output of an excimer pumped dye laser. The signal was investigated as a function of laser power, NO₂ concentration and buffer gas pressure. In addition, spectra of NO₂ in the region 450 to 480 nm were obtained.Signals were then sought in both a cold air/NO₂ gas flow and an ignited mixture of propane and air seeded with NO₂, using a DFWM imaging geometry. The resulting images from the flame demonstrate the disappearance of the NO₂ molecules in the flame interaction zone.This work was done when previously employed by AEA Technology at Harwell     

Sensitivity enhancement in thermal lens laser spectrometry

A novel experimental configuration for thermal lens detection is described. The method makes use of optical filtering of the probe beam by means of a circular aperture. This considerably reduces noise associated with intensity fluctuations of the probe beam. The technique provides an enhancement of the signal-to-noise ratio by almost one order of magnitude as compared to other thermal lens laser spectrometers. A theoretical calculation of the signal enhancement associated with optical filtering of the probe beam is presented. Furthermore, experiments on methyl blue dissolved in ethylalcohol are described which verify the theoretical predictions.     

Spatial mapping of flame radical emission using a spectroscopic multi-colour imaging system

An intensified multi-colour digital imaging system allowing simultaneous monitoring of light from an object in four wavelength bands was used for flame emission studies. The spatial distribution of the molecular emission from different flame radicals, such as OH, C₂, CH, and CN was recorded, also in the presence of a heavy background due to Planck-radiating soot particles. Exposure times down to 8 s could be reached allowing studies of turbulent flames. The imaging spectroscopic recordings were supported by simultaneous point monitoring of the full emission spectrum. A technique for imaging flow measurements using a spectroscopic gas correlation technique is proposed.     

A new method to measure the wavelength of single-mode pulsed lasers with a scanning Michelson interferometer

We report on the possibility to measure the wave-lengths of pulsed single-mode lasers by means of a two-beam Michelson interferometer in motion [1,2]. The corner reflector moves with a nearly constant speed creating a path differenceL so thatL/C 1/, being the spectral width of the laser to be measured. The reference laser is a stabilized He-Ne (Spectra-Physics, model 117 A) to a precision of the order of two parts in 10⁹. The fringe pattern of the two beams (reference beam and measured beam) is sampled simultaneously with a repetition rate of 40 ms. With this new method, the frequency doubled injection-seeded Nd: YAG laser wavelength has been measured with an accuracy of the order of 1.5 in 10⁸3 × 10^–4 cm^–1 at 532nm.     

Detection of methane in air using diode-laser pumped difference-frequency generation near 3.2 μm

Spectroscopic detection of the methane in natural air using an 800 nm diode laser and a diode-pumped 1064 nm Nd:YAG laser to produce tunable light near 3.2 µm is reported. The lasers were pump sources for ring-cavity-enhanced tunable difference-frequency mixing in AgGaS₂. IR frequency tuning between 3076 and 3183 cm^–1 was performed by crystal rotation and tuning of the extended-cavity diode laser. Feedback stabilization of the IR power reduced intensity noise below the detector noise level. Direct absorption and wavelength-modulation (2f) spectroscopy of the methane in natural air at 10.7 kPa (80 torr) were performed in a 1 m single-pass cell with 1 µW probe power. Methane has also been detected using a 3.2 µm confocal build-up cavity in conjunction with an intracavity absorption cell. The best methane detection limit observed was 12 ppb m (Hz.)^–1/2.     

Studies on the enhancement of photoacoustic signals from non-porous solids in the presence of volatile liquids

Studies have been carried out on the enhancement of photoacoustic signals from non-porous solids in the presence of volatile liquids in order to understand the mechanism of enhancement. Dependence of enhancement on equilibration time, absorption coefficient, length of gas phase, illumination intensity, coupling gas together with influence of wall temperature, and relative vapour pressure have been presented. Experimental results are discussed in terms of existing theories and the role of the adsorbed liquid layer in the enhancement has been emphasized. A brief theoretical discussion has been presented to show that the enhancement is due to the more efficient transfer of heat to the gas phase from the solid.Contribution No. 379 from Solid State and Structural Chemistry Unit     

Temperature measurement using degenerate four-wave mixing with non-saturating laser powers

We report the use of Degenerate Four-Wave Mixing (DFWM) in the OHA ^{2 +} X ² ( = 0 = 0) band for temperature determination in a propane/air flame using laser powers below the saturation level. We show that at these low power levels the dependence of the signal on the dipole moment for the transition has to be established before meaningful temperature data can be obtained. This presents a paradox in that the temperature has to be known before the form of the dependence on the dipole moment can be determined. Solutions to this paradox are presented. We also show that absorption of the laser beams in this OH band system cannot be neglected and that failure to correctly account for the absorption leads to a large over estimate of the flame temperature. Furthermore, we show that the accuracy of the absorption-corrected temperature is critically dependent on the accuracy with which the measurement position within the flame is known. Finally, the temperature calculated from DFWM spectra using the correct dipole moment power and absorption is compared to the temperatures obtained using Laser-Induced Fluorescence (LIF) and Coherent Anti-Stokes Raman Spectroscopy (CARS).     

Sampling comb generation and precision in FIR interferometric spectrometers

Maximum acceptable random errors in the sampling comb of FIR interferometers are discussed in relation to required resolving power. Direct measurements of sampling interval variability are presented for two stepper motors and two continuous motor drives. All four systems give variations greater than that permitted by a relation due to Sakai for high resolution measurements at wavenumbers above 40 cm⁻¹.     

Negative excess noise in quantum conductors

We predict that in quantum conductors the excess noise can be absent or even negative provided the energy dependence of the electron transmission probability at the Fermi energy is sufficiently sharp. In other words the current (or voltage) fluctuations under transport conditions can be less than in equilibrium. As examples for this surprising behavior we consider resonant tunneling, ballistic point contacts and the integer quantum Hall effect.Work performed within the research program of the Sonderforschungsbereich 341, Köln-Aachen-Jülich     

One-dimensional semiconductor in a polar solvent: Solvation and low-frequency dynamics of an excess charge carrier

Due to solvation, excess charge carriers on 1d semiconductor nanostructures immersed in polar solvents undergo self-localization into polaronic states. Using a simplified theoretical model for small-diameter structures, we study low-frequency dynamical properties of resulting 1d adiabatic polarons. The combined microscopic dynamics of the electronic charge density and the solvent leads to macroscopic Langevin dynamics of a polaron and to the appearance of local dielectric relaxation modes. Polaron mobility is evaluated as a function of system parameters. Numerical estimates indicate that the solvated carriers can have mobilities orders of magnitude lower than the intrinsic values.     

Preparation and Size Characterization of Silver Nanoparticles Produced by Femtosecond Laser Ablation in Water

Femtosecond laser ablation of silver plate placed in water is used to produce nanoparticle suspension. The method is easy to operate and the suspension is relatively stable. The optical properties and the size distribution of the suspension are studied with UV-vis absorption spectroscopy and dynamic light scattering, respectively. The shape of the nanoparticles is investigated by an atomic force microscope, which is near spherical. There are two kinds of nanoparticles, small particles with diameter about 35 nm, and large particles with diameter about 120 nm.     

High-stability reference setup for photoacoustic spectroscopy

2 laser at 9.676 μm. Received: 2 December 1996/Revised version: 2 April 1997     

Amplitude noise suppression in high-repetition-rate pulse train generation from a frequency-modulated Er-Yb laser

A detailed experimental analysis of the amplitude noise in high-repetition-rate picosecond pulse trains generated by spectral filtering of a frequency-modulated Er-Yb:glass laser is reported. Two distinct sources of noise are identified, and stabilization techniques for noise suppression are proposed and experimentally demonstrated. Intensity noise suppression of ∼20 dB, corresponding to less than 2% residual amplitude fluctuations of the pulse train, has been achieved at repetition rates of 2.5 GHz and 5 GHz with pulse durations of ∼50 ps. Received: 28 July 1999 / Revised version: 13 September 1999 / Published online: 20 October 1999     

Second-harmonic interferometric spectroscopy of buried interfaces of column IV semiconductors

The technique of combined optical second-harmonic (SH) intensity and phase spectroscopy, which is the spectroscopic modification of SH phase measurements, is proposed to study the nonlinear optical response of semiconductor interfaces with spectrally close resonant contributions. The spectral dependences of SH intensity and phase from oxidised Si (111) and Ge (111) surfaces are studied in the range of 3.5- to 5-eV SH photon energy. The resonant behaviour of combined SH spectra is associated with a superposition of contributions from direct interband transitions at several critical points of Si and Ge band structures. Received: 16 October 2001 / Revised version: 16 April 2002 / Published online: 6 June 2002